Conference Program & Book of Abstracts

CONFERENCE PROGRAM
AND BOOK OF ABSTRACTS
w w w.e aaop4.com
CONFERENCE
PROGRAM AND
BOOK OF ABSTRACTS

Organised By:

EAAOP
CO N F ER EN C E
P RO G R AM A N D
BOOK O F A BS T RACTS
21-24 October, 2015 Athens Greece
EDIT O RI A L Ma n tza vinos Dionissios , Dept. of
T EA M Chemical Engineering, University of
Patras, Greece

Po u l i o s I oannis , Dept. of Chemistry,

Aristotle University of Thessaloniki,
Greece

Ber b er i d ou, C. , Dept. of Chemistry,

AUTh

K i tsi o u , V. , Dept. of Chemistry, AUTh

Tso u machidou S . , Dept. of Chemistry,

AUTh

C O N TEN T Ga n i ti s Dimitrios
EDIT O RS K o kko tz is Evang elos

IN T ER IO R K o kko tz is Evang elos

DES IGN &
C OV ER

2
 WELCO ME
T O EAAO P 4
C O N FERENCE

O n behalf of the Organizing and International Scientific Committees, we are glad to invite
you to attend the 4th European Conference on Environmental Applications of Advanced
Oxidation Processes EAAOP4 that will be held in Athens, Greece, on October 21-24, 2015.

T he objective of the conference is to bring together scientists, engineers and other environ-
mental professionals to present their findings and discuss future trends and directions con-
cerning various Environmental Applications of Advanced Oxidation Processes (AOPs).

T he presentations will focus on the scientific and technological advances of AOPs for the
remediation of surface water, drinking water, groundwater, municipal and industrial waste-
water, air and soil contaminated with various recalcitrant compounds, either alone or in con-
junction with other processes.

T his is the fourth event of the well-established EAAOP conferences with the previous three
having been held in Chania, Greece (2006), Nicosia, Cyprus (2009) and Almeria, Spain
(2013).

T he Organizing Committee truly hopes that the EAAOP 4 program will reflect the high
commitment and exceptional profile of the international community working in this field.
Young researchers are called to participate and to interact closely with senior scientists, com-
panies and stakeholder representatives, engaging open and vivid discussions throughout the
whole meeting. Invited lectures, oral presentations and poster sessions will take place at the
premises of luxurious TITANIA Hotel, while an appealing social program is being planned to
provide you with a taste of genuine Hellenic hospitality.

F ollowing the conference, the Scientific Committee shall invite the authors of selected con-
tributions to submit full papers for publication in special issues of various journals.

Looking forward to meeting you in Athens in October 2015 (21-24 October 2015).

On behalf of the Organizing and Scientific Committees,

Dionissios Mantza vinos

Ioannis Poulios
Organizing Chairs

3
 INDEX

PA G E S PA G E S PA G E S

24-27 28-53 54-57

123
SECTION SECTION SECTION

COMMITTEES PROGRAM DISTIN-

GUISHED
TA L K

O rg a n iz in g Chai rs.. . . . . . . . . . . . 26 Di s ti ng u i s hed Ta l k.................. 30 D T 1 ...............................................56

O rg a n iz in g Commi ttee .. . . . . 26
S ci en tific Commi ttee . . . . . . . . . 2 7
Pl ena r y Ta l ks
1 st DAY ................................... 30
2 nd DAY .................................. 37
3 r d DAY ................................... 38
O r a l Pr es enta ti ons
1 st DAY ................................... 30
2 nd DAY .................................. 34
3 r d DAY ................................... 38
Pos ter Pr es enta ti ons
1 st DAY ................................... 42
2 nd DAY .................................. 46
3 r d DAY ................................... 50

4
 EAAOP 2015

PA G E S PA G E S PA G E S

58-69 70-143 144-219

456
SECTION SECTION SECTION

P L E N A RY ORAL POSTER
TALKS PRESENTATIONS PRESENTATIONS

1 s t DAY 1 st DAY 1 s t DAY

Room B........................................60
PT2 .............................................60
2 ndDAY
Room B........................................62
PT4 .............................................62
3 r d DAY
Room B........................................63
PT5 .............................................63
Room A..........................................72 Poster Session 1...........................146
Room B..........................................80
2 n d DAY
Room C..........................................88
Poster Session 2...........................172
2 nd DAY
3 r d DAY
Room A..........................................96
Poster Session 3...........................196
Room B........................................104
Room C........................................112
3 r d DAY
Room A........................................122
Room B........................................128
Room C........................................136

5
 INDEX
SECTION PA G E S

DISTIN-
3 GUISHED
TA L K
54-57
DT1 Prof. Christos S. Zerefos MAN-MADE INTERFERENCE WITH THE OXIDIZING 56
CAPACITY OF THE ATMOSPHERE OVER THE
EASTERN MEDITERRANEAN

SECTION PA G E S

P L E N A RY
4 TALKS 58-69
PT1 Prof. Timothy J. Mason SONOCHEMISTRY AND ITS USE IN ADVANCED
OXIDATION PROCESSES
PT2 Dr.Silvio Canonica INDIRECT PHOTOTRANSFORMATION OF ORGANIC 60
CONTAMINANTS IN SURFACE WATERS: EXCITED
TRIPLET STATES AS PHOTOOXIDANTS
PT3 Prof. Dimitrios Kondarides PRODUCTION OF RENEWABLE HYDROGEN OVER
IRRADIATED SEMICONDUCTOR PHOTOCATALYSTS
PT4 Prof. Dionysios D. Dionysiou TREATMENT OF CONTAMINANTS OF EMERGING 62
CONCERN IN WATER USING SULFATE
RADICAL-BASED ADVANCED OXIDATION
PROCESSES
PT5 Prof. Manuel A. Rodrigo ELECTROCHEMICAL OXIDATION WITH DIAMOND 63
ELECTRODES: FACTS AND PROMISES

SECTION PA G E S

ORAL
5 PRESENTATIONS 70-143
PHOTOCATALYTIC OXIDATION
MORPHOLOGY-DEPENDENT PHOTOCATALYTIC
ACTIVITY OF OCTAHEDRAL ANATASE PARTICLES
A1-1 Z. Wei, E. Kowalska, B. Ohtani 72
PREPARED BY ULTRASONICATION-HYDRO-
THERMAL REACTION
M. Stucchi, C. Bianchi, C. Pirola, G.
COPPER NPS DECORATED TITANIA TO IMPROVE THE
Cerratob, S. Morandi, C. Argirusis, G.
A1-2 PHOTOACTIVITY UNDER VISIBLE LIGHT: A NOVEL 72
Sourkouni, A. Naldoni, S. Vitalia V. Ca-
SYNTHESIS BY HIGH ENERGY US
pucci
C. Bianchi, M. Stucchi, C. Pirola, G. Cer- PHENOL PHOTODEGRADATION IN PRESENCE OF
A1-3 rato, S. Morandi, B. Sacchia, S. Vitali, V. NANO OR MICRO-TiO2: PERFORMANCE COMPARISON 73
Capucci AND STUDY OF THE DIFFERENT BY-PRODUCTS
PHOTOCATALYTIC OXIDATION USING COMPOSITE
A1-4 D. Selishchev, D. Kozlov PHOTOCATALYSTS FOR EFFECTIVE 73
NEUTRALIZATION OF CHEMICAL WARFARE AGENTS

6
 EAAOP 2015

PREPARATION AND CHARACTERIZATION OF

TITANIUM DIOXIDE PHOTOCATALYST SUPPORTED
A1-5 M.Visa and A. Duta 74
ON FLY ASH PARTICLES. EVALUATION OF PHOTO-
CATALYTIC ACTIVITY IN WASTEWATER TREATMENT
INFLUENCE OF FLAVINS ADSORPTION ON TiO2 IN
M. Pandiri, N. Shaham-Waldmann, Y.
A1-6 THE PHOTO OXIDATION EFFICIENCY OF AIR 74
Paz, F.W. Foss, K. Rajeshwar
CONTAMINANTS
PHOTOCATALYTIC ACTIVITY OF Li AND KDOPED
A1-7 H. Benhebal, St. D. Lambert 75
ZnO UNDER SOLAR LIGHT IRRADIATION
PHOTOCATALYTIC EFFICIENCY OF RETICULATED
M. Konyar, T. Yldz, M. Aksoy, H.C. Yat-
A1-8 ZnO STRUCTURE IN DEGRADATION OF ACID RED 88 75
maz, K. ztrk
AZO DYE
INFLUENCE OF THE SYNTHESIS METHOD ON THE
M. J. Rivero, P. Ribao, S. Dominguez, I.
A1-9 PHOTOCATALYTIC ACTIVITY OF GRAPHENE OXIDE/ 76
Ortiz
TITANIUM DIOXIDE COMPOSITES
A.W. Morawski , A. Wanag, E. Kusiak
PREPARATION AND CHARACTERIZATION OF
Nejman, J. Kapica-Kozar, . Kowalczyk,
A1-10 VISIBLE LIGHT-ACTIVE TiO2-REDUCED GRAPHENE 76
B. Ohtani, J. Ostrowska, M. Aksienionek,
OXIDE PHOTOCATALYSTS
L. Lipiska
M. L. Gimenes, J.C.M. Vicentini, M.H.N.
A NOVEL PHOTOCATALYSIS APPLICATION WITH
A1-11 Olsen Scaliante, N.R.C. Fernandes-Mach- 77
REDUCED SIZE CRYSTALLITE TiO2
ado, M. de Souza
BISMUTH OXIDE THIN FILMS DEPOSITED BY
A1-12 J.C. Medina, M. Bizarro, S.E. Rodil MAGNETRON SPUTTERING WITH INTERESTING 77
PHOTOCATALYTIC PROPERTIES
P. Garca-Muoz, G.Pliego, B. Barbero,
ILMENITE AND ILMENITE MODIFIED AS CATALYST
A1-13 J. Zazo, J.A. Casas, A. Bahamonde, J.J. 78
FOR CWPO-PHOTOASSISTED PROCESS
Rodrguez
J. Marugn, C. Casado, C. COMPARATIVE STUDY BETWEEN THE ACTIVITY OF
A1-14 Garca-Caibano, C. Adn, R. van Griek- TiO2 NANOPARTICLES AND TiO2 NANOTUBES ON 78
en PHOTOCATALYTIC MEMBRANES
ELECTROCHEMICAL PRODUCTION AND PHOTO-
A1-15 B.Haspulat, H. Kam CATALYTIC ACTIVITY OF Ag DOPED POLYANILINE 79
FILMS
ADVANCED OXIDATION PROCESSES BASED ON
A1-16 M. Zhou, Y. Pan, X. Li, L. Xu PRE-MAGNETIZATION IRON FOR HIGHLY EFFICIENT 79
ENVIRONMENTAL REMEDIATION

OZONATION
OZONATION OF p-HYDROXYBENZOIC ACID IN A
B1-1 M.S. Lucas, N.M. Reis, G. Li Puma 80
MULTI-ORIFICE OSCILLATORY BAFFLED REACTOR
A.G. Gonalves, J.J.M. rfo, M.F.R. CATALYTIC OZONATION OF BEZAFIBRATE IN
B1-2 Pereira SIMULATED NATURAL WATER
80
V.R. Urbano, M.G. Maniero, M.Prez- INFLUENCE OF pH AND OZONE DOSE ON
B1-3 Moya, J.R. Guimares SULFAQUINOXALINE OZONATION
81
C. Aguilar, J. Chairez, J. Rodrguez, E. STUDY OF ETHANOL EFFECT AS Co-SOLVENT IN THE
B1-4 Palacios, T. Poznyak NAPROXEN OZONATION IN PRESENCE OF NiO
81
CATALYTIC OZONATION OF ANALGESIC PHARMA-
B1-5 N.H. Ince, A.Z.-Yavas CEUTICALS USING COMMERCIAL AND 82
Pt-SUPPORTED NANOCOMPOSITES OF Al2O3
I.C. Guzmn, T. Poznyak, C. Aguilar, J. CATALYTIC OZONATION OF PHENOL AND
B1-6 Rodrguez-Santilln, I. Hernndez Prez, 4-CHLOROPHENOL IN THE PRESENCE OF THE CeO2 82
R.T. Hernndez Lpez FILM AND SUSPENSION

7
 INDEX

SEMICONTINUOUS OZONATION OF MUNICIPAL

M. Marce, B. Domejoud, S. Baig, S. Es-
B1-7 WASTEWATER EFFLUENTS: IMPORTANCE OF THE 83
plugas
WATER MATRIX
IMPACT OF OZONE AND PEROXONE ADVANCED
M. Meshref, Md. Shahinoor Islam, N. OXIDATION PROCESSES ON THE DEGRADATION OF
B1-8 Klamerth, M. Gamal El-Din NAPHTHENIC ACIDS SPECIES AND DETOXIFICATION
83
OF OIL SANDS PROCESS-AFFECTED WATER
INFLUENCE OF OZONATION AND BIODEGRADATION
K. Padzior, J. Wrbiak, A. Klepacz-Sm-
B1-9 ON THE INDUSTRIAL TEXTILE WASTE-WATER 84
ka, L. Biliska, M. Gmurek, S. Ledakowicz
TOXICITY
M.I. Aydin, B. Yuzer, B. Yurdakul, A. On- COLOR REMOVAL FROM BIOLOGICALLY TREATED
B1-10 gen, H. Selcuk TEXTILE WASTEWATER AND COST ANALYSIS
84
OCCURRENCE AND REMOVAL OF SPECIFIC
POLLUTANTS IN TREATED DENIM AND
B1-11 E. Bahadr, S.Meric 85
COTTON-POLYSTER TEXTILE WASTEWATERS BY
MEANS OF OZONE OXIDATION
PERFORMANCE EVALUATION OF NITROGEN
K. Skalska, S. Ledakowicz, R. Louwe, R. OXIDES OZONATION IN FLUE GASES FROM
B1-12 Szymczak PHOSPHATE ROCK DIGESTION PROCESS-PILOT
85
SCALE TRIALS
URBAN WASTEWATER ORGANIC MATTER AND
C. Crousier, J.-S. Pic, J. Albet, S. Baig, M.
B1-13 MICROPOLLUTANTS REMOVAL BY CATALYTIC 86
Roustan
OZONATION
TiO2 BASED MATERIALS APPLIED TO THE PHOTO-
B1-14 C.A. Orge, J.L. Faria, M.F.R. Pereira 86
CATALTYIC OZONATION OF METOLACHLOR
OPTIMIZATION OF COUPLED ADVANCED OXIDATION
F. Parrino, S. Cataldo, A. Iann, V. Loddo,
B1-15 PROCESSES AND ACTIVATED CARBONS FOR 87
E. Mirenda, L. Palmisano, D. Piazzese
PURIFICATION OF SALT WATER

CATALYTIC REDOX PROCESSES

DEGRADATION OF NAPROXEN IN AQUEOUS
C1-1 N. Dulova, I. Epold, M. Trapido SOLUTION BY H2O2, S2O82- AND COMBINED H2O2/S2O82- 88
ACTIVATED WITH CITRIC ACID CHELATED Fe2+
OXIDATION OF PRIORITY AND EMERGING
POLLUTANTS WITH PERSULFATE ACTIVATED BY
C1-2 S. Rodriguez, A. Santos, A. Romero 88
IRON. EFFECT OF IRON VALENCE AND PARTICLE
SIZE
HIERARCHICALLY-STRUCTURED CuBi2O4
C1-3 W.D. Oh, T.T. Lim, Z.L. Dong COMPOSITE FOR SULFANILAMIDE REMOVAL VIA 89
PEROXYMONOSULFATE ACTIVATION
MAGNETIC CORE-SHELL MnO2 NANOCATALYSTS
S. Wang, Y. Wang, H. Sun, H. Ming Ang,
C1-4 FOR AQUEOUS ORGANIC DEGRADATION IN 89
M. O. Tad
ADVANCED OXIDATION PROCESSES
KINETICS OF SULFATE RADICAL-MEDIATED
C1-5 W.D. Oh, T.T. Lim, Z.L. Dong OXIDATION OF BISPHENOL A CATALYZED BY CUBIC 90
CuFe2O4-Fe2O3 CATALYST
THE ROLES OF POLYCARBOXYLATES IN Cr(VI)
C1-6 B. Jiang, J. Zheng REDUCTION INDUCED BY SULFITE: INVOLVEMENT 90
OF ACTIVE RADICALS
THE UNPREDICTABLE EFFECT OF CHLORIDE AND
A. Bianco, A.B. Tour, G. Mailhot, M.
C1-7 CARBONATE RADICAL ANIONS DURING ADVANCED 91
Brigante
OXIDATION PROCESSES

8
 EAAOP 2015

REMOVAL OF METHYLENE BLUE BY FENTON LIKE

C1-8 D.I. ifi, S.Meri OXIDATION PROCESS USING NANO-ZERO-VALENT 91
IRON SUPPORTED PUMICE STONE
AN INTENSIFIED FENTON PROCESS IN A
R. Molina, M.I. Pariente, J.A. Siles, J.A.
C1-9 CONTINUOUS FIXED BED REACTOR USING LOW 92
Melero, F. Martnez
COST Fe/SiO2 CATALYSTS
DECONTAMINATION OF ANTIBIOTICS AND
P. Karaolia, E. Hapeshi, I. Michael, C.
INACTIVATION OF ANTIBIOTIC-RESISTANT
C1-11 Drosou, N. Xekoukoulotakis, D. Fat- 92
BACTERIA IN URBAN MBR WASTEWATER USING
ta-Kassinos
NOVEL GRAPHENE-BASED COMPOSITES
P. Fernndez-Ibez, M.Castro-Alfrez, MECHANISTIC MODEL FOR BACTERIA PHOTO-
C1-12 M.I. Polo-Lpez, S. Malato, J.Marugn INACTIVATION IN WATER USING SOLAR RADIATION
93
VISIBLE LIGHT PHOTOLYTIC/PHOTOCATALYTIC
DISINFECTION OF WATER SAMPLES USING
C1-13 T. Tiler, B. Erjavec, M. Plahuta, A. Pintar 93
Cu-DEPOSITED TITANATE NANOTUBE-BASED
CATALYSTS
EFFECT OF H2O2/SUNLIGHT PROCESS IN THE
G. Ferro, F. Guarino, S. Castiglione, L. SIMULTANEOUS INACTIVATION OF MULTI-DRUG
C1-14 Rizzo RESISTANT BACTERIA AND REMOVAL OF
94
ANTIBIOTIC RESISTANT GENES
COMPARATIVE EVOLUTION BETWEEN OXIDATION
PROCESSES USED FOR BACTERIAL INACTIVATION
C1-15 C. Pulgarin, M. Voumard, S. Giannakis 94
AFTER THREE DIFFERENT SECONDARY TREATMENT
METHODS
INACTIVATION AND MUTAGENICITY OF ANTIBIOTIC
C1-16 A. Fiorentino, C. Merlin, L. Rizzo RESISTANT SALMONELLA AFTER DISINFECTION BY 95
UV-C RADIATION AND TiO2 PHOTOCATALYSIS

PHOTOCATALYTIC OXIDATION
ABATEMENT OF PHARMACEUTICAL POLLUTANTS
P. Ghute, S. Sable, A. Rey, F. Beltrn, F.
A2-1 UNDER UVA LIGHT BY MAGNETICALLY SEPARABLE 96
Medina, S. Contreras
TiO2 PHOTOCATALYST
MAGNETIC SEMICONDUCTOR PHOTOCATALYSTS
A. Zieliska-Jurek, I. Wysocka, Z. Bielan,
A2-2 FOR THE DEGRADATION OF RECALCITRANT 96
J. Strychalska, J. Hupka
CHEMICALS FROM FLOW BACK WATER
EFFECT OF SINTERING TEMPERATURE AND TIME ON
J. Morales-Meja, Y.M. Vargas-Rodr-
A2-3 ANATASE AND RUTILE PHASES OF TiO2 PREPARED 97
guez, R. Almanza
BY SOL-GEL METHOD
SIGNIFICANT ENHANCEMENT OF PHOTOCATA-
A.Zieliska-Jurek, M. Janczarek, Z. Wei,
A2-4 LYTIC ACTIVITY OVER Pt-TiO2 PHOTOCATALYSTS 97
E. Kowalska
FOR PHENOL DEGRADATION
C. Trapalis, M.V. Sofianou, N. Todorova,
MORPHOSYNTHESIS OF TiO2/METAL OXIDE NANO-
A2-5 T. Giannakopoulou, T. Georgakopoulos, 98
STRUCTURES FOR OXIDATION OF AIR POLLUTANTS
K. Pomoni
ANATASE-TiO2 VERSUS RUTILE-TiO2 TO
W. Macyk, M. Buchalska,M.Kobielusz, A.
A2-6 UNDERSTAND THE DIFFERENCE IN 98
Matuszek, M.Pacia, S.Wojtya
PHOTOCATALYTIC ACTIVITY
DEGRADATION OF FLAME RETARDANT TRIS
M. Antonopoulou, P. Karagianni, I.K. (1-CHLORO-2-PROPYL) PHOSPHATE (TCPP) BY TiO2
A2-7 Konstantinou PHOTOCATALYSIS: KINETIC AND MECHANISTIC
99
STUDY
MODIFIED PP SURFACE BY PECVD FOR USE AS
M.C. Canela, M.S. Curcio, W.R. Wald-
A2-8 SUPPORT FOR TiO2 IN THE PHOTODEGRADATION OF 99
man, E. C. Rangel
FORMALDEHYDE IN GASEOUS PHASE

9
 INDEX

DETERMINATION OF PHOTOCATALYTIC ACTIVITY

A2-9 J. Krsa, M. Baudys, A. Mills 100
OF SELF-CLEANING PAINTS USING SMART INKS
SOLAR PHOTOCATALYSIS TREATMENT USING
D. Hermosilla, H. Barndk, C. Han, D.D. IMMOBILIZED NF-TIO2 COMPOSITE WITH MONO-
A2-10 Dionysiou, C. Negro, A. Blanco DISPERSE TIO2 NANOPARTICLES OF INDUSTRIAL
100
WASTEWATER CONTAINING 1,4 DIOXANE
OPTIMIZATION OF TTIP THIN-FILMS FOR REMOVAL
A2-11 C. zkal, S. Meri, D. Mantzavinos OF METHYLENE BLUE AND AMPICILLINE AND 101
INACTIVATION OF E. COLI BACTERIA
THE INFLUENCE OF INERT INGREDIENTS IN
A. Tomaevi, S. Gai, R. urovi- FORMULATIONS ON THE RATE OF
A2-12 Pejev, D. Mijin, A. Marinkovi PHOTOCATALYTIC DEGRADATION OF PESTICIDES
101
METHOMYL AND CARBOFURAN
PHOTOCATALYTIC OXIDATION OF SWEETENERS
J. Morales-Meja, D. Lpez, S. Silva, R.
A2-13 SACCHARIN AND ACESULFAME K. EFFECT OF 102
Almanza
INITIAL pH AND PERSULFATE CONCENTRATION.
A NEW SUPPORTED TiO2 FILM DEPOSITED ON
S. Murgolo, G. Mascolo, D. Nasuhoglu,
STAINLESS STEEL FOR THE PHOTOCATALYTIC
A2-14 R. Gerbasi, F. Visentin, N. El Habra, V. 102
DEGRADATION OF EMERGING ORGANIC
Yargeau
CONTAMINANTS
UV-LED TIO2 PHOTOCATALYSIS FOR THE
K. Davididou, R. Nelson, E. Chatzisyme- DEGRADATION OF BISPHENOL-A: LED VS BLACK
A2-15 on LIGHT FLUORESCENT LAMP & INVESTIGATION OF
103
KEY PARAMETERS
.L. Faria, L.M. Pastrana-Martinez, S. ASSEMBLING CELLULOSE MEMBRANES WITH
A2-16 Morales-Torres, J.L. Figueiredo, A.M.T. GO-TiO2 COMPOSITES FOR THE TREATMENT OF 103
Silva ORGANICS IN SALTY WATER

FENTON & FENTON LIKE PROCESSES

S. Esplugas, A. Afkhami, P. Marco, J. DIPHENHYDRAMINE DEGRADATION BY PHOTO-
B2-1 Gimnez FENTON UNDER DIFFERENT LIGHT SOURCES
104
EFFECT OF WATER COMPOSITION ON IRON CHELATE
B2-2 A. De Luca, R.F. Dantas, S. Esplugas 104
BASED PHOTO-FENTON PROCESS EFFICIENCY
DEGRADATION OF A NAPHTHENIC ACID MODEL
B2-3 Y. Zhang, N. Klamerth, M. Gamal El-Din COMPOUND BY NITRILOTRIACETIC ACID-MODIFIED 105
FENTON PROCESS
ACRYLIC TEXTILE DYEING WASTEWATER
L. Madeira, B.M. Esteves, C. Rodrigues, TREATMENT BY COMBINATION OF
B2-4 Rui. Boaventura, F. Maldonado-Hdar HETEROGENEOUS FENTONS OXIDATION IN A CSTR
105
AND BIOLOGICAL DEGRADATION IN A SBR
OXIDATIVE AND REDUCTIVE DEGRADATION OF AN
V.A. Sijumon, U.K. Aravind, C.T. Aravin-
B2-5 AZO DYE, AMARANTH, USING ZERO VALENT IRON 106
dakumar
NANO PARTICLES
SYNTHESIS AND EVALUATION OF A NEW
Fe/ALGINATE HETEROGENEOUS CATALYST FOR
B2-6 C. Sans, A. Cruz, S. Esplugas 106
PHOTO-FENTON AND SIMULATED SOLAR
PHOTO-FENTON AT NEUTRAL pH
TREATMENT OF REAL EFFLUENTS BY
S. Malato, S. Miralles, J.A. Sn-
B2-7 NANOFILTRATION AND SOLAR PHOTO-FENTON: 107
chez-Prez, I. Olle, A, Agera,, M. Llorca
ANALYTICAL AND TOXICOLOGY ASSESSMENT
HETEROGENEOUS FENTON-LIKE DEGRADATION OF
N. Klamerth, M. Meshref, M. Gamal El- NAPHTHENIC ACIDS MODEL COMPOUNDS BY
B2-8 Din ACTIVATED AND MESOPOROUS CARBON
107
IMPREGNATED WITH Fe, Fe2O3 AND -FeOOH.

10
 EAAOP 2015

F. Martinez, M.I. Pariente, Y. Segura, R. TOWARDS AN ENHANCED BIODEGRADABILITY OF

B2-9 Molina, I. Rodriguez, J.A. Melero AN ACTUAL PHARMACEUTICALWASTEWATER
108
CATALYTIC REMOVAL OF BINARY MIXTURE OF
H. Issa Hamoud, B. Azambre, G. Finque- DYES WITH OPPOSITE AND SIMILAR CHARGES IN
B2-10 neisel THE PRESENCE OF CERIA/H2O2 FENTON-LIKE
108
SYSTEM
EFFECT OF HYDROXYL GROUPS SUBSTITUTED IN
B2-11 N. Villota, L.M. Camarero, L.M. Lomas THE CHANGES OF SOLUTION TURBIDITY DURING 109
THE OXIDATION OF AROMATIC CONTAMINANTS
ADSORPTION-OXIDATION PROCESSES FOR
S.S. Sable, P.P. Ghute, A. Georgi, F. Medi- REMOVAL OF ORGANIC CONTAMINANTS BY
B2-12 na, S. Contreras HETEROGENEOUS FENTON-LIKE PROCESS USING
19
Pd/Fe-ZEOLITE BASEDCATALYSTS
PHOTOCATALYTIC REDUCTION OF Cr(VI) OVER
B.A. Marinho, R.O. Cristvo, J.C. Lopes,
B2-13 Fe(III)-CITRATE COMPLEXES IN A SIMULATED SOLAR 110
R.A.R. Boaventura, V.J.P. Vilar
SYSTEM
DESIGN OF TWO-COLUMN PHOTO-ELECTRO-
M. Pazos, A.Dez, E. Rosales, M.A. San-
B2-14 FENTON REACTOR FOR THE TREATMENT OF 110
romn
WINERY WASTEWATER
M. Vinatoru, M.Dukkanci, M. Shestakova THE USE OF ULTRASOUNDS FOR OXIDATION OF
B2-15 and T. Mason WATER POLLUTANTS
111
M. Trapido, T. Tenno, A. Goi, N. Dulova, BIO-RECALCITRANT POLLUTANTS REMOVAL FROM
B2-16 E. Kattel, A. Kivi, D. Klauson, K. Klein, WASTEWATER WITH COMBINATION OF THE FENTON 111
M. Viisimaa TREATMENT AND BIOOXIDATION

AOPS FOR ENERGY PRODUCTION

G. Iervolino, V. Vaiano, D. Sannino, L. PHOTOCATALYTIC HYDROGEN PRODUCTION FROM
C2-1 Rizzo, J.J. Murcia, M. Chidalgoand, J. DEGRADATION OF GLUCOSE OVER FLUORINATED 112
Navo Pt-TiO2 CATALYSTS
A. Marinas, F.J. Tenllado, V. Montes, F.J. UNEXPECTEDLY HIGH ACTIVITY OF SUPPORTED
C2-2 Urbano, J.M. Marinas, L. Ilieva, T. Taba- NOBLE METAL TiO2 IN PHOTOCATALYTIC H2 112
kova, J. Hidalgo, F.Reid PRODUCTION FROM PROPAN-2-OL
M. Gmurek, K. Bednarczykand, M. Stel- INFLUENCE OF PROCESS PARAMETERS ON
C2-3 machowski PHOTOCATALYTIC HYDROGEN PRODUCTION
113
PRODUCTION OF ENERGY-RICH GASES VIA
A. Pintar, I.G. Osojnik rnivec, P. Dji- CATALYTIC DECARBOXYLATION OF FORMIC AND
C2-4 novi, B. Erjavec ACETIC ACID IN A TRICKLE-BED REACTOR OVER
113
Ru/TiO2
WASTEWATER SLUDGES PRE-TREATED BY
Y. Segura, L. Ballesteros, F. Martnez, J.A. DIFFERENT OXIDATION SYSTEMS TO MAXIMIZE THE
C2-5 Melero BIOGAS PRODUCED IN A SUBSEQUENT ANAEROBIC
114
PROCESS
J.A. Byrne, J.W.J. Hamilton, P.K. Sharma,
A. Brown, P.S.M. Dunlop, M. Nolan, K.A. NOVEL PHOTOCATALYTIC MATERIALS FOR SOLAR
C2-6 Gray, K. Schwartzenberg, J. Notestein, E. DRIVEN CO2 REDUCTION
114
Weitz

WET AIR AND SUPERCRITICAL OXIDATION

PEROXO-GOLD MODIFIED TITANIUM NANOTUBES
C2-7 N. Drainac, B. Erjavec, A. Pintar FOR EFFECTIVE REMOVAL OF METHYL ORANGE 116
WITH CWPO UNDER AMBIENT CONDITIONS
V. Doluda, N. Lakina, V. Matveeva, E.
POLYMER-BASED NANOCATALYSTS FOR WET AIR
C2-8 Sulman, V. Molchanov, V. Bykov, A. Ste- 116
OXIDATION OF PHENOL
pacheva

11
 INDEX

SURFACTANT ENCAPSULATED HETEROPOLY-ANION

C2-9 S.K. Lua, T.T. Lim, Z.L. Dong WITH BIOLOGICAL MEMBRANE LIKE STRUCTURE 117
FOR CATALYTIC WET AIR OXIDATION
L.M. Madeira, C. Rodrigues, S. Cara- ORANGE II DYE DEGRADATION BY WET PEROXIDE
C2-10 bineiro, F. Maldonado-Hdar OXIDATION USING AN Au/Al2O3 CATALYST
117
E.M. Sulman, V.G. Matveeva, O.V.
YDROLYTIC HYDROGENATION OF CELLULOSE IN
C2-11 Manaenkov, O.V. Kistlitsa, A.E. Filatova, 118
SUBCRITICAL WATER
V.Yu. Doluda, A.I. Sidorov, M.G. Sulman

RADIATION PROCESSES
V. Salomatova, I. Pozdnyakov, V. Grivin, PHOTODEGRADATION OF BISPHENOLS:
C2-13 P. Sherin, V. Plyusnin, N. Bazhin MECHANISTIC ASPECTS
120
C. Rodrigues-Silva, M. Caianelo, M.G. GATIFLOXACIN DEGRADATION BY HYDROXYL
C2-14 Maniero, J.R. Guimares RADICALS:BYPRODUCTS AND RESIDUAL TOXICITY
120
DEGRADATION OF 17-ETHINYL ESTRADIOL IN
F. Anschuetz, M. Franke, P. Braeutigam,
C2-15 WATER BY HYDRODYNAMIC-ACOUSTIC- 121
A. Stolle, B. Ondruschka
CAVITATION: FREQUENCY EFFECTS
AMICARBAZONE DEGRADATION BY UVA-
C2-16 C. Graa, A. Velosa, A.C.Teixeira ACTIVATED PERSULFATE IN THE PRESENCE OF 121
HYDROGEN PEROXIDE OR Fe2+

PHOTOCATALYTIC OXIDATION
HETEROGENOUS AND HOMOGENOUS CATALYSIS IN
A3-1 S. Klementova, L. Doubkova 122
PHOTOCHEMICAL DEGRADATION OF CORTISOL
PROCESS INTENSIFICATION IN THE PHOTO-
W.S. Wan Mansor, E.A.C. Emmanuelson, CATALYTIC SPINNING DISC REACTOR: THE
A3-2 D.A. Patterson EFFECT OF PHOTOCATALYST MACROSTRUCTURE
122
ON TREATMENT EFFICIENCY
PHOTOCATALYTIC NO DEGRADATION:
A3-3 R. Dillert 123
MECHANISTIC AND KINETIC ASPECTS
EFFECTIVE TREATMENT OF ACRYLIC FIBRE
A3-4 W. Szeto, J.T. li, H.B. Huang, Y.C. Leung MANUFACTURING WASTEWATER USING ADVANCED 123
OXIDATION PROCESSES
FLUIDIZED-BED PHOTOCATALYTIC REACTOR:
N. Pronina, D. Klauson, S. Kamenev, T.
INFLUENCE OF OPERATING CONDITIONS ON THE
A3-5 Rudenko, K. Knnis-Beres, A. Moiseev, J. 124
ELIMINATION OF PERSISTENT EMERGING
Deubener, M. Krichevskaya
MICROPOLLUTANTS
REMOVAL OF ARSENIC FROM AQUEOUS SOLUTIONS
M.J. Lpez-Muoz, A. Arencibia, Y. Segu-
A3-6 THROUGH A COUPLED SYSTEM OF 124
ra, J.M. Arsuaga, J.M. Raez
PHOTOCATALYSIS AND ZERO-VALENT IRON
PHOTOCATALYTIC REMOVAL OF TOXICITY AND
B. Erjavec, P. Hudoklin, K. Perc. T. Tiler,
A3-7 ESTROGENICITY OF WATER DISSOLVED BIS- 125
M. Sollner Dolenc, A. Pintar
PHENOLS (BISPHENOL A, F AND AF) IN BR AND CSTR
ESR INVESTIGATION OF THE PHOTOCATALYSIS
A. Hiskia, T. Fotiou, T.M. Triantis, T. Ka-
A3-8 MECHANISM OF CYANOTOXINS UNDER VISIBLE 125
loudis, N. Ioannidis
LIGHT
AQUEOUS PHOTOCATALYTIC DEGRADATION OF
D. Klauson, M. akaravili, N. Pronina,
A3-9 SELECTED MICROPOLLUTANTS BY Pd-MODIFIED 126
M. Krichevskaya, E. Krber, V. Mikli
TITANIUM DIOXIDE
HATR-FTIR ONLINE ANALYSIS OF SURFACE SPECIES
A3-10 K. Skalska ON P25 AND Au MODIFIED TiO2 DURING PHOTO- 126
CATALYTIC OXIDATION OF NITROGEN MONOXIDE

12
 EAAOP 2015

GAS-PHASE PHOTOCATALYTIC OXIDATION OF

M. Krichevskaya, A. Moiseev, S. Preis, J.
A3-11 MIXTURES OF REFRACTORY ORGANIC COMPOUNDS: 127
Deubener
THROUGH THE NET OF PROCESS LIMITATIONS

ELECTROCHEMICAL / PHOTOELCTROCHEMICAL PROCESSES

APPLICABILITY OF ELECTROCHEMICAL OXIDATION
C. Sez, F. Souza, S. Quijorna, M.R.V.
B3-1 USING DIAMOND ANODES TO THE TREATMENT OF A 128
Lanza, P. Caizares, M. Rodrigo
SULFONYLUREA HERBICIDE
SELECTIVE ELECTROCHEMICAL DEGRADATION
J. De Coster, W. Vanherck, L. Appels, R.
B3-2 OF 4-CHLOROPHENOL AT A Ti/RuO2-IrO2 ANODE IN 128
Dewil
CHLORIDE RICH WASTEWATER
TRANSITION METAL MODIFIED CATHODE FOR
B3-3 M. Zhou, F. Yu, Y. An HETEROGENEOUS ELECTRO FENTON: PREPARATION 129
AND PERFORMANCE
AVOIDING THE FORMATION OF CHLORATES DURING
S. Cotillas, J. Llanos, P. Caizares, M.A.
B3-4 THE ELECTRODISIFECTION OF URBAN 129
Rodrigo
WASTEWATER WITH BDD ANODES
SYNERGETIC TREATMENT OF PESTICIDE
CONTAMINATED DRINKING WATER BY COMBINED
B3-5 J. Muff, H.T. Madsen, E.G. Sgaard 130
RO SEPARATION AND ELECTROCHEMICAL
DEGRADATION
ELECTROCHEMICAL DEGRADATION OF IODINATED
CONTRAST MEDIA AND OTHER PERSISTENT
ORGANIC CONTAMINANTS BY ELECTRO-
B3-6 A. Farhat, S. Tait, J. Keller, J. Radjenovic 130
CHEMICALLY ACTIVATED SULFATE AND
PERSULFATE IONS AT BORON DOPED DIAMOND
ANODES
ELECTROCATALYTIC AND PHOTOASSITED
B3-7 A. Urtiaga, B. Gmez, I. Ortiz 131
DEGRADATION OF PERFLUOROOCTANOIC ACID
PHOTOCATALYTIC DEGRADATION OF SODIUM
B3-8 H. Nguyen, C. Phan, T. Sen DODECYL SULPHATE BASED ON -Fe2O3 NANO- 131
STRUCTURE
DEGRADATION OF MICROCONTAMINANTS IN
S. W. da Silva, M.A. Siqueira Rodrigues,
B3-9 WASTEWATER BY PHOTO-ASSISTED ELECTRO- 132
A.M. Bernardes
CHEMICAL OXIDATION
IRRADIATED-ASSISTED ELECTROCHEMICAL
M.J. Martn de Vidales, C. Sez, P. PROCESSES FOR THE REMOVAL OF PERSISTENT
B3-10 Caizares, M.A. Rodrigo POLLUTANTS FROM BIOLOGICALLY TREATED
132
URBAN WASTEWATER
STUDY OF METHANOL REFORMING USING
B3-11 J. Vakros, B. Hasa, A. Katsaounis DIFFERENTIAL ELECTROCHEMICAL MASS 133
SPECTROMETRY (DEMS)

FENTON & FENTON LIKE PROCESSES

REMOVAL OF IOPAMIDOL, AN IODINATED X-RAY
I. Arslan-Alaton, T. Olmez-Hanc, G.
B3-12 CONTRAST MEDIA, BY ZERO-VALENT 134
Korkmaz, C. Sahin
ALUMINUM-ACTIVATED H2O2 AND S2O82- OXIDATION
Z. Frontistis, M. Antonopoulou, N. DEGRADATION OF ETHYL PARABEN BY HEAT-
B3-13 Potakis, A. Michailidi, B. Matthaiou, I. ACTIVATED PERSULFATE: STATISTICAL 134
Konstantinou, D. Mantzavinos EVALUATION OF OPERATING FACTORS
J.L. Casas Lpez, G. Rivas Ibaez, I. de
HOTOVOLTAIC-DRIVEN UV-LED PHOTO-FENTON: A
B3-14 la obra, M. Prez Garca, J.A. Snchez 135
NEW APPROACH FOR MICROPOLLUTANT REMOVAL
Prez

13
 INDEX

COUPLING AOP WITH OTHER PROCESSES, PILOT-SCALE STUDIES AND FIELD

APPLICATIONS
COMBINATION OF MEMBRANE TECHNOLOGY AND
O. Autin, S. Tyrrel, E. Cartmell, A. Parker,
C3-1 UV-LED/TiO2 FOR THE REMOVAL OF PATHOGENS 136
L. Williams, A. Kolios, E. McAdam
AND VOCs FROM URINE
OXIDATION AND ADSORPTION OF ARSENITE IN
C3-2 W. Ding, W. Zhou, F. Wu, J. Li AQUEOUS SOLUTIONS USING Fe-DOPED SBA-15 AND 136
PERSULFATE
NOVEL PILOT SCALE CONTINUOUS PHOTO-
A.J Karabelas, V.C. Sarasidis, K.V. Plak- CATALYTIC MEMBRANE REACTOR FOR THE
C3-3 as, S.I. Patsios, A.M. Lekkas REMOVAL OF RECALCITRANT MICRO-POLLUTANTS
137
FROM WATER
TERTIARY TREATMENT OF WASTEWATER BY
M. Brienza, S. Gutirrez Alfaro, G. Plan-
ADSORPTION AND SOLAR PHOTOCATALYSIS FOR
C3-4 tard, S. Nir, S.A. Bufo, V. Goetzand S. 137
DECONTAMINATION AND DISINFECTION OF
Chiron
SECONDARY EFFLUENTS
B. Snchez, S. Surez, I. Jansson, O. Vila-
ASSESSMENT OF THE KEY PARAMETERS OF THE
nova, B.Cadavid, J. Perez, J.O. Marrn,
PHOTOCATALYTIC PROPERTIES FOR
C3-5 A. Moral, M. Snchez, M .Palacios, L. 138
CONSTRUCTION MATERIALS: LIFE-MINOX-STREET
Nuez, B. Artiano, M. Pujadas, D. Ig-
EUROPEAN PROJECT
lesia
M. Race, R. Andreozzi, I. Di Somma, M
SOLAR PHOTOCATALYTIC PROCESSES FOR SOIL
C3-6 .Fabbricino, R. Marotta, L. Onotri, F. 138
WASHING WASTEWATER TREATMENT
Pirozzi, A. Siciliano
ELIMINATION OF ANTIBIOTIC ACTIVITY OF WATERS
CONTAMINATED WITH OXACILLIN BY PHOTO-
R.A. Torres-Palma, E. Serna-Galvis, J.
FENTON, TiO2-PHOTOCATALYSIS, SONO-
C3-7 Silva-Agredo, A. Giraldo-Aguirre, O. 139
CHEMICAL AND ELECTROCHEMICAL PROCESSES - A
Florez
COMPARATIVE STUDY ON THE EFFECTS OF
ADDITIVES
PILOT-SCALE SLURRY AND FIXED-BED SOLAR-
C3-8 A.Verma, N. T. Prakashand, A.P. Toor PHOTOCATALYTIC REACTOR FOR THE 139
DEGRADATION OF HERBICIDE ISOPROTURON
THE HEALTH RISK DECREASE WITH SIMULTANEOUS
ELIMINATION OF VOCs AND POPs CONTAINING
PARTICLES EMITTED FROM ELECTRONIC WASTE
C3-9 T.C. An, J.Y. Chen, D.L. Zhang, G.Y. Li 140
DISMANTLING WORKSHOP BY AN INTEGRATED
TECHNIQUE OF DEDUSTING WITH
DECONTAMINATION
PILOT STUDIES OF A NOVEL ELECTRO-FENTON
K. Plakas, A. Karabelas, S. Sklari, V.
C3-10 FILTER FOR THE REMOVAL OF ORGANIC 140
Zaspalis, D. Yiankakis, G. Sideropoulos
MICROPOLLUTANTS FROM POTABLE WATER
NOVEL ADVANCED OXIDATION PROCESS ON A
M.A. Morsy, Abdel-Nasser M. Kawde,
C3-11 CHEMICALLY MODIFIED GRAPHITE SURFACE WITH 141
Mohamed A. Daous, A.U. Dogan
NANOMETAL
PESTICIDE REMOVAL AND EVALUATION OF
C3-12 I. Carra, B. Jefferson, P. Jarvis DISINFECTION-BY PRODUCT FORMATION WITH 141
LED-BASED AOPs
QUANTITATIVE DETERMINATION OF H2S GAS USING
C3-13 N. Shahzad, S. Iqbal 142
KMnO4

14
 EAAOP 2015
SECTION PA G E S

P O ST ER
6 PRESENTATIONS 144-219
PHOTOCATALYTIC OXIDATION
R.G. Marques, A.M. Ferrari-Lima, V.S. USE OF ZnO AND Nb2O5 IMPREGNATED WITH SILVER
PP1-1 Santana, M. Luiz Gimenes and N.R.C. OR IRON FOR PHOTOCATALYTIC DEGRADATION OF 146
Fernandes-Machado CELLULOSE AND PAPER WASTEWATER
NOVEL ANATASE/RUTILE/BROOKITE TiO2 NANO-
. Pintar, R. Kaplan, B. Erjavec, G. COMPOSITE WITH SUPERIOR MINERALIZATION
PP1-2 Drai and J. Grdadolnik POTENTIAL FOR PHOTOCATALYTIC DEGRADATION
146
OF WATER POLLUTANTS
C. Belver, J. Bedia, M.A. lvarez-Montero SUNLIGHT PHOTOCATALYTIC PURIFICATION OF
PP1-3 and J.J. Rodriguez WATER WITH NOVEL HETERO-STRUCTURES
147
SURFACE RECONSTRUCTION OF TITANIA WITH
Kah Hon Leong, Sze Ling Liu, Min Jang, g-C3N4 AND Ag FOR EFFICIENT ELECTRONS
PP1-4 S. Ibrahim and P. Saravanan MIGRATION AND ENHANCED VISIBLE LIGHT
147
PHOTOCATALYSIS
PHOTOCATALYTIC DEGRADATION OF NOX IN A
C. L. Bianchi, M. Stucchi, C. Pirola, F. CONTINUOUS BENCH-SCALE REACTOR USING
PP1-5 Galli, S. V. and V. Capucci ACTIVE TILES, EXPERIMENTAL DATA AND
148
SIMULATIONS
M. Krichevskaya, A. Moiseev, D. Klau- IMPLEMENTATION OF TIO2 OXYGEN ADSORPTION
PP1-6 son, N. Pronina, G.Hauser, A. P. Weber, B. CAPACITIES FOR THE EVALUATION OF PHOTO- 148
Lohrengel and J. Deubener CATALYSTS ACTIVITY IN POLLUTANTS OXIDATION
PREPARATION OF TiO2 AND GRAPHENE FILM
Huiling Liu, X. Cheng, Y. Tian, F. Cui, J. DECORATED TiO2 NANO-TUBE ARRAY PHOTO-
PP1-7 Nan, J. Yao and Z. Chen ELECTRODE AND ENHANCED VISIBLE LIGHT
149
PHOTOCATALYTIC MECHANISM
PHOTODEGRADATION OF SPIRODICLOFEN,
I. Garrido, J. Fenoll, P. Flores, P. Helln, SPIROMESIFEN AND SPIROTETRAMAT IN WATER
PP1-8 N. Vela and S. Navarro USING BINARY AND TERNARY OXIDES OF TITANIUM
149
AND ZINC
I. Papailias, N. Todorova, T. Giannako- PHOTOCATALYTIC ACTIVITY OF g-C3N4-TiO2 NANO-
PP1-9 poulou, C. Trapalis and D. Demotikali COMPOSITES FOR NOX REMOVAL
150
J. Subrt, T. Sazavska, L. Krikavova, M.
SiO2-TiO2 NANOCOMPOSITE AND ITS UTILIZATION IN
PP1-10 Jakubickova, J. Jirkovsky, F. Peterka and 150
ECOLOGICAL PHOTOCATALYSIS
J. Kupcik
DEGRADATION OF EMERGING POLLUTANTS UNDER
M. Tobajas, C. Belver and J. Jose Rodri-
PP1-11 SOLAR IRRADIATION USING NOVEL TiO2-ZnO/CLAY 151
guez
NANOARCHITECTURES
SPECTROSCOPIC AND PHOTOCATALYTIC
P. Bro, M. Surwka, M. Buchalska and CHARACTERIZATION OF MODIFIED TITANIUM
PP1-12 W. Macyk DIOXIDE-BASED MATERIALS FOR WATER
151
DECONTAMINATION
PRODUCTION AND VISIBLE LIGHT PHOTO-
PP1-13 B. Haspulat, H. Kam and H. Memi CATALYTIC ACTIVITY OF Mn-DOPED ZnO 152
MICROPARTICLES
PHOTOCATALYTIC DEGRADATION OF EMERGING
P. Falaras, M. Arfanis, P. Adamou, N.
PP1-14 CONTAMINANTS VIA ADVANCED TITANIUM 152
Moustakas, M. Antoniadou and A. Kontos
DIOXIDE NANOSTRUCTURES

15
 INDEX

A SOLAR ANNULAR PHOTOREACTOR PACKED WITH

C. Rodrigues-Silva, R. Monteiro, M.
PP1-15 A MONOLITH COVERED WITH AN ACTIVE SOL-GEL 153
Dezotti, A. Silva and V. Vilar
TiO2 TO PURIFY A GAS STREAM
SYNTHESIS, CHARACTERIZATION AND PHOTO-
J. Marugan, L. A. Morais, C. Adn,
PP1-16 CATALYTIC ACTIVITY OF NIOBIUM OXIDE 153
M.P.M.A. Guedes and A.S. Arajo
MATERIALS
M. Janus, K. Zajc, J. Zatorska, E. Ku-
MODIFIED GYPSUM PLASTERS FOR PHOTO-
PP1-17 siak-Nejman, A. Czyewski and A. W. 154
CATALYTIC DEGRADATION OF ACETALDEHYDE
Morawski
THERMAL AND PHOTOCATALYTIC REACTION OF NO
PP1-18 F. Solymosi, G. Halasi and T. Bnsgi 154
WITH ETHANOL
I. Fuentes, J. L. Rodrguez, H. Tiznado, EFFECT OF LEDS DISTRIBUTION IN THE PHOTO-
PP1-19 J.M. Romo-Herrera, T. Poznyak and J.I. CATALYTIC REACTOR DURING THE TEREPHTHALIC 155
Chairez ACID OZONATION WITH VXOY/ZnO
PHOTOCATALYTIC REMOVAL OF BISPHENOL A WITH
PP1-20 S. Dominguez, M. Rivero and I. Ortiz A MAGNETICALLY SEPARABLE TiO2 155
NANOCOMPOSITE
A.Z. Yavas, B. Savun-Hekimoglu and N. SONOPHOTOCATALYTIC DEGRADATION OF
PP1-21 Ince PARACETAMOL USING Pt-TiO2 NANO-COMPOSITE
156
EFFECT OF Ag ON THE PHOTOCATALYTIC ACTIVITY
J.L. Faria, M.J. Sampaio, M.J. Lima, D.L.
PP1-22 OF ZnO SEMICONDUCTORS ASSESSED BY PHENOL 156
Baptista, A. Silva and C. Silva
CONVERSION IN AQUEOUS SOLUTIONS
S. Karapati, T. Giannakopoulou, N.
NOVEL PHOTO-EFFICIENT ANISOTROPICALLY
PP1-23 Todorova, N. Boukos, D. Dimotikali and 157
FUNCTIONALIZED PHOTOCATALYSTS
C. Trapalis
B. Lyson-Sypien, A. Kusior, M. Radecka, MODIFICATION OF GAS SENSING PROPERTIES OF
PP1-24 M. Rekas, J. ukrowski, M. Gajewska, K. TiO2 NANOMATERIALS BY ALIOVALENT AND 157
Michalow-Mauke, T. Graule ISOVALENT CATIONS
and K. ZakrzewskaM.J. Lpez-Muoz, PHOTOCATALYTIC OXIDATION OF AS(III) IN
PP1-25 L. Cerro, J.M. Raez, R. Snchez and N. AQUEOUS SOLUTION WITH TiO2 OBTAINED BY A 158
Milln MODIFIED SOLGEL METHOD
PHOTOCATALYTIC DEGRADATION OF ORGANIC DYE
J.-H. Yu, S.-H. Nam, K.-H. Hwang, H. Seo
PP1-26 (METHYLENEBLUE) OVER SULFUR DOPED TiO2 158
and J.-H. Boo
PREPARED BY SOL-GEL PROCESS
EFFECT OF OXIDATION SILVER STATE ON TiO2-CeO2
J.C. Arevalo, J.G. Torres Torres and A. PHOTOCATALYSTS FOR THE PHOTODEGRADATION
PP1-27 Silahua-Pavon OF PHENOL USING SOLAR AND SIMULATED SOLAR
159
SUNLIGHT
PHOTODEGRADATION OF 17
D. de La Cruz, J. C. Arvalo and J. G. -METHYLTESTOSTERONE WITH SIMULATED
PP1-28 Torres SOLAR RADIATION USING SUNTEST CPS+ WITH
159
TiO2-Gd3+ AND TiO2-Sm3+
P. Karagianni, M. Antonopoulou, A. Gi- PHOTOCATALYTIC DEGRADATION OF PHENOL BY
PP1-29 annakas, V. Makrigianni, I. Deligiannakis CHAR/N-TiO2 AND CHAR/N-F-TIO2 COMPOSITE 160
and I. Konstantinou PHOTOCATALYSTS
PHOTOCATALYTIC REDUCTION OF Cr(VI) BY char/
M. Antonopoulou, I. Chondrodimou and I. TiO2 COMPOSITE PHOTOCATALYSTS: OPTIMIZATION
PP1-30 Konstantinou AND MODELING USING THE RESPONSE SURFACE
160
METHODOLOGY (RSM)
S. Karapati, T. Giannakopoulou, N.
FUNCTIONALIZED TiO2 CONTAINING PAINTS FOR
PP1-31 Todorova, N. Boukos, D. Dimotikali and 161
LONG-TERM NO POLLUTANT OXIDATION
C. Trapalis

16
 EAAOP 2015

TiO2/GRAPHENE OXIDE PHOTOCATALYSTS:

N. Todorova, A. Trapalis, I. Papailias, T.
PP1-32 COMPARATIVE INVESTIGATION OF COMPOSITES 161
Giannakopoulou and J. Yu
WITH EX- AND IN-SITU SYNTHESIZED TiO2
M.L. Gimenes, A.M. Ferrari-Lima, R.G. PHOTODEGRADATION OF BTX UNDER UV-A LIGHT
PP1-33 Marques and N.R.C. Fernandes-Machado WITH N-DOPED CATALYSTS
162
PREPARATION OF B-DOPED TiO2 WITH ENHANCED
C. Drosou, N. Xekoukoulotakis, K. Tyro-
PP1-34 PHOTOCATALYTIC ACTIVITY UNDER VISIBLE-LIGHT 162
vola and F. Panagiotou
IRRADIATION
GREYWATER AS A SUSTAINABLE WATER SOURCE: A
S. Tsoumachidou, T. Velegraki and I.
PP1-35 PHOTOCATALYTIC TREATMENT TECHNOLOGY 163
Poulios
UNDER ARTIFICIAL AND SOLAR ILLUMINATION
PHOTOCATALYTIC DEGRADATION OF ACETONE
G. Skouras, G. Tatsi, N. Todorova, C. Tra-
PP1-36 USING TITANIA PREPARED BY ELECTROSPINNING 163
palis and T. Vaimakis
TECHNIQUE
AN ECOTOXICITY BASED LAB-SCALE
S. Meri, C.B. zkal, L. Rizzo and M. OPTIMIZATION FOR REMOVAL OF THREE ANTI-
PP1-37 Marotta BIOTICS IN A SUSPENDED PHOTOCATALYTIC
164
REACTOR
THE INFLUENCE OF POLYCHROMATIC LIGHT ON
PP1-38 A. Tomaevi CARBOFURAN DEGRADATION IN ZnO AQUEOUS 164
SUSPENSION
PREPARATION OF OCTAHEDRAL ANATASE TITANIA
Z. Wei, M. Endo, B. Ohtani and E. Kow-
PP1-39 PARTICLES FOR DECOMPOSITION OF CHEMICAL 165
alska
AND MICROBIOLOGICAL POLLUTANTS
POLYMER MODIFICATION OF TIO2 NANOPARTICLES
E. Vasilaki, M. Kaliva, N. Katsarakis and VIA THE GRAFTING TO APPROACH, FOR
PP1-40 M. Vamvakaki ENHANCEMENT OF THEIR PHOTOCATALYTIC
165
PERFORMANCE
MONOLITHIC CATALYTIC BED COATED WITH TiO2
PP1-41 B. Marinho P25 TOWARDS THE PHOTOCATALYTIC REDUCTION 166
OF Cr(VI) IN A SIMULATED SOLAR SYSTEM
FABRICATION ON PDMS FILMS OF TEXTURED
J.-H. Yu, S.-H. Nam, K.-H. Hwang, H.-J.
PP1-42 PYRAMIDAL STRUCTURE VIA PS BEADS WITH 166
Seo and J.-H. Boo
DIFFERENT SIZE FOR SELF-CLEANING APPLICATION
NEW COMPOSITES OBTAINED BY FRIENDLY
PP1-43 M. Visa and A. Chelaru CONDITIONS FOR ADVANCED WASTE-WATERS 167
PROCESS
GREEN TECHNOLOGIES BASED ON ADVANCED
M.E. Borges, P. Esparza, M. Sierra, J.C.
OXIDATION PROCESSES (AOPs): WATER
PP1-44 Ruiz-Morales , P. Martn-Zarza, J. Mn- 167
DECONTAMINATION BY PHOTOCATALYSIS USING
dez-Ramos , P. Mora
SOLAR LIGHT
SUBSTITUENT EFFECTS ON THE PHOTOCATALYTIC
J. Dostanic, D. Loncarevic, M. Zlatar, F.
PP1-45 DEGRADATION OF ARYLAZO PYRIDONE DYE: AN 168
Vlahovic and D. Jovanovic
EXPERIMENTAL AND THEORETICAL STUDY
Z. Frontistis, A. Liangou, O. Zervaki, S. ENHANCING PHOTOCATALYTIC DEGRADATION OF
PP1-46 Arapitsa, M.I. Karga, D. Venieri, D. Man- CYANOTOXINS WITH THE ADDITION OF 168
tzavinos SULFATE-RADICAL PRODUCING OXIDANTS
R. Tessinari, I. Jansson, M. Canela, R. SOLAR LIGHT-ZnO DEGRADATION OF
PP1-47 Portela, S. Surez, P. vila and B. San- ETHYLPARABEN: STATISTICAL EVALUATION OF 169
chez OPERATING FACTORS AND ESTROGENIC ACTIVITY
PREPARATION AND APPLICATION OF HYBRID
Y. Kanigaridou, A. Petala, Z. Frontistis,
PP1-48 PHOTOCATALYSTS BASED ON BRAZILIAN CLAYS 169
D. Kondarides and D. Mantzavinos
AND TiO2 FOR NOX DEGRADATION

17
 INDEX

A. Petala, R. Bontemps, A. Spartatouille,

DEGRADATION OF ENDOCRINE DISRUPTORS USING
PP1-49 Z. Frontistis, D. Kondarides and D. Man- 170
SIMULATED SOLAR IRRADIATION AND Cu2O/BiVO4
tzavinos
SOLAR LIGHT INDUCED DEGRADATION OF ETHYL
V. Sakkas, C. Hadjicostas, P. Calza, C.
PP1-50 PARABENS WITH Cu2O/BiVO4-STATISTICAL 170
Minero, M. Kalaboka and T. Albanis
EVALUATION OF OPERATING FACTORS
PHOTOCATALYTIC TRANSFORMATION OF THE
ANTIPSYCHOTIC DRUG RISPERIDONE IN AQUEOUS
E. Klontza, N. Xekoukoulotakis and E.
PP1-51 MEDIA ON REDUCED GRAPHENE OXIDE-TIO2 171
Diamadopoulos
COMPOSITES: SYNTHESIS, CHARACTERIZATION
AND DEGRADATION KINETICS
FENTON AND FENTON LIKE PROCESSES CATALYTIC REDOX PROCESSES
COUPLING AOPS WITH OTHER PROCESSES PILOT-SCALE STUDIES AND FIELD
APPLICATION OZONATION
PHOTO-FENTON DEGRADATION OF PHARMA-
S. Esplugas, S. Plaza, A. De Luca, P. Mar-
PP2-1 CEUTICAL DIPHENHYDRAMINE IN WATER AT 172
co and J. Gimenez
CIRCUMNEUTRAL pH
STUDY OF AMICARBAZONE PHOTODEGRADATION
PP2-2 M. Silva and A.C. Teixeira 172
BY DIFFERENT ADVANCED OXIDATION PROCESSES
COMBINED NANO ZERO-VALENT IRON
PP2-3 X. Wang and P. Liu IMMOBILIZATION AND HETEROGENEOUS FENTON 173
PROCESSES FOR REMOVAL OF METRONIDAZOLE
INTERMEDIATES OF DEGRADATION GENERATED
N. Villota, J.M. Lomas and L.M. Camare-
PP2-4 DURING THE FIRST OXIDATION STATES OF PHENOL 173
ro
IN A PHOTO-FENTON SYSTEM
DETERMINATION OF THE DEGRADATION PATHWAYS
P. Villegas-Guzman, F. Hofer, C. Pulgar- INVOLVED DURING THE TREATMENT OF
PP2-5 in and R. Torres-Palma CIPROFLOXACIN BY PHOTO-ELECTRO FENTON
174
PROCESS
ELECTRO-FENTON TECHNOLOGY FOR THE
M A. Sanroman, E. Bocos, Elena Alfaya,
PP2-6 TREATMENT OF DYE AND PHARMACEUTICAL 174
O. Iglesias, E. Rosales and M. Pazos
EFFLUENTS
M A. Sanroman, C. Sandu, M. Popescu, ELECTROKINETIC-FENTON TECHNOLOGY: A
PP2-7 E. Rosales, E. Bocos, G. Lazar and M. SOLUTION IN THE IN SITU REMEDIATION OF 175
Pazos HYDROCARBONS POLLUTED SOILS
APPLICATION OF ELECTRO-FENTON TREATMENT
M. Pazos, E. Bocos, E. Rosales and M A.
PP2-8 FOR THE ELIMINATION OF IMIDAZOLIUM IONIC 175
Sanromn
LIQUIDS FROM POLLUTED WATER
F. Moura, A. Martins, A. Salviano, A. Ol- HIGHLY ORDERED SPHERICAL SBA FOR
PP2-9 iveira and M. Rosmaninho CONTAMINANTS REMOVAL VIA FENTON PROCESS
176
E. Giannakopoulos, G. Psarras, G. Oron REMOVAL OF BETA-BLOCKERS FROM AQUEOUS
PP2-10 and I. Kalavrouziotis MEDIA BY ADSORPTION ONTO GRAPHENE OXIDE
176
PHOTO-FENTON REACTIONS PROMOTED BY Fe/C
M. Rosmaninho, F. Mendona, J. Domin- COMPOSITES PRODUCED FROM IRON RICH
PP2-11 gos Ardisson, R. Lago and J. Tristo MINERAL WASTES AND BIO-OIL AQUEOUS ACID
177
FRACTION
USE OF PHOTO-FENTON PROCESS TO REMOVE
M. Silva, E. Oliveira Rodrigues, F. Soares
PP2-12 ORGANIC MATTER FROM FULLER CLAY CONTAMI- 177
Silva, M. Matiko Kondo and R. Gimene
NATED WITH INSULATING OIL
STUDY OF REDUCTIVE REACTIONS INVOLVED IN
A.M. Amat, L. Santos-Juanes, R.F. Verch-
PP2-13 THE PHOTO-FENTON PROCESS USING ZERO VALENT 178
er and A. Arques
IRON (ZVI)

18
 EAAOP 2015

R.F. Vercher, S. Garca Ballesteros, M. SOLAR PHOTO FENTON TREATMENT OF PHENOLIC

PP2-14 Mora, C. Sabater, M A. Castillo, A. COMPOUNDS COMMONLY FOUND IN FOOD 178
Arques and A.M. Amat PROCESSING INDUSTRY
C. Berberidou, V. Kitsiou, D. Michail- PHOTO-FENTON MEDIATED DEGRADATION,
PP2-15 idou, D. Lambropoulou, A. Kouras and I. MINERALIZATION AND DETOXIFICATION OF THE 179
Poulios INSECTICIDE THIACLOPRID IN AQUEOUS MEDIA
C. Berberidou, V. Kitsiou, F. Kondyli-Sa- HOMOGENOUS PHOTOCATALYTIC DEGRADATION
PP2-16 rika, D. Lambropoulou, A. Kouras and I. OF THE HERBICIDE CLOPYRALID IN AQUEOUS 179
Poulios MEDIA: KINETICS, MINERALIZATION AND TOXICITY
HOMOGENEOUS PHOTOCATALYSIS FOR THE
REMOVAL OF UV FILTER PARA-AMINOBENZOIC
PP2-17 S. Tsoumachidou and I. Poulios 180
ACID IN AQUEOUS SOLUTIONS BY MEANS OF
ARTIFICIAL ILLUMINATION
M. Lucas, J. Rodriguez-Chueca, T. Silva, HSO5-/Mn+/UV-A LED AND PHOTO-FENTON
PP2-18 C. Amor, G. Li Puma and J. Peres PROCESSES FOR WINERY WASTEWATER TREATMENT
180
HIGHLY STABLE IRON CATALYSTS OBTAINED BY
J. Bedia, V.M. Monsalvo, A.F. Mohedano
PP2-19 CHEMICAL ACTIVATION OF SEWAGE SLUDGE WITH 181
and J.J. Rodriguez
FeCl3 FOR CWPO
HYBRID MAGNETIC GRAPHITIC NANOCOMPOSITES
R.S. Ribeiro, A.M.T. Silva, J. L. Figueire-
PP2-20 FOR CATALYTIC WET PEROXIDE OXIDATION 181
do, J.L. Faria and H.T. Gomes
APPLICATIONS
E.D. Nieto, I. Fernndez Mena, A. Fer- SYNTHESIS OF Fe ON CARBON CATALYSTS
PP2-21 nandez Mohedano and J.J. Rodrguez OBTAINED FROM GRAPE SEEDS FOR CWPO OF 182
Jimnez BISPHENOL A
R.S. Ribeiro, M. Martin-Martinez, B.F.
CARBON NANOTUBES AS CATALYSTS FOR WET
Machado, P. Serp, S. Morales-Torres, A.
PP2-22 PEROXIDE OXIDATION: STRUCTURE-REACTIVITY 182
Silva, J. Figueiredo, J.L. Faria and H.
RELATIONSHIPS
Gomes
EFFECT OF THE GOLD ADDITION TO Ag/ZrO2-CeO2
PP2-23 A. Silahua, G. Torres and J. Beltramini CATALYSTS BY RECHARGE METHOD IN THE 183
CATALYTIC WET AIR OXIDATION (CWAO) OF PHENOL
J.G. Torres Torres, Z. Guerra Que, H. EFFECT OF CRYSTAL SIZE AND METAL DISPERSION
PP2-24 Prez Vidal, I. Cuauhtmoc, A. Espinosa OVER Ag/ZrO2-CeO2 FOR THE CATALYTIC WET AIR 183
and J. Beltramini OXIDATION OF METHYL TERT-BUTYL ETHER (MTBE)
J.G. Torres Torres, A. Cervantes Uribe, CATALYTIC WET AIR OXIDATION OF METHYL
PP2-25 M.A. Lunagmez Rocha and G.A. Del n- TERT-BUTYL ETHER (MTBE) USING Rh/TiO2-CeO2 AND 184
gel Montes RhAu/TiO2-CeO2 CATALYSTS
OZONE ENHANCED OXIDATION OF CYANOTOXIN
PP2-26 W.-J. Huang, C.-C. Wu and B.-R. Lu 184
CYLINDROSPERMOPSIN WITH TiO2 CATALYST
NANOSTRUCTURED CeO2 AS CATALYSTS FOR
A.Rey, E.Mena, E.M. Rodrguez and F.J.
PP2-27 DIFFERENT AOPS BASED IN THE APPLICATION OF 185
Beltrn
OZONE AND SOLAR RADIATION
PHOTOCATALYTIC OZONATION OF EMERGING
A. Rey, A.M. Chvez, P.M. lvarez and
PP2-28 CONTAMINANTS IN MUNICIPAL WASTEWATER WITH 185
F.J. Beltrn
A MAGNETIC TIO2-ACTIVATED CARBON CATALYST
S.E. Bottrel, E. Costa, G. Cipriano, M. KINETIC STUDY OF ETHILENETHIOUREA REMOVAL
PP2-29 Leo and C. Amorim IN WATER BY OZONATION PROCESS
186
DEGRADATION OF 8 POLLUTANTS COMMONLY
R.F. Vercher, S. Garca-Ballesteros, A. FOUND IN FOOD PROCESSING EFFLUENTS BY
PP2-30 Arques and A.M. Amat ADVANCED OXIDATION PROCESS: O3 AND
186
O3/UVA-VIS

19
 INDEX

L. Ioannou, C. Michael, N. Vakondios, C. REVERSE OSMOSIS FOLLOWED BY SOLAR

PP2-31 Drosou, E. Diamadopoulos, N. Xekoukou- PHOTO-FENTON OXIDATION FOR THE INTEGRATED 187
lotakis and D. Fatta-Kassinos TREATMENT OF WINERY WASTEWATER
SOLAR PHOTO-FENTON WITH SIMULTANEOUS
S. Sanchis, L. Meschede, A. Serra, G. Six-
PP2-32 ADDITION OF OZONE FOR WASTEWATER 187
to and J. Garcia-Montao
TREATMENT
FENTON AND ELECTROCHEMICAL OXIDATION FOR
C. Sez, J.F. Prez, C. Lpez, J.M. Rodri- THE TREATMENT OF ACTUAL WASTEWATER
PP2-33 go and P. Caizares COMING FROM AN ORGANIC-SYNTHESIS CHEMICAL
188
PLANT
EFFECT OF FEED COMPOSITION ON THE
PERFORMANCE OF A POLYETHERSULFONE UF
PP2-34 S. Mozia, D. Darowna and A. Morawski 188
MEMBRANE IN A PHOTOCATALYTIC MEMBRANE
REACTOR
TREATMENT OF LAUNDRY WASTEWATER USING A
S. Mozia, M. Janus, P. Broek, S. Bering, HYBRID SYSTEM COUPLING BIOLOGICAL METHOD
PP2-35 K. Tarnowski, J. Mazur and A. Morawski WITH UV/O3 OXIDATION AND MEMBRANE
189
SEPARATION
PERFORMANCE OF A PHOTOCATALYTIC MEMBRANE
PP2-36 A. Morawski, K. Szymaski and S. Mozia REACTOR WITH A TiO2 UF MEMBRANE DURING 189
REMOVAL OF HUMIC ACIDS FROM WATER
ANTIBIOTICS CONTAMINATED WASTEWATER
R. Marcelino, C. Amorim, A. Emrich and
PP2-37 TREATMENT BY OZONATION AND OZONATION 190
M. Leo
COMBINED WITH BIOLOGICAL PROCESS
MINERALIZATION OF ANILINE AND REACTIVE DYE
PP2-38 C.A. Orge, M F R. Pereira and J L. Faria BLUE 5 SOLUTIONS BY PHOTOCATALYTIC 190
OZONATION
COMBINED BIOLOGICAL-CHEMICAL TREATMENT
PP2-39 K. Klein, A. Kivi, M. Trapido and T. Tenno OF LANDFILL LEACHATE APPLYING CONTINUOUS 191
SLUDGE REUSE IN FENTON PROCESS
EVALUATION OF AN ALTERNATIVE METHOD FOR
V. Kitsiou, C. Berberidou, D. Lambropou-
WASTEWATER TREATMENT CONTAINING
PP2-40 lou, A. Antoniadis, E. Ntonnou, G. Zalidis 191
PESTICIDES USING PHOTOCATALYTIC OXIDATION
and I. Poulios
AND CONSTRUCTED WETLANDS
T. Tatoulis, A. Stefanakis, S. Zapantiotis, TREATMENT OF TABLE OLIVE WASHING WATERS
PP2-41 Z. Frontistis, A.G. Tekerlekopoulou, C.S. USING CONSTRUCTED WETLANDS FOLLOWED BY 192
Akratos , D. Mantzavinos, D.V. Vayenas ELECTROOXIDATION
DESIGN OF HETEROGENEOUS FENTON FILM-
R. Molina, M.M. Benacherine, Y. Segura, BASED PHOTO-REACTOR FOR THE TREATMENT OF
PP2-42 J.A. Melero, F. Martnezui PHARMACEUTICAL COMPOUNDS IN WASTEWATER
192
STREAMS
MODIFIED FENTON CHEMISTRY TO REMEDIATE
L.. Andrade, C.. Amorim, F. Morais, A. GROUNDWATER CONTAMINATED BY COMMERCIAL
PP2-43 Almeida, S. Arajo, M. Leo GASOLINE/ETHANOL BLEND: APPROACHES TO
193
APPLY H2O2
M.C. Starling, B. Reis, C. Amorim, M. ACUTE TOXICITY EVALUATION OF REAL TEXTILE
PP2-44 Leo, WASTEWATER TREATED BY SOLAR-PHOTO-FENTON
193
PHOTO-FENTON TREATMENT OF THE
A. Koltsakidou, M. Sykiotou, E. Ev-
PP2-45 ANTINEOPLASMATIC DRUG 5-FLUOROURACIL: 194
genidou and D. Lambropoulou
KINETICS AND TRANSFORMATION PRODUCTS
MULTISTAGE TREATMENT SYSTEM FOR BIODIESEL
C. Amorim, L.O. Gonalves, C M. Leo,
PP2-46 WASTEWATER BY MOVING BED BIOFILM REACTOR 194
D. Oliveira, R.G.P. Prado
AND ADVANCED OXIDATION PROCESSES

20
 EAAOP 2015

OXIDATION OF WATER SOLUBLE BIOSOLIDS BY

E. Giannakopoulos, G. Psarras, G. Oron
PP2-47 FREE RADICALS MECHANISM. A UV/VIS 195
and I. Kalavrouziotis
SPECTROSCOPY STUDY
I.M. Romn Snchez, M.Segura, A.
COST ESTIMATION OF SOLAR PHOTO-FENTON
M. Freitas, G.Rivas Ibez, M.Cam-
PP2-48 PROCESS IN RACEWAY POND REACTORS AS 195
pos-Maas, S. Arzate and J.A.Snchez
TERTIARY TREATMENT
Prez
DISINFECTION ELECTROCHEMICAL PROCESSES AOPS FOR ENERGY
PRODUCTION RADIATION PROCESSES
ECO-EFFICIENT TREATMENT OF EFFLUENTS OF THE
S. Sanchis, D. Gali, M. Aliaguilla, D.
MANUFACTURING INDUSTRY:
PP3-1 Anguera, A. Serra, F.X. Simon and J. Gar- 196
ELECTROCOAGULATION PROCESS WITHIN
cia-Montao
ECOWAMA PROJECT
M.A. Rodrigo, E. Vieira Dos Santos, C. ELECTROIRRADIATED TECHNOLOGIES FOR THE
PP3-2 Saez, C.A. Martinez-Huitle and P. Caiza- REMOVAL OF OXYFLUORFEN FROM SOIL WASHING 196
res WASTES
REMOVAL OF ORGANIC MATTER OF OIL FIELD
E. Saggioro, G. Dos Santos Cunha and
PP3-3 EFFLUENT WATER BY ELECTROCHEMICAL 197
A.J. Bourdot
OXIDATION AND ELECTROFLOTATION TREATMENT
NEW INSIGHTS INTO THE ELECTRO-OXIDATION OF
M. Rivero, C. Escudero, O. Iglesias, S.
PP3-4 A MODEL PHENOLIC COMPOUND, p-CRESOL: EFFECT 197
Dominguez and I. Ortiz
OF ELECTRODE MATERIAL AND ELECTROLYTE
PHOTOELECTROCHEMICAL STUDY OF TiO2 NANO-
J. Krysa, S. Kment, Z. Hubicka, K. Lee
PP3-5 TUBES GROWN BY ANODIZATION ON SPUTTERED 198
and P. Schmuki
VS. EVAPORATED TI LAYER
PREPARATION AND PHOTOELECTROCHEMICAL
PP3-6 J. Krysa and M. Zlamal PROPERTIES OF WO3 LAYERS PREPARED BY 198
SEDIMENTATION AND SPRAY-PYROLYSIS
Y. Segura, F. Martnez, A.L. Petre, J.A. DIFFERENT APPROACHES OF ADVANCED
PP3-7 Perdign, S. lvarez, J. Garca, G. Pliego OXIDATION PROCESSES FOR THE TREATMENT OF A 199
and P. Garca-Muoz PHARMACEUTICAL WASTEWATER
J. Krysa, J. Olejnicek, M. Brunclikova, Z.
WO3 THIN FILMS PREPARED BY SEDIMENTATION
PP3-8 Hubicka, S. Kment, P. Ksrov, M. Cada 199
AND PLASMA SPUTTERING
and M. Zlamal
A COMPARATIVE STUDY OF SOL-GEL AND
A. Chatzitakis, A. Papaderakis, N. Ka-
ANODICALLY GROWN TIO2 PHOTOANODES AND
PP3-9 ranasios, J. Georgieva, E. Pavlidou, G. 200
THEIR APPLICATION IN THE PHOTOOXIDATION OF
Litsardakis, I. Poulios and S. Sotiropoulos
CHLORAMPHENICOL
BORON-DOPED DIAMOND ANODIC OXIDATION OF
Z. Frontistis, A. Ioannidi, K. Kassara, G.
AMOXICILLIN WASTEWATER: STATISTICAL
PP3-10 Voukelatos, D. Venieri and D. Mantzavi- 200
EVALUATION OF OPERATING FACTORS AND
nos
ANTIBIOTIC RESISTANCE
OPTIMIZATION AND MODELING OF IOHEXOL
S. Giannakis, M.P. Gelabert, S. Schindel-
PP3-11 TREATMENT BY ADVANCED OXIDATION PROCESSES 201
holz, J.-M. Fuerbringer and C. Pulgarin
IN ENVIRONMENTALLY RELEVANT MATRICES
SONOPHOTOLYTIC MINERALIZATION OF
A.J. Expsito, A. Durn and J.M. Mon-
PP3-12 CARBAMAZEPINE IN AQUEOUS SOLUTION: KINETIC 201
teagudo
MODELLING
PHOTODEGRADATION OF 2,4-DICHLOROPHENOL IN
S. Ledakowicz, M. Foszpanczyk, D. Gryg-
PP3-13 AQUEOUS SYSTEMS UNDER SIMULATED AND 202
lik and M. Gmurek
NATURAL SUNLIGHT
A NEW APPROACH TO HETEROGENEOUS KINETIC OF
PP3-14 M. Gmurek and S. Ledakowicz 202
PHOTOSENSITIZED OXIDATION

21
 INDEX

J. A. Snchez Prez, G. Rivas Ibez, P. MICROPOLLUTANT REMOVAL BY HO* IN LOW-

PP3-15 Soriano, J.L. Casas Lpez, L. Ponce Ro- FREQUENCY ULTRASOUND TREATMENT OF AN 203
bles and A. Agera AGROFOOD INDUSTRY SEWAGE SLUDGE
N. Garkusheva, N. VorobEva, G. Mata- DEGRADATION OF TRICLOSAN IN NATURAL WATER
PP3-16 fonova and V. Batoev AND WASTEWATER USING KrCl EXCILAMP (222 nm)
203

PP3-17 J. Pawlat RF ATMOSPHERIC PRESSURE PLASMA JET 204

FLUORESCENCE EVOLUTION OF HUMIC-LIKE
SUBSTANCES OBTAINED FROM SOLID URBAN
PP3-18 A.M. Amat, R. Vicente and M. Mora 204
WASTES IN SOLAR PHOTOCHEMICAL PROCESSES
FOR WATER TREATMENT
UV-C AND UV-C/H2O2 DEGRADATION OF TWO
C. Drosou, N. Xekoukoulotakis, K. Tyro-
PP3-19 ARTIFICIAL SWEETENERS, ACESULFAME-K AND 205
vola, T. Neromilioti and E. Kourounioti
SUCRALOSE
S. Ledakowicz, M. Olak-Kucharczyk, M. PHOTOSENSITIVE CHITOSAN FOR VISIBLE-LIGHT
PP3-20 Foszpanczyk and M. Gmurek WATER POLLUTANT DEGRADATION
205
J. Diatczyk, J. Pawlat, H. Danuta Strycze- MINI GLIDING ARC ATMOSPHERIC PRESSURE
PP3-21 wska, M. Kwiatkowski and P. Terebun PLASMA REACTOR
206
REMOVAL OF EMERGING CONTAMINANTS FROM
M.G. Antoniou, N. Tsiarta, S. Rodriguez
PP3-22 WATER VIA PEROXYMONOSULFATE ACTIVATION 206
and A. Santos
WITH VARIOUS IRON SOURCES (Fe+2, Fe+3, ZVI)
N. Potakis, Z. Frontistis and D. Mantza- DEGRADATION OF ENDOCRINE DISRUPTING
PP3-23 vinos CHEMICALS BY HEAT-ACTIVATED PERSULFATE
207
M. Edris Taheri, A. Petala, Z. Frontistis, FAST DEGRADATION OF ENDOCRINE DISRUPTORS
PP3-24 D. Kondarides and D. Mantzavinos BY Ag3PO4/TiO2 SOLAR PHOTOCATALYSIS
207
SOLAR PHOTOCATALYTIC DEGRADATION AND
E. Ioannidou, Z. Frontistis, D. Venieri, D.
PP3-25 ANTIBIOTIC INACTIVATION OF SULFA- 208
Kondarides and D. Mantzavinos
METHOXAZOLE BY TUNGSTEN-MODIFIED TiO2
NEW PATHWAYS IN HETEROGENEOUS AND HOMO-
S. Giannakis, C. Ruales-Lonfat and C. GENEOUS NEAR-NEUTRAL PHOTO-FENTON
PP3-26 Pulgarin BACTERIAL INACTIVATION BY IRON OXIDES AND
208
IRON CITRATE COMPLEXES
J.A. Snchez Prez, A. Freitas, A. Cabre- ECOTOXICITY EVALUATION OF SECONDARY
PP3-27 ra, G. Rivas Ibez, M. Campos-Maas, EFFLUENT TREATED BY SOLAR PHOTO-FENTON AT 209
J. L Casas Lpez and A. Agera NEUTRAL PH IN A RACEWAY POND REACTOR
SIMULTANEOUS SOLAR DISINFECTION AND
A.J. Expsito, J.M. Monteagudo and A.
PP3-28 PHOTOCATALYTIC TREATMENT OF CONTAMINATED 209
Durn
DRINKING WATER
I.M. Romn Snchez, M. Segura, J.A.
COST ANALYSIS OF PHOTO-FENTON DISINFECTION
PP3-29 Snchez Prez, E. Ortega Gomez and P. 210
IN REAL MUNICIPAL WASTEWATER
Fernandez Ibaez
G. Skouras, G.Tatsi, M. Tsoulfa, C. Nan-
PHOTOCATALYTIC AND ANTIMICROBIAL
PP3-30 nou, S. Tsafou, A. Mitsionis, N. Todorova, 210
EFFICIENCY OF TIO2-BASED INTERIOR PAINTS
T. Albanis, C. Trapalis and T. Vaimakis
M.J. Abeledo-Lameiro, A. Rebore- PHOTOCATALYTIC INACTIVATION OF THE WATER-
do-Fernndez, M.I. Polo-Lopez, P. Fer- BORNE PROTOZOAN PARASITE CRYPTOSPORIDIUM
PP3-31 nandez-Ibaez, E. Ares-Mazas and H. PARVUM USING TIO2/H2O2 UNDER SIMULATED AND
211
Gmez-Couso NATURAL SOLAR CONDITIONS
M. Janus, P. Rokicka, A. Stelmach, E.
THE ANTIBACTERIAL PROPERTIES OF CONCRETES
Kusiak-Nejman, A. Markowska-Szczupak,
PP3-32 SUPPLEMENTED WITH TITANIUM PHOTOCATALYST 211
K. Zajc, J. Zatorska, A. Czyewski and
UNDER VISIBLE IRRADIATION
A. W. Morawski

22
 EAAOP 2015

SOLAR PHOTOCATALYSIS AS DISINFECTION

D. Venieri, I. Gounaki, M. Bikouvaraki, V.
TECHNIQUE: INACTIVATION OF KLEBSIELLA
PP3-33 Binas, A. Zachopoulos, G. Kiriakidis and 212
PNEUMONIAE IN SEWAGE AND INVESTIGATION OF
D. Mantzavinos
CHANGES IN ANTIBIOTIC RESISTANCE PROFILE
D. Venieri, F. Tournas, I. Gounaki, V. Bi- INACTIVATION OF STAPHYLOCOCCUS AUREUS IN
PP3-34 nas, A. Zachopoulos, G. Kiriakidis and D. WATER BY MEANS OF SOLAR PHOTOCATALYSIS 212
Mantzavinos USING METAL DOPED TiO2 SEMICONDUCTORS
ENHANCING PHOTOCATALYTIC DEGRADATION OF
M.G. Antoniou, J. Boraei, C. Kyriakou,
PP3-35 CYANOTOXINS WITH THE ADDITION OF 213
M. Abhishek, C. Edwards and L. Lawton
SULFATE-RADICAL PRODUCING OXIDANTS
ASSESSMENT OF SUPPORTING ELECTROLYTES ON
CO2 REDUCTION BY PHOTO-ELECTROCATALYSIS AT
PP3-36 J.F. De Brito and M.V. B. Zanoni 213
Ti/TiO2/CuO N-P HETEROJUNCTION
SEMICONDUCTOR
A. Perez-Larios, R. Gomez, R. Zanella MIXED OXIDE AS PHOTOCATALYST: TiO2-FeXOY FOR
PP3-37 and J. Bedia H2 PRODUCTION BY WATER SPLITTING METHOD
214
PHOTOCATALYTIC ACTIVITY OF TiO2-CoO AS MIXED
A. Perez Larios, R. Gomez, R. Zanella and
PP3-38 OXIDE FOR IMPROVED H2 PRODUCTION BY WATER 214
C. Belver
SPLITTING METHOD
P. Falaras, N. Moustakas, F. Katsaros, A. VISIBLE LIGHT ACTIVE HYBRID CORE-SHELL TiO2
PP3-39 Papavasiliou, E. Kouvelos, A. Kontos, T. PHOTOCATALYSTS FOR THE PRODUCTION OF 215
Steriotis and G. Romanos USEFUL HYDROCARBONS FROM CO2
A. Marinas, F. J. Tenllado, V. Montes, F.J. H2 PRODUCTION FROM BIO-ALCOHOLS VIA
PP3-40 Urbano, J.M. Marinas, L. Ilieva, T. Taba- PHOTOREFORMING USING Au/TiO2 AND Pt/TiO2 AS 215
kova, A. Diaz-Lozano and J. Hidalgo HETEROGENEOUS CATALYSTS
PHOTOELECTROCATALYTIC HYDROGEN
PP3-41 I. Tantis, L.-C. Pop and P. Lianos PRODUCTION USING NITROGEN CONTAINING 216
WATER SOLUBLE WASTES
P. Lianos, O. Monfort, L.-C. Pop and S. VISIBLE LIGHT RESPONSIVE BiVO4 PHOTOANODES
PP3-42 Sfaelou FOR HYDROGEN PRODUCTION
216
A SOL-GEL METHOD FOR PREPARATION OF NANO-
S. Sfaelou, L. Cristian Pop, O. Monfort
PP3-43 STRUCTURED WO3 PHOTOANODES USED FOR 217
and P. Lianos
PHOTOELECTROCHEMICAL WATER SPLITTING
Z. Frontistis, M. Yazirdagi, Z. Kilinc, A. BORON-DOPED DIAMOND ANODIC OXIDATION OF
PP3-44 Katsaounis, D. Mantzavinos CONTAMINANTS OF EMERGING CONCERN
217
OXIDATIVE DEGRADATION OF TRITON X-45 USING
II. Arslan-Alaton, T. Olmez-Hanci, S.
PP3-45 ZERO VALENT ALUMINUM IN THE PRESENCE OF 218
Khoei, H.Fakhri
HYDROGEN PEROXIDE AND PERSULFATE
STUDY OF HYDROGEN OXIDATION USING
PP3-46 J. Vakros and A. Katsaounis DIFFERENTIAL ELECTROCHEMICAL MASS 218
SPECTROSCOPY (DEMS)
BENEFIT AND RISKS FROM ELECTROCHEMICAL
H.Bergmann, T. Iourtchouk and A.S. Ko-
PP3-47 ADVANCED OXIDATION PROCESSES (EAOP) IN 219
paral
WATER TREATMENT THE (PER)BROMATE PROBLEM
PHOTOCHEMICAL DEGRADATION OF THE
N.P. Xekoukoulotakis,Y. Bertakis, A.
CARBAPENEM ANTIBIOTICS IMIPENEM AND
PP3-48 Agera,A.B. Martnez-Piernas, J.A. Sn- 219
MEROPENEM IN AQUEOUS SOLUTIONS UNDER
chez Prez,A. Cabrera
SOLAR IRRADIATION

23
SECTION

1
COMMITTEES

Organizing Chairs.......................................................................................................................26
Organizing Committee...............................................................................................................26
Scientific Committee..................................................................................................................27
 COMMITTEES

ORG A Ma n tza vinos Dionissios , Dept. of

NI Z I N G Chemical Engineering, University of

CH AIR S Patras, Greece

Po u l i o s I oannis , Dept. of Chemistry,

Aristotle University of Thessaloniki,

Greece

ORG A Ber b er i d ou, C. , Dept. of Chemistry,

NI Z I N G AUTh

CO M MI
T TEE Fr o n ti stis, Z. , Dept. of Chemical Engi-
neering, UP

K i tsi o u , V. , Dept. of Chemistry, AUTh

Tso u machidou S . , Dept. of Chemistry,

AUTh

26
 EAAOP 2015

Al fan o, O. Argentina
An , T. C . China
SC I EN An dr eozz i, R. Italy
TI F I C An to n i adis, A. Greece
Ar slan -Alaton, I . Turkey
CO M MI Bahn emann, D. Germany

T TEE Ber gma nn, H.

Besso n , M.
Germany
France
Br emn er, D.H. United Kingdom
Byr n e, JA Ireland
Cr etescu , I . Romania
D ewi l, R . Belgium
D i o n ysi ou, D. USA
D u r a n , A. Spain
Esp lu ga s, S . Spain
Fal a r a s, P. Greece
Far i a , J. Portugal
Fatta-K assinos, D. Cyprus
Fer n a n d ez-I banez,P. Spain
Gu i mar aes, J.R. Brazil
K a tsar akis, N. Greece
K r ysa , J. Czech Republic
K o n dar i des, D. Greece
K o n sta n t inou, I . Greece
Led a ko wicz, S . Poland
Le veq u e, J.M . France
Li P u ma, G . United Kingdom
Ma lato, S . Spain
Ma sco lo, G . Italy
Mer i c, S . Turkey
Mo r awsk i, A.W. Poland
O r ti z, I. Spain
O tu r an , M .A. France
Per es, J. A . Portugal
Phi l i ppo poulos, C. Greece
Pi n ta r, A . Slovenia
Pr ei s, S . China
Pu l gar i n, C. Switzerland
Ri zz o, L . Italy
Ro d r i go, M . Spain
Soga a r d , E.G . Denmark
So ti r o p o ulos, S . Greece
To r r es-Palma, R.A. Colombia
Tr a p i do, M . Estonia
Ven i er i , D. Greece
V l yssi d es, A. Greece
Xekoukoulotakis, N.P. Greece

27
SECTION

2
PROGRAM

Distinguished Talk................................................................ 30
Plenar y Talks
1 st DAY ............................................................................. 30
2 n d DAY ............................................................................ 34
3 rd DAY ............................................................................. 38
Oral Pr esentations
1 st DAY ............................................................................. 30
2 n d DAY ............................................................................ 34
3 rd DAY ............................................................................. 38
Poster Pr esentations
1 st DAY ............................................................................. 42
2 n d DAY ............................................................................ 46
3 rd DAY ............................................................................. 50
 PROGRAM

Wednesday, 21 October 2015

17:00-20:30 Registration
EAAOP4 Opening

2015-2100 DISTINGUISHED TALK: Prof. Christos S. Zerefos

DT1 Man-made interference with the oxidizing capacity of the atmosphere over the Eastern Mediterranean

Thursday, 22 October 2015

08:00-09:30 Registration
EAAOP4 Opening

09:30-10:15 PLENARY TALK 1: Prof. Timothy J. Mason

PT1 Sonochemistry and its use in Advanced Oxidation Processes

ROOM A ROOM B ROOM C

Session 1A: Session 1B: Session 1C:

PHOTOCATALYTIC OZONATION CATALYTIC
OXIDATION REDOX PROCESSES
CHAIRS: J. Faria & CHAIRS: N.H. Ince & CHAIRS: R. Molina & S. Ledakowicz
C.L. Bianchi S. Meric

10:15-10:30 A1-1 B1-1 C1-1

MORPHOLOGY-DEPENDENT
PHOTOCATALYTIC ACTIVI-
TY OF OCTAHEDRAL ANA-
TASE PARTICLES PREPARED
BY ULTRASONICATION-
HYDRO-THERMAL
REACTION
Z. Wei, E. Kowalska, B. Ohtani
OZONATION OF DEGRADATION OF NAPROXEN
p-HYDROXYBENZOIC ACID IN AQUEOUS SOLUTION BY H2O2,
IN A MULTI-ORIFICE S2O82- AND COMBINED H2O2/S2O82-
OSCILLATORY BAFFLED ACTIVATED WITH CITRIC ACID
REACTOR CHELATED Fe2+
M.S. Lucas, N.M. Reis, G. Li N. Dulova, I. Epold, M. Trapido
Puma

10:30-10:45 A1-2 B1-2 C1-2

COPPER NPS DECORATED
TITANIA TO IMPROVE THE
PHOTOACTIVITY UNDER
VISIBLE LIGHT: A NOVEL
SYNTHESIS BY HIGH
ENERGY US
M. Stucchi, C. Bianchi, C. Piro-
la, G. Cerratob, S. Morandi, C.
Argirusis, G. Sourkouni, A. Nal-
doni, S. Vitalia V. Capucci
10:45-11:00 A1-3
PHENOL PHOTODEGRA-
DATION IN PRESENCE OF
NANO OR MICRO-TiO2:
PERFORMANCE COMPA-
RISON AND STUDY OF THE
DIFFERENT BYPRODUCTS
C. Bianchi, M. Stucchi, C. Piro-
la, G. Cerrato, S. Morandi,
B. Sacchia, S. Vitali, V. Capucci
CATALYTIC OZONATION OF OXIDATION OF PRIORITY AND
BEZAFIBRATE IN EMERGING POLLUTANTS WITH
SIMULATED NATURAL PERSULFATE ACTIVATED BY IRON.
WATER EFFECT OF IRON VALENCE AND
A.G. Gonalves, J.J.M. rfo, PARTICLE SIZE
M.F.R. Pereira S. Rodriguez, A. Santos, A. Romero
B1-3 C1-3
INFLUENCE OF pH AND HIERARCHICALLY-STRUCTURED
OZONE DOSE ON CuBi2O4 COMPOSITE FOR SULFA-
SULFAQUINOXALINE NILAMIDE REMOVAL VIA
OZONATION PEROXYMONOSULFATE
V.R. Urbano, M.G. Maniero, ACTIVATION
M.Prez-Moya, J.R. Guimares W.D. Oh, T.T. Lim, Z.L. Dong

30

A1-4
11:00-11:15 PHOTOCATALYTIC OXIDA-
TION USING COMPOSITE
PHOTOCATALYSTS FOR
EFFECTIVE NEUTRALIZA-
TION OF CHEMICAL
WARFARE AGENTS
D. Selishchev, D. Kozlov
Coffee Break
Session 2A:
PHOTOCATALYTIC
OXIDATION
CHAIRS: J. Marugan &
K. Skalska
12:00-12:15 A1-5
PREPARATION AND
CHARACTERIZATION OF
TITANIUM DIOXIDE PHOTO-
CATALYST SUPPORTED ON
FLY ASH PARTICLES.
EVALUATION OF PHOTO-
CATALYTIC ACTIVITY IN
WASTEWATER TREATMENT
M.Visa and A. Duta
12:15-12:30 A1-6
INFLUENCE OF FLAVINS
ADSORPTION ON TiO2 IN
THE PHOTO OXIDATION
EFFICIENCY OF AIR
CONTAMINANTS
M. Pandiri, N. Shaham-Wald-
mann, Y. Paz, F.W. Foss, K.
Rajeshwar
12:30-12:45 A1-7
PHOTOCATALYTIC
ACTIVITY OF Li AND
KDOPED ZnO UNDER
SOLAR LIGHT IRRADIATION
H. Benhebal,St. D. Lambert
12:45-13:00 A1-8
PHOTOCATALYTIC
EFFICIENCY OF
RETICULATED ZnO
STRUCTURE IN
DEGRADATION OF ACID NAPHTHENIC ACIDS
RED 88 AZO DYE
M. Konyar, T. Yldz, M. Aksoy, TION OF OIL SANDS
H.C. Yatmaz, K. ztrk
EAAOP 2015
B1-4
STUDY OF ETHANOL
EFFECT AS Co-SOLVENT IN
THE NAPROXEN
OZONATION IN PRESENCE
OF NiO
C. Aguilar, J. Chairez, J. Rodr-
guez, E. Palacios, T. Poznyak
Session 2B:
OZONATION
CHAIRS: J.R. Guimaraes &
L. Rizzo
B1-5
CATALYTIC OZONATION OF
ANALGESIC PHARMACEU-
TICALS USING
COMMERCIAL AND
Pt-SUPPORTED NANO-
COMPOSITES OF Al2O3
N.H. Ince, A.Z.-Yavas
B1-6
CATALYTIC OZONATION OF
PHENOL AND 4-CHLORO-
PHENOL IN THE PRESENCE
OF THE
CeO2 FILM AND SUSPENSION
I.C. Guzmn, T. Poznyak, C.
Aguilar, J. Rodrguez-Santilln,
I. Hernndez Prez, R.T. Hernn-
dez Lpez
B1-7
SEMICONTINUOUS OZONA-
TION OF MUNICIPAL
WASTEWATER EFFLUENTS:
IMPORTANCE OF THE
WATER MATRIX
M. Marce, B. Domejoud, S. Baig,
S. Esplugas
B1-8
IMPACT OF OZONE AND
PEROXONE ADVANCED
OXIDATION PROCESSES
ON THE DEGRADATION OF
SPECIES AND DETOXIFICA-
PROCESS-AFFECTED WATER
M. Meshref, Md. Shahinoor Is-
lam, N. Klamerth, M. Gamal El-
Din
31
Session 2C:
CATALYTIC REDOX
PROCESSES
CHAIRS: D. Klauson & M. Segura
C1-5
KINETICS OF SULFATE RADI-
CAL-MEDIATED OXIDATION OF
BISPHENOL A CATALYZED BY
CUBIC CuFe2O4-Fe2O3 CATALYST
W.D. Oh, T.T. Lim, Z.L. Dong
C1-6
THE ROLES OF
POLYCARBOXYLATES IN Cr(VI)
REDUCTION INDUCED BY
SULFITE: INVOLVEMENT OF
ACTIVE RADICALS
B. Jiang, J. Zheng
C1-7
THE UNPREDICTABLE EFFECT
OF CHLORIDE AND CARBONATE
RADICAL ANIONS DURING
ADVANCED OXIDATION
PROCESSES
A. Bianco, A.B. Tour, G. Mailhot, M.
Brigante
C1-8
REMOVAL OF METHYLENE BLUE
BY FENTON LIKE OXIDATION
PROCESS USING NANO-ZERO-
VALENT IRON SUPPORTED
PUMICE STONE
D.I. ifi, S.Meri
 PROGRAM

13:00-13:15 A1-9 B1-9 C1-9

INFLUENCE OF THE INFLUENCE OF OZONATION AN INTENSIFIED FENTON
SYNTHESIS METHOD ON AND BIODEGRADATION ON PROCESS IN A CONTINUOUS
THE PHOTOCATALYTIC THE INDUSTRIAL TEXTILE FIXED BED REACTOR USING LOW
ACTIVITY OF GRAPHENE WASTE-WATER TOXICITY COST Fe/SiO2 CATALYSTS
OXIDE/TITANIUM DIOXIDE K. Padzior, J. Wrbiak, A. Kle- R. Molina, M.I. Pariente, J.A. Siles, J.A.
COMPOSITES pacz-Smka, L. Biliska, M. Melero, F. Martnez
M.J. Rivero, P. Ribao, S. Domin- Gmurek, S. Ledakowicz
guez, I. Ortiz
13:15-13:30 A1-10 B1-10
PREPARATION AND COLOR REMOVAL FROM
CHARACTERIZATION OF BIOLOGICALLY TREATED
VISIBLE LIGHT-ACTIVE TEXTILE WASTEWATER AND
TiO2-REDUCED GRAPHENE COST ANALYSIS
OXIDE PHOTOCATALYSTS M.I. Aydin, B. Yuzer, B. Yurdakul,
A.W. Morawski , A. Wanag, E. A. Ongen, H. Selcuk
Kusiak-Nejman, J. Kapica-Kozar,
. Kowalczyk, B. Ohtani, J. Os-
trowska, M. Aksienionek, L. Lip-
iska
13:30-17:00 Lunch break + Poster viewing
PS1 Poster Session 1

17:00-17:45 PLENARY TALK 2: Dr.Silvio Canonica

PT2 Indirect Phototransformation of Organic Contaminants in Surface Waters: Excited Triplet States as Photooxi-
dants
Session 3A: Session 3B: Session 3C:
PHOTOCATALYTIC OZONATION DISINFECTION
OXIDATION
CHAIRS: A. Fernandez CHAIRS: H. Selcuk & CHAIRS: D. Venieri &
Mohedano & A. Morawski C. Guzman P. Fernandez-Ibanez

A1-11 B1-11 C1-11

17:45-18:00 A NOVEL PHOTO- OCCURRENCE AND DECONTAMINATION OF
CATALYSIS APPLICATION REMOVAL OF SPECIFIC ANTIBIOTICS AND INACTIVATION
WITH REDUCED SIZE POLLUTANTS IN OF ANTIBIOTIC-RESISTANT
CRYSTALLITE TiO2 TREATED DENIM AND BACTERIA IN URBAN MBR WASTE-
M. L. Gimenes, J.C.M. Vicentini, COTTON-POLYSTER WATER USING NOVEL
M.H.N. Olsen Scaliante, TEXTILE WASTEWATERS BY GRAPHENE-BASED COMPOSITES
N.R.C. Fernandes-Machado, M. MEANS OF OZONE P. Karaolia, E. Hapeshi, I. Michael, C.
de Souza OXIDATION Drosou, N. Xekoukoulotakis, D. Fat-
E. Bahadr, S.Meric ta-Kassinos

18:00-18:15 A1-12 B1-12 C1-12

BISMUTH OXIDE THIN
FILMS DEPOSITED BY
MAGNETRON SPUTTERING
WITH INTERESTING PHOTO-
CATALYTIC PROPERTIES
J.C. Medina, M. Bizarro, S.E.
Rodil
PERFORMANCE MECHANISTIC MODEL FOR
EVALUATION OF BACTERIA PHOTO-INACTIVATION
NITROGEN OXIDES IN WATER USING SOLAR
OZONATION IN FLUE RADIATION
GASES FROM PHOSPHATE P. Fernndez-Ibez, M.Castro-Alfrez,
ROCK DIGESTION M.I. Polo-Lpez, S. Malato, J.Marugn
PROCESS-PILOT SCALE
TRIALS
K. Skalska, S. Ledakowicz, R.
Louwe, R. Szymczak

32
 EAAOP 2015

18:15-18:30 A1-13 B1-13 C1-13

ILMENITE AND ILMENITE URBAN WASTEWATER VISIBLE LIGHT PHOTOLYTIC /
MODIFIED AS CATALYST ORGANIC MATTER AND PHOTOCATALYTIC
FOR CWPO-PHOTOASSISTED MICROPOLLUTANTS DISINFECTION OF WATER
PROCESS REMOVAL BY SAMPLES USING Cu-DEPOSITED
P. Garca-Muoz, G.Pliego, B. CATALYTIC OZONATION TITANATE NANOTUBE-BASED
Barbero, J. Zazo, J.A. Casas, C. Crousier, J.-S. Pic, J. Albet, S. CATALYSTS
A. Bahamonde, J.J. Rodrguez Baig, M. Roustan T. Tiler, B. Erjavec, M. Plahuta, A.
Pintar

18:30-18:45 A1-14 B1-14 C1-14

COMPARATIVE STUDY TiO2 BASED MATERIALS EFFECT OF H2O2/SUNLIGHT
BETWEEN THE ACTIVITY OF APPLIED TO THE PHOTO PROCESS IN THE SIMULTANEOUS
TiO2 NANOPARTICLES AND CATALTYIC OZONATION OF INACTIVATION OF MULTI-DRUG
TiO2 NANOTUBES ON METOLACHLOR RESISTANT BACTERIA AND
PHOTOCATALYTIC C.A. Orge, J.L. Faria, M.F.R. REMOVAL OF ANTIBIOTIC
MEMBRANES Pereira RESISTANT GENES
J. Marugn, C. Casado, C. G. Ferro, F. Guarino, S. Castiglione, L.
Garca-Caibano, C. Adn, R. Rizzo
van Grieken

A1-15 B1-15 C1-15

18:45-19:00 ELECTROCHEMICAL OPTIMIZATION OF COUPLED COMPARATIVE EVOLUTION
PRODUCTION AND PHOTO ADVANCED OXIDATION BETWEEN OXIDATION
CATALYTIC ACTIVITY OF Ag PROCESSES AND PROCESSES USED FOR
DOPED POLYANILINE FILMS ACTIVATED CARBONS FOR BACTERIAL INACTIVATION AFTER
B.Haspulat, H. Kam PURIFICATION OF SALT THREE DIFFERENT SECONDARY
WATER TREATMENT METHODS
F. Parrino, S. Cataldo, A. Iann, C. Pulgarin, M. Voumard, S. Giannakis
V. Loddo, E. Mirenda, L. Palmi-
sano, D. Piazzese
19:00-19:15 A1-16 C1-16
ADVANCED OXIDATION INACTIVATION AND
PROCESSES BASED ON MUTAGENICITY OF ANTIBIOTIC
PRE-MAGNETIZATION IRON RESISTANT SALMONELLA AFTER
FOR HIGHLY EFFICIENT DISINFECTION BY UV-C
ENVIRONMENTAL RADIATION AND TiO2
REMEDIATION PHOTOCATALYSIS
M. Zhou, Y. Pan, X. Li, L. Xu A. Fiorentino, C. Merlin, L. Rizzo

33
 PROGRAM

Friday, 23 October 2015

09:00-09:45 PLENARY TALK 3: Prof. Dimitrios Kondarides
PT3 Production of Renewable Hydrogen over Irradiated Semiconductor Photocatalysts

ROOM A ROOM B ROOM C

Session 4A: Session 4B: Session 4C:

PHOTOCATALYTIC FENTON & FENTON AOPS FOR ENERGY
OXIDATION LIKE PROCESSES PRODUCTION
CHAIRS: I. Konstantinou & CHAIRS: M. Trapido & CHAIRS: J.A. Byrne &
C. Pulgarin M.J. Lopez-Munoz P. Lianos

09:45-10:00 A2-1 B2-1 C2-1

ABATEMENT OF PHARMA- DIPHENHYDRAMINE PHOTOCATALYTIC
CEUTICAL POLLUTANTS DEGRADATION BY HYDROGEN PRODUCTION
UNDER UVA LIGHT BY PHOTOFENTON UNDER FROM DEGRADATION OF
MAGNETICALLY DIFFERENT LIGHT GLUCOSE OVER
SEPARABLE TiO2 PHOTO- SOURCES FLUORINATED Pt-TiO2
CATALYST S. Esplugas, A. Afkhami, P. Mar- CATALYSTS
P. Ghute, S. Sable, A. Rey, F. Bel- co, J. Gimnez G. Iervolino, V. Vaiano, D.
trn, F. Medina, S. Contreras Sannino, L. Rizzo, J.J. Murcia,
M. Chidalgoand, J. Navo
10:00-10:15 A2-2 B2-2 C2-2
MAGNETIC EFFECT OF WATER UNEXPECTEDLY HIGH
SEMICONDUCTOR PHOTO- COMPOSITION ON IRON ACTIVITY OF SUPPORTED
CATALYSTS FOR THE CHELATE BASED NOBLE METAL TiO2 IN
DEGRADATION OF PHOTO-FENTON PROCESS PHOTOCATALYTIC H2
RECALCITRANT CHEMI- EFFICIENCY PRODUCTION FROM
CALS FROM FLOW BACK A. De Luca, R.F. Dantas, S. Es- PROPAN-2-OL
WATER plugas A. Marinas, F.J. Tenllado, V.
A. Zieliska-Jurek, I. Wysoc- Montes, F.J. Urbano, J.M. Ma-
ka, Z. Bielan, J. Strychalska, J. rinas, L. Ilieva, T. Tabakova, J.
Hupka Hidalgo, F.Reid
10:15-10:30 A2-3 B2-3 C2-3
EFFECT OF SINTERING DEGRADATION OF A INFLUENCE OF PROCESS
TEMPERATURE AND TIME NAPHTHENIC ACID PARAMETERS ON PHOTO-
ON ANATASE AND RUTILE MODEL COMPOUND BY CATALYTIC HYDROGEN
PHASES OF TiO2 PREPARED NITRILOTRIACETIC PRODUCTION
BY SOL-GEL METHOD ACID-MODIFIED FENTON M. Gmurek, K. Bednarczykand,
J. Morales-Meja, Y.M. Var- PROCESS M. Stelmachowski
gas-Rodrguez, R. Almanza Y. Zhang, N. Klamerth, M.
Gamal El-Din
10:30-10:45 A2-4 B2-4 C2-4
SIGNIFICANT ACRYLIC TEXTILE DYEING PRODUCTION OF
ENHANCEMENT OF WASTEWATER TREATMENT ENERGY-RICH GASES VIA
PHOTOCATA- LYTIC BY COMBINATION OF CATALYTIC DECARBO-
ACTIVITY OVER Pt-TiO2 HETEROGENEOUS XYLATION OF FORMIC AND
PHOTOCATALYSTS FOR FENTONS OXIDATION IN ACETIC ACID IN A
PHENOL DEGRADATION A CSTR AND BIOLOGICAL TRICKLE-BED
A.Zieliska-Jurek, M. Jancza- DEGRADATION IN A SBR REACTOR OVER Ru/TiO2
rek, Z. Wei, E. Kowalska L. Madeira, B.M. Esteves, C. A. Pintar, I.G. Osojnik rnivec,
Rodrigues, Rui. Boaventura, P. Djinovi, B. Erjavec
F. Maldonado-Hdar

34
 EAAOP 2015

A2-5 B2-5 C2-5

10:45-11:00 MORPHOSYNTHESIS OF OXIDATIVE AND WASTEWATER SLUDGES
TiO2/METAL OXIDE NANO- REDUCTIVE DEGRA- PRE-TREATED BY
STRUCTURES FOR DATION OF AN AZO DYE, DIFFERENT OXIDATION
OXIDATION OF AIR AMARANTH, USING ZERO SYSTEMS TO MAXIMIZE
POLLUTANTS VALENT IRON NANO THE BIOGAS PRODUCED IN
C. Trapalis, M.V. Sofianou, N. PARTICLES A SUBSEQUENT
Todorova, T. Giannakopoulou, V.A. Sijumon, U.K. Aravind, ANAEROBIC PROCESS
T. Georgakopoulos, K. Pomoni C.T. Aravindakumar Y. Segura, L. Ballesteros, F.
Martnez, J.A. Melero

A2-6 B2-6 C2-6

11:00-11:15 ANATASE-TiO2 VERSUS RU- SYNTHESIS AND NOVEL PHOTOCATALYTIC
TILE-TiO2 TO EVALUATION OF A NEW MATERIALS FOR SOLAR
UNDERSTAND THE Fe/ALGINATE HETERO- DRIVEN CO2 REDUCTION
DIFFERENCE IN GENEOUS CATALYST FOR J.A. Byrne, J.W.J. Hamilton,
PHOTOCATALYTIC PHOTO-FENTON AND P.K. Sharma, A. Brown, P.S.M.
ACTIVITY SIMULATED SOLAR Dunlop, M. Nolan, K.A. Gray, K.
W. Macyk, M. Buchalska,M.Ko- PHOTO-FENTON AT Schwartzenberg, J. Notestein, E.
bielusz, A. Matuszek, M.Pacia, NEUTRAL pH Weitz
S.Wojtya C. Sans, A. Cruz, S. Esplugas

Coffee break

Session 5A: Session 5B: Session 5C:

PHOTOCATALYTIC FENTON & FENTON WET AIR AND SUPER-
OXIDATION LIKE PROCESSES CRITICAL OXIDATION
CHAIRS: P. Falaras & CHAIRS: S. Esplugas & CHAIRS: A. Pintar & J. Muff
W. Macyk K. Plakas

12:00-12:15 A2-7 B2-7 C2-7

DEGRADATION OF
FLAME RETARDANT TRIS
(1-CHLORO-2-PROPYL)
PHOSPHATE (TCPP) BY TiO2
PHOTOCATALYSIS: KINETIC
AND MECHANISTIC STUDY
M. Antonopoulou, P. Karagi-
anni, I.K. Konstantinou
TREATMENT OF REAL PEROXO-GOLD MODIFIED
EFFLUENTS BY TITANIUM NANOTUBES
NANOFILTRATION AND FOR EFFECTIVE REMOVAL
SOLAR PHOTO-FENTON: OF METHYL ORANGE WITH
ANALYTICAL AND CWPO UNDER AMBIENT
TOXICOLOGY ASSESSMENT CONDITIONS
S. Malato, S. Miralles, J.A. Sn- N. Drainac, B. Erjavec, A. Pin-
chez-Prez, I. Olle, A, Agera,, tar
M. Llorca

12:15-12:30 A2-8 B2-8 C2-8

MODIFIED PP SURFACE
BY PECVD FOR USE AS
SUPPORT FOR TiO2 IN THE
PHOTODEGRADATION OF
FORMALDEHYDE IN
GASEOUS PHASE
M.C. Canela, M.S. Curcio, W.R.
Waldman, E. C. Rangel
HETEROGENEOUS POLYMER-BASED NANO-
FENTON-LIKE DEGRADA- CATALYSTS FOR WET AIR
TION OF NAPHTHENIC OXIDATION OF PHENOL
ACIDS MODEL COMPOUNDS V. Doluda, N. Lakina, V. Matve-
BY ACTIVATED AND eva, E. Sulman, V. Molchanov, V.
MESOPOROUS CARBON Bykov, A. Stepacheva
IMPREGNATED WITH Fe,
Fe2O3 AND -FeOOH.
N. Klamerth, M. Meshref, M.
Gamal El-Din

35
 PROGRAM

12:30-12:45 A2-9 B2-9 C2-9

DETERMINATION OF TOWARDS AN ENHANCED SURFACTANT
PHOTOCATALYTIC BIODEGRADABILITY OF AN ENCAPSULATED HETERO-
ACTIVITY OF SELF- ACTUAL PHARMACEU- POLY-ANION WITH
CLEANING PAINTS USING TICALWASTEWATER BIOLOGICAL MEMBRANE
SMART INKS F. Martinez, M.I. Pariente, Y. LIKE STRUCTURE FOR
J. Krsa, M. Baudys, A. Mills Segura, R. Molina, I. Rodriguez, CATALYTIC WET AIR
J.A. Melero OXIDATION
S.K. Lua, T.T. Lim, Z.L. Dong
A2-10 B2-10 C2-10
12:45-13:00 SOLAR PHOTOCATALYSIS CATALYTIC REMOVAL OF ORANGE II DYE
TREATMENT USING BINARY MIXTURE OF DYES DEGRADATION BY WET
IMMOBILIZED NF-TIO2 WITH OPPOSITE AND PEROXIDE OXIDATION U
COMPOSITE WITH SIMILAR CHARGES IN THE SING AN Au/Al2O3 CATALYST
MONODISPERSE TIO2 PRESENCE OF CERIA/H2O2 L.M. Madeira, C. Rodrigues, S.
NANOPARTICLES OF FENTON-LIKE SYSTEM Carabineiro, F. Maldonado-H-
INDUSTRIAL WASTEWATER H. Issa Hamoud, B. Azambre, G. dar
CONTAINING 1,4 DIOXANE Finqueneisel
D. Hermosilla, H. Barndk, C.
Han, D.D. Dionysiou, C. Negro,
A. Blanco
A2-11 B2-11 C2-11
13:00-13:15 OPTIMIZATION OF TTIP EFFECT OF HYDROXYL YDROLYTIC
THIN-FILMS FOR REMOVAL GROUPS SUBSTITUTED IN HYDROGENATION OF
OF METHYLENE BLUE AND THE CHANGES OF CELLULOSE IN
AMPICILLINE AND SOLUTION TURBIDITY SUBCRITICAL WATER
INACTIVATION OF E. COLI DURING THE OXIDATION E.M. Sulman, V.G. Matveeva,
BACTERIA OF AROMATIC O.V. Manaenkov, O.V. Kistlitsa,
C. zkal, S. Meri, D. Mantza- CONTAMINANTS A.E. Filatova, V.Yu. Doluda, A.I.
vinos N. Villota, L.M. Camarero, L.M. Sidorov, M.G. Sulman
Lomas

13:15-13:30 A2-12 B2-12

THE INFLUENCE OF INERT
INGREDIENTS IN
FORMULATIONS ON THE
RATE OF PHOTO-
CATALYTIC DEGRADATION
OF PESTICIDES METHOMYL
AND CARBOFURAN
A. Tomaevi, S. Gai, R. BASEDCATALYSTS
urovi-Pejev, D. Mijin, A.
Marinkovi
ADSORPTION-OXIDATION
PROCESSES FOR
REMOVAL OF
ORGANIC CONTAMINANTS
BY HETEROGENEOUS
FENTON-LIKE PROCESS
USING Pd/Fe-ZEOLITE
S.S. Sable, P.P. Ghute, A. Geor-
gi, F. Medina, S. Contreras

Lunch Break + Poster Viewing

13:30-17:00 Poster Session 2
PS2

36
 EAAOP 2015

17:00-17:45 PLENARY TALK 4: Prof. Dionysios D. Dionysiou

PT4 Treatment of Contaminants of Emerging Concern in Water using Sulfate Radical-Based Advanced
Oxidation Processes
Session 6A: Session 6B: Session 6C:
PHOTOCATALYTIC FENTON & FENTON RADIATION
OXIDATION LIKE PROCESSES PROCESSES
CHAIRS: R. Dillert & CHAIRS: L. Ioannou & CHAIRS: Z. Frontistis &
A. Hiskia R. Dewil R. Torres Palma

17:45-18:00 A2-13 B2-13 C2-13

PHOTOCATALYTIC PHOTOCATALYTIC PHOTODEGRADATION OF
OXIDATION OF REDUCTION OF Cr(VI) OVER BISPHENOLS:
SWEETENERS SACCHARIN Fe(III)-CITRATE MECHANISTIC ASPECTS
AND ACESULFAME K. COMPLEXES IN A V. Salomatova, I. Pozdnyakov, V.
EFFECT OF INITIAL pH AND SIMULATED SOLAR Grivin, P. Sherin, V. Plyusnin, N.
PERSULFATE SYSTEM Bazhin
CONCENTRATION. B.A. Marinho, R.O. Cristvo,
J. Morales-Meja, D. Lpez, S. J.C. Lopes, R.A.R. Boaventura,
Silva, R. Almanza V.J.P. Vilar

18:00-18:15 A2-14 B2-14 C2-14

A NEW SUPPORTED TiO2
FILM DEPOSITED ON
STAINLESS STEEL FOR THE
PHOTOCATALYTIC DEGRA-
DATION OF EMERGING
ORGANIC CONTAMINANTS
S. Murgolo, G. Mascolo, D. Na-
suhoglu, R. Gerbasi, F. Visentin,
N. El Habra, V. Yargeau
A2-15
UV-LED TIO2 PHOTO-
CATALYSIS FOR THE
18:15-18:30 DEGRADATION OF
BISPHENOL-A: LED VS
BLACK LIGHT
FLUORESCENT LAMP &
INVESTIGATION OF KEY
PARAMETERS
K. Davididou, R. Nelson, E.
Chatzisymeon
DESIGN OF TWO-COLUMN
PHOTO-ELECTRO-FENTON
REACTOR FOR THE
TREATMENT OF WINERY
WASTEWATER
M. Pazos, A.Dez, E. Rosales,
M.A. Sanromn
B2-15
THE USE OF ULTRASOUNDS
FOR OXIDATION OF WATER
POLLUTANTS
M. Vinatoru, M.Dukkanci, M.
Shestakova and T. Mason
GATIFLOXACIN DEGRA-
DATION BY HYDROXYL
RADICALS:BYPRODUCTS
AND RESIDUAL TOXICITY
C. Rodrigues-Silva, M. Caiane-
lo, M.G. Maniero, J.R. Guim-
ares
C2-15
DEGRADATION OF
17-ETHINYL ESTRADIOL IN
WATER BY
HYDRODYNAMIC-
ACOUSTIC-CAVITATION:
FREQUENCY EFFECTS
F. Anschuetz, M. Franke, P.
Braeutigam, A. Stolle, B. On-
druschka

A2-16 B2-16 C2-16

18:30-18:45 ASSEMBLING CELLULOSE
MEMBRANES WITH
GO-TiO2 COMPOSITES FOR
THE TREATMENT OF
ORGANICS IN SALTY WATER
J.L. Faria, L.M. Pastrana-Mar-
tinez, S. Morales-Torres, J.L.
Figueiredo, A.M.T. Silva
BIO-RECALCITRANT AMICARBAZONE DEGRA-
POLLUTANTS REMOVAL DATION BY UVA-
FROM WASTEWATER WITH ACTIVATED PERSULFATE IN
COMBINATION OF THE THE PRESENCE OF
FENTON TREATMENT AND HYDROGEN PEROXIDE OR
BIOOXIDATION Fe2+
M. Trapido, T. Tenno, A. Goi, C. Graa, A. Velosa, A.C.Teix-
N. Dulova, E. Kattel, A. Kivi, D. eira
Klauson, K. Klein, M. Viisimaa

37
 20:30 Gala Dinner
PROGRAM

Saturday, 24 October 2015

09:00-09:45 PLENARY TALK 5: Prof. Manuel A. Rodrigo
PT5 Electrochemical oxidation with diamond electrodes: facts and promises

ROOM A ROOM B ROOM C

Session 7A: Session 7B: Session 7C:

PHOTOCATALYTIC ELECTROCHEMICAL/ COUPLING AOP WITH
OTHER PROCESSES,
OXIDATION PHOTO- PILOT-SCALE STUDIES
ELCTROCHEMICAL AND FIELD
PROCESSES APPLICATIONS
CHAIRS: A. Zielinska- Jurek CHAIRS: A. Katsaounis & CHAIRS: S. Malato &
& C. Trapalis A. Urtiaga M. Pazos

09:45-10:00 A3-1 B3-1 C3-1

HETEROGENOUS AND APPLICABILITY OF COMBINATION OF
HOMOGENOUS CATALYSIS ELECTROCHEMICAL MEMBRANE TECHNOLOGY
IN PHOTOCHEMICAL OXIDATION USING AND UV-LED/TiO2 FOR THE
DEGRADATION OF DIAMOND ANODES TO THE REMOVAL OF PATHOGENS
CORTISOL TREATMENT OF A AND VOCs FROM URINE
S. Klementova, L. Doubkova SULFONYLUREA O. Autin, S. Tyrrel, E. Cartmell,
HERBICIDE A. Parker, L. Williams, A. Kolios,
C. Sez, F. Souza, S. Quijorna, E. McAdam
M.R.V. Lanza, P. Caizares,
M. Rodrigo
10:00-10:15 A3-2 B3-2 C3-2
PROCESS INTENSIFICATION SELECTIVE ELECTRO- OXIDATION AND
IN THE PHOTO-CATALYTIC CHEMICAL DEGRADATION ADSORPTION OF ARSENITE
SPINNING DISC REACTOR: OF 4-CHLOROPHENOL AT IN AQUEOUS SOLUTIONS
THE EFFECT OF PHOTO- A Ti/RuO2-IrO2 ANODE IN USING Fe-DOPED SBA-15
CATALYST MACRO- CHLORIDE RICH AND PERSULFATE
STRUCTURE ON WASTEWATER W. Ding, W. Zhou, F. Wu, J. Li
TREATMENT EFFICIENCY J. De Coster, W. Vanherck, L.
W.S. Wan Mansor, E.A.C. Em- Appels, R. Dewil
manuelson, D.A. Patterson
A3-3 B3-3 C3-3
10:15-10:30 PHOTOCATALYTIC NO TRANSITION METAL NOVEL PILOT SCALE
DEGRADATION: MODIFIED CATHODE FOR CONTINUOUS PHOTO-
MECHANISTIC AND HETEROGENEOUS CATALYTIC MEMBRANE RE-
KINETIC ASPECTS ELECTRO FENTON: ACTOR FOR THE
R. Dillert PREPARATION AND REMOVAL OF
PERFORMANCE RECALCITRANT
M. Zhou, F. Yu, Y. An MICRO-POLLUTANTS FROM
WATER
A.J Karabelas, V.C. Sarasidis,
K.V. Plakas, S.I. Patsios, A.M.
Lekkas

38
 EAAOP 2015

10:30-10:45 A3-4 B3-4 C3-4

EFFECTIVE TREATMENT OF
ACRYLIC FIBRE MANU-
FACTURING WASTEWATER
USING ADVANCED
OXIDATION PROCESSES
W. Szeto, J.T. li, H.B. Huang,
Y.C. Leung
A3-5
10:45-11:00 FLUIDIZED-BED PHOTO-
CATALYTIC REACTOR:
INFLUENCE OF OPERATING
CONDITIONS ON THE
ELIMINATION OF
PERSISTENT EMERGING
MICROPOLLUTANTS
N. Pronina, D. Klauson, S.
Kamenev, T. Rudenko, K. Kn-
nis-Beres, A. Moiseev, J. Deu-
bener, M. Krichevskaya
11:00-11:15 A3-6
REMOVAL OF
ARSENIC FROM AQUEOUS
SOLUTIONS THROUGH A
COUPLED SYSTEM OF
PHOTOCATALYSIS AND
ZERO-VALENT IRON
M.J. Lpez-Muoz, A. Arencib-
ia, Y. Segura, J.M. Arsuaga, J.M.
Raez
AVOIDING THE FORMATION
OF CHLORATES DURING
THE ELECTRODISIFECTION
OF URBAN WASTEWATER
WITH BDD ANODES
S. Cotillas, J. Llanos, P. Caiza-
res, M.A. Rodrigo
B3-5
SYNERGETIC TREATMENT
OF PESTICIDE
CONTAMINATED DRINKING
WATER BY COMBINED RO
SEPARATION AND
ELECTROCHEMICAL
DEGRADATION
J. Muff, H.T. Madsen, E.G.
Sgaard
B3-6
ELECTROCHEMICAL
DEGRADATION OF
IODINATED CONTRAST
MEDIA AND OTHER
PERSISTENT ORGANIC
CONTAMINANTS BY
E L E C T R O C H E M I C A L LY
ACTIVATED SULFATE AND
PERSULFATE IONS AT
BORON DOPED DIAMOND
ANODES
A. Farhat, S. Tait, J. Keller, J.
Radjenovic
TERTIARY TREATMENT OF
WASTEWATER BY
ADSORPTION AND SOLAR
PHOTOCATALYSIS FOR
DECONTAMINATION AND
DISINFECTION OF
SECONDARY EFFLUENTS
M. Brienza, S. Gutirrez Alfaro,
G. Plantard, S. Nir, S.A. Bufo, V.
Goetzand S. Chiron
C3-5
ASSESSMENT OF THE KEY
PARAMETERS OF THE
PHOTOCATALYTIC
PROPERTIES FOR
CONSTRUCTION
MATERIALS: LIFE-MINOX-
STREET EUROPEAN
PROJECT
B. Snchez, S. Surez, I. Jans-
son, O. Vilanova, B.Cadavid,
J. Perez, J.O. Marrn, A. Mor-
al, M. Snchez, M .Palacios, L.
Nuez, B. Artiano, M. Pujadas,
D. Iglesia
C3-6
SOLAR PHOTO-
CATALYTIC PROCESSES
FOR SOIL WASHING
WASTEWATER TREATMENT
M. Race, R. Andreozzi, I. Di
Somma, M .Fabbricino, R. Ma-
rotta, L. Onotri, F. Pirozzi, A.
Siciliano

39
 PROGRAM

Coffee Break

Session 8A: Session 8B: Session 8C:

PHOTOCATALYTIC ELECTROCHEMICAL/ COUPLING AOP
OXIDATION PHOTO- WITH OTHER
ELCTROCHEMICAL PROCESSES,
PROCESSES PILOT-SCALE
STUDIES AND FIELD
APPLICATIONS
CHAIRS: N. Xekoukoulotakis CHAIRS: J. Vakros & T.C.An CHAIRS: I. Carra & P. Jarvis
& M.G. Antoniou

12:00-12:15 A3-7 B3-7 C3-7

PHOTOCATALYTIC ELECTROCATALYTIC AND ELIMINATION OF
REMOVAL OF TOXICITY PHOTOASSITED ANTIBIOTIC ACTIVITY OF
AND ESTROGENICITY OF DEGRADATION OF WATERS CONTAMINATED
WATER DISSOLVED P E R F L U O R O O C TA N O I C WITH OXACILLIN BY
BISPHENOLS (BISPHENOL A, ACID PHOTO-FENTON, TiO2-
F AND AF) IN BR AND CSTR A. Urtiaga, B. Gmez, I. Ortiz PHOTOCATALYSIS,
B. Erjavec, P. Hudoklin, K. Perc. SONO-CHEMICAL AND
T. Tiler, M. Sollner Dolenc, A. ELECTROCHEMICAL
Pintar PROCESSES - A
COMPARATIVE STUDY ON
THE EFFECTS OF
ADDITIVES
R.A. Torres-Palma, E. Ser-
na-Galvis, J. Silva-Agredo, A.
Giraldo-Aguirre, O. Florez
A3-8 B3-8 C3-8
12:15-12:30 ESR INVESTIGATION OF PHOTOCATALYTIC DEGRA- PILOT-SCALE SLURRY AND
THE PHOTOCATALYSIS DATION OF SODIUM FIXED-BED SOLAR-
MECHANISM OF DODECYL SULPHATE PHOTOCATALYTIC
CYANOTOXINS UNDER BASED ON -Fe2O3 NANO- REACTOR FOR THE DEGRA-
VISIBLE LIGHT STRUCTURE DATION OF HERBICIDE
A. Hiskia, T. Fotiou, T.M. Trian- H. Nguyen, C. Phan, T. Sen ISOPROTURON
tis, T. Kaloudis, N. Ioannidis A.Verma, N. T. Prakashand, A.P.
Toor
12:30-12:45 A3-9 B3-9 C3-9
AQUEOUS PHOTO- DEGRADATION OF THE HEALTH RISK
CATALYTIC DEGRADATION MICROCONTAMINANTS IN DECREASE WITH
OF SELECTED WASTEWATER BY SIMULTANEOUS
MICROPOLLUTANTS BY PHOTO-ASSISTED ELIMINATION OF VOCs AND
Pd-MODIFIED TITANIUM ELECTROCHEMICAL POPs CONTAINING
DIOXIDE OXIDATION PARTICLES EMITTED FROM
D. Klauson, M. akaravili, N. S. W. da Silva, M.A. Siqueira Ro- ELECTRONIC WASTE
Pronina, M. Krichevskaya, E. drigues, A.M. Bernardes DISMANTLING WORKSHOP
Krber, V. Mikli BY AN INTEGRATED
TECHNIQUE OF DEDUSTING
WITH DECONTAMINATION
T.C. An, J.Y. Chen, D.L. Zhang,
G.Y. Li

40
 EAAOP 2015

A3-10 B3-10 C3-10

12:45-13:00 HATR-FTIR ONLINE I R R A D I AT E D - A S S I S T E D PILOT STUDIES OF A NOVEL
ANALYSIS OF SURFACE ELECTROCHEMICAL ELECTRO-FENTON FILTER
SPECIES ON P25 AND Au PROCESSES FOR THE FOR THE REMOVAL OF
MODIFIED TiO2 DURING REMOVAL OF PERSISTENT ORGANIC
PHOTOCATALYTIC POLLUTANTS FROM MICROPOLLUTANTS FROM
OXIDATION OF NITROGEN BIOLOGICALLY TREATED POTABLE WATER
MONOXIDE URBAN WASTEWATER K. Plakas, A. Karabelas, S. Sk-
K. Skalska M.J. Martn de Vidales, C. Sez, lari, V. Zaspalis, D. Yiankakis, G.
P. Caizares, M.A. Rodrigo Sideropoulos
13:00-13:15 A3-11 B3-11 C3-11
GAS-PHASE PHOTO- STUDY OF METHANOL NOVEL ADVANCED
CATALYTIC OXIDATION OF REFORMING USING OXIDATION PROCESS ON
MIXTURES OF DIFFERENTIAL ELECTRO- A CHEMICALLY MODIFIED
REFRACTORY ORGANIC CHEMICAL MASS GRAPHITE SURFACE WITH
COMPOUNDS: THROUGH SPECTROMETRY (DEMS) NANOMETAL
THE NET OF PROCESS J. Vakros, B. Hasa, A. Katsaou- M.A. Morsy, Abdel-Nasser M.
LIMITATIONS nis Kawde, Mohamed A. Daous,
M. Krichevskaya, A. Moiseev, S. A.U. Dogan
Preis, J. Deubener
13:15-16:00 Lunch Break + Poster Viewing
PS3 Poster Session 3

Session 9B: Session 9C:

FENTON & FENTON COUPLING AOP WITH
OTHER PROCESSES
LIKE PROCESSES PILOT-SCALE STUDIES
AND FIELD
APPLICATIONS
CHAIRS: J. Krysa & CHAIRS: N. Klamerth &
I. Arslan-Alaton N. Dulova
16:00-16:15 B3-12 C3-12
REMOVAL OF IOPAMIDOL, AN PESTICIDE REMOVAL AND
IODINATED X-RAY CONTRAST EVALUATION OF
MEDIA, BY ZERO-VALENT DISINFECTION-BY
ALUMINUM-ACTIVATED H2O2 PRODUCT FORMATION WITH
AND S2O82- OXIDATION LED-BASED AOPs
I. Arslan-Alaton, T. Olmez-Hanc, I. Carra, B. Jefferson, P. Jarvis
G. Korkmaz, C. Sahin
B3-13 C3-13
DEGRADATION OF ETHYL QUANTITATIVE
16:15-16:30
PARABEN BY HEAT- DETERMINATION OF H2S GAS
ACTIVATED PERSULFATE: USING KMnO4
STATISTICAL EVALUATION OF N. Shahzad, S. Iqbal
OPERATING FACTORS
Z. Frontistis, M. Antonopoulou,
N. Potakis, A. Michailidi, B. Mat-
thaiou, I. Konstantinou, D. Mant-
zavinos

B3-14
PHOTOVOLTAIC-DRIVEN
16:30-16:45
UV-LED PHOTO-FENTON: A
NEW APPROACH FOR MICRO-
POLLUTANT REMOVAL
J.L. Casas Lpez, G. Rivas Ibaez,
I. de la obra, M. Prez Garca, J.A.
Snchez Prez

16:45 Closing Ceremony - NEXT EAAOP5

41
 PROGRAM
Poster Presentation 1
Thursday, 22 October 2015
PS1 Room: Foyer
Photocatalytic Oxidation

USE OF ZnO AND Nb2O5 IMPREGNATED WITH SILVER OR IRON FOR PHOTOCATALYTIC
PP1-1 DEGRADATION OF CELLULOSE AND PAPER WASTEWATER
R.G. Marques, A.M. Ferrari-Lima, V.S. Santana, M. Luiz Gimenes and N.R.C. Fernandes-Machado

NOVEL ANATASE/RUTILE/BROOKITE TiO2 NANOCOMPOSITE WITH SUPERIOR MINERALIZATION

PP1-2 POTENTIAL FOR PHOTOCATALYTIC DEGRADATION OF WATER POLLUTANTS
. Pintar, R. Kaplan, B. Erjavec, G. Drai and J. Grdadolnik

SUNLIGHT PHOTOCATALYTIC PURIFICATION OF WATER WITH NOVEL HETERO-STRUCTURES

PP1-3 C. Belver, J. Bedia, M.A. lvarez-Montero and J.J. Rodriguez

SURFACE RECONSTRUCTION OF TITANIA WITH g-C3N4 AND Ag FOR EFFICIENT ELECTRONS

PP1-4 MIGRATION AND ENHANCED VISIBLE LIGHT PHOTOCATALYSIS
Kah Hon Leong, Sze Ling Liu, Min Jang, S. Ibrahim and P. Saravanan

PHOTOCATALYTIC DEGRADATION OF NOX IN A CONTINUOUS BENCH-SCALE REACTOR USING

PP1-5 ACTIVE TILES, EXPERIMENTAL DATA AND SIMULATIONS
C. L. Bianchi, M. Stucchi, C. Pirola, F. Galli, S. V. and V. Capucci

IMPLEMENTATION OF TIO2 OXYGEN ADSORPTION CAPACITIES FOR THE EVALUATION OF PHOTO-

PP1-6 CATALYSTS ACTIVITY IN POLLUTANTS OXIDATION
M. Krichevskaya, A. Moiseev, D. Klauson, N. Pronina, G.Hauser, A. P. Weber, B. Lohrengel and J. Deubener

PREPARATION OF TiO2 AND GRAPHENE FILM DECORATED TiO2 NANO-TUBE ARRAY

PP1-7 PHOTOELECTRODE AND ENHANCED VISIBLE LIGHT PHOTOCATALYTIC MECHANISM
Huiling Liu, X. Cheng, Y. Tian, F. Cui, J. Nan, J. Yao and Z. Chen

PHOTODEGRADATION OF SPIRODICLOFEN, SPIROMESIFEN AND SPIROTETRAMAT IN WATER

PP1-8 USING BINARY AND TERNARY OXIDES OF TITANIUM AND ZINC
I. Garrido, J. Fenoll, P. Flores, P. Helln, N. Vela and S. Navarro

PHOTOCATALYTIC ACTIVITY OF g-C3N4-TiO2 NANOCOMPOSITES FOR NOX REMOVAL

PP1-9 I. Papailias, N. Todorova, T. Giannakopoulou, C. Trapalis and D. Demotikali

SiO2-TiO2 NANOCOMPOSITE AND ITS UTILIZATION IN ECOLOGICAL PHOTOCATALYSIS

PP1-10 J. Subrt, T. Sazavska, L. Krikavova, M. Jakubickova, J. Jirkovsky, F. Peterka and J. Kupcik

DEGRADATION OF EMERGING POLLUTANTS UNDER SOLAR IRRADIATION USING NOVEL

PP1-11 TiO2-ZnO/CLAY NANOARCHITECTURES
M. Tobajas, C. Belver and J. Jose Rodriguez

SPECTROSCOPIC AND PHOTOCATALYTIC CHARACTERIZATION OF MODIFIED TITANIUM

PP1-12 DIOXIDE-BASED MATERIALS FOR WATER DECONTAMINATION
P. Bro, M. Surwka, M. Buchalska and W. Macyk

42
 EAAOP 2015

PRODUCTION AND VISIBLE LIGHT PHOTOCATALYTIC ACTIVITY OF Mn-DOPED ZnO

PP1-13 MICROPARTICLES
B. Haspulat, H. Kam and H. Memi

PHOTOCATALYTIC DEGRADATION OF EMERGING CONTAMINANTS VIA ADVANCED TITANIUM

PP1-14 DIOXIDE NANOSTRUCTURES
P. Falaras, M. Arfanis, P. Adamou, N. Moustakas, M. Antoniadou and A. Kontos

A SOLAR ANNULAR PHOTOREACTOR PACKED WITH A MONOLITH COVERED WITH AN ACTIVE

PP1-15 SOL-GEL TiO2 TO PURIFY A GAS STREAM
C. Rodrigues-Silva, R. Monteiro, M. Dezotti, A. Silva and V. Vilar

SYNTHESIS, CHARACTERIZATION AND PHOTOCATALYTIC ACTIVITY OF NIOBIUM OXIDE

PP1-16 MATERIALS
J. Marugan, L. A. Morais, C. Adn, M.P.M.A. Guedes and A.S. Arajo

MODIFIED GYPSUM PLASTERS FOR PHOTOCATALYTIC DEGRADATION OF ACETALDEHYDE

PP1-17 M. Janus, K. Zajc, J. Zatorska, E. Kusiak-Nejman, A. Czyewski and A. W. Morawski

THERMAL AND PHOTOCATALYTIC REACTION OF NO WITH ETHANOL

PP1-18 F. Solymosi, G. Halasi and T. Bnsgi

EFFECT OF LEDS DISTRIBUTION IN THE PHOTOCATALYTIC REACTOR DURING THE

PP1-19 TEREPHTHALIC ACID OZONATION WITH VXOY/ZnO
I. Fuentes, J. L. Rodrguez, H. Tiznado, J.M. Romo-Herrera, T. Poznyak and J.I. Chairez

PHOTOCATALYTIC REMOVAL OF BISPHENOL A WITH A MAGNETICALLY SEPARABLE TiO2

PP1-20 NANOCOMPOSITE
S. Dominguez, M. Rivero and I. Ortiz

SONOPHOTOCATALYTIC DEGRADATION OF PARACETAMOL USING Pt-TiO2 NANO-COMPOSITE

PP1-21 A.Z. Yavas, B. Savun-Hekimoglu and N. Ince

EFFECT OF Ag ON THE PHOTOCATALYTIC ACTIVITY OF ZnO SEMICONDUCTORS ASSESSED BY

PP1-22 PHENOL CONVERSION IN AQUEOUS SOLUTIONS
J.L. Faria, M.J. Sampaio, M.J. Lima, D.L. Baptista, A. Silva and C. Silva

NOVEL PHOTO-EFFICIENT ANISOTROPICALLY FUNCTIONALIZED PHOTOCATALYSTS

PP1-23 S. Karapati, T. Giannakopoulou, N. Todorova, N. Boukos, D. Dimotikali and C. Trapalis

MODIFICATION OF GAS SENSING PROPERTIES OF TiO2 NANOMATERIALS BY ALIOVALENT AND

ISOVALENT CATIONS
PP1-24 B. Lyson-Sypien, A. Kusior, M. Radecka, M. Rekas, J. ukrowski, M. Gajewska, K. Michalow-Mauke, T. Graule
and K. Zakrzewska

PHOTOCATALYTIC OXIDATION OF AS(III) IN AQUEOUS SOLUTION WITH TiO2 OBTAINED BY A

PP1-25 MODIFIED SOLGEL METHOD
M.J. Lpez-Muoz, L. Cerro, J.M. Raez, R. Snchez and N. Milln

PHOTOCATALYTIC DEGRADATION OF ORGANIC DYE (METHYLENEBLUE) OVER SULFUR DOPED

PP1-26 TiO2 PREPARED BY SOL-GEL PROCESS
J.-H. Yu, S.-H. Nam, K.-H. Hwang, H. Seo and J.-H. Boo

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 PROGRAM

EFFECT OF OXIDATION SILVER STATE ON TiO2-CeO2 PHOTOCATALYSTS FOR THE PHOTO-

PP1-27 DEGRADATION OF PHENOL USING SOLAR AND SIMULATED SOLAR SUNLIGHT
J.C. Arevalo, J.G. Torres Torres and A. Silahua-Pavon

PHOTODEGRADATION OF 17 -METHYLTESTOSTERONE WITH SIMULATED SOLAR RADIATION

PP1-28 USING SUNTEST CPS+ WITH TiO2-Gd3+ AND TiO2-Sm3+
D. de La Cruz, J. C. Arvalo and J. G. Torres

PHOTOCATALYTIC DEGRADATION OF PHENOL BY CHAR/N-TiO2 AND CHAR/N-F-TIO2 COMPOSITE

PP1-29 PHOTOCATALYSTS
P. Karagianni, M. Antonopoulou, A. Giannakas, V. Makrigianni, I. Deligiannakis and I. Konstantinou

PHOTOCATALYTIC REDUCTION OF Cr(VI) BY char/TiO2 COMPOSITE PHOTOCATALYSTS:

PP1-30 OPTIMIZATION AND MODELING USING THE RESPONSE SURFACE METHODOLOGY (RSM)
M. Antonopoulou, I. Chondrodimou and I. Konstantinou

FUNCTIONALIZED TiO2 CONTAINING PAINTS FOR LONG-TERM NO POLLUTANT OXIDATION

PP1-31 S. Karapati, T. Giannakopoulou, N. Todorova, N. Boukos, D. Dimotikali and C. Trapalis

TiO2/GRAPHENE OXIDE PHOTOCATALYSTS: COMPARATIVE INVESTIGATION OF COMPOSITES

PP1-32 WITH EX- AND IN-SITU SYNTHESIZED TiO2
N. Todorova, A. Trapalis, I. Papailias, T. Giannakopoulou and J. Yu

PHOTODEGRADATION OF BTX UNDER UV-A LIGHT WITH N-DOPED CATALYSTS

PP1-33 M.L. Gimenes, A.M. Ferrari-Lima, R.G. Marques and N.R.C. Fernandes-Machado

PREPARATION OF B-DOPED TiO2 WITH ENHANCED PHOTOCATALYTIC ACTIVITY UNDER

PP1-34 VISIBLE-LIGHT IRRADIATION
C. Drosou, N. Xekoukoulotakis, K. Tyrovola and F. Panagiotou

GREYWATER AS A SUSTAINABLE WATER SOURCE: A PHOTOCATALYTIC TREATMENT TECHNO-

PP1-35 LOGY UNDER ARTIFICIAL AND SOLAR ILLUMINATION
S. Tsoumachidou, T. Velegraki and I. Poulios

PHOTOCATALYTIC DEGRADATION OF ACETONE USING TITANIA PREPARED BY

PP1-36 ELECTROSPINNING TECHNIQUE
G. Skouras, G. Tatsi, N. Todorova, C. Trapalis and T. Vaimakis

AN ECOTOXICITY BASED LAB-SCALE OPTIMIZATION FOR REMOVAL OF THREE ANTIBIOTICS IN A

PP1-37 SUSPENDED PHOTOCATALYTIC REACTOR
S. Meri, C.B. zkal, L. Rizzo and M. Marotta

THE INFLUENCE OF POLYCHROMATIC LIGHT ON CARBOFURAN DEGRADATION IN ZnO AQUEOUS

PP1-38 SUSPENSION
A. Tomaevi

PREPARATION OF OCTAHEDRAL ANATASE TITANIA PARTICLES FOR DECOMPOSITION OF

PP1-39 CHEMICAL AND MICROBIOLOGICAL POLLUTANTS
Z. Wei, M. Endo, B. Ohtani and E. Kowalska

POLYMER MODIFICATION OF TIO2 NANOPARTICLES VIA THE GRAFTING TO APPROACH, FOR

PP1-40 ENHANCEMENT OF THEIR PHOTOCATALYTIC PERFORMANCE
E. Vasilaki, M. Kaliva, N. Katsarakis and M. Vamvakaki

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MONOLITHIC CATALYTIC BED COATED WITH TiO2 P25 TOWARDS THE PHOTOCATALYTIC
PP1-41 REDUCTION OF Cr(VI) IN A SIMULATED SOLAR SYSTEM
B. Marinho

FABRICATION ON PDMS FILMS OF TEXTURED PYRAMIDAL STRUCTURE VIA PS BEADS WITH

PP1-42 DIFFERENT SIZE FOR SELF-CLEANING APPLICATION
J.-H. Yu, S.-H. Nam, K.-H. Hwang, H.-J. Seo and J.-H. Boo

NEW COMPOSITES OBTAINED BY FRIENDLY CONDITIONS FOR ADVANCED WASTE-WATERS

PP1-43 PROCESS
M. Visa and A. Chelaru

GREEN TECHNOLOGIES BASED ON ADVANCED OXIDATION PROCESSES (AOPs): WATER

PP1-44 DECONTAMINATION BY PHOTOCATALYSIS USING SOLAR LIGHT
M.E. Borges, P. Esparza, M. Sierra, J.C. Ruiz-Morales , P. Martn-Zarza, J. Mndez-Ramos , P. Mora

SUBSTITUENT EFFECTS ON THE PHOTOCATALYTIC DEGRADATION OF ARYLAZO PYRIDONE DYE:

PP1-45 AN EXPERIMENTAL AND THEORETICAL STUDY
J. Dostanic, D. Loncarevic, M. Zlatar, F. Vlahovic and D. Jovanovic

SOLAR LIGHT-ZnO DEGRADATION OF ETHYLPARABEN: STATISTICAL EVALUATION OF

PP1-46 OPERATING FACTORS AND ESTROGENIC ACTIVITY
Z. Frontistis, A. Liangou, O. Zervaki, S. Arapitsa, M.I. Karga, D. Venieri, D. Mantzavinos

PREPARATION AND APPLICATION OF HYBRID PHOTOCATALYSTS BASED ON BRAZILIAN CLAYS

PP1-47 AND TiO2 FOR NOX DEGRADATION
R. Tessinari, I. Jansson, M. Canela, R. Portela, S. Surez, P. vila and B. Sanchez

DEGRADATION OF ENDOCRINE DISRUPTORS USING SIMULATED SOLAR IRRADIATION AND

PP1-48 Cu2O/BiVO4
Y. Kanigaridou, A. Petala, Z. Frontistis, D. Kondarides and D. Mantzavinos

SOLAR LIGHT INDUCED DEGRADATION OF ETHYL PARABENS WITH Cu2O/BiVO4-STATISTICAL

PP1-49 EVALUATION OF OPERATING FACTORS
A. Petala, R. Bontemps, A. Spartatouille, Z. Frontistis, D. Kondarides and D. Mantzavinos

PHOTOCATALYTIC TRANSFORMATION OF THE ANTIPSYCHOTIC DRUG RISPERIDONE IN

AQUEOUS MEDIA ON REDUCED GRAPHENE OXIDE-TIO2 COMPOSITES: SYNTHESIS,
PP1-50 CHARACTERIZATION AND DEGRADATION KINETICS
V. Sakkas, C. Hadjicostas, P. Calza, C. Minero, M. Kalaboka and T. Albanis

HETEROGENEOUS PHOTOCATALYSIS AND OZONE OXIDATION FOR THE REMOVAL OF

PP1-51 NONYLPHENOL AND SHORT-CHAIN NONYLPHENOL ETHOXYLATES FROM AQUEOUS MATRICES
E. Klontza, N. Xekoukoulotakis and E. Diamadopoulos

45
 PROGRAM
Poster Presentation 2
Friday, 23 October 2015
Room: Foyer
Fenton and Fenton like processes
PS2 Catalytic Redox Processes
Coupling AOPs with other processes
Pilot-scale studies and field application
Ozonation

PHOTO-FENTON DEGRADATION OF PHARMACEUTICAL DIPHENHYDRAMINE IN WATER AT

PP2-1 CIRCUMNEUTRAL pH
S. Esplugas, S. Plaza, A. De Luca, P. Marco and J. Gimenez

STUDY OF AMICARBAZONE PHOTODEGRADATION BY DIFFERENT ADVANCED OXIDATION

PP2-2 PROCESSES
M. Silva and A.C. Teixeira

COMBINED NANO ZERO-VALENT IRON IMMOBILIZATION AND HETEROGENEOUS FENTON

PP2-3 PROCESSES FOR REMOVAL OF METRONIDAZOLE
X. Wang and P. Liu

INTERMEDIATES OF DEGRADATION GENERATED DURING THE FIRST OXIDATION STATES OF

PP2-4 PHENOL IN A PHOTO-FENTON SYSTEM
N. Villota, J.M. Lomas and L.M. Camarero

DETERMINATION OF THE DEGRADATION PATHWAYS INVOLVED DURING THE TREATMENT OF

PP2-5 CIPROFLOXACIN BY PHOTO-ELECTRO FENTON PROCESS
P. Villegas-Guzman, F. Hofer, C. Pulgarin and R. Torres-Palma

ELECTRO-FENTON TECHNOLOGY FOR THE TREATMENT OF DYE AND PHARMACEUTICAL

PP2-6 EFFLUENTS
M A. Sanroman, E. Bocos, Elena Alfaya, O. Iglesias, E. Rosales and M. Pazos

ELECTROKINETIC-FENTON TECHNOLOGY: A SOLUTION IN THE IN SITU REMEDIATION OF

PP2-7 HYDROCARBONS POLLUTED SOILS
M A. Sanroman, C. Sandu, M. Popescu, E. Rosales, E. Bocos, G. Lazar and M. Pazos

APPLICATION OF ELECTRO-FENTON TREATMENT FOR THE ELIMINATION OF IMIDAZOLIUM IONIC

PP2-8 LIQUIDS FROM POLLUTED WATER
M. Pazos, E. Bocos, E. Rosales and M A. Sanromn

HIGHLY ORDERED SPHERICAL SBA FOR CONTAMINANTS REMOVAL VIA FENTON PROCESS
PP2-9 F. Moura, A. Martins, A. Salviano, A. Oliveira and M. Rosmaninho

REMOVAL OF BETA-BLOCKERS FROM AQUEOUS MEDIA BY ADSORPTION ONTO GRAPHENE

PP2-10 OXIDE
D. A. Lambropoulou, G. Kyzas, A. Koltsakidou, S. Nanaki, D. Bikiaris

PHOTO-FENTON REACTIONS PROMOTED BY Fe/C COMPOSITES PRODUCED FROM IRON RICH

PP2-11 MINERAL WASTES AND BIO-OIL AQUEOUS ACID FRACTION
M. Rosmaninho, F. Mendona, J. Domingos Ardisson, R. Lago and J. Tristo

USE OF PHOTO-FENTON PROCESS TO REMOVE ORGANIC MATTER FROM FULLER CLAY

PP2-12 CONTAMINATED WITH INSULATING OIL
M. Silva, E. Oliveira Rodrigues, F. Soares Silva, M. Matiko Kondo and R. Gimene

46
 EAAOP 2015

STUDY OF REDUCTIVE REACTIONS INVOLVED IN THE PHOTO-FENTON PROCESS USING ZERO

PP2-13 VALENT IRON (ZVI)
A.M. Amat, L. Santos-Juanes, R.F. Vercher and A. Arques
SOLAR PHOTO FENTON TREATMENT OF PHENOLIC COMPOUNDS COMMONLY FOUND IN FOOD
PROCESSING INDUSTRY
PP2-14 R.F. Vercher, S. Garca Ballesteros, M. Mora, C. Sabater, M A. Castillo, A. Arques
and A.M. Amat
PHOTO-FENTON MEDIATED DEGRADATION, MINERALIZATION AND DETOXIFICATION OF THE
PP2-15 INSECTICIDE THIACLOPRID IN AQUEOUS MEDIA
C. Berberidou, V. Kitsiou, D. Michailidou, D. Lambropoulou, A. Kouras and I. Poulios
HOMOGENOUS PHOTOCATALYTIC DEGRADATION OF THE HERBICIDE CLOPYRALID IN AQUEOUS
MEDIA: KINETICS, MINERALIZATION AND TOXICITY
PP2-16 C. Berberidou, V. Kitsiou, F. Kondyli-Sarika, D. Lambropoulou, A. Kouras and I. Poulios

HOMOGENEOUS PHOTOCATALYSIS FOR THE REMOVAL OF UV FILTER PARA-AMINOBENZOIC

PP2-17 ACID IN AQUEOUS SOLUTIONS BY MEANS OF ARTIFICIAL ILLUMINATION
S. Tsoumachidou and I. Poulios

HSO5-/Mn+/UV-A LED AND PHOTO-FENTON PROCESSES FOR WINERY WASTEWATER TREATMENT

PP2-18 M. Lucas, J. Rodriguez-Chueca, T. Silva, C. Amor, G. Li Puma and J. Peres

HIGHLY STABLE IRON CATALYSTS OBTAINED BY CHEMICAL ACTIVATION OF SEWAGE SLUDGE

PP2-19 WITH FeCl3 FOR CWPO
J. Bedia, V.M. Monsalvo, A.F. Mohedano and J.J. Rodriguez

HYBRID MAGNETIC GRAPHITIC NANOCOMPOSITES FOR CATALYTIC WET PEROXIDE OXIDATION

APPLICATIONS
PP2-20 R.S. Ribeiro, A.M.T. Silva, J. L. Figueiredo, J.L. Faria and H.T. Gomes

SYNTHESIS OF Fe ON CARBON CATALYSTS OBTAINED FROM GRAPE SEEDS FOR CWPO OF

PP2-21 BISPHENOL A
E.D. Nieto, I. Fernndez Mena, A. Fernandez Mohedano and J.J. Rodrguez Jimnez
CARBON NANOTUBES AS CATALYSTS FOR WET PEROXIDE OXIDATION: STRUCTURE-REACTIVITY
RELATIONSHIPS
PP2-22 R.S. Ribeiro, M. Martin-Martinez, B.F. Machado, P. Serp, S. Morales-Torres, A. Silva, J. Figueiredo, J.L. Faria
and H. Gomes
EFFECT OF THE GOLD ADDITION TO Ag/ZrO2-CeO2 CATALYSTS BY RECHARGE METHOD IN THE
PP2-23 CATALYTIC WET AIR OXIDATION (CWAO) OF PHENOL
A. Silahua, G. Torres and J. Beltramini

EFFECT OF CRYSTAL SIZE AND METAL DISPERSION OVER Ag/ZrO2-CeO2 FOR THE CATALYTIC WET
PP2-24 AIR OXIDATION OF METHYL TERT-BUTYL ETHER (MTBE)
J.G. Torres Torres, Z. Guerra Que, H. Prez Vidal, I. Cuauhtmoc, A. Espinosa and J. Beltramini

CATALYTIC WET AIR OXIDATION OF METHYL TERT-BUTYL ETHER (MTBE) USING Rh/TiO2-CeO2
PP2-25 AND RhAu/TiO2-CeO2 CATALYSTS
J.G. Torres Torres, A. Cervantes Uribe, M.A. Lunagmez Rocha and G.A. Del ngel Montes

OZONE ENHANCED OXIDATION OF CYANOTOXIN CYLINDROSPERMOPSIN WITH TiO2 CATALYST

PP2-26 W.-J. Huang, C.-C. Wu and B.-R. Lu

NANOSTRUCTURED CeO2 AS CATALYSTS FOR DIFFERENT AOPS BASED IN THE APPLICATION OF

PP2-27 OZONE AND SOLAR RADIATION
A.Rey, E.Mena, E.M. Rodrguez and F.J. Beltrn

PHOTOCATALYTIC OZONATION OF EMERGING CONTAMINANTS IN MUNICIPAL WASTEWATER

PP2-28 WITH A MAGNETIC TIO2-ACTIVATED CARBON CATALYST
A. Rey, A.M. Chvez, P.M. lvarez and F.J. Beltrn

47
 PROGRAM

KINETIC STUDY OF ETHILENETHIOUREA REMOVAL IN WATER BY OZONATION PROCESS

PP2-29 S.E. Bottrel, E. Costa, G. Cipriano, M. Leo and C. Amorim

DEGRADATION OF 8 POLLUTANTS COMMONLY FOUND IN FOOD PROCESSING EFFLUENTS BY

PP2-30 ADVANCED OXIDATION PROCESS: O3 AND O3/UVA-VIS
R.F. Vercher, S. Garca-Ballesteros, A. Arques and A.M. Amat

REVERSE OSMOSIS FOLLOWED BY SOLAR PHOTO-FENTON OXIDATION FOR THE INTEGRATED

PP2-31 TREATMENT OF WINERY WASTEWATER
L. Ioannou, C. Michael, N. Vakondios, C. Drosou, E. Diamadopoulos, N. Xekoukoulotakis and D. Fatta-Kassinos

SOLAR PHOTO-FENTON WITH SIMULTANEOUS ADDITION OF OZONE FOR WASTEWATER

PP2-32 TREATMENT
S. Sanchis, L. Meschede, A. Serra, G. Sixto and J. Garcia-Montao

FENTON AND ELECTROCHEMICAL OXIDATION FOR THE TREATMENT OF ACTUAL WASTEWATER

PP2-33 COMING FROM AN ORGANIC-SYNTHESIS CHEMICAL PLANT
C. Sez, J.F. Prez, C. Lpez, J.M. Rodrigo and P. Caizares

EFFECT OF FEED COMPOSITION ON THE PERFORMANCE OF A POLYETHERSULFONE UF

MEMBRANE IN A PHOTOCATALYTIC MEMBRANE REACTOR
PP2-34 S. Mozia, D. Darowna and A. Morawski

TREATMENT OF LAUNDRY WASTEWATER USING A HYBRID SYSTEM COUPLING BIOLOGICAL

PP2-35 METHOD WITH UV/O3 OXIDATION AND MEMBRANE SEPARATION
S. Mozia, M. Janus, P. Broek, S. Bering, K. Tarnowski, J. Mazur and A. Morawski

PERFORMANCE OF A PHOTOCATALYTIC MEMBRANE REACTOR WITH A TiO2 UF MEMBRANE

PP2-36 DURING REMOVAL OF HUMIC ACIDS FROM WATER
A. Morawski, K. Szymaski and S. Mozia

ANTIBIOTICS CONTAMINATED WASTEWATER TREATMENT BY OZONATION AND OZONATION

COMBINED WITH BIOLOGICAL PROCESS
PP2-37 R. Marcelino, C. Amorim, A. Emrich and M. Leo

MINERALIZATION OF ANILINE AND REACTIVE DYE BLUE 5 SOLUTIONS BY PHOTOCATALYTIC

PP2-38 OZONATION
C.A. Orge, M F R. Pereira and J L. Faria

COMBINED BIOLOGICAL-CHEMICAL TREATMENT OF LANDFILL LEACHATE APPLYING

PP2-39 CONTINUOUS SLUDGE REUSE IN FENTON PROCESS
K. Klein, A. Kivi, M. Trapido and T. Tenno

EVALUATION OF AN ALTERNATIVE METHOD FOR WASTEWATER TREATMENT CONTAINING

PP2-40 PESTICIDES USING PHOTOCATALYTIC OXIDATION AND CONSTRUCTED WETLANDS
V. Kitsiou, C. Berberidou, D. Lambropoulou, A. Antoniadis, E. Ntonnou, G. Zalidis and I. Poulios

TREATMENT OF TABLE OLIVE WASHING WATERS USING CONSTRUCTED WETLANDS FOLLOWED

BY ELECTROOXIDATION
PP2-41 T. Tatoulis, A. Stefanakis, S. Zapantiotis, Z. Frontistis, A.G. Tekerlekopoulou, C.S. Akratos , D. Mantzavinos, D.V.
Vayenas

DESIGN OF HETEROGENEOUS FENTON FILM-BASED PHOTO-REACTOR FOR THE TREATMENT OF

PP2-42 PHARMACEUTICAL COMPOUNDS IN WASTEWATER STREAMS
R. Molina, M.M. Benacherine, Y. Segura, J.A. Melero, F. Martnezui

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 EAAOP 2015

MODIFIED FENTON CHEMISTRY TO REMEDIATE GROUNDWATER CONTAMINATED BY

PP2-43 COMMERCIAL GASOLINE/ETHANOL BLEND: APPvROACHES TO APPLY H2O2
L.. Andrade, C.. Amorim, F. Morais, A. Almeida, S. Arajo, M. Leo

ACUTE TOXICITY EVALUATION OF REAL TEXTILE WASTEWATER TREATED BY SOLAR

PP2-44 PHOTOFENTON
M.C. Starling, B. Reis, C. Amorim, M. Leo,

PHOTO-FENTON TREATMENT OF THE ANTINEOPLASMATIC DRUG 5-FLUOROURACIL: KINETICS

PP2-45 AND TRANSFORMATION PRODUCTS
A. Koltsakidou, M. Sykiotou, E. Evgenidou and D. Lambropoulou

MULTISTAGE TREATMENT SYSTEM FOR BIODIESEL WASTEWATER BY MOVING BED BIOFILM

PP2-46 REACTOR AND ADVANCED OXIDATION PROCESSES
C. Amorim, L.O. Gonalves, C M. Leo, D. Oliveira, R.G.P. Prado

OXIDATION OF WATER SOLUBLE BIOSOLIDS BY FREE RADICALS MECHANISM. A UV/VIS

PP2-47 SPECTROSCOPY STUDY
E. Giannakopoulos, G. Psarras, G. Oron and I. Kalavrouziotis

COST ESTIMATION OF SOLAR PHOTO-FENTON PROCESS IN RACEWAY POND REACTORS AS

TERTIARY TREATMENT
PP2-48 I.M. Romn Snchez, M.Segura, A. M. Freitas, G.Rivas Ibez, M.Campos-Maas, S. Arzate and J.A.Snchez
Prez

49
 PROGRAM
Poster Presentation 3
Saturday, 24 October 2015

PS3 Room: Foyer

Disinfection
Electrochemical processes
AOPs for energy production
Radiation processes
ECO-EFFICIENT TREATMENT OF EFFLUENTS OF THE MANUFACTURING INDUSTRY:
PP3-1 ELECTROCOAGULATION PROCESS WITHIN ECOWAMA PROJECT
S. Sanchis, D. Gali, M. Aliaguilla, D. Anguera, A. Serra, F.X. Simon and J. Garcia-Montao

ELECTROIRRADIATED TECHNOLOGIES FOR THE REMOVAL OF OXYFLUORFEN FROM SOIL

PP3-2 WASHING WASTES
M.A. Rodrigo, E. Vieira Dos Santos, C. Saez, C.A. Martinez-Huitle and P. Caizares

REMOVAL OF ORGANIC MATTER OF OIL FIELD EFFLUENT WATER BY ELECTROCHEMICAL

PP3-3 OXIDATION AND ELECTROFLOTATION TREATMENT
E. Saggioro, G. Dos Santos Cunha and A.J. Bourdot

NEW INSIGHTS INTO THE ELECTRO-OXIDATION OF A MODEL PHENOLIC COMPOUND,

PP3-4 p-CRESOL: EFFECT OF ELECTRODE MATERIAL AND ELECTROLYTE
M. Rivero, C. Escudero, O. Iglesias, S. Dominguez and I. Ortiz

PHOTOELECTROCHEMICAL STUDY OF TiO2 NANOTUBES GROWN BY ANODIZATION ON

PP3-5 SPUTTERED VS. EVAPORATED TI LAYER
J. Krysa, S. Kment, Z. Hubicka, K. Lee and P. Schmuki

PREPARATION AND PHOTOELECTROCHEMICAL PROPERTIES OF WO3 LAYERS PREPARED BY

PP3-6 SEDIMENTATION AND SPRAY-PYROLYSIS
J. Krysa and M. Zlamal

DIFFERENT APPROACHES OF ADVANCED OXIDATION PROCESSES FOR THE TREATMENT OF A

PP3-7 PHARMACEUTICAL WASTEWATER
Y. Segura, F. Martnez, A.L. Petre, J.A. Perdign, S. lvarez, J. Garca, G. Pliego and P. Garca-Muoz

WO3 THIN FILMS PREPARED BY SEDIMENTATION AND PLASMA SPUTTERING

PP3-8 J. Krysa, J. Olejnicek, M. Brunclikova, Z. Hubicka, S. Kment, P. Ksrov, M. Cada and M. Zlamal

A COMPARATIVE STUDY OF SOL-GEL AND ANODICALLY GROWN TIO2 PHOTOANODES AND THEIR
APPLICATION IN THE PHOTOOXIDATION OF CHLORAMPHENICOL
PP3-9 A. Chatzitakis, A. Papaderakis, N. Karanasios, J. Georgieva, E. Pavlidou, G. Litsardakis, I. Poulios and S. So-
tiropoulos

BORON-DOPED DIAMOND ANODIC OXIDATION OF AMOXICILLIN WASTEWATER: STATISTICAL

PP3-10 EVALUATION OF OPERATING FACTORS AND ANTIBIOTIC RESISTANCE
Z. Frontistis, A. Ioannidi, K. Kassara, G. Voukelatos, D. Venieri and D. Mantzavinos

OPTIMIZATION AND MODELING OF IOHEXOL TREATMENT BY ADVANCED OXIDATION

PP3-11 PROCESSES IN ENVIRONMENTALLY RELEVANT MATRICES
S. Giannakis, M.P. Gelabert, S. Schindelholz, J.-M. Fuerbringer and C. Pulgarin

SONOPHOTOLYTIC MINERALIZATION OF CARBAMAZEPINE IN AQUEOUS SOLUTION: KINETIC

PP3-12 MODELLING
A.J. Expsito, A. Durn and J.M. Monteagudo

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PHOTODEGRADATION OF 2,4-DICHLOROPHENOL IN AQUEOUS SYSTEMS UNDER SIMULATED

PP3-13 AND NATURAL SUNLIGHT
S. Ledakowicz, M. Foszpanczyk, D. Gryglik and M. Gmurek

A NEW APPROACH TO HETEROGENEOUS KINETIC OF PHOTOSENSITIZED OXIDATION

PP3-14 M. Gmurek and S. Ledakowicz

MICROPOLLUTANT REMOVAL BY HO* IN LOW-FREQUENCY ULTRASOUND TREATMENT OF AN

PP3-15 AGRO-FOOD INDUSTRY SEWAGE SLUDGE
J. A. Snchez Prez, G. Rivas Ibez, P. Soriano, J.L. Casas Lpez, L. Ponce Robles and A. Agera

DEGRADATION OF TRICLOSAN IN NATURAL WATER AND WASTEWATER USING KrCl EXCILAMP

PP3-16 (222 nm)
N. Garkusheva, N. VorobEva, G. Matafonova and V. Batoev

RF ATMOSPHERIC PRESSURE PLASMA JET

PP3-17 J. Pawlat

FLUORESCENCE EVOLUTION OF HUMIC-LIKE SUBSTANCES OBTAINED FROM SOLID URBAN

PP3-18 WASTES IN SOLAR PHOTOCHEMICAL PROCESSES FOR WATER TREATMENT
A.M. Amat, R. Vicente and M. Mora

UV-C AND UV-C/H2O2 DEGRADATION OF TWO ARTIFICIAL SWEETENERS, ACESULFAME-K AND

PP3-19 SUCRALOSE
C. Drosou, N. Xekoukoulotakis, K. Tyrovola, T. Neromilioti and E. Kourounioti

PHOTOSENSITIVE CHITOSAN FOR VISIBLE-LIGHT WATER POLLUTANT DEGRADATION

PP3-20 S. Ledakowicz, M. Olak-Kucharczyk, M. Foszpanczyk and M. Gmurek

MINI GLIDING ARC ATMOSPHERIC PRESSURE PLASMA REACTOR

PP3-21 J. Diatczyk, J. Pawlat, H. Danuta Stryczewska, M. Kwiatkowski and P. Terebun

REMOVAL OF EMERGING CONTAMINANTS FROM WATER VIA PEROXYMONOSULFATE

PP3-22 ACTIVATION WITH VARIOUS IRON SOURCES (Fe+2, Fe+3, ZVI)
M.G. Antoniou, N. Tsiarta, S. Rodriguez and A. Santos

DEGRADATION OF ENDOCRINE DISRUPTING CHEMICALS BY HEAT-ACTIVATED PERSULFATE

PP3-23 N. Potakis, Z. Frontistis and D. Mantzavinos

FAST DEGRADATION OF ENDOCRINE DISRUPTORS BY Ag3PO4/TiO2 SOLAR PHOTOCATALYSIS

PP3-24 M. Edris Taheri, A. Petala, Z. Frontistis, D. Kondarides and D. Mantzavinos

SOLAR PHOTOCATALYTIC DEGRADATION AND ANTIBIOTIC INACTIVATION OF

PP3-25 SULFAMETHOXAZOLE BY TUNGSTEN-MODIFIED TiO2
E. Ioannidou, Z. Frontistis, D. Venieri, D. Kondarides and D. Mantzavinos

NEW PATHWAYS IN HETEROGENEOUS AND HOMOGENEOUS NEAR-NEUTRAL PHOTO-FENTON

PP3-26 BACTERIAL INACTIVATION BY IRON OXIDES AND IRON CITRATE COMPLEXES
S. Giannakis, C. Ruales-Lonfat and C. Pulgarin

51
 PROGRAM

ECOTOXICITY EVALUATION OF SECONDARY EFFLUENT TREATED BY SOLAR PHOTO-FENTON AT

PP3-27 NEUTRAL PH IN A RACEWAY POND REACTOR
J.A. Snchez Prez, A. Freitas, A. Cabrera, G. Rivas Ibez, M. Campos-Maas, J. L Casas Lpez and A. Agera

SIMULTANEOUS SOLAR DISINFECTION AND PHOTOCATALYTIC TREATMENT OF CONTAMINATED

PP3-28 DRINKING WATER
A.J. Expsito, J.M. Monteagudo and A. Durn

COST ANALYSIS OF PHOTO-FENTON DISINFECTION IN REAL MUNICIPAL WASTEWATER

PP3-29 I.M. Romn Snchez, M. Segura, J.A. Snchez Prez, E. Ortega Gomez and P. Fernandez Ibaez

PHOTOCATALYTIC AND ANTIMICROBIAL EFFICIENCY OF TIO2-BASED INTERIOR PAINTS

PP3-30 G. Skouras, G.Tatsi, M. Tsoulfa, C. Nannou, S. Tsafou, A. Mitsionis, N. Todorova, T. Albanis, C. Trapalis and T.
Vaimakis

PHOTOCATALYTIC INACTIVATION OF THE WATERBORNE PROTOZOAN PARASITE CRYPTO-

SPORIDIUM PARVUM USING TIO2/H2O2 UNDER SIMULATED AND NATURAL SOLAR CONDITIONS
PP3-31 M.J. Abeledo-Lameiro, A. Reboredo-Fernndez, M.I. Polo-Lopez, P. Fernandez-Ibaez, E. Ares-Mazas and H.
Gmez-Couso
THE ANTIBACTERIAL PROPERTIES OF CONCRETES SUPPLEMENTED WITH TITANIUM
PHOTOCATALYST UNDER VISIBLE IRRADIATION
PP3-32 M. Janus, P. Rokicka, A. Stelmach, E. Kusiak-Nejman, A. Markowska-Szczupak, K. Zajc, J. Zatorska, A.
Czyewski and A. W. Morawski
SOLAR PHOTOCATALYSIS AS DISINFECTION TECHNIQUE: INACTIVATION OF KLEBSIELLA
PNEUMONIAE IN SEWAGE AND INVESTIGATION OF CHANGES IN ANTIBIOTIC RESISTANCE
PP3-33 PROFILE
D. Venieri, I. Gounaki, M. Bikouvaraki, V. Binas, A. Zachopoulos, G. Kiriakidis and D. Mantzavinos
INACTIVATION OF STAPHYLOCOCCUS AUREUS IN WATER BY MEANS OF SOLAR
PP3-34 PHOTOCATALYSIS USING METAL DOPED TiO2 SEMICONDUCTORS
D. Venieri, F. Tournas, I. Gounaki, V. Binas, A. Zachopoulos, G. Kiriakidis and D. Mantzavinos

ENHANCING PHOTOCATALYTIC DEGRADATION OF CYANOTOXINS WITH THE ADDITION OF

PP3-35 SULFATE-RADICAL PRODUCING OXIDANTS
M.G. Antoniou, J. Boraei, C. Kyriakou, M. Abhishek, C. Edwards and L. Lawton

ASSESSMENT OF SUPPORTING ELECTROLYTES ON CO2 REDUCTION BY PHOTO-

PP3-36 ELECTROCATALYSIS AT Ti/TiO2/CuO N-P HETEROJUNCTION SEMICONDUCTOR
J.F. De Brito and M.V. B. Zanoni

MIXED OXIDE AS PHOTOCATALYST: TiO2-FeXOY FOR H2 PRODUCTION BY WATER SPLITTING

PP3-37 METHOD
A. Perez-Larios, R. Gomez, R. Zanella and J. Bedia

PHOTOCATALYTIC ACTIVITY OF TiO2-CoO AS MIXED OXIDE FOR IMPROVED H2 PRODUCTION BY

PP3-38 WATER SPLITTING METHOD
A. Perez Larios, R. Gomez, R. Zanella and C. Belver

VISIBLE LIGHT ACTIVE HYBRID CORE-SHELL TiO2 PHOTOCATALYSTS FOR THE PRODUCTION OF
PP3-39 USEFUL HYDROCARBONS FROM CO2
P. Falaras, N. Moustakas, F. Katsaros, A. Papavasiliou, E. Kouvelos, A. Kontos, T. Steriotis and G. Romanos

H2 PRODUCTION FROM BIO-ALCOHOLS VIA PHOTO-REFORMING USING Au/TiO2 AND Pt/TiO2 AS

HETEROGENEOUS CATALYSTS
PP3-40 A. Marinas, F. J. Tenllado, V. Montes, F.J. Urbano, J.M. Marinas, L. Ilieva, T. Tabakova, A. Diaz-Lozano and J.
Hidalgo

52
 EAAOP 2015

PHOTOELECTROCATALYTIC HYDROGEN PRODUCTION USING NITROGEN CONTAINING WATER

PP3-41 SOLUBLE WASTES
I. Tantis, L.-C. Pop and P. Lianos

VISIBLE LIGHT RESPONSIVE BiVO4 PHOTOANODES FOR HYDROGEN PRODUCTION

PP3-42 P. Lianos, O. Monfort, L.-C. Pop and S. Sfaelou

A SOL-GEL METHOD FOR PREPARATION OF NANOSTRUCTURED WO3 PHOTOANODES USED FOR

PP3-43 PHOTOELECTROCHEMICAL WATER SPLITTING
S. Sfaelou, L. Cristian Pop, O. Monfort and P. Lianos

BORON-DOPED DIAMOND ANODIC OXIDATION OF CONTAMINANTS OF EMERGING CONCERN

PP3-44 Z. Frontistis, M. Yazirdagi, Z. Kilinc, A. Katsaounis, D. Mantzavinos

OXIDATIVE DEGRADATION OF TRITON X-45 USING ZERO VALENT ALUMINUM IN THE PRESENCE
PP3-45 OF HYDROGEN PEROXIDE AND PERSULFATE
II. Arslan-Alaton, T. Olmez-Hanci, S. Khoei, H.Fakhri

STUDY OF HYDROGEN OXIDATION USING DIFFERENTIAL ELECTROCHEMICAL MASS

PP3-46 SPECTROSCOPY (DEMS)
J. Vakros and A. Katsaounis

BENEFIT AND RISKS FROM ELECTROCHEMICAL ADVANCED OXIDATION PROCESSES (EAOP) IN

PP3-47 WATER TREATMENT THE (PER)BROMATE PROBLEM
H.Bergmann, T. Iourtchouk and A.S. Koparal

PHOTOCHEMICAL DEGRADATION OF THE CARBAPENEM ANTIBIOTICS IMIPENEM AND

PP3-48 MEROPENEM IN AQUEOUS SOLUTIONS UNDER SOLAR IRRADIATION
N.P. Xekoukoulotakis,Y. Bertakis, A. Agera,A.B. Martnez-Piernas, J.A. Snchez Prez,A. Cabrera

53
SECTION

3
D I S T I N G U I S H E D TA L K

DT1...............................................................................................................................................56
 D I S T I N G U I S H E D TA L K

D IS T
IN G U IS
H ED TA LK Pr of . Christos S . Zer efos

MAN-MADE INTERFERENCE WITH THE OXIDIZING CAPACITY OF

THE ATMOSPHERE OVER THE EASTERN MEDITERRANEAN

56
EAAOP 2015

57
SECTION

4
P L E N A RY TA L K S

1 st DAY
ROOM B.................................................................................................................................60
PT2......................................................................................................................................60
2 nd DAY
ROOM B.................................................................................................................................62
PT4......................................................................................................................................62
3 rd DAY
ROOM B.................................................................................................................................62
PT5......................................................................................................................................63
 P L E N A RY TA L K S

INDIRECT PHOTOTRANSFORMATION OF ORGANIC CONTAMINANTS IN SURFACE WA-

Indirect
TERS: Phototransformation
EXCITED TRIPLET STATESof Organic Contaminants in Surface
AS PHOTOOXIDANTS PT2
Waters: Excited Triplet States as Photooxidants
S. Canonica1. (1) Eawag, Swiss Federal Institute of Aquatic Science and Technology, berlandstrasse 133,
P.O. Box 611, CH-8600 Dbendorf, Switzerland, silvio.canonica@eawag.ch.

The chromophoric components of dissolved organic matter

(DOM) are generally the main absorbers of sunlight in surface
waters and therefore a source of transient reactants under
irradiation. Excited triplet states of chromophoric DOM,
3
CDOM*, play a major role as photooxidants initiating the
transformation and degradation of several organic chemical
contaminants, which include phenols, anilines, phenylurea
herbicides, and sulfonamide antibiotics. There are various pieces
of evidence suggesting electron transfer from the contaminant to
the excited triplets of DOM to be the initial reaction step. In this
contribution, recent advances related to the kinetics and
mechanisms of triplet-induced transformations, as well as the
dual role of DOM as a sensitizer and inhibitor of such reactions
will also be presented.

The chromophoric components of dissolved of oxygen concentration on transformation rates.4

organic matter (DOM) are considered to be the
main absorbers of sunlight in surface waters. They
are therefore a source of transient reactants under
irradiation. Such short-lived species can be
relevant for the fate of various classes of chemical
contaminants in the aquatic environment. Excited
triplet states of chromophoric DOM, 3CDOM*,
play a major role as photooxidants initiating the
transformation and degradation of several organic
chemical contaminants.1 3CDOM* were first
proposed in the mid 1990s as key photooxidants
in the sunlight-induced transformation of electron-
rich phenols.2 This hypothesis was later fortified
by the results of transient absorption investigations
using aromatic ketones as model photosensitizers3
and by a more recent careful analysis of the effect
During the last two decades, the variety of
aquatic contaminants shown to be affected by
triplet-induced transformation has kept increasing,
phenylurea herbicides,5 sulfonamide antibiotics,6
and some phytoestrogens7 being prominent
examples. Further research conducted in our team
has shown that the triplet-induced transformation
of some specific contaminants, in particular those
containing an aniline moiety, is partly inhibited by
antioxidant components of the DOM.8, 9 This
example shows that to understand and quantify
oxidation reactions initiated by 3CDOM*, a
comprehensive knowledge about the redox
chemistry of DOM is needed.10, 11

Acknowledgements
I would like to thank the Swiss National Science Foundation for financial support of several projects, whose results are
presented in this lecture.

References
1. Canonica, S. Oxidation of aquatic organic contaminants induced by excited triplet states. Chimia 2007, 61
(10), 641-644.
2. Canonica, S.; Jans, U.; Stemmler, K.; Hoign, J. Transformation kinetics of phenols in water:
Photosensitization by dissolved natural organic material and aromatic ketones. Environ. Sci. Technol. 1995, 29 (7),
1822-1831.
3. Canonica, S.; Hellrung, B.; Wirz, J. Oxidation of phenols by triplet aromatic ketones in aqueous solution. J.
Phys. Chem. A 2000, 104 (6), 1226-1232.
4. Golanoski, K. S.; Fang, S.; Del Vecchio, R.; Blough, N. V. Investigating the mechanism of phenol
photooxidation by humic substances. Environ. Sci. Technol. 2012, 46 (7), 3912-3920.
5. Gerecke, A. C.; Canonica, S.; Mller, S. R.; Schrer, M.; Schwarzenbach, R. P. Quantification of dissolved
natural organic matter (DOM) mediated phototransformation of phenylurea herbicides in lakes. Environ. Sci. Technol.
2001, 35 (19), 3915-3923.
6. Boreen, A. L.; Arnold, W. A.; McNeill, K. Triplet-sensitized photodegradation of sulfa drugs containing six-
membered heterocyclic groups: Identification of an SO2 extrusion photoproduct. Environ. Sci. Technol. 2005, 39 (10),
3630-3638.

60 1
 EAAOP 2015

7. Felcyn, J. R.; Davis, J. C. C.; Tran, L. H.; Berude, J. C.; Latch, D. E. Aquatic photochemistry of isoflavone
phytoestrogens: Degradation kinetics and pathways. Environ. Sci. Technol. 2012, 46 (12), 6698-6704.
8. Canonica, S.; Laubscher, H. U. Inhibitory effect of dissolved organic matter on triplet-induced oxidation of
aquatic contaminants. Photochem. Photobiol. Sci. 2008, 7 (5), 547-551.
9. Wenk, J.; von Gunten, U.; Canonica, S. Effect of dissolved organic matter on the transformation of
contaminants induced by excited triplet states and the hydroxyl radical. Environ. Sci. Technol. 2011, 45 (4), 1334-1340.
10. Aeschbacher, M.; Graf, C.; Schwarzenbach, R. P.; Sander, M. Antioxidant properties of humic substances.
Environ. Sci. Technol. 2012, 46 (9), 4916-4925.
11. Wenk, J.; Aeschbacher, M.; Sander, M.; von Gunten, U.; Canonica, S. Photosensitizing and inhibitory
effects of ozonated dissolved organic matter on triplet-induced contaminant transformation. Environ. Sci. Technol.
2015, 49 (14), 8541-8549.

61 2
 P L E N A RY TA L K S

TREATMENT OF CONTAMINANTS OF EMERGING CONCERN IN WATER USING SULFATE

RADICAL-BASED ADVANCED OXIDATION
Treatment of Contaminants of EmergingPROCESSES
Concern in Water using PT4
Sulfate Radical-Based Advanced Oxidation Processes
Prof. Dionysios (Dion) D. Dionysiou Environmental Engineering and Science Program University of incinnati,
Cincinnati, Ohio, USA E-mail: dionysios.d.dionysiou@uc.edu Tel: +1-513-556-0724; Fax: +1-513-556-4162

While most of Advanced Oxidation Processes (AOPs) are based on the generation of hydroxyl
radicals, sulfate radicals-based AOPs (SR-AOPs) are also gaining popularity. This presentation
will provide an overview of research studies conducted in Prof. Dionysious group and
collaborators as well as other emerging studies on the development and related mechanistic
aspects of SR-AOPs for the degradation of contaminants of emerging concern in drinking water
and wastewater, such as pharmaceuticals and personal care products, pesticides, and cyanotoxins.
The presentation will include fundamental aspects of the generation and reactivity of sulfate
radicals, reaction mechanisms, and on-going and potential applications of these technologies.
Details will be provided with respect to (i) sulfate radicals generation via photolysis, thermolysis,
or activation by transition metals of persulfate or peroxymonosulfate. Examples will be provided
on the application of SR-AOTs for the destruction of pesticides (e.g., atrazine, endosulfan,
lindane), (ii) effects of inorganic ions and natural organic matter on degradation efficiencies of
antibiotics by UV activated SR-AOPs, (iii) mechanism of SR-AOPs and comparison with
hydroxyl radical attack for the destruction of cyanotoxins and pharmaceuticals, (iv) formation of
disinfection byproducts during SR-AOPs, and (v) formation of sulfate radicals on heterogeneous
surfaces such as cobalt oxides and biochars.

62
 EAAOP 2015

ELECTROCHEMICAL OXIDATION
Electrochemical oxidation WITH DIAMOND
with diamond ELECTRODES:
electrodes: facts and FACTS AND PROMIS-
ES
promises
PT5
M.A. Rodrigo, M.J. Martn de Vidales, S. Cotillas, J. Llanos, C. Sez, P. Caizares. Department of Chemical
Engineering. Faculty of Chemical Science and Technology. University of Castilla-La Mancha. Campus
Universitario s/n 13071 Ciudad Real. Soain, , manuel.rodrigo@uclm.es

During the recent years, the treatability of wastewater using

electrolysis with diamond anodes has been the subject of many
studies. This work summarizes the state of the art of the
technology. To do this, results on the treatment of different types
of wastewater are analyzed, pointing out the advantages and
drawbacks of the technology. Special attention is paid to
intermediates, mineralization and economy. It is also discussed
the causes which explain why, after two decades of exhaustive
research, this technology is not widely applied at the industrial
scale. The work also faces the challenges of the technology for
the near future pointing out the direction in which research has to
be carried out in order to generate attractive processes, which
could be implemented at the industrial scale.

Introduction
Electrochemical technology has been widely
applied in the industry for a long time. Two
examples illustrate this affirmation: The chlor-
alkali industry, which produces several of the most
important commodities nowadays and the batteries,
one of the key elements of modern life because they
are required for all portable electronic devices and
usually they become the bottleneck in their use.
These two examples are indicative of the good
health of this knowledge area, just at the cutting
edge between chemical engineering,
electrochemistry and material science.
In the frame of the new technologies developed,
several decades ago scientist specialist on
electrochemical technology started thinking of
applications in the field of environmental
remediation and they contribute with an exhaustive
work to their development. Some of them are
reference technologies nowadays in environmental
technology, such as electrodialysis for the
desalination of brackish water and
electroremediation for the treatment of soils
polluted with heavy metals. Others become an
eternal promise because they are always about to be
applied but finally they are never applied at the full
scale or, if finally applied, application is very
limited as compared with their potential
applicability [1].
One of these technologies is the electrolysis of
industrial wastewater polluted with organic
compounds. Pioneer works were published four
decades ago and the driving force for such works
was the very good results obtained in the oxidation
of chloride to chlorine in the industry and the
development of new anode materials for this
process [2, 3]. These novel materials were the key
in the research in the eighties and nineties of the last
century, in particular the so-called Dimensionally
Stable Anodes (DSA), made of mixtures of
conductive metal oxides (mainly ruthenium oxide
but also oxides of iridium, molybdenum, titanium,
tantalum, etc.). As chlorine is a powerful oxidant
for organics it was thought that a process that
combined production of chlorine and direct
electrochemical oxidation of organics contained in
wastewater could be of a great interest.
Unfortunately, the technology found two important
walls:
The production of organo-chlorinated
intermediates and final products, typically more
hazardous than the parent compounds and
The formation of polymeric intermediates that
blocked the anode surface reducing the efficiency
of the processes.
This was the context at the end of the nineties. In
that moment the first works focused on the
application as anode of the boron-doped diamond
(BDD) were published [4, 5]. Outstanding
properties capable of overcoming limitations of
former anodes were presented and the promising
features promote many studies from that moment
about application of this novel material to the
treatment of synthetic and real wastewater. After
that, other applications such as the production of
oxidants or the disinfection were proposed [6].

63 1
 P L E N A RY TA L K S

Likewise application not directly related to the
environmental remediation were also proposed for
this material, such as the electro-analytical
applications but they are far of the goal of this work.
Figure 1 illustrates the significance of the research
with the number of publications and citations
attained in the last decades according to the JCR.
Published items in each year
opposite to what happens with the electrochemical
oxidation with other anode materials or with other
single advanced oxidation processes (AOPs). This
robustness is the main strong point of the
technology (Figure 2).
To explain this outstanding behavior it should be
taken into account the mechanisms of the oxidation
with diamond anodes [3, 8, 9]. The oxidation of
water to form oxygen is a key point in the
electrolysis of wastewater with any type of anodic
material. This oxidation occurs on the surface of the
anode by the direct subtraction of electrons to the
water molecule. One important intermediate in this
process is the hydroxyl radical, formed in all
electrochemical processes. From this point of view,
all electrochemical oxidation processes should be
considered as AOPs.
-1 1
effectiveness (COD) / g COD g COO

0.8

0.6

0.4
Citations in each year
0.2

0
Graphite DSA Ti/PbO2 BDD

100

80
COD removal / %

60

40

20

0
chl

doo
2-p
et h
but l

thi
2,6
phe
2-n
4-c thol
oli
che

bio
oph tic ac

ve
oro
ano l
yri

-di

hlo

l og factu
rop

aph

mi
nol yl -py

r m roces
mi
ca

me

cal
ace
ene

rop

ica
ano

a n
ll p
ci d

th

u
l tr ing p
p
hen

roc

eat

Figure 1. Number of publications in the JCR with the

ol

ess
id

me ocess
r
rid

entries diamond and water or wastewater during the

nt
ine

last twenty years

Applicability of boron-doped diamond anodes
in the treatment of wastewater.
The most important feature of the electrolysis with
boron-doped diamond anodes is the high efficiency
attained in the oxidation of any type of organic
compounds, regardless the characteristic of the
wastewater in which these species are contained
[7]. To the authors knowledge there are no
examples of refractory molecules to this treatment,
Figure 2. Comparison of the efficiency and oxidation
capacity with other single electrochemical (part a) and
AOP (part b) technologies in the oxidation of synthetic
and actual wastewater. Part a) comparison of electrodes
performance with Synthetic wastewater (Phenol)
Actual wastewater (Chemical process) Part b) comparison
of technologies electrolysis with diamond anodes
Ozonation Fenton
However, with most anodic materials, the hydroxyl
radical reacts directly and rapidly with the anodic
material instead of reacting with the organics
contained in the wastewater, and it is a higher

64 2
 EAAOP 2015
oxidation state of the anode the responsible for the
oxidation of the pollutant.
This explain the softer oxidation, as compared with
the diamond anode, in which hydroxyl radicals
cannot react with the anode surface (only sp3 carbon
and low concentration of boron are contained in the
surface) and hence the oxidation of organics and the
oxidation of salts contained in the wastewater is
promoted. This particular behavior of diamond with
respect to the production and use of hydroxyl
radicals was first studied with formation of adducts
by the group of Comninellis in 2003 [10] in what it
was a first demonstration of the role of the
electrochemical oxidation as an AOP. It explains
the formation of many stable oxidants such as
peroxosulphates, peroxophosphates,
peroxocarbonates, hydrogen peroxide, ozone, etc.,
reported in many papers in the literature in the last
two centuries and whose production was not
efficient with other anodic materials.
Transport of these oxidants from the surface of
diamond to the bulk of the wastewater transforms
the surface electrochemical process into a more
efficient volumetric oxidation process. Interactions
between these oxidants in the bulk are known to
produce radicals very efficient in the oxidation of
organics (peroxosulfate, peroxocarbonate,
hydroxyl radicals, etc.). Consequently, in the bulk
of the electrochemical cell following the production
of hydroxyl radicals a cocktail of oxidants and
oxidation mechanism helps to explain the better
performance of this technology and the absence of
refractory species.
Promotion of this cocktail of oxidants is one of the
hot topics nowadays in the development of this
electrochemical technology [11]. To do this,
activation of oxidants with the help of irradiation
technologies is aimed. Goal is not to produce
oxidants irradiating UV light or US but to promote
the formation of radicals from these oxidants in the
bulk, once they are formed on the electrodes and
transported far away from this surface. Figure 3
shows how UV light irradiation can improve
synergistically the efficiency of the oxidation of
organics with different compounds
0.021
0.0189
0.0168
0.0147
0.0126
-1
K / min
0.0105
0.0084
0.0063
0.0042
0.0021
0
0.0084
0.0063
-1
K / min 0.0042
0.0021
0
Figure 3. Synergistic effect of UV light irradiation in
electrochemical processes with diamond anodes. Part a:
first order kinetic constant of the oxidation of the raw
molecule; Part b: first order kinetic constant of the
mineralization Symbols: Photolysis electrolysis with
diamond anodes photo electrolysis with diamond
anodes sum of the constants of the single photolysis and
electrolysis processes
Is diamond a standard material?
One of the most controversial points in the
application of diamond is the comparison of results
between papers published in the literature.
Except for the general conclusions attained in most
of the works found in the literature (complete
mineralization if the required electric charge is
passed and very high efficiency), some
discrepancies can be found in comparing results.
The most important cause of these discrepancies are
not the experimental conditions but the wrong
consideration of diamond as a standard material.
Lacks of providers and insufficient information
during the nineties made that most research groups
working on the application of electrochemical
oxidation with diamond to the treatment of
wastewater considered boron-doped diamond as a
commercial material with standard characteristics
and that electrocatalytic properties of this material
65 3

were neglected. However, features such as boron
content, sp3/sp2 carbon ratio, thickness of the
diamond layer, supporting material were found to
be important to explain the differences between
results presented in the literature [12, 13]. Figure 4
compares the effect of some of these features of
diamond on the efficiency of the oxidation of
organics and in the production of oxidants. As it can
be observed, high sp3/sp2 ratio is a very important
parameter and the correct tailoring of diamond for
particular applications could help to increase the
efficiency even in folds. However, it is not the only
parameter and in the future further studies have to
be carried out in order to clarify this point. At this
point, the large differences between results shown
in the figure are due to the different type of cell used
in the three experiments and points out that not only
characteristics of diamond but also constructive
details in the desing of the cell are important in the
electrolytic technology.
20
18
Eficacia / mg eliminados (Ah)-1
16
14
12
10
8
6 (ElectroCell A/S, Denmark), the FC01-LC (former
4 ICI Chemicals and Polymers Ltd., now INEOS
2 Chlor-chemicals, UK) and the DIACELL (former
0 ADAMANT TECH, Switzerland, now WaterDiam)
0 50 100
proporcin sp3/sp2
Figure 4. Effect of diamond characteristics on the
efficiency of the electrochemical oxidation of organics
with diamond ( Enrofloxacine 2,4-D rhodamine B).
Tests with enrofloxacine were carried out in an
electrochemical cell with a much higher turbulence.
Scale-up of the electrolysis with diamond
anodes
Electrolysis with diamond electrodes has reached
the maturity at the lab scale but it is still at a very
early stage at pilot plant and, of course, at full-scale
applications. Main weaknesses are related to the
scale-up and the role of small medium companies
in this technological development stage, because
this scale up is often out of the scope of academics,
especially because of the lack of resources [14].
Scale up in electrochemical technology is not
simple. As with many other electrochemical
technologies (a good example are the fuel cells
technology), reactor engineering is more complex
than reaction engineering. Hence, the development
of pilot plant and full scale applications requires of
P L E N A RY TA L K S
the design of electrochemical reactors for which
the flow patterns conditions and constructive details
such as the electrode connections, inlet and outlet,
flow distributor, current feeders, etc. are of an
extreme significance. A non-uniform current
density distribution can decrease the efficiency of
the removal of organics by folds, regardless of the
electrodic material used. Lower turbulence can
explain worse degration rates as illustrated in
Figure 4. Hence, the effort made in the development
of new materials can be worthless without a similar
effort in the cell design. As it is shown in Figure 5,
different setups for the connection of electrodes in
a commercial cell lead also to very different
efficiencies [15]. This plot points out that not only
the electrode is important to attain good results but
the complete cell. Importance of the CFD
modelling is out of discussion for this application
but still at a very early stage [16-18]. Unfortunately,
this is a very important drawback for the
technology, which becomes even worse because
there are almost no electrochemical cells specially
developed for this application and most of the cells
used were designed not for wastewater treatment
but for other purpose. Thus, the three more applied
cells in the electrolysis with diamond (according to
the scientific literature) are the ELECTROCELL
150 200 250 300 350
and only the last one was specially designed for
wastewater treatment. Staking of the cells in order
to provide for the large surface areas required for
industrial applications has also been very scarcely
studied.
1.6
1.4
1.2
energy efficiency / g C kWh-1
1
0.8
0.6
0.4
0.2
0
1 2 3 4 5
Number of anodes
Figure 5. Influence of electrode connection on the
efficiency of the removal of 2,4-D and caffeine by
electrolysis with diamond anodes. Bipolar 2,4-D
Monopolar 2,4D Monopolar caffeine
At this point, it is important to take into account that
there are many other points in the scale-up with a
great significance that becomes weaknesses
66 4
 EAAOP 2015

because of the lack of studies. Supplying large becomes a promising solution for this important
current intensities needs for a proper design of the drawback..
current feeders, which at the same time help to
minimize the cell voltage and hence reduce energy
cost. Ohmic loses produced huge amounts of heat Table 1. Decrease in the production of chlorates with in
that should be dissipated and hydrogen produced in electrolysis assisted with hydrogen peroxide
the cathode should be properly managed in order to Disinfection Removal of POPs
prevent explosions. All these points are indicative j: 7 A m-2 j: 50 A m-2
of the necessity of further work in the development Q: 0.1 A h dm-3 Q: 3.5 A h dm-3
of the technology, which becomes the main Without H2O2 With H2O2 Without H2O2 With H2O2
challenge for the technology in the future. Cl-(ClO3- + ClO4-) Cl-(ClO3- + ClO4-) Cl-(ClO3- + ClO4-) Cl-(ClO3- + ClO4-)
/ mmol A-1 h-1 / mmol A-1 h-1 / mmol A-1 h-1 / mmol A-1 h-1

Main advantages and drawbacks of the 0.037 0 0.969 0.564

electrolysis with diamond

The main advantage of the electrolysis with Conclusions

diamond is its robustness. There are no refractory
species and efficiencies obtained in the oxidation Electrolysis with diamond is a very promising
are always higher than those obtained with other technology for the treatment of organics contained
electrochemical technologies. In fact, these in wastewater and also for disinfection. Main
efficiencies are almost 100% (in terms of current advantage is the robustness of the technology,
supplied) when the concentration of pollution is the capable of mineralizing all organics tested. Main
wastewater is over 1500 ppm of COD, that it is a drawback is the lack of studies focused on the scale
very important value for wastewater treatment up of the technology, which also becomes the main
because typically industrial wastewater can be challenge for the near future. If this main challenges
discharged to municipal sewers if their is overcome this technology can become a reference
concentration is around this value and no priorities for the treatment of small flowrates of industrial
species are contained. Obviously, the charge wastewater which pollutants refractories to other
required depends almost linearly on the organic types of AOP and in disinfection.
load of the wastewater. In comparing with other
technologies [19], it has been demonstrated that it
can compete with many other oxidation
technologies in the range 1500-20000 ppm of COD.
Investment cost are important and lack of
experience in the scale-up made that the present
more important target are small flowrates of
industrial wastewater with pollutants refractories to
other types of AOPs. Another important target is the
disinfection of water and wastewater because
previous works have demonstrated a very high
efficiency related to the very efficient production of
oxidants from the salts contained in the water [20] ,
even for very low concentrations [21].

Main drawback of the technology is the formation

of perchlorates in wastewater containing chlorides
[22, 23]. Because of the very harsh oxidation
conditions produced in the reaction media, the
oxidation of chlorides does not end with the
formation of chlorine but it follows up to the
formation of perchlorates. Currently many research
works are focused on solving this problem and
previous results demonstrate that hydrogen
peroxide may play a very important role in
preventing this problem. Thus, Table 1 shows how
hydrogen peroxide helps to prevent the formation
of chlorate and perchlorate inseveral system in what

67 5
 P L E N A RY TA L K S

Acknowledgements

The authors acknowledge funding support from the EU and Spanish Government through the MINECO Project
CTM2013-45612-R, FEDER 2007-2013 PP201010 (Planta Piloto de Estacin de Estacin de Regeneracin de Aguas
Depuradas) and INNOCAMPUS.

References

1. S. Bebelis, K. Bouzek, A. Cornell, M. G. S. Ferreira, G. H. Kelsall, F. Lapicque, C. P. de Leon, M. A. Rodrigo and F.

C. Walsh, Chemical Engineering Research & Design, 2013, 91, 1998-2020.
2. C. A. Martinez-Huitle and E. Brillas, Applied Catalysis B-Environmental, 2009, 87, 105-145.
3. M. Panizza and G. Cerisola, Electrochimica Acta, 2005, 51, 191-199.
4. G. Foti, D. Gandini, C. Comninellis, A. Perret and W. Haenni, Electrochemical and Solid State Letters, 1999, 2, 228-
230.
5. D. Gandini, P. A. Michaud, I. Duo, E. Mahe, W. Haenni, A. Perret and C. Comninellis, New Diamond and Frontier
Carbon Technology, 1999, 9, 303-316.
6. P. Canizares, C. Saez, A. Sanchez-Carretero and M. A. Rodrigo, Journal of Applied Electrochemistry, 2009, 39, 2143-
2149.
7. M. A. Rodrigo, P. Canizares, A. Sanchez-Carretero and C. Saez, Catalysis Today, 2010, 151, 173-177.
8. P. Canizares, C. Saez, J. Lobato, R. Paz and M. A. Rodrigo, Journal of the Electrochemical Society, 2007, 154, E37-
E44.
9. M. Panizza and G. Cerisola, Applied Catalysis B-Environmental, 2007, 75, 95-101.
10. B. Marselli, J. Garcia-Gomez, P. A. Michaud, M. A. Rodrigo and C. Comninellis, Journal of the Electrochemical
Society, 2003, 150, D79-D83.
11. I. Sirs, E. Brillas, M. A. Oturan, M. A. Rodrigo and M. Panizza, Environmental Science and Pollution Research,
2014.
12. E. Guinea, F. Centellas, E. Brillas, P. Canizares, C. Saez and M. A. Rodrigo, Applied Catalysis B-Environmental,
2009, 89, 645-650.
13. D. M. de Araujo, P. Canizares, C. A. Martinez-Huitle and M. Andres Rodrigo, Electrochemistry Communications,
2014, 47, 37-40.
14. M. A. Rodrigo, N. Oturan and M. A. Oturan, Chemical Reviews, 2014, 114, 8720-8745.
15. F. L. Souza, C. Saez, M. R. V. Lanza, P. Canizares and M. A. Rodrigo, Chemical Engineering Journal, 2015, 264,
310-315.
16. A. Frias-Ferrer, I. Tudela, O. Louisnard, V. Saez, M. D. Esclapez, M. I. Diez-Garcia, P. Bonete and J. Gonzalez-
Garcia, Chemical Engineering Journal, 2011, 169, 270-281.
17. S. A. Martinez-Delgadillo, H. Mollinedo-P, V. X. Mendoza-Escamilla and O. Huerta, in Pres 2011: 14th International
Conference on Process Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction, Pts 1 and 2,
eds. J. J. Klemes, P. S. Varbanov and H. L. Lam, 2011, vol. 25, pp. 315-320.
18. H. R. Mollinedo-Ponce-de-Leon, S. A. Martinez-Delgadillo, V. X. Mendoza-Escamilla, C. C. Gutierrez-Torres and
J. A. Jimenez-Bernal, Industrial & Engineering Chemistry Research, 2012, 51, 5947-5952.
19. P. Canizares, R. Paz, C. Saez and M. A. Rodrigo, Journal of Environmental Management, 2009, 90, 410-420.
20. E. Lacasa, E. Tsolaki, Z. Sbokou, M. Andres Rodrigo, D. Mantzavinos and E. Diamadopoulos, Chemical Engineering
Journal, 2013, 223, 516-523.
21. A. Cano, P. Canizares, C. Barrera-Diaz, C. Saez and M. A. Rodrigo, Chemical Engineering Journal, 2012, 211, 463-
469.
22. H. Bergmann, A. T. Koparal, A. S. Koparal and F. Ehrig, Microchemical Journal, 2008, 89, 98-107.
23. M. E. H. Bergmann, A. S. Koparal and T. Iourtchouk, Critical Reviews in Environmental Science and Technology,
2014, 44, 348-390.
.

6
68
EAAOP 2015

69
SECTION

O R A L P R E S E N T AT I O N S

1 st DAY
5
Room A...................................................................................................................................72
Photocatalytic Oxidation.................................................................................................72
Room B...................................................................................................................................80
Ozonation..........................................................................................................................80
Room C...................................................................................................................................88
Catalytic Redox Processes...............................................................................................88
2 nd DAY
Room A...................................................................................................................................96
Photocatalytic Oxidation.................................................................................................96
Room B.................................................................................................................................104
Fenton & Fenton Like Processes.................................................................................104
Room C.................................................................................................................................112
Aops For Energy Production.......................................................................................112
Wet Air And Supercritical Oxidation...........................................................................116
Radiation Processes........................................................................................................120
3 rd DAY
Room A.................................................................................................................................122
Photocatalytic Oxidation...............................................................................................122
Room B.................................................................................................................................128
Electrochemical/Photoelctrochemical Processes......................................................128
Fenton & Fenton Like Processes.................................................................................134
Room C.................................................................................................................................136
Coupling Aop With Other Processes, Pilot-Scale Studies And Field Applications...........136
 O R A L P R E S E N TA T I O N S - 1 st D A Y

MORPHOLOGY-DEPENDENT PHOTOCATALYTIC ACTIVITY OF OCTAHEDRAL ANATASE

Morphology-dependent
PARTICLES PREPARED BY photocatalytic activity of octahedral anataseREACTION
ULTRASONICATION-HYDRO-THERMAL A1-1
particles prepared by ultrasonicationhydrothermal reaction
Z. Wei, E. Kowalska, B. Ohtani.
Institute for Catalysis (Catalysis Research Center), Hokkaido University, Sapporo 001-0021, Japan,
wei@cat.hokudai.ac.jp.
The influence of synthesis parameters on properties and
photocatalytic activities of octahedral anatase particles (OAPs)
prepared by ultrasonicationhydrothermal reaction was
examined. It was found that change in one parameter of
hydrothermal reaction (duration or temperature) resulted in
changes of all properties and photocatalytic activities. On the
other hand, duration of ultrasonication influenced only the
morphology of final products (change in OAP content). Those
samples exhibited almost the same structural/physical properties
but only differed in morphology and photocatalytic activity,
which enabled clarification of the correlation between
morphology and photocatalytic activity, i.e., the higher the total
OAP content was, the higher was the level of photocatalytic
activity.

Octahedral anatase particles (OAPs) were prepared differed in morphology and photocatalytic activity
by an ultrasonication (US)hydrothermal (HT) [3]. This enabled clarification of the correlation
reaction of partially proton-exchanged potassium between morphology and photocatalytic activity,
titanate nanowires (TNWs). [1,2] Photocatalytic i.e., the higher the total OAP content was, the
activities of samples were examined under UV/vis higher was the level of photocatalytic activity [1].
irradiation for oxidative decomposition of acetic Photocatalytic activities correlated with maximum
Copper
COPPER
acid NPs
and NPS Decorated Titania
DECORATED
dehydrogenation ofTITANIA to Improve
methanol TO IMPROVE
under theintensity
Photoactivity
THEof PHOTOACTIVITY
TRMC Under
signal (Imax), UNDER
which VISIBLE
tended to
VisibleALight:
LIGHT:
deaerated NOVEL
conditions. a Novel Synthesis
SYNTHESIS
Total density BY HIGHby electron
of High ENERGYEnergy beUS US.
proportional to total OAP content. Assuming A1-2
traps (ETs) was measured by double-beam that Imax corresponds to the product of density of
photoacoustic
Marta Stucchispectroscopy.
a,1
Mobility
, Claudia Bianchi a,1
, Carloand lifetime
Pirola a,1
electrons
, Giuseppina inb,1mobile
Cerrato shallowb,1,ETs
, Sara Morandi and Argirusis
Christos their mobility,
c
,
ofGeorgia
photogenerated
Sourkounid,electrons were a,investigated
Alberto Naldoni Stefania Vitaliby a,1
the results
,Valentino Capuccisuggest
d
that OAP
. (a) Universit particles
degli studi di have higher
Milano,
Dip.
the Chimica - 20133
time-resolved Milano, Italy,
microwave marta.stucchi@unimi.it.
conductivity (TRMC) (b) Universit
density degli studishallow
of beneficial di Torino,
ETs Dip. Chimica
and & the
thereby
NIS Interdept
method in the centre - 10125ofTorino,
Laboratory Physical Italy. (c) National
Chemistry of Technical
OAPUniversity of Athens,the
content governs School of Chemical activities.
photocatalytic
Engineering,
Paris-Sud 15780 Zografou-Athens,
University. The influence Greece. (d) Energy Research
of synthesis Thus, Centre of Lower Saxony, Am Stollen
morphology-dependent 19A,
photocatalytic
38640 Goslar, Germany. (e) GranitiFiandre SpA, 42014 Castellarano, Italy. (1) Consorzio INSTM, Firenze, Italy.
parameters (HT duration, HT temperature and US activity of OAP-containing particles was
duration) on properties and photocatalytic reasonably interpreted by density of ETs
activities of final products were examined in detail.
Different samples presumably located and
of commercial on the exposed {101}
micrometer TiO2facets.
were
The sample prepared with 1-h US duration and 6-hwith copper nanoparticles by means of high-energy
decorated
HT duration at 433-K using 267 mg of TNWs in and they were tested on the photodegradationextend
ultrasounds,
To enhance photocatalytic activity and to
of
80 mL of Milli-Q water exhibited VOCs the highest working range to visible region of solar spectrum,
in gas phase OAPs under visible
were light, studyingwith
surface-modified in particular the
nanoparticles
photocatalytic activity. It was found that effectchange
of the copper
in HT duration or HT temperature performances resulted in using (NPs) ofamount
noble metals,first, andi.e., also
gold, the difference
silver, platinum,
and acopper.
LED lamp It was at found
different
that irradiation
noble metalpower.
NPs i)
changes of all properties and photocatalytic The results are consistent with the characterization data, showing
activity. On the other hand, duration worked as an electron
of US of the photoactivity and the absorption in the visible sinks hindering
an increase of charge carriers (decrease in Imax
treatment, before HT reaction, influenced spectra with the the recombination
increase of under
the copper amount, butand onlyii)upactivate
to a
morphology of both the reagent (by TNWs of TRMC) UV irradiation,
certain value. titania under visible irradiation, due to localized
breaking) and final products (change in total OAP
content), and those samples exhibited almost the surface plasmon resonance (LSPR) absorption.
Background
same structural/physical properties but only Objectives
TiO2 is the most widely investigated As very few studies on the photocatalytic
References
photocatalyst because of its suitable properties in performance of Cu nanoparticles (Cu NPs) have
[1] Z. of
term Wei, E. Kowalska and
photo-activity B. Ohtani,
as well as cost, Chem.
lowLett., 2014, 3, 346-348.
toxicity been reported so far, different samples of Cu-
[2] Z.stability;
and Wei, E. Kowalska
even if TiO Ohtani,toMolecules,
and B.needs have a higher 2014, 19, 19573-19587.
decorated-TiO2 were tested in this work regarding
2
[3] Z. Wei, E. Kowalska, J. Verrett, C. Colbeau-Justin, H. Remita and B. Ohtani, Nanoscale, 2015, 7, 12392-12404.
activity to be economically competitive, from a the photodegradation of VOCs in gas phase under
practical point of view alternative materials that visible light studying in particular the effect of the
are as advantageous as TiO2 are hard to be found copper amount first, and also the difference
[1]. The recombination of photogenerated charge performances using a LED lamp at different
carriers is one of the main limitations in
semiconductor photocatalysis, and the crucial
72 irradiation power. Every sample has been prepared
by means of high-energy ultrasounds, according to
1
problem related to the practical use of the TiO2 is the procedure usually used for the decoration of
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

PHENOL PHOTODEGRADATION IN PRESENCE OF NANO OR MICRO-TiO2:

Phenol Photodegradation
PERFORMANCE COMPARISONin Presence of Nano
AND STUDY OFor Micro-TiO2:
THE DIFFERENT BY-PRODUCTS A1-3
Performance Comparison and Study of the Different By-products.
C. Bianchia,1,, M. Stucchia,1, C. Pirolaa,1, G. Cerratob,1, S. Morandib,1, B. Sacchia,1, S. Vitalia,1,V. Capuccic. (a)
Universit degli studi di Milano, Dip. Chimica - 20133 Milano, Italy, claudia.bianchi@unimi.it. (b) Universit
degli studi di Torino, Dip. Chimica & NIS Interdept centre - 10125 Torino, Italy. (c) GranitiFiandre SpA, 42014
Castellarano, Italy. (1) Consorzio INSTM, Firenze, Italy.

In the present work the degradation of phenol in water was

performed comparing the use of a commercial micro-sized TiO2
(1077 by Kronos) with a nano-TiO2 (P25 by Evonik), as well as
with commercially available photoactive porcelain grs tiles; in
particular, the photoefficiency of the micro-sized sample was
evaluated both as powder form and immobilized on tiles, in
order to make a comparison and point out the main differences
and changes in term of diffusion of the pollutant, absorption,
photoactivity and efficiency.

Background Objectives
Phenol and phenolic derivatives are the major In the present work the degradation of phenol in
pollutants of the aquatic environment because of water was performed comparing the use of a
their widespread use [1,2] and they are known as commercial micro-sized TiO2 (1077 by Kronos)
recalcitrant organic compounds or POPs with a nano-TiO2 (P25 by Evonik), as well as with
(persistent organic pollutants). Phenol is also commercially available photoactive porcelain grs
relevant in the field of environmental research tiles (ActiveTM tiles by GranitiFiandre). In
because it has been chosen frequently as a model particular, the photoefficiency of the micro-sized
pollutant. The traditional
PHOTOCATALYTIC physical techniques
OXIDATION are
USING COMPOSITE sample PHOTOCATALYSTS
was evaluated both asFOR powder form and
EFFECTIVE
Photocatalytic
only be able to transfer oxidation
organicusing composite
compounds fromphotocatalysts
immobilizedfor oneffective
tiles, in order to make
will be filled
A1-4
NEUTRALIZATION OF CHEMICAL WARFARE AGENTS in by a
neutralization
water to another phase,of chemical warfare
thus creating agents
secondary comparison and point out the main differences and
EAAOP4
pollution [3,4,5].
D. Selishchev 1,2,3 On the contrary, photocatalysis
, D. Kozlov1,2,3. (1) Boreskov Instituteisof Catalysis,
changes in Lavrentieva
pr. Ak. term of diffusion of the
5, Novosibirsk, pollutant,
Russia,
able to induce the complete
selishev@catalysis.ru. oxidation
(2) Novosibirsk State reactions, absorption,
University, st. Pirogova photoactivity
2, Novosibirsk, and
Russia. (3)efficiency.
Research andSamples
leading the Center
Educational most part of the elements
for Energoefficient to (NSU),
Catalysis their st. Pirogova
were characterized
2, Novosibirsk, and analyzed with XRD, SEM
Russia.
higher oxidation state, namely CO2. Titanium and TEM.
dioxide (TiO2) is considered one of Composite the best TiO2/activated carbon and TiO2/SiO
Phenol photodegradation was2 photocatalysts
followed over
photocatalysts, owing its outstandingarefeatures synthesizedtime, by the TiOSO4 thermal
considering also the hydrolysis
development method and
of different
including photocatalytic activity, inertness, investigated in the photocatalytic oxidation of
byproducts and the mineralization, i.e. the diethyl sulfide
physical and chemical stability, full availability vapor which iscompletely
a simulant for one of the of
conversion best phenol
known chemical
in CO2,
even as commercial product, and low cost. warfare
In spiteagentscomparing
mustard gas. Acetaldehyde,
different startingformicpollutant
acid,
of these advantages, many authors evidenced ethylene and SO are registered
concentrations as well.
2 as the gas-phase intermediate
serious problems about the use of nano-sized products which By finally
means areofcompletely oxidized on
the FT-IR analysis to the
thesamples
final
2
materials, e.g. difficulty on both sample handling, oxidation products H O, CO , CO and SO ions.
after the catalytic reaction, it was possible to
2 2 4

separation and collection, and the possible The influence

side- of the support
evaluate on the kinetics
the by-products remainedof diethyl
on the sulfide
different
effects on human health as well [6,7,8,9].photocatalytic TiO oxidation
2 surface.
and photocatalyst stability during
One of the main applications of the TiO multiply long-term experiments a isnewdiscussed.
2 is its Moreover, phenol photodegradation
use in the building materials, as tiles orThe TiO2/SiO2pathway
cements: photocatalyst with TiO
has been 2 content
proposed, equaledfrom
starting to 40the
in particular in this instance, working with micro- wt. % reveals the highest oxidation
experimental data collected. rate and stability.
powders instead of nano could be extremely useful
and advantageous. Even if the main drawback of Methods
the use of photocatalytic tiles is the decrease of the Two commercial TiO2 powders were chosen as
Background The main objective of the study is to investigate
amount of available photocatalyst, with a nano-size and micro-size photocatalysts,
PCO of diethyl sulfide (DES) as one of the good
consequent loss of agents
Chemical warfare photo-activity,
(CWAs) are theforfinal
the respectively. P25 by Evonik is usually used as
simulants of mustard gas CWA and to compare
separation step between
most part volatile organic the catalyst containing
compounds and the reference material, while TiO2 1077 by Kronos is
depolluted TiO2 and composite photocatalysts
as pigment.in1077 the multiple
N, S, P or water is simpler and
Cl heteroatoms. Onemakes
of thethis product
widespread commercially classified
long-term experiments.
is also
suitable for a wide range of applications.
CWAs is bis(2-chloroethyl) sulfide or mustard gas used in commercially available photoactive
(HD), which is a highly toxic vesicant. The porcelain
Methods grs tiles (named Orosei ActiveTM) [10].
median lethal dose (LD50) for HD inhalation is Phenol (Sigma Aldrich 99%) is purchased and
about 1.5 mgmin/L [1]. The development of Composite photocatalysts TiO2 deposited on
effective method for CWAs neutralization is
important for environmental protection and human
73activated
were
carbon (TiO2/AC) or silica (TiO2/SiO2)
synthesized by thermal hydrolysis of titanyl 1
safety. sulfate in the presence of a certain amount of AC
 O R A L P R E S E N TA T I O N S - 1 st D A Y

Preparation and
PREPARATION ANDcharacterization
CHARACTERIZATIONof titaniumOF dioxide photocatalyst
TITANIUM DIOXIDE supported on fly ash
PHOTOCATALYST
particles. Evaluation
SUPPORTED ON FLY ASH of photocatalytic
PARTICLES.activity in wastewater
EVALUATION treatment
OF PHOTO-CATALYTIC ACTIVITY IN
WASTEWATER
Visa Maria1, DutaTREATMENT
Anca1,11R&D Center Renewable Energy Systems and Recycling, Transilvania University of Brasov, A1-5
Eroilor 29, 500036, Romania.

The paper reports on a novel TiO 2-fly ash (TiO2-FA) composite obtained through mild hydrothermal
synthesis, as a possible adsorption and VIS-activated photocatalysis substrate able to simultaneously remove
pollutants in advanced wastewater treatment processes. Combining FA with TiO 2 has the following
advantages: (1) the TiO2 crystallites grow on the alkaline activated FA forming a stable composite where
photocatalytic VIS-active tandem systems can result by associating titania with semiconductor oxides from
FA; (2) the organic pollutant molecules migrate to the surface of TiO2 and can be photocatalytically
degraded and (3) activated fly ash substrates can adsorb inorganic (heavy metal) pollutants and organics,
thus supporting photocatalysis and the in situ regeneration of the FA matrix. The composites surface
properties were evaluated SEM, AFM and BET surface characterisation and PZC measurements, the phase
composition and crystallinity by XRD and the optical band gap was estimated based UV-VIS spectroscopy.
The adsorption and the UV and VIS-photocatalytic properties of the composites were evaluated in three
pollutants systems containing food dyes (Carmine 50% P-WSE-120) and FD&C Blue) and a heavy metal
(Cu2+). The kinetic data allow the investigation of the simultaneous removal of both dyes and of heavy metal
in a stepwise mechanism.

INFLUENCE OF FLAVINS ADSORPTION ON TiO2 IN THE PHOTO OXIDATION EFFICIENCY

Influence of Flavins Adsorption on TiO2 in the Photo Oxidation will be filled
OF AIR CONTAMINANTS in by A1-6
Efficiency of Air Contaminants
EAAOP4
Manjula Pandiri1, Nurit Shaham-Waldmann1, Yaron Paz1*, Frank W. Foss2, Krishnan Rajeshwar2. (1) Technion-
Israel Institute of Technology, Department of Chemical Engineering, Technion, Haifa, Israel,
manju.pandiri@gmail.com. (2) The University of Texas, Arlington, USA.

The use of photocatalyst assemblies to degrade air pollutants is a

promising means for environmental remediation. Various
photocatalyst assemblies have been explored in the past for
highly efficient photocatalysts. However, still the existing
photocatalysts are suffering from low efficiency. A novel
photocatalyst assembly has been developed in this work which
has two components: a metal oxide semiconductor and a
bioredox Flavin-derivative molecule. Flavins improve light
absorption, thus enhancing overall photo oxidation efficiency.
The mechanism by which they operate and the effect of their
1
structure on charge transport and consequently their effect on
photocatalysis will be discussed.

There is an increased interest in the development of

artificial systems that mimics photosynthesis. The
heterogeneous photocatalyst assemblies with
multiple integrated functional components could
able to combine the advantages of dierent
components in order to overcome the drawbacks of
single component photocatalysts in such a way by
enhancing the light absorption range, promoting the
charge separation and transportation. The present
work focuses on the influence of chemically- Figure 2. Adsorption-Activity graph of different
adsorbed flavins on TiO2 in degrading air-born 74
TiO /Flavin composites.
2
pollutants. The photocatalyst assembly is made of Figure 2 shows the relationship between ethanol
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

PHOTOCATALYTIC ACTIVITY OF Li AND K_DOPED ZnO UNDER SOLAR LIGHT

Photocatalytic activity of Li and Kdoped ZnO under solar light irradiation
IRRADIATION A1-7
Hadj Benhebala * and Stphanie D. Lambertb aUniversite ibn-Khaldoun de Tiaret, BP 78 Zaaroura,
Tiaret 14000, Algeria bLaboratoire de Gnie chimique, B6a, Universit de Lige, B-4000 Lige, Belgium

In this work, we present the photocatalytic degradation of methylene blue in aqueous solution using zinc
oxide powders doped with lithium and potassium under solar light irradiation. The photocatalysts were
synthesized by solgel process with zinc acetate and oxalic acid precursors and were characterized by
different techniques such as X-ray diffraction, scanning electron microscopy, UVVis diffuse reflectance
and nitrogen adsorption isotherms. Doping ZnO with lithium, sodium and potassium reduces band gap
energy. All photocatalysts are active with decolorizing rate greater than 90%.

PHOTOCATALYTIC EFFICIENCY OF RETICULATED ZnO STRUCTURE IN DEGRADATION

Photocatalytic Efficiency of Reticulated ZnO Structure in will be filled
OF ACID RED 88 AZO DYE in by A1-8
Degradation of Acid Red 88 Azo Dye
EAAOP4
M. Konyar1, T. Yldz1, M. Aksoy1, H.C. Yatmaz2, K. ztrk1
(1) Gebze Technical University, Materials Science and Engineering Dept., Gebze Kocaeli 41400 TURKEY
mehmetkonyar@gtu.edu.tr
(2) Gebze Technical University, Environmental Engineering Dept., Gebze Kocaeli 41400 TURKEY

The reticulated ZnO catalysts were processed by replicating the

shape of a polyurethane sponge through the ZnO powder slurry
impregnation method. The ceramic pre-forms obtained by
sintering at the initial stage were then subjected to two
consecutive slurry coating and sintering processes to improve
the strength of the skeletal structure. They were used as
photocatalysts for the degradation of Acid Red 88 inside a batch
reactor by using UVA and UVC wavelengths for 180 minutes.
The degradation of the aqueous Acid Red 88 solution (40 mg/L)
was monitored by the color change and total organic content
(TOC). Final degradation rates were 63% and 78% for the color
removal percentages and 11% and 14.4% for the mineralization
under UVA and UVC irradiations, respectively.

1. Introduction
Immobilization of semiconductor photocatalysts
has been investigated extensively for the last few
decades. Among the photocatalysts, ZnO ceramics
gained attraction due to their exceptional
photocatalytic behavior [1-3]. ZnO structures (e.g.
powders [4], coatings [5] and self-supporting 75Figure 1. Molecular Structure of Acid Red 88
(C H N NaO S)
20 13 2 4
bodies [6, 7]) are widely used and have similar
 O R A L P R E S E N TA T I O N S - 1 st D A Y

INFLUENCE OF THE SYNTHESIS METHOD ON THE PHOTOCATALYTIC ACTIVITY OF

Influence of the Synthesis Method on the Photocatalytic activity of
GRAPHENE OXIDE/TITANIUM DIOXIDE COMPOSITES
will be filled
A1-9
in by
Graphene Oxide/Titanium Dioxide Composites.
EAAOP4
M.J. Rivero1, P. Ribao1, S. Dominguez1 and I. Ortiz1. (1) Department of Chemical and Biomolecular Engineering,
University of Cantabria, Av, de los Castros s/n, 39005, Santander, Spain, mariajose.rivero@unican.es
There is a growing interest on the use of GO/TiO2
composites as photocatalysts because they can
enhance photocatalytic properties of TiO2. However,
further research is needed to deepen on the influence
of the variables that determine the preparation of the
composites on their photocatalytic activity. This
work studies the influence of the synthesis method
and GO/TiO2 weight ratio on the properties and
photocatalytic performance of the composites in the
oxidation of Dichloroacetic acid (DCA) solutions.
The results indicated that, the performance of the
composites is influenced by the synthesis method
and the GO/TiO2 weight ratio, leading to differences
in the photocatalytic activity.
Photocatalysis is an attractive technology for the
removal of organic and inorganic pollutants from
water, due to its ambient operating temperature
and pressure and absence of secondary pollution.
Up to now, TiO2 is the most promising material
used as catalyst. However, the photocatalytic
activity of this compound is limited. Graphene
PREPARATION AND CHARACTERIZATION
oxide (GO), a perfectly
Preparation and characterization of visibleOF
functionalized graphene VISIBLE LIGHT-ACTIVE TiO2-REDUCED
light-active TiO2 reduced will be filled
GRAPHENE
from chemical OXIDE PHOTOCATALYSTS
exfoliation,
graphene oxide photocatalysts has been applied to in by A1-10
build inorganic or organic hybrid nanocomposite EAAOP4
1 1 1 1 1 2 3
A.W. Morawski
systems because3 GO , A. was
Wanag , E. Kusiak-Nejman
found to be amenable, J.toKapica-Kozar , . Kowalczyk , B. Ohtani , J. Ostrowska ,
3
M. Aksienionek , L. Lipiska
additional functionalization. The use of graphene
(1) Institute
oxide coupled of with
Chemical
TiO2and Environmental
presents Engineering, West Pomeranian University of Technology, Szczecin,
three advantages
Puaskiego 10, 70-322 Szczecin, Poland , amor@zut.edu.pl
in(2)
theCatalysis
photocatalytic activity: (i) a band-gap tuning
Research Center, Hokkaido University, Sapporo 001-0021, Japan
and/or extension
(3) Institute of excitation
of Electronic wavelength
Materials could
Technology; be
Wlczyska 133, 01-919 Warszawa, Poland
achieved; (ii) the graphene oxide could trap and
move the charge carriers avoiding recombination
. The main aim of this study was the preparation of visible
and, (iii) the composite would provide adequate
quality and quantity of active sites. light- active TiO2- reduced graphene oxide photocatalysts.
The graphene oxide was prepared according to the
GO/TiO2 composites were synthesized modified by Hummers method with potassium permanga-
hydrothermal, solvothermal and mechanical nate in a medium of concentrated inorganic acid. The
methods. Furthermore, they were characterized by clearly show the enhancement of the photocatalytic
results
several techniques including FT-IR, atom force Figure
TiO1. Mineralization of DCA for all synthesis methods
activity of 2-graphene photocatalysts in comparison
microscopy (AFM) and thermogravimetric with starting GO/TiO2 weight
with titanium ratios
dioxide. of 1%
The (a), 5%of(b)
content andwt.%
0.5 10% (c).
of
analysis (TGA). Specific surface areas were reduced graphene
In these oxide
working was examinedtheasresults
conditions, the optimal
indicated
measured by the BrunauerEmmettTeller (BET) content of that,rGO
the to obtain the photocatalyst
photocatalytic with theby
activity is influenced
method and bandgap values were obtaininghighest by photoactivity under visible light irradiation.
the synthesis method and the GO/TiO2 weight
diffuse reflectance measurements.
ratio of the composites. All the composites showed
Photocatalytic activity was studied by better photoactivity than TiO2, being the
degradation and mineralization of DCA. mechanical synthesis the method that led to worst
1. Introduction
Experiments were carried out in a Heraeus transfer through
results. a C-Ti bond,
Furthermore, a high which increasedload
graphene the
Laboratory UV Reactor. The light source was a number ofthe
decreases holes participatingactivity.
photocatalytic in the photocatalytic
Finally, it is
In the last decade, graphene, a two-
150 W Hg lamp process duethat
concluded to markedly decreased
the composites the recombi-
synthesized by
dimensional novelwithcarbonemission spectra with
nanomaterial between
zero
200 and 600 nm. nation of electron-
hydrothermal methodholeandpairs.
with a weight ratio of
band gap, large specific surface area, excellent
mechanical, electrical, optical and thermal 5% (H5%) provided the best results.
2. Experimental
properties and its applications in sensors and
biosensors, electronic devices, liquid crystalline
displays, capacitors solar cells, H2 production, 76 1.1. Preparation of TiO2-rGO photocatalysts

energy storage and nanocomposites including Carbon-modified TiO2 photocatalysts were

 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

A NOVEL PHOTOCATALYSIS APPLICATION WITH REDUCED SIZE CRYSTALLITE TiO

A novel photocatalysis application with reduced size crystallite TiO2
will be filled
2
in by A1-11
EAAOP4
M. L. Gimenes1, J. C. M. Vicentini1, M. H. N. Olsen Scaliante1, N. R. C. Fernandes-Machado1, M. deSouza1.
(1) State University of Maring, Colombo Avenue, 5790, Maring, Brazil, marcelino@deq.uem.br.

ZSM5
P
The study evaluates the photocatalytic activity of
1,0
F1
F2
reduced size crystallite TiO2 supported on zeolite
F3 ZSM5 in the degradation of the RB250 dyes
F4
F5 under UV-vis radiation. TiO2 size was reduced
F6
Photolysis varying the grinding parameters in planetary ball-
0,5 milling, before its physical deposition on zeolite.
C/Co

The comminute treatment of the semiconductor

indicated reduction of the crystallite size and
switching from anatase to rutile phase. The
photocatalytic tests showed better results for
0,0

0 1 2 3 4 5
catalysts supported presenting lower content of
Time (h) active phase and for the less intense comminuted
TiO2.
RB250 degradation.
INTRODUCTION
MATERIALS AND METHODS
Despite the pioneered incorporation of
environmental practices in Textile Industry, this The ZSM5 zeolite with Si/Al ratio equal to 30
kind of industry still present high consumption of was obtained by sol-gel method using 178.65g of
water and fuel and additional chemicals. This deionized water, 1.5g of ZSM5 seed, 15g of SiO2,
contributes with numerous environmental 2.83g of Al2(SO4)3.18H2O, 3.6g of NaOH and
Bismuthassociated
BISMUTH
problems Oxide
OXIDEThin with Films
THIN FILMS
disposal Deposited
DEPOSITED
of By Magnetron
waste water 11.5g Sputtering
BY MAGNETRON of ethyl With
SPUTTERING WITH
alcohol. Chemicals will be filled
were
INTERESTING
and effluent, whose
Interesting PHOTOCATALYTIC
contain highProperties
Photocatalytic PROPERTIES
load organic and homogenized for 20 min, autoclaved for 4 days in by at A1-12
inorganic materials which may be recalcitrant to 170C and calcined for 5h at 500C. EAAOP4
conventional
Juan C. Medinatreatments
1,2 [1,2]., S.E. Rodil . (1) Universidad Nacional Autnoma de Mxico - Instituto de
, M. Bizarro 1 1

Investigaciones en Materiales, A. P. 70-360, Coyoacn C.P. 04510, D.F.,

TiO2 sizeMxico
reduction treatment was performed in
com (2) Posgrado en Ciencia e
Ingeniera de Materiales, UNAM, Mxico. first author e-mail:21.juancarlos@gmail.com model Pulverizzette 6
The heterogeneous photocatalysis is a good way a planetary ball-milling
to complete degradation of these contaminants. It Fritsch. Parameters such as grinding time, speed
is a generating hydroxyl radical technique with millingsputtering
RF Magnetron and media used (dry
technique andthe
allows with acetone)
formation
radiation absorption by semiconductor oxidesofin Bi2O3 were investigated
thin films for constant
with different ratiostructures.
crystalline of balls mass
contact with water, which provide the complete to TiO2 material.
mineralization of pollutants. TiO2 is one of -phase the BiThe
2O3 films presented
supported the highest
catalysts photocatalytic
preparation was made
most used semiconductors due to its advantages activity to degrade methyl orangeofdye in2 comparison
by physical
and characteristics [3] and also the possibilitytheofother bismuth oxide phases. deposition TiO prepared intothe
immobilization on supports such as zeolites, which previous step. To accomplish this TiO 2 and ZSM5
were spread out in deionized water at the
confers rigidity and porosity to the catalyst, then The results pointed out that12%
the (w/w).
photocatalytic activityhad
solving the difficulty of separation in solution was proportions
and always 3 and This mixture
larger for
complete Bi2O3 films
evaporation of than
water foronTiOa2 films.
rotatory
offering opportunity to reuse [4]. Moreoverevaporator
the activityunderwas also larger
vacuum condition 2O3 in
for atBi70C and
The size crystallite of the semiconductor is comparison
a aftertoitequivalent mass-amounts
was calcined of TiO2 powders
for 5h at 500C.
decisive factor for a good photocatalytic activity (P25)
as under the same experimental conditions.
it can be better dispersed on the surface and in the The catalysts were characterized by XRD using
zeolite pores, avoiding the excessive catalyst loss. a Bruker D8 Advance X ray diffractometer. The
The physical grinding is a technique to reduce the textural properties of catalysts were measured by
X-ray diffraction, profilometry, scanning
During the Quantachrome NOVA apparatus, the band gap
crystallite size,last
which decades,
is alsosemiconductor driven
capable of changing electron microscopy, and optical transmission
photocatalysis has shown
the physical, chemical andgreat potential properties
mechanical for water energy was measured by photoacoustic
were used to characterize the films. The
treatment as a low-cost
of the material [5]. and environmental friendly spectroscopy and metal ions concentrations were
photocatalytic activity for each one of the Bi2O3
process. Oxide semiconductors have been used for measured by atomic absorption spectrometry on
phases was evaluated by the evolution of the
The the
either aimsoxidation
of this study are tocompounds
of organic evaluate the in flame with Spectra AA equipment, 50B model
absorbance spectrum of an aqueous solution of
interference
residual waterof[1-the 3], grinding parameters
or reduction on the
of pollutants or Varian.
methyl orange dye (C14H4N3SO3Na) as a function
kineticsgases
toxic and (airphotocatalytic
purification) activity
[4] as ofwellTiO as2 ofPhotolysis
the irradiationand time (under UV tests
photocatalytic light),with
resulting
both
supported on ZSM5ofunder
oxidation-reduction heavyUV-vis
metalsradiation
in soils foror that the delta-phase Bi2O3 thin films had the
water effluents [5-6]. highest photocatalytic performance.
In the case of water purification, the 77 The absorption spectra of the solution were
1
semiconductor photocatalytic materials are usually measured each 30 minutes during 3 hours using a
 O R A L P R E S E N TA T I O N S - 1 st D A Y

ILMENITE AND ILMENITE MODIFIED AS CATALYST FOR CWPO-PHOTOASSISTED

Ilmenite and ilmenite modified as catalyst for CWPO-Photoassisted will be filled
PROCESS in by A1-13
process
EAAOP4
P. Garca-Muoz(1), G.Pliego(1), B. Barbero(2), J. Zazo(1), J.A. Casas(1), A. Bahamonde(1),, J. J. Rodrguez(1)
(1) Department of Chemical Engineering, Universidad Autnoma de Madrid , Madrid (Spain) patricia.garciam@uam.es
(2)Department of Chemistry, Universidad Nacional de San Luis, San Luis (Argentina)

The aim of this work is to study the viability of the mineral

ilmenite as catalyst in a CWPO-Photoassisted process under
Vis-LED light for the removal of phenolic compounds in
water. Natural ilmenite, which has a mixture of Fe(III) and
Fe(II) in its surface, was treated with H2 in order to modified
its iron surface oxidation state: first as Fe(II) and after as
Fe(0). A comparative study based on phenol conversion and
TOC removal rates for each catalysts was performed. The
best result was obtained using the most reduced ilmenite.

Introduction
TiOSO4 method. Leached iron was obtained by
The use of simultaneous CWPO (Catalytic Wet ortho-phenanthroline method.
Hydrogen Peroxide Oxidation) and photocatalysis
have demonstrated to improve the mineralization of
organic compounds [1].
Results
Recently, light emitting diodes (LEDs) are
The three catalysts were characterized. The
promising replacement for conventional light
results of TXRF initial characterization of natural
sources in many applications.
COMPARATIVE In this work,THE
STUDY BETWEEN ilmenite
ACTIVITY OF TiO
Comparative study between of TiOilmenite gave2 NANOPARTICLES
contains 36 andAND
that itand 37 %TiO
be w/w2 Fe
for the activity 2 nanoparticles will filled
catalyst
NANOTUBES (FeTiO3ON) was employed
PHOTOCATALYTIC phenol CWPO-
MEMBRANES A1-14
TiO2 nanotubes on photocatalytic membranes. and Ti, respectively. N 2 adsorption-desorption in bywas
photoassisted oxidation under Vis-light LED lamp EAAOP4
also measured and the external area value was 6
irradiation
J. Marugn, at mild C.experimental
C. Casado, Garca-Caibano, condition.
C. Adn, R. van
m2Grieken.
g-1. XRD shows that natural ilmenite mineral
Moreover,
Departmentilmenite wasand
of Chemical pre-treated to obtain
Environmental iron ESCET, Universidad Rey Juan Carlos, C/ Tulipn s/n,
Technology, has two phases mainly: rutile phase and ilmenite
with
28933different
Mstolesoxidation states
Madrid, Spain, in order to notice
javier.marugan@urjc.es. phase (data not shown). These patterns showed a
how these states affect to the process.
formation
TiO2 nanotubes haveofbeennewsynthesized
diffraction peaks when ilmenite
by anodization on
Materials and methods mineral under
titanium membranes was reduced
different a 5% H2 in Arconditions.
in experimental atmosphere
1000 oC, these
untilparameters were related to thethe
appearance
The experiments were carried out in a The synthesis
tubular of Fe(II) and
significantly
Fe(0) [2].
affect final
reactor with an optical length of 1 cm where morphology
the of the nanotubes. The high surface areas of the
irradiance corresponding to Vis-LED radiation membranes
was considerably
Catalysts with increase
different the reduction
intensity treatments
during
-2. Vis-LED light emits at 405 nmanodization process in comparison with flat surfaces. This
10 Wm with a were employed in CWPO-Photoassisted process
power of 48 W. The reaction volume was fact 100 promotes
mL the accumulation
under Vis-LED light. of a debris
Fig. 1surface
showsofthe TiOphenol
2 or

and the starting concentration of phenol 100 mgL Ti(OH) - particles via hydrolysis reaction. The goal of this
4 degradation with these catalysts. Phenol
1. The catalyst load was 450 mgL-1 and the workH2Ois2 to study the activity
disappearance rate for methanolas oxidation
increased catalysts andwere
concentration was 100% of the stoichiometric E.coli inactivation
previouslyof photocatalytic
reduced. Natural membranes
ilmenite wasbasedableon to
amount which is 500 mgL-1. Ilmenite wastitania millednanotubes
oxidizein comparison
100 mgL-1 with phenol equivalent
in 150 membranes
min. When a
until dp<100 m. The temperature in theprepared reactor by coating
reduction with P25-TiOwas
treatment 2 nanoparticles
employed, ilmenite was
was controlled at 50 oC and pH0=3. Phenol and reduced at 500 C for 1 h, Fe(II) in its structure
aromatic oxidation by-products were quantified by increased, then, the rate was faster yielding total
means of work
HPLCwe(Varian Pro-Star 240) using a Figure 2at 60
oxidation shows the when
min, but comparison
ilmenitebetween
was reduced the
In this report the synthesis conditions photocatalytic activities TiO2 nanotubes
of upa oxidising
diode array detector (330 PDA).
for the preparation of TiO2 nanotubes by Short-chain at 1000 C, the velocity phenol
organic acids membrane andmin. membrane preparedFe(0)by was the
anodization of Ti were analyzed
membranes as a new by strategy
an ion to solution in 30
incorporation of 0.2 g
At this condition
of TiO 2 nanoparticles in the
chromatograph with chemical
immobilize TiO2 photocatalyst suppression
with high surface observed. These behaviour seems to be associated
(Metrohm 790 IC)stage
usingofa this
conductivity oxidation
to differentof redox
methanol to formaldehyde. Although
area. In a second study wedetector.
make a the
surface reactions, in which the
Total organic study
comparison carbon of
(TOC) was results
these measuredwithusingTia metallic surface generates ferrous species (eq. Ti
results obtained with the anodized 1)
TOC analyzercoated
(Shimadzu, membrane
which then showreactsawith
slightly
H2O2higher
givingkinetic
HO and constant,
Fe(III)
membranes with model 5000A),
TiO2-P25 while the
nanoparticles differences
residual
for methanolhydrogen peroxide
oxidation concentration
and E. coli inactivation.was (eq. 2) and in activity
finally Fe(0)with the use
is able of nanoparticles
to reduce Fe(III) to
determined by colorimetric titration using the are inside the experimental error,
Fe(II) again (eq. 3) [3]. This effect added but in bothto cases
light
TiO2 nanotubes can be obtained by anodization significantly higher than the use of a naked
membrane without TiO2 functionality.Similarly,
of titanium foils in a non-aqueous electrolyte. The
microfiltration and photocatalytic experiments 78
the results of the inactivation of bacteria (not 1
have been carried out in a photocatalytic shown) show a higher reduction of the number of
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

ELECTROCHEMICAL PRODUCTION AND PHOTO-CATALYTIC ACTIVITY OF Ag DOPED

Electrochemical Production and Photocatalytic Activity of Ag Doped will be filled
POLYANILINE FILMS in by A1-15
Polyaniline Films
EAAOP4
B.Haspulat1, H. Kam1 (1) Seluk Universty, Department of Chemical Engineering, Konya, Turkey,
bircanhaspulat@hotmail.com.

Electrochemically synthesized Ag doped polyaniline films on

ITO coated glass substrate and pencil graphite substrate were
used as photocatalyst for decolorization of methylene blue and
malachite green organic dyes under UV light irradation. The
electrochemically synthesized polymer film photocatalyst were
characterized by using scanning electron microscopy, FT-IR
spectra, UV-Vis spectroscopy measurements were used. The
photocatalytic property of polymer films were evaluated by
decolorization of methylene blue and malachite green (1.5x10-5
M) dyes under UV light irradation. After 45 min later, in the
presence of Ag doped polyaniline on ITO coated glass substrate
and pencil graphite substrate, the decolorization efficiency of
malachite green dye is 79% and 100% under UV light
irradation, respectively.

Photocatalysis has attracted great attention photocatalysis of the PANI and its composite for
owing to its promising application such as in the degradation of organic dyes [10]. In the
photocatalytic degradation of organic dyes. literature, the photocatalysts are usually in powder
Organic dyes used in textile and food industries form and placed in solutions. Therefore, solutions
are their important sources of the environmental need remediation after photocatalytic
ADVANCED OXIDATION PROCESSES
contaminations
Advanced Oxidation due to their non-bio
Processes BasedBASED
degradability ON PRE-MAGNETIZATION
decolorization,
on Pre-magnetization which
Iron forwould IRON FOR
inevitably
will result
be filled in
HIGHLY
and high EFFICIENT
toxicity to ENVIRONMENTAL
aquatic
Highly Efficient Environmental Remediation creatures REMEDIATION
and some disavantages, like difficult recoveryin by and A1-16
carcinogenic effects on humans [1]. In order to secondary pollution. In order to eliminate EAAOP4 this
1 1
M. Zhou
reduce damage, Y. Pan , X. Li1by
caused Xu1
, L.organic dye pollution to disavantages, authors have reported a similar
(1) Key Laboratory of
environment and humans, the use Pollution Process and Environmentalstudy.
of photocatalyst Criteria,InMinistry of Education,
this study, College of
the photocatalytic activity
toEnvironmental
degrade organic Science and Engineering,
compounds Nankai University,
in contaminated air Tianjin 300071, China,
decolarization of fourzhoumh@nankai.edu.cn
commercial textile dyes has
or water or to convert them into harmless been investigated using electrochemically
chemicals has been extensively studied. Advanced
In this oxidation processes
synthesized (AOPs)
PANI and have
Fe ionshown
dopedpromising
PANI on ITO for
manner conductive polymers such astoxic and persistent
polyaniline glassorganic pollutants
substrate in aqueousabatement,
solution however,
under UV they light
[1], polypyrolle [2], poly(3-hexylthiophene) are still not
[3] widely used for practical
irradation[11]. Similarly,application
fabricationdue of toAghighions
has been extensively used to degrade treatment non-cost ordopedlimitedpolyaniline
application (PANI/Ag)
scope. In this work, with
catalyst we
biodegradable organic dyes by photocatalytical reported some novel AOPs basedpolymerization
electrochemical on pre-magnetization of cheapis
on solid support
routes. iron by a weak very magnetic field, for
important for advanced
example, pre-magnetization
the photocatalytic
Polyaniline (PANI) has been extensively Fe0/Hstudied
2O2 and Fe
0
/persulfate,
activity and the which
practicalnot only enhanced the
applications.
due to its high environmental stability,pollutants interesting degradation
The aimrateofeven more was
this study thanto10 times, but
investigate effectalsoof
redox behavior, simple synthesis extended procedure,the suitable
Ag ionapplied scope (e.g.,activity
to photocatalytic pH). Therefore,
of PANI theseunder
controllable electrical and optical properties processes[4].would provide
UV light a promising alternative
irradation for environmentalof
for decolorization
The potential applications of polyaniline remediation
include duemethylene
to its high blue efficiency, low costgreen
(MB) and malachite and (MG).
high
organic light emitting diodes [5], electrochromic compatibility without Also,modification
the second aim on present
of this apparatus.
study was to enhance
devices [6], sensors, photocatalysis [1, 7] etc. The the photocatalytic activity of PANI/Ag by using
addition of metal particles to semiconductor both indium tin oxide (ITO) coated glass substrate
photocatalyst to increase the light-absorption and pencil graphite (PG) substrate as solid
efficiency and photocatalytic activity is of great asupports.
model dye. The Forobjects
this of
purpose,
this studythewere
effective
to (1)
Advanced
interest. Whenoxidation
conducting process
polymers(AOPs) is a
are loaded polymeric
explore materials ofhave
the feasibility been prepared
pre-magnetization AOPs; by
potential
with metaltechnology
nanoparticles, to the
degrade
propertiestoxicof and
the electrochemical
(2) investigate the polymerization of PANI
important operating presence
parameters
persistent nanocomposites
resulting contaminants such areasdifferent
phenols and fromdyes,
the of the Agprocess;
ions in (3) aqueous H2SO4 mechanism
explore possible solution and for
based on the generation
parent conducting polymer. of powerful hydroxyl photocatalytically
pollutant degradation.characterized using the
radicals
PANI has [1]. been
Fenton and persulfate
synthesized oxidation
easily with are
chemical decolorization of MB and MG organic dyes under
moreor frequently
[8] electrochemical applied[9]because
oxidationtheirmethods
relativelyof UV Batch
light experiments
irradation. were conducted to explore
simple and
aniline. Recentefficient process.
studies haveHowever,
reported these on the influences of initial pH (2-6.5), H2O2 or
processes also have some problems limited their persulfate dosage (0.25-2 mol), and Fe0 dosage
wide application, for example, Fenton process
would produce large amounts of iron sludge and
79(0.5- 3 mmol) on the performance of tartrazine
degradation. Fe0 magnetized by a weak magnetic
1
perform well under a narrow pH range (2-3). field and suitable amount of reagent were mixed
 O R A L P R E S E N TA T I O N S - 1 st D A Y

OZONATION OF p-HYDROXYBENZOIC ACID IN A MULTI-ORIFICE OSCILLATORY

Ozonation
BAFFLED of p-Hydroxybenzoic Acid in a Multi-Orifice Oscillatory
REACTOR B1-1
Baffled Reactor
Marco S. Lucas, Nuno M. Reis, Gianluca Li Puma. Chemical Engineering Department, Loughborough University,
Loughborough, LE11 3TU, United Kingdom M.P.Lucas@lboro.ac.uk

A disruptive ozonation technology using a Multi-Orifice

Oscillatory Baffled Reactor (MOBR) will change the water and
wastewater treatment field. A reduction of 5-fold to one-order of
magnitude in volume can be estimated to achieve the same rate of
ozone mass transfer obtained in conventional ozonation reactors,
Pump

Ozone

diminishing treatment costs and carbon footprint. The

Generator
Water In
Ozone outlet

p-hydroxybenzoic acid (p-HBA) solution was degraded by ozone

Gas flow
meter

Ozone outlet Ozone

inlet
(O3) in an MOBR, with 100% O3 utilisation (no waste of O3). The
p-HBA degradation and mineralization was always higher in the
Ozone
destroyer Gas flow controller

Ozone

Water
Analyser
MOBR comparatively to a bubble column (BC). In fact, the
MOBR can mineralize the p-HBA 8-fold faster than a BC. These
Oxygen
sampling Ozone cylinder
inlet
Water Out Gas flow

features make ozonation economically attractive to be applied

Piston controller

from small to industrial scale wastewater treatment plants.

Ozonation has been intensively applied as an be easily mimicked at pilot and industrial-scale
advanced technology in water and wastewater processes. The application of OBC and/or MOBC
treatment due to its high oxidation capacity and in the ozonation of real or synthetic wastewater has
ability to remove contaminants [1,2]. However, not been studied. Thus, the aim of this work was to
ozone and ozone-driven treatment processes evaluate the performance of a novel MOBC in the
(ozone/UV; ozone/UV/H2O2; ozone/UV/TiO2) can degradation of p-hydroxybenzoic acid solutions
CATALYTIC
be costly to applyOZONATION OF BEZAFIBRATE
at industrial scale. These costs are INbenchmarking
SIMULATED NATURAL WATERwillagainst
its performance be filled a
CATALYTIC OZONATION OF BEZAFIBRATE
mainly related with the inherent inefficiency of
IN SIMULATED
conventional BC, in continuous flow-through B1-2
in by
NATURAL
current designsWATER
of gas-liquid contacting reactors mode. This was monitored in terms of p-HBA and
EAAOP4
(e.g.
A.G.bubble
Gonalvescolumns
1 (BC),
, J. J. M. packed
rfo 1
, M. F.columns
R. Pereira(PC),
1 TOC de
. (1) Laboratrio conversion, as well
Catlise e Materiais as Laboratrio
(LCM), their removal
stirred tanks
Associado (CSTR), Departamento
LSRE/LCM, air-lift reactors (ALRs) and
de Engenharia efficiencies.
Qumica, Faculdade de Engenharia, Universidade do Porto,
static mixers
Rua Dr. Robertoor Frias,
venture ozonePorto,
4200-465 injectors systems
Portugal; agg@fe.up.ptThe ozonation experiments were conducted in a
followed by bulky gas-liquid contacting units), Multi-Orifice Oscillatory Baffled Column (internal
which usually require large contact time Theandinfluence
gas of the most
diameter common
0.150 m andinorganic ions and
column height of natural
0.540 m)
aeration rates [3-8] organic matter present
and in ainBubble
naturalColumn
water in(internal
the catalytic ozonation
diameter 0.150 m
ezafibrateColumns (OBCs) of
Oscillatory Bezafibrate
Baffled bezafibrate
have been (BZF) over multi-walled
and column height of 0.540 carbon nanotubes was
m). Experiments were
Simulated applied to aUltrapure
successfully wide range ofevaluated.
chemicalFor that purpose,intwo
performed differentmode
continuous matrices
withwere used inlet
an ozone in
Natural Water
and biological
Water processes, including the preparation
gas-liquid and of the BZF solutions:
concentration of 23 g O /m3, a p-HBA
a 3simulated natural water of
solution
other multiphase systems. The eddy mixing (SNW) and an ultrapure
in the 50 mg/L (pHwater10(UPW). A better performance
0.1, unbuffered) and varyinginthe
periodic baffles can deliver intensive radial the mixing
mineralization of BZF
ozone was(2.1
flow rate 4.7 L/min).
obtained when SNW is used as
The phenolic acid
and secondary flow, which is very effective matrix, which
for may be explained
aqueous solution by the increase
inside of pH and
of the reactor was thekept
controllingO3the+bubble size and enhancing presencethe in solution
alwaysof at
species that act
a constant of 9 L. The p-HBA
as initiator/promoters
volume in
contact between immiscible phases in the theozone
entiredecomposition Theand
concentration acute
thetoxicity
organic towards V. fischeri
matter mineralization
contacting volume [9,10]. OBCs are very is lower
efficientwhen SNW(TOC) is used matrix. p-HBA aqueous solutions
wereasfollowed.
in respect toCO + H2O gas-liquid mass transfer
maximizing
2 were supplied to both reactors (BC and MOBC)
and can easily be scaled-up by increasing the with a water flow rate of 4.0 L/min, corresponding
number of baffles. to a hydraulic retention time (HRT) of 2.25 min. In
Al-Abduly and co-authors [11] studied the effect the MOBC, sinusoidal fluid oscillations were
of OBCs on ozone-water mass transfer and imposed on the fluid using a servo-hydraulic system
world and consequently has been frequently
described
Introductionthat a single-orifice OBC was more that controlled a 125 mm o.d. piston attached to the
detected in the environment [3, 4]. In Germany,
efficient for ozone-water mass transfer than a bottom of the column. This moving base piston was
Considering BZF has been found in sewage treatment plant
standard bubblethe concern about the occurrence of
column. capable of delivering combinations of values for
endocrine disrupting compounds (EDCs) and (STP) effluents in concentrations up to 4.6 g L-1
A Multi-Orifice Oscillatory Baffled Column oscillation frequency (f) and oscillation amplitude
pharmaceutical and personal care products and median values of 2.2 g L-1 [3, 5]. BZF has
(MOBC) intends to scale-up the single-orifice OBC centre to peak (x0) in the ranges of 0-10 Hz and 0-
(PPCPs) in surface been found in rivers and water streams of
technology, allowingand ground water,
reproduction which
of the mixingare 10 mm, respectively.
the two major sources for drinking water, there is a Germany at median concentrations of 0.35 g L-1
and flow conditions produced at laboratory scale to MOBC and BC reactors were equipped with a
need for developing efficient technologies for their [5], whereas concentrations up to 57.15 g L-1
have been found in Italian rivers [6]. In surface
removal. Catalytic ozonation is among the most
promising solutions for this application. 80
waters this drug has been identified at median 1
concentrations of 3.1 g L-1 [3].
 ROOM B - OZONATION

INFLUENCE OF PH AND OZONE DOSE ON SULFAQUINOXALINE OZONATION

Influence of pH and ozone dose on sulfaquinoxaline ozonation B1-3
V.R. Urbano1, M.G. Maniero1, M.Prez-Moya2, J.R. Guimares1*. (1) School of Civil Engineering, Architecture
and Urban Design, University of Campinas, 951 Albert Einstein Avenue, Campinas, Brazil,
*jorober@fec.unicamp.br. (2) Escola Universitria dEnginyeria Tcnica Industrial de Barcelona, CEIB,
Chemical Engineering Department,UPC. BARCELONATECH, C/Comte dUrgell 187, 08036 Barcelona, Spain
1.0 Ozonation was effective to degrade
O3
0.8
O3 + OH sulfaquinoxaline: more than 99% of efficiency
0.6 OH was obtained using an ozone dose of 2.8 mg L-1
and pH 3. A design of experiments with two
C/C0

0.4

0.2

0.0 variables, pH and ozone dose, was used for

0 10 20 30 40
-1
O3 doses (mg L )
50 60 70 80
planning. There was no significant interaction
1.0
pH 3 pH 7 pH11 between these variables and ozone doses played
0.8 the most important role regarding the contaminant
0.6 degradation. However, regarding toxicity ozone
process at pH 3 did not inhibit the luminescence
C/C0

0.4

0.2
of the bacteria even though different
0.0
intermediates were formed and identified by mass
0 2 4 6
-1
8 10 12 spectra. At pH 7 inhibition of luminescence
O3 doses (mg L )
remained almost constant (around 30%)
throughout
(OH). ozonation time.
Sulfaquinoxaline is a sulfonamide routinely used
in prophylactic veterinary treatment to prevent The experimental setup for the study consists of
coccidiosis and bacterial infections [1]. Its an ozone generator (O3R Philozon), a glass
presence in both surface (4.5 to 40.4 ng L-1) [2] contact column (50 cm height x 7 cm diameter,
and groundwater (0.01 to 112.1 ng L-1) [3] is an volume of 1 L) and a reaction vessel for ozone gas
issue of great importance for ecosystems
STUDY OF ETHANOL EFFECT AS Co-SOLVENT measurement. and IN THE NAPROXEN One glass diffuser wasINused to
OZONATION
Studyhealth.
human of ethanol
Issues effect as co-solvent in the Naproxen Ozonation in the solution will at abeconstant
filled
PRESENCE OF NiO such as acute and chronic sparge ozone gas into
in by B1-4
presence
effects of NiO on ecosystems and potential
of antibiotics -1
flow rate of 4.0 L min . The ozone generation was
-1 -1 EAAOP4
rise of antibiotic-resistant
1 1, bacteria are
2 not well 2 5.52 2 0.32 mg min L . The experiments were
C. Aguilar J. Chairez J. Rodrguez T. Poznyak E. Palacios (1) Unidad Profesional Interdisciplinaria de
understood and they
Biotecnologa areTicoman,07340
IPN. at the root of increasing
Mxico, D.F. Mxico.conducted at room temperature
assiram_12hotmail.com. (20 de1C),
(2) Escuela Superior
public concern [4]. Ozonation
Ingeniera is an effective
Qumica e Industrias varying
Extractivas - IPN, reaction
Zacatenco, time from
07738Mxico D.F.0 Mxico
to 15 minutes, i.e.,
alternative to conventional treatments when this present
In the ozone doseafrom
work, 0 to 80 mg
degradation L-1. of naproxen, a
study
type of pollutant is present. Two main oxidants nonsteroidal Gaseous
anti-inflammatory found inwaseffluents
(molecular O3 and OH radical) may be acting in ozone concentration determinedofby
wastewater treatment plants was performed by2350catalytic
the ozonation reaction. Lower pH (pH 4)ozonation favors using NiO. The effect of organic matter inE)the
a potassium iodide method (Method [5].
the oxidation via molecular ozone. Increasesystem In the control experiment,
of pH was evaluated with mixtures ethanol:water in oxygen gas was
favors O3 decomposition into hydroxyl radicals. In continuously bubbled into the solution at the same
proportions 30:70rate
flow andas50:50used which
for theadditionally improved
ozonation experiments
pH 10, O3 is instantaneously decomposed the into
solubilityand
of naproxen. It has been found that the samples
results indicated that sulfaquinoxaline was not
hydroxyl radicals. In pH 7 both oxidants with can be50 % stripped
of co-solvent interfered
from the aqueous in the degradation of
phase.
acting. Due the scarcity of scientific research in
naproxen and its by-products. On the other hand, the
the literature about sulfaquinoxaline degradation presence of NiO Solutions submitted
on ozonation had to an degradation
effect on theprocess
formation were
by ozonation process, the objectives of thisofstudy by-productsconcentrated
as seen in the by UV-Vis
solid phasespectrums extraction
and HPLC. using
were to evaluate the sulfaquinoxaline degradation The naproxen Varian C18 (500
degradation mg/6.0 by
was achieved mL)the cartridges,
first 10
and toxicity reduction in different ozone doses and reaching
minutes conditioned with methanol
a 98% according to the(6.0
HPLC mL)analysis.
and ultrapure
pH values. Moreover, the intermediates formed water (6.0 mL). Analytes were eluted with
during ozonation were evaluated. methanol (4.0 mL) and the extract was filtered
1. Introduction of thismtreatment.
(0.22 The application
porous membrane). of catalyst has
The concentration of
The presence of highly stable compounds in overcame such disadvantages. Indeed, the
residual sulfaquinoxaline was quantified by HPLC
wastewater such as pharmaceutical drugs has increment of OH concentration yields to
Methods with a photodiode array detector (Waters, USA).
triggered researching on enhancing conventional
-1 The limit ofthe
enhanced mineralization
quantification was effectiveness
0.04 g L-1. [5,6].
degradation treatments.
Sulfaquinoxaline workingPharmaceuticals
solutions (500mayg Lbe Several catalysts have been evaluated in catalytic

able1.67
or to change
mol the L-1)reproduction
were prepared cyclesinin1aquatic
L of ozonation
Microtox(TiO 2, SiOanalyzer
toxicity 2, Al2O3, (Vibrio
etc.). Among them,
fischeri, 30
species. Moreover,
ultrapure water. A wide these organics
range are hardly
of pH (3-11) was NiO hasofshown
minutes contact)a superior
was used mineralization
to assess the capacity
toxicity
affected
used by either
to evaluate biological ordegradation
the sulfaquinoxaline chemical over
of the TiO 2 [7].submitted
solutions In real towastewater
ozonation. treatment
Analyses

conventional
due to molecular treatments
ozone (O3)[1,2]. Among radical
and hydroxyl these systems,
were the out
carried presence of phosphates,
according to Microtoxorganic test
compounds, anti-inflammatory drugs are matter, carbonates,
procedures standard sulphates,
(81.9% screeningsurfactants
test).and co-
frequently found in effluents of wastewater solvents affect the performance of ozonation (O3-
treatment plants. Naproxen (NAP) is a non- 81
conv) and catalytic ozonation (O3-cat) negatively. 1
steroidal anti-inflammatory drug which is The inhibition of OH has been associated with the
 O R A L P R E S E N TA T I O N S - 1 st D A Y

CATALYTIC OZONATION OF ANALGESIC PHARMACEUTICALS USING COMMERCIAL

Catalytic ozonation of analgesic pharmaceuticals using commercial will be filled
AND Pt-SUPPORTED NANOCOMPOSITES OF Al2O3
and Pt-supported nanocomposites of Al2O3 in by B1-5
EAAOP4
Nilsun H. Ince1, Asu Ziylan-Yavas1
1
Bogazici University, Institute of Environmental Sciences, 34342 Istanbul, Turkey, ince@boun.edu.tr

The presence of pharmaceutical residues in fresh water bodies

O3 O3 is an emerging issue due to their undesirable effects on
Al2O3 aquatic organisms. The present study is about the elimination
Pt-Al2O3 and mineralization of a common anti-inflammatory
pharmaceutical-paracetamol in water by ozonation and
catalytic ozonation using commercial and Pt-supported
alumina that was prepared in the laboratory as a
nanocomposite. The data showed that at neutral pH ozonation
alone was partially effective for the oxidation of the
paracetamol compound, while catalytic ozonation particularly with Pt-
supported alumina rendered not only complete destruction,
HCO3 - but also 33% mineralization in the presence of OH
>90 PCT removal
18% mineralization HA 100% PCT removal
23% mineralization
scavengers. The data also showed that OH radical scavengers
slowed down the decay and mineralization of PCT only
during ozonation alone, but acceleerated them in the presence
100% PCT removal
8-10% mineralization
100% PCT removal
25-35% mineralization of the catalysts, implying the predominance of surface
reactions over OH-mediated oxidation in the bulk liquid.
O3 decomposition, the production of OH radicals
Pharmaceutical compounds are frequently and the effect of solution matrix.
detected in sewage treatment plant effluents,
surface water and groundwater aquifers [1]. The results showed that ozonation alone
Ozonation
Catalytic is aozonation
well-known of process and
phenol in 4-chlorophenol
water providedinappreciable
the presence elimination of PCT
of PRESENCE Will(k=0.42
filled
CATALYTIC OZONATION OF PHENOL AND 4-CHLOROPHENOL IN THE OF
treatment, owing to the high oxidation potential of min-1), but with only 18% C-mineralization. Al2O3
THEthe CeO CeO
O3 that promotes 2
FILM
2 filmAND and suspension
SUSPENSION
oxidation of recalcitrant organics was ineffective in catalyzing the mineralization
in by B1-6
and inactivation1 of pathogens. However, the process, but n-Pt-Al2O3 3 was very effective. EAAOP4
processI.C. Guzmn
has major Poznyak1, C. as
, T. drawbacks Aguilar 2
high, J.stability,
Rodrguez-Santilln 1
, I. Hernndez
Comparison Prez ,activities
of catalytic R. T. Hernndez
in terms Lpez 3
of the
(1) - Escuela Superior de Ingeniera Qumica e Industrias Extractivas IPN, Zacatenco, 07738 Mxico D.F. Mxico
high (2)production
Unidad Profesional cost, Interdisciplinaria
low solubilitydeand high fraction
Biotecnologa of O3 decomposed,
IPN. Ticoman,07340 (3) DivisinOH
the quantity
Mxico, D.F. Mxico. de
selectivity O3. Ae Ingeniera
CienciasofBsicas promising optionAv.toSnimprove
UAM-A, Pablo No 180 formed and %
CP. 02200 Mxico D.F.,mineralization
Mxico showed that
the efficiency of ozonation is the use of a solid maximum O3 decomposition, mineralization and
catalyst to enhance the decomposition and to OH formation were accomplished with nPt-
benefit from the advantages of heterogeneous In the presentalumina,
work, thewhich was alsoofmore
decomposition phenoleffective than ZVI.
and 4-chlorophenol
chemistry. by the catalytic ozonation with the CeO2 suspension and film in
The impact of solution matrix as tested by
comparison with the conventional ozonation was studied. The CeO2
The most effective catalysts in heterogeneous adding humic
film was synthesized using theacid and bicarbonate
technique was such
of ultrasonic spray that
pyrolysis.
ozonation are metal oxides (MnO2, TiO2, The Al2O 3)
comparisonwhile both treatment
of three reagents systems
slowed ofdown the reactions
the phenol and the 4-in
and their metal-supported composites, 1.0
O cat (s) the chlorophenol
activity
3 the absence
(conventional of
andthe catalyst,
catalytic they
ozonation accelerated
in the them
presence of
O cat (f)
of which is based on their potential to accelerate
0.8

in its presence.
both CeO2) observed
3

that theThe results

effect of awere explained
catalyst on the by the
initial
the decomposition of ozone to generate reactive compound decomposition
contributionis not of significant, but the
COmechanism
3 , andof the the
0.6

HA and 2-
A/A0

0.4

radicals [2]. In case of metal-supportedreaction

0.2
metal was dominance
different in theof absence and in the reactions
surface-mediated presence ofover the
oxides, catalytic activity increases via electron catalyst. Probably the formation of OH radicals was carried out with
OH-mediated oxidation.
0.0
0 5 10 15 20

Time, min

transfer from the supporting metal to ozone2. to CeO In particular, the profiles of the intermediates and the oxalic
acid, as the final product, demonstrated the effect of the presence of a
produce ozonide (O3-) and OH. Acknowledgements
catalyst in the system.
The aim of this study was to synthesize a Pt- The research was funded by Bogazici University
supported alumina nanocomposite (n-Pt-Al2O3) to Research Fund through projects 10380 and
1. INTRODUCTION
compare its catalytic activity (in the elimination catalyst is difficult. For this reason, the catalyst in
14Y00P7.
and mineralization of paracetamol (PCT) by film diminished the previous disadvantage. The
Phenolic References
ozonation)compounds
with that ofare common alumina.
commercial pollutantsThein metal oxides (MnO2, TiO2, Al2O3, and CeO2),
wastewater
performanceofofoiltherefinery,
catalyst petrochemical, coke,
was also compared doped metalBenitez,
[1] F. Javier oxidesJ.L.(Pt/Al 2O3,F.J.Co/Al
Acero, Real,2OG.
3,
and
with grease, due, steel
ZVI, which and textile
is commonly industries
used [1].
in catalytic Cu/Al 2 O3 , TiO 2 /Al 2 O3 ), granular
Roldan, Chemosphere,77(1) (2009) 53-59. activated carbon
They can beThe
ozonation. formed indirectly
process during chlorination
was further assessed in or metal
[2] modified zeolites ,areApplied
B. Kasprzyk-Hordern used asCatalysis
catalysts B:
in
of municipal
terms or industrial
of the impact wastewater,
of surface bleaching
reactions, in
the rate of ozonation [5, 6]. The cerium
Environmental, 46(4) (2003) 639-669. oxide (CeO 2)
paper industry, or during bioconversion of low possesses an excellent optical and electrical
molecular weight compounds. Phenol and its properties and high mechanical resistance that
chlorinated derivatives like 4-chlorophenol and
2,4-dichlorophenol are difficult to remove from
82
makes it suitable for catalytic ozonation. CeO2 1
by far the most studied lanthanide oxide. Most of
is
 ROOM B - OZONATION

SEMICONTINUOUS OZONATION OF MUNICIPAL WASTEWATER EFFLUENTS: will be filled

Semicontinuous
IMPORTANCE ozonation
OF THE of municipal wastewater effluents:
WATER MATRIX in by B1-7
importance of the water matrix. EAAOP4
1 2 2 1
M. Marce , B. Domejoud , S. Baig , S. Esplugas . (1) Chem. Eng. Dpt., Uni. of Barcelona, Mart i
Franqus, 1, 08028, Barcelona, Spain. mireiamarceescale@ub.edu (2) Suez environnement, 183,
avenue du 18 juin 1940, 92508, Rueil-Malmaison Cedex, France

Wastewater treatment plants (WWTP) have been

designed to improve the water quality along the
treatment. Among different treatments, the ozone
application has shown enhancements in terms of
water quality and disinfection. Other ozone
application points should be investigated in order to
optimize the technology and improve the results at
the end of the treatment line. According to these
semicontinuos experiments were carried out using
different effluents of the WWTP to analyze the
important of the water matrix.

wastewater reutilization are focused on ozonation

The current needs of our society demand high as a promising treatment process. Ozonation
levels of industrialization and worldwide food processes perform well improving water quality as
supply, causing a negative impact by decreasing observed in its aggregate
IMPACT
Impact
water
OF OZONE
of Ozone
resources.
AND
Theseand
PEROXONE
Peroxone
factors
ADVANCED
along advanced
OXIDATION
with the oxidation processes on parameters
PROCESSES ON THEbefore and
DEGRADATION OF NAPHTHENIC ACIDS afterAND
SPECIES its usage. Nevertheless, additional
DETOXIFICATION OF OIL studies
SANDS
the Degradation
continuous increase of Naphthenic Acidsare
global population Species and to
detoxification of as pre-biological
PROCESS-AFFECTED
placing the natural WATER
water resources under stress.
related ozone application B1-8
Oil Sands Process-affected Water treatment stages should be considered for a better
M. Meshref1,treatment
Wastewater Md. Shahinoor
playsIslam
1
, N. Klamerth
an important
1
, M. Gamal
role in El-Din1 of its effects on water quality as
understanding
(1)University
removing of Alberta, Department
contaminants from theof Civil & Environmental
municipal well asEngineering, Edmonton,
on the existing processCanada, T6G 2W2,
performances.
14122233 Me shr ef OSPW .r aw : 1

meshref@ualberta.ca
wastewater. It is designed to eliminate solids, For
Thethisremoval
study, samples
of Naphthenic of primary Acids,(P)the and
particulate Raw
contaminants, nutrients and dissolved
5.0

OSPW
biological secondary after responsible
sand filtration for the(S)
Raw OSPW
C-NAs (mg/L)

predominant compounds
4.5

biodegradable organic matter [1]. However, theC-NAs S/N-NAs

wastewaters
oil sandsfrom a costal Wastewater Treatment
4.0

process-affected water (OSPW)

Drift time [ms]

oxy-NAs

conventional secondary biological treatment have

3.5

3.0
Planttoxicity,
(WWTP) has been investigated using ozone of
located in the province
14122233 Me shr ef OSPW .r aw : 1

shown unsuccessfully removals of biorefractory

ISTD
14122221 Me shr ef OSPW .r aw : 1

Tarragona (SPAIN).
14122233 Me shr ef OSPW .r aw : 1
2.5

and peroxone processes. A 91 % removal of

14122233 Me shr ef OSPW .r aw : 1

substances [1, 2].

-Z

2.0
14122224 M e s hr e f OSPW .r aw : 1
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
5.0

classical-NAs waswere achieved using at50lab mg/L

5.0

50 mg/L50Omg/L
Raw O
OSPW tR [min]
, 20 mg/L H O
Ozone experiments performed scale
5.0
3 3 2 2
Raw OSPW 5.0
4.5
4.5
Raw OSPW
Regarding this fact, municipal wastewater is the
C-NAs S/N- NAs

of L
utilized O3 dose at a Hfilled
2O2:Owith 3 ratio of 1:2
C-NAs (mg/L)

4.5
S/N-NAs 50 mg/L O
S/N-NAs

in 2.5 semi-batch reactor a working

4.5
4.0
C-NAs
C-NAs oxy- NAs 3
4.0
C-NAs S/N-NAs
4.0
C-NAs S/N-NAs

major source of pharmaceuticals and personal care

[ms][ms]

oxy-NAs
[ms]

compared to an Gas
84%flow removal
rate using 3.
only Oinlet
4.0
oxy-NAs
3.5 oxy-NAs

volume of 2 L[2]. and ozone

time
time[ms]

3.5
oxy-NAs
Drift time

3.5
3.5
Drift
Drifttime

products (PPCP) in the aquatic environment.

3.0
ISTD

The inhibition levelconstant

in acute toxicity
LN/h of
3.0
ISTD ISTD
Drift

3.0

concentration were kept at 60 and

3.0 ISTD
ISTD
14122221
14122221 Me shr ef OSPW Me
.r awshr
: 1ef OSPW .r aw : 1
2.5 14122221 Me shr ef OSPW .r aw : 1

Since it is unworkable to reduce the consumption

2.5
2.5

OSPWduring showed thetreatment

same trend andprimary
the
2.5
-Z

40 mg/L all the for the

2.0
2.0 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
2.0
2.0

of these compounds, OH the improvement of the

4.0 4.5 5.0 5.5t [min]6.0 6.5 7.0 7.5
4.0 4.5 5.05.0 5.5 6.0 6.0 6.5 6.57.0 7.0 7.5

and highest toxicityeffluents.

reduction Experiments
was achieved were in
5.04.0 4.5 5.5 R 7.5
5.0
5.0 t [min]

secondary
50
50 mg/L
50mg/L
mg/LOOO
,,20
20 mg/L
mg/L
, 20 HO
H
mg/L O
tRR[min]
t [min]
33 3 22 22 2
R

50 mg/L O , 20 mg/L H O at H O :O =1:2 2

C-NAs (mg/L)

4.5 3 2 2 2 2 3

wastewater treatment is one of the few options to

4.5
4.5

4.0
4.0
4.0
C-NAs
C-NAs
C-NAs
S/N-NAs
S/N-NAs
S/N-NAs OSPWwithout
performed treated pH withadjustment,
H2O2:O3 ofat1:2. Results
20 C. Ozone
significantly diminish the release of them [3].
Drift time [ms]

oxy-NAs
[ms][ms]

oxy-NAs

obtained from thisbottom

oxy-NAs
workofwill enable withthe a
3.5

gas was injected at the the reactor

3.5
timetime

3.5
DriftDrift

3.0
3.0

evaluation of O and O /H O processes as a

ISTD
ISTD

porous plate and the mechanical mixing ensured

3.0

Chemical oxidation for complete mineralization 3 3 2 2

2.5
2.5
ISTD

the potential treatment processesthe for OSPW.

2.5

of these pollutants is generally expensive because good contact between liquid and gas
2.0
2.0
-Z

4.0
4.0 4.5
4.5 5.0
5.0 5.5
5.5 6.0
6.0 6.5
6.5 7.0
7.0 7.5
7.5

2.0 tRtR[min]
[min]

phases.
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

the oxidation intermediates formed during the

tR [min]

The Canadian
treatment tendoils to sands
be morein northern
resistantAlberta to theirare treatment. Thus relatively high costs of potential
Different aggregate parameters have been
the complete
third largest
chemicaloil deposits
degradation worldwide and the
and furthermore, powerfulsuch
analyzed treatments may limitOxygen
as Chemical their applications
Demand in
they all consume
subsequent extractionenergy and chemical
of bitumen producereagents large large-scale treatments. The
(COD), Dissolved Organic Carbon (DOC), main objective of this
which of
amounts increase
oil sands the treatment
process line[4].
affected For waterthese study wasabsorbance
Turbidity, to investigate,at 254 fornmthe(UV254), first time
reason, new
(OSPW). Theapplications
industry and is management
following aof these self- accordingCarbon
Inorganic to our(IC)knowledge,
and total solids the impact(TS). of
advanced oxidation
implemented zero discharge processespractice.
should beThus studied. huge peroxonethese
Indeed, (O3/Hparameters
2O2) AOP on the speciation
provided useful of
9
amounts m3) ofstudies
(10published
Recent OSPW are continuously
concerning water and NAs (classical
information and oxy-NAs
regarding distribution)
the degrees and the
of oxidation,
stored in tailings pond while there is a growing overall toxicity of OSPW, towards Vibrio fischeri
need to develop methods to treat OSPW to be
released safely back into the environment.
83 at various utilized ozone doses. The study explores
1
the relative efficiency of O3, O3/H2O2 AOPs on the
 O R A L P R E S E N TA T I O N S - 1 st D A Y

INFLUENCE OF OZONATION AND BIODEGRADATION ON THE INDUSTRIAL TEXTILE

Influence of Ozonation and Biodegradation on the Industrial Textile will be filled
WASTEWATER TOXICITY in by B1-9
Wastewater Toxicity
EAAOP4
K. Padzior1, J. Wrbiak1, A. Klepacz-Smka1, L. Biliska1, M. Gmurek1, S. Ledakowicz1.
(1) Lodz University of Technology, Faculty of Process and Environmental Engineering, ul. Wlczaska 213,
90-924 d, Poland, katarzyna.pazdzior@p.lodz.pl.
The textile wastewater contains wide spectrum of chemicals.
Estimation of their influence on the aquatic systems is a very
important issue.
In this work the acute toxicity assessments of the textile
wastewater before and after: chemical, biological as well as two
stages combined chemical-biological treatment were done. The
Microtox toxicity assay was used.
Untreated wastewater have the highest toxicity (EC50 value in the
range: 3 - 6 %). Ozonation caused from 2 to 2.5 times reduction of
the toxicity. Biodegradation in batch reactors resulted in reduction
of the toxicity in the range from 3.3 to 3.7 times. However, there
was no synergistic effect combined chemical-biological
treatment resulted in only 4.2 - 6 times reduction of the toxicity.

Background Materials and methods

The textile industry is a very water consuming The real industrial textile wastewater has been
branch. It generates huge amounts of wastewater used. The concentrated effluent stream containing
loaded by wide spectrum of both organic and baths from washing with bleaching, dyeing and
inorganicREMOVAL
COLOR compounds [1]. FROM The BIOLOGICALLY
most characteristicsTREATED first rinse after dyeing
TEXTILE WASTEWATER was used. AND They
COST are
Colorforremoval
aspects
ANALYSIS from biologically
this wastewater treated textile
are time variability, wastewater
characterized by and cost
higher amounts of both organic B1-10
analysis
basic pH, high colour, low BOD5/COD ratio and and inorganic pollutants than the other baths
significant
M. I. Aydinsalinity
1 [2].1, A
, B. Yuzer lot of dyes
B. Yurdakul 2 used in
, A. Ongen 1 the
, H. Selcuk1(mostly rinses).
. (1) Istanbul The experiments
University, were carried out
Faculty of Engineering,
textile wastewater
Department are xenobiotic
of Environmental substances.
Engineering, TheyIstanbul,
Avcilar, forTrkiye.
the same tape of effluents (2)
iberia@istanbul.edu.tr collected in Winter
Sun Tekstil A..
canTorbali/
be toxicIzmir,orTrkiye.
can be degraded to toxic and (I - 22.03.15) and in Spring (II - 14.05.15).
mutagenic
4000 compounds [3]. Ozonation was carried out in a semi-bath mode
The textile industry is known to be one of the most complicated
Although,
3500 many papersT=0 concerning chemical and (heterogeneous gasliquid system). Set-up was
T=5 min industry among manufacturing industries. As a result of toxic
biological treatment of the textile wastewater are previously described by Biliska and coworkers
3000 T=10 min chemicals that are used in textile processes, textile wastewaters
available in the literatureT=20 [2-9],
min there is still not [5]. Two ozone doses were applied: 0.42 for I and
may be toxic even after biological -3 treatment. Textile effluents are
enough2500investigations targeted to environmental for II. For ofboth
1.68 gO3by dmthe BOD,effluents the
Color, PtCo

generally characterized parameters COD, pH,

impact of the treated wastewater [3, 10]. ozonation treatment were carried out without
2000 suspended solids and color. Except color other parameters can be
changing ofbiological
reduced by conventional pH. activated sludge treatment
1500
Objectives
methods to meet The discharge
biodegradation limits.experiments
In this work different
were conducted
1000
The aim of this study was to determine commercial
the decolorants
in two singleand ozonation processinwere
SBR reactors used together
parallel. A very
influence
500 of the chemical, biological as forwell
the decolorization
as of biologically
similar equipment treated
was used textile experiments
in earlier wastewater
two stages
0 combined (BTTWW). Cost
chemical-biological analysisbywas
described made by
Pazdzior using
et al. [8].operational unit
However, there
treatment 0on the 100 environmental
200 300 400 impact 500 ofdecolorant
the high- and are ozonesomecostsignificant
at optimumdifferences.
decolorant Thedosages.
SBR had a
loaded effluentsConcentration, mg/L
from the dyeing factory. As a working volume of 1.5 dm3. Experiments were
chemical treatment ozonation has been selected. carried out at the 30C. All bioreactors were
Bilogical
Since dyestreatment was carried
are developed out in
to resist the batch
degradation, inoculatedsludge
volume by the activated
is usually sludge taken from
produced the
during
reactors. In combined
thus some non-biodegradable dyes may possesschemical-biological textile wastewater treatment plant.
operation. The high cost of sludge disposal is a The SBR
treatment,
toxic, mutagenic firstand wascarcinogenicozonation while
characteristics reactors
main were working
drawback in the 12
of conventional hourcoagulation
metal cycle (30
biodegradation
[1]. Therefore, was a second
a proper stage.isFurthermore,
treatment required to min. sedimentation,
processes. 38 min. have
Synthetic polymers drawing, 72 used
long been min.
to
meetexamine the progress
the pollution of degradation,
control requirements. organic
Otherwise, filling,
as primaryalmost 11 h mixing
coagulants and 8 h aeration)
or flocculants with
aids in textile
carbon compounds
the presence contentdyes
of residual (BOD in5,the
COD, TOC),
secondary HRT 48 h. treatment.
wastewater One bioreactor treated with
Compared raw textile
metal
colour
treated and toxicity
textile towards Vibrio
wastewater reduces fisheri have
sunlight wastewater, the
coagulants, thesuperior
secondperformance
one wastewater after
of synthetic
been done. and depletion of the dissolved oxygen
penetration ozonation.is their wider working pH range and the
coagulant
in aquatic environment. Due to their toxic non- lower dosage requirement for the equivalent
biodegradable properties, dyes can also contribute removal efficiency. However, its high cost limits its
to the failure of biological processes in wastewater
treatment plants. Protection of human health and
84 application in wastewater treatment. The
ecotoxicological and hazardous nature of synthetic
1
 ROOM B - OZONATION
Occurrence and removal of specific pollutants in treated will be filled
in by
denim andAND
OCCURRENCE cotton-polyster
REMOVAL OF textile wastewaters
SPECIFIC POLLUTANTS byINmeans
TREATEDof DENIM AND
EAAOP4
ozone oxidationTEXTILE WASTEWATERS BY MEANS OF OZONE OXIDATION
COTTON-POLYSTER B1-11
E. Bahadr1, S.Meric2*. (1) Namk Kemal University, NABLTEM, Tekirda, Turkey; (2) Department of
Environmental Engineering, orlu Engineering Faculty, Namk Kemal University, orlu 59860- Tekirda,
TURKEY Most of the dye molecules have polyaromatic structure with
high molecular weight and contain atoms of nitrogen, sulfur and
metals, therefore it is very difficult to break them down by any
biological methods. In order to overcome these problems
advanced oxidation processes (AOPs) have been attempted to
generate hydroxyl free radicals. This study investigates the
effectiveness of ozone oxidation on removal of COD, color and
specific pollutants in biologically treated effluents from two
textile industries. Samples from prior and post ozonation were
submitted to toxicity test using Daphnia magna. ozonation was
found to be effective to remove COD and color to comply with
discharge standards however higher doses are required to
remove emerging pollutants in textile effluents.

Keywords: Textile wastewater, Ozone oxidation, Specific

pollutants, Color and COD removal, Ecotoxicity, Intermediates

Textile industries are intensive water consuming Chemical and biological treated samples were
and concentrated with various pollutants. The high collected fro two textile industries located in orlu-
concentration of dyes cause substantial treatment erkezky area (Tekirda, Turkey). In the cotton
problems [1]. Most of the dye molecules have and polyester fabrics are dyed using reactive dyes.
polyaromatic structure with high molecular weight Two hundred and fifty employees work in this
PERFORMANCE
and contain atoms EVALUATION
of nitrogen, sulfur OFandNITROGEN
metals,ozonationOXIDES
industry. OZONATION IN FLUEwill GASES
Performance evaluation of nitrogen oxides in Total process
flue gases fromwastewater orginated
be filledfrom
FROM
thereforePHOSPHATE ROCK
it is very difficult DIGESTION
to break them down PROCESS-PILOT
by the industrySCALE is around TRIALS 1500 m3/day. Raw in by and B1-12
phosphate rock digestion process pilot scale trials
any biological method and they cannot be treated biologically treated wastewater samples collected
EAAOP4
efficiently
K. Skalska1, S.by an activated
Ledakowicz 1
, R. Louwesludge
2
or some
, R. Szymczak 2
twoof Process
. (1) Faculty times to andcharacterize
Environmentalthem. The samples
Engineering,
combination
Lodz Universityof biological,Wlczaska
of Technology, chemical 213, 90-924, d, delivered
or physical to the laboratory cooled
Poland, kinga.skalska@p.lodz.pl. and kept at 4 0C
(2) Yara
methods [2-3].
Technology In order 67,to3936
Centre, Hydrovegen overcome
Porsgrunn, Norway. during experimental study without adding any
these
problems advanced oxidation processes (AOPs) chemicals. Chemical analyses were performed
have been attempted to generate hydroxyl free Fluewithin 1 dayphosphate
gases from and while rocktoxicity
digestion analyses
containafter
radicals by different techniques and to react with nitrogen ozonation experiments
oxides NOx, H2were conducted
O vapour, in 30 min
hydrogen
recalcitrants present in raw or treated textile fluoride after (HF)
aeration
and the samples.
silicon tetra-fluoride (SiF4). The
wastewaters. Among AOPs which proved 90% of present Ozone
paperwas supplied
describes bothbylaban scale
air-ozone
resultsgenerator
and
the chemical oxygen demand (COD) reduction, pilot(LAB2B Degremont
scale results for NOTechnologies-Triogen
x ozonation of simulated model
ozone (O3) oxidation has been preferable since it and with a maksimum
real flue gases. First 4 g/h capacity)
of all and transfered
the usefulness of
can react with several classes of compounds this through method for a closed cylindrical
NOx removal pyrex glassThe
was determined. reactor
through direct or indirect reactions (mainly, OH required with a molar
diameterratioof 40 Omm 3/NOandx height
togetherof 1100
withmm.
radical) [4]. A tubular
residence timecylindrical porous diffuser
and the influence of waterwas replaced
vapour
Various biotests including Daphnia magna have wereatassessed. the bottom of the reactor to transfer input O3 gas
been evaluated as a good organisms to test effluent It was intoconfirmed
aqueous solution.
for the firstTeflon
timetubing line was used
that ozonation
toxicity in textile wastewater [5, 6] and dyes [3,7- of flue fort he connection
gases between rock
from phosphate generator and the
digestion
9]. reactor.
process is a Two
viableappropriate
solution for O3NOconcentrations
x removal. (4,8 and
The main objective of this study is to investigates 10.8 mg/L.min) were adjusted by changing the
the effectiveness of ozone oxidation on removal of electrical
In the finalcurrent
series of of experiments
the ozone performed
generator. onAll
COD, are
There color
twoand specific
ways pollutants
of producing NPK in biologically
fertilizers real flue gases containing high amountstemperature
experiments were performed at room of water
treated
based effluents from
of phosphate two textile
rock digestion. Oneindustries.
of the (25 oC)
vapour andand at original dust
post-digestion pH fromof wastewater. After
the pilot plant
Samples
methods of from prior rock
phosphate and post ozonation
digestion is the were
process also theozonation,
efficiencythe ofsamples were aerated
the ozonation for 5 min
process was to
submitted
where to toxicity test
concentrated using acid
nitric Daphniais magna remove possible
used.for evaluated. Graphical residual O3. The
illustration O3 concentrations
presents results of
safe guard of the
Unfortunately, thistreated samples.generates NOx
technology in input
these seriesandof off-gas
experimentswere destroyed
with the by sametwo
emission, which have to be removed from flue residence time but increasing O3/NO2 ratio (0.44,of
sequential washing bottles containing 250 mL
gases before their introduction into the 0.64, 0.95). It is clear that NO2 removal efficiency
atmosphere. Thus, there is a need for rises with the increasing O3/NO2 ratio from 40.4 to 1
environmentally friendly and cost effective
85
97 %.
methods for NOx removal from flue gases. The
application of pre-ozonation was proposed as the In order to analyze the ozonation process in wider
possible solution to NO emission problem in range of O3/NO2 ratio (0.2-1) additional two series
 O R A L P R E S E N TA T I O N S - 1 st D A Y

URBAN WASTEWATER
URBAN WASTEWATER ORGANIC
ORGANIC MATTER
MATTER AND
AND MICROPOLLUTANTS will beBY
REMOVAL filled
in by
MICROPOLLUTANTS REMOVAL BY CATALYTIC
CATALYTIC OZONATION B1-13
EAAOP4
OZONATION
C. Crousier1, J.-S. Pic1, J. Albet2,3., S.Baig4, M.Roustan1 (1) Universit de Toulouse LISBP (UMR INSA/CNRS
5504 & INRA 792) INSA 135 avenue de Rangueil, 31077 Toulouse Cedex 4, France, crousier@insa-toulouse.fr,
(2) Universit de Toulouse, INPT-ENSIACET, LCA (Laboratoire de Chimie Agro-industrielle), F-31030 Toulouse,
France, (3) INRA, UMR 1010 CAI, F-31030 Toulouse, France, (4) Suez Environnement, Treatment solutions,
Scientific Department - Degrmont, 183 avenue du 18 juin 1940, 92508 Rueil-Malmaison cedex, France
Catalytic ozonation appears to be an interesting advanced
oxidation process for degrading organic micropollutants and
recalcitrant organic matter during urban wastewaters tertiary
treatment. Therefore, the present work deals with organic
matter mineralization efficiency using the TOCCATA
catalytic process. Experiments were carried out to understand
the kinetics and mechanisms that are involved in this process
by comparing it to single ozonation and single adsorption. A
focus on adsorption was particularly made on adsorption to
determine kinetics in relation to the global catalytic rate
during organic carbon removal. Further analyses are to be
made for micropollutants and adsorption isotherms, in order
to model and predict the process behaviour as a wastewater
tertiary treatment.
Figure 1. Experimental Setup

Background and objectives Methods and procedures:

Conventional wastewater treatment plants
TiO2 BASED MATERIALS APPLIED TO THE PHOTO-CATALTYIC OZONATION OF
(WWTPs) processes
TiO2 Based are not Applied
Materials successfultointhe
reducing Methods:
Photocataltyic Ozonation of will be filled
METOLACHLOR
numerous mineral and organic pollutants [1]. Wastewater effluents were collected at the in outlet
by B1-14
Metolachlor
Indeed, single ozonation is a usual and efficient of a biological treatment plant. TOCCATA EAAOP4
oxidation process
C. A. Orge, J. L.but remains
Faria, selective
M. F. and creates
R. Pereira. Laboratrio catalyst
AssociadoisLSRE-LCM,
a solid under granular deshape
Departamento with a
Engenharia
Qumica,by-products
undesired Faculdade dewithEngenharia
organicda Universidade
matter [2]. do Porto,
mediumRua Dr.
sizeRoberto
of some Frias,
mm.4200-465 Porto, Portugal,
carlaorge@fe.up.pt
Therefore, advanced oxidation processes such as The experimental setup (Figure 1) consisted in two
catalytic ozonation appear to be an interesting The main semi-batch
goal of thiscolumn
work isreactors,
to studyone the empty
photocatalytic
and one
solution as a tertiary treatment for organic ozonation packed
of metolachlor
with 50 cm(MTLC)
of catalystin onthe a presence of
support grid.
micropollutants and refractory organic matter. commercial titanium dioxide (P25) and a composite
The work was carried out with a total liquid of P25
Ozone decomposition creates radical speciesand thatmulti-walled carbon
recirculation nanotubes
through a 1 L(P25/MWCNT).
buffer tank and Non- with a
have a stronger oxidation potential and increase catalytic co-current
combined upflow methodof (O 3+Light),oxygen
ozonized as wellgas andas
the reactivity with organic matter [3]. individual The methods
liquid were also carried out. With the
solution.
TOCCATA catalytic process involves a exception solid of photolysis,
Carbon dioxideMTLC was completely
produced converted
during oxidation was
catalyst that enhances ozonation efficiency [4]. after 30 min of reaction by all tested processes.
trapped with a sodium hydroxide solution The rate ofas
Therefore, the present work investigates organic conversionInorganic
increasedCarbon
when (IC)
the atcomposite
the gaseous wasoutput
testedof as
the
matter and micropollutants mineralization catalyst in the presence of O and light. The
reactor. Residual ozone in the off-gas was then
3 advantage of
enhancement using the TOCCATA catalytic using (photo)catalysts
degraded by is more obvious
a thermal destructorin terms
and the of off-gas
TOC
process with ozone. It aims first to compare single removal, with
flowhigh mineralization
released degrees achieved after 1
to the atmosphere.
ozonation, single at 1adsorption
%TOC removal h of reaction h of reaction
and catalytic GaseousduringO3photocatalytic
concentrations ozonation, especially
were continuously
ozonation efficiency towards global organic matter with P25/MWCNT
analysed composite.
at the inlet and the outlet of the column.
removal. A global understanding of which Dissolved ozone was measured at the top of the
mechanisms are involved in catalytic ozonation catalytic bed. Samples for dissolved organic and
will enable experimental optimization for modified carbon
inorganic by the(DOCaddition
/ DIC), of chemical
catalystsoxygen
and/or
Introduction irradiation to improve the efficiency. Generally,
wastewater pollution degradation. demand (COD), UV absorbance, conductivity anda
TheMetolachlor
work will(MTLC)then focusis a onchloroacetanilide
the specific combination
pH of several
were regularly methodsMicropollutants
collected. improves the
elimination of selected
selective herbicide micropollutants.
extensively used asThis an removalwere
samples of analysed
pollutants
usingfrom the wastewater
LC-MS-MS method.
particular study
emulsifiable is still in progress.
concentrate in various cultures. This compared with the individual treatments.
herbicide and its metabolites are suspected or Irradiation of O3 in aqueous solutions by UV light
confirmed carcinogens. Of the acetanilide produces additional HO radicals, and
herbicides, metolachlor is referenced to be the consequently, the efficiency of contaminants
removal should increase.
most persistent [1] and has the potential to leach to
1
ground water because of its relatively high water
solubility (530 mg/L at 20 C) and mobility from
86
The present study aims to describe
photocatalytic ozonation as a promising alternative
for MTLC degradation. In order to better
 ROOM B - OZONATION

OPTIMIZATION OF COUPLED ADVANCED OXIDATION PROCESSES AND ACTIVATED

Optimization
CARBONS FORofPURIFICATION
coupled advanced
OF oxidation
SALT WATERprocesses and activated B1-15
carbons for purification of salt water
F. Parrino1, S. Cataldo2, A. Iann1, V. Loddo1, E. Mirenda2, L. Palmisano1, D. Piazzese2.
(1) Dipartimento di Energia, Ingegneria dellInformazione e Modelli Matematici (DEIM), Universit di
Palermo,viale delle Scienze, Ed. 6, 90128 Palermo, Italy.
(2) Dipartimento di Fisica e Chimica, Universit di Palermo, viale delle Scienze, Ed. 17, 90128 Palermo, Italy.
francesco.parrino@unipa.it
C
B
O2+He Photocatalysis, ozonation and activated carbons were
A investigated separately and in combination as tools for the
I purification of polluted salt water. Coupling different processes
He
D
O2+O3+He
enables to overcome many drawbacks related to the use of the
single technologies and at the same time to exploit possible
O2

H
synergistic effects. In this work a kinetic analysis was
performed for modelling the degradation of 4-nitrophenol
G
(4NP) as a probe pollutant molecule in synthetic seawater.
E Thus, the optimum synergistic conditions of the three processes
F
acting together were determined and discussed.

of the effluent. For these reasons, in this work it is

One of the main source of marine degradation is
represented by the disposal at sea of oily waste
water. This is primarily generated by the washing
operations of the ships fuel tanks containing
petroleum products (slops) and by bilge water
which originates from seawater infiltration and
leakage of engine oil and fuel. The discharge into
the marine environment of oily wastewater is an
issue of considerable technical and scientific
interest, in relation to the toxic effects that such
substances may have on the environment and
human health.
For these reasons, the International Maritime
Organization (IMO) has enacted MARPOL 73/78
convention in which effluents from ships are now
limited to a maximum oil content of 15 ppm [1].
This type of wastewater shows high variability in
the composition, depending on the type of
petroleum products transported, and contains large
amounts of organic contaminants, mainly
aliphatic, alicyclic and aromatic hydrocarbons.
Furthermore, as the washing operations of ships
fuel tanks are performed through the use of sea
water pumped at high pressures, the wastewater
shows high levels of salinity and relevant amounts
of other pollutants, including emulsifiers,
corrosion inhibitors, heavy metals and other
inorganic compounds (e.g. halides, sulphates,
phosphates, sulfides) [2], present both in solution
and in the suspended solid phase.
Several technologies have been proposed for
facing this problem. Nevertheless the degradation
efficiency is strongly affected by the high salinity
proposed an integrated treatment system, obtained
by combining ozonation, photocatalysis and
granular activated carbon (GAC) adsorption and
the optimum working conditions have been
investigated.
The bench-scale experimental setup is
schematically depicted in the Graphical
Illustration. A simulated seawater solution of 4NP
is moved by the pump (F) from the tank (E) to the
photocatalytic fixed bed reactor (G). The
photoactive bed, made of TiO2-covered Pyrex
spheres, is both internally and externally irradiated
through a 125W medium pressure Hg-lamp
(power supplied by (A)) and through 6 fluorescent
tubes (8W each), respectively. The effluent exiting
the photocatalytic reactor splits through the valve
(I) flowing partially through the activated carbons
bed (H) being the rest recycled into (E). The ozone
produced by means of the ozonator (C) bubbles
into the tank (E). The ozone concentration and its
mass flow values are monitored by means of a
spectrophotometer (D) and a mass flow controller
(A), respectively.
GAC adsorption is particularly useful as it
allows separation of big amount of pollutant and it
is quite easy to scale up. In this work GAC were
previously employed alone for purification of
simulated seawater in the presence of 4NP as the
probe pollutant and the equilibrium parameters
were determined and reported in Table 1.

87 1
 O R A L P R E S E N TA T I O N S - 1 st D A Y

DEGRADATION OF NAPROXEN IN AQUEOUS SOLUTION BY H2-2O2, S2O82- AND COMBINED

HDegradation of Naproxen
O /S O 2- ACTIVATED
2 2 2 8
WITH
2-
in CITRIC
AqueousACID
Solution by H2O2Fe
CHELATED , S2+2O8 and
2+
C1-1
Combined H2O2/S2O8 Activated with Citric Acid Chelated Fe
N. Dulova1, I. Epold1, M. Trapido1. (1) Tallinn University of Technology, Ehitajate tee 5, Tallinn, Estonia,
niina.dulova@ttu.ee.

The efficacies of Fe2+-citric acid (CA)-activated hydrogen

peroxide, persulfate and combined hydrogen peroxide/persulfate
systems for degrading naproxen (NPX) in aqueous solutions
were investigated and compared. Among the studied processes,
the Fenton system showed the highest performance both in NPX
degradation and mineralization, followed by the combined
H2O2/S2O82-/Fe2+ process. The addition of CA substantially
accelerated the degradation of NPX by the S2O82-/Fe2+ and
H2O2/S2O82-/Fe2+ processes. The studied technologies proved
promising techniques for in situ treatment of groundwater
containing NPX, with a particularly high potential for the Fe2+-
CA-activated persulfate and hydrogen peroxide/persulfate
systems.

Naproxen (NPX) is a non-steroidal anti- Thus, 42 and ~58% of NPX was removed during
inammatory drug (NSAID) with analgesic and the first minute and the rest of the 2-h oxidation,
antipyretic properties, widely used for the respectively, in the S2O82-/Fe2+ system at a
treatment of rheumatoid arthritis and in the NPX/S2O82-/Fe2+ m/m/m of 1/10/1 (pH 3). In the
veterinary medicine. Similarly to other NSAIDs, case of combined H2O2/S2O82-/Fe2+ system, 55 and
NPX has been detected in different environments ~45% of NPX was removed during the first
OXIDATIONOxidation
at concentrations of priority
OF ranging
PRIORITY fromAND and
ng Lemerging
to g Lpollutants
EMERGING
-1
minutewith
-1 POLLUTANTS
. andpersulfate
WITH
the rest of the 2-hwill
PERSULFATE be
oxidation,
ACTIVATED activated
BY by
IRON. Iron.
EFFECT
Therefore, developing effective remediationEffect OF of iron
IRON valence
VALENCE and particle
AND size
PARTICLE SIZE
respectively, at a NPX/H2O2/S2O8 /Fe m/m/m of 2- filled
2+ in by
C1-2
technology for elimination of NSAIDs, including 1/10/10/1 (pH 3). Notably, the efficacy EAAOP4 of NPX
NPX, from groundwater
S. Rodriguez, A. Santos, and is A.ofRomero
great scientific and degradation was found to decrease gradually with
Complutense
public interest.University
In situ of Madrid, oxidation
chemical Madrid, Spain. (ISCO)srvega@quim.ucm.es
the increase in the initial pH value in all the
is mainly based on the generation of highly studied systems. The activation of H2O2, S2O82-,
-
reactive hydroxyl (HO ) and sulfate (SO4 ) and combined H2O2/S2O82- systems by CA-
radicals arising from the activated, mainly
Persulfate (PS) activated with iron to generate sulfate by iron chelated
radicalsFe2+is was studied atoxidation
a promising pH values 3, 5, 7, and
technology
2+
inand
its ferrous form, decomposition of oxidants such 9. The addition of CA
it was employed in the oxidation of Diuron (selected as an example of priority pollutant), Caffeine at a Fe /CA m/m of 1/1
asand
hydrogen
Ibuprofen peroxide and persulfate.
(examples of emerging the presentwhoseproved
In pollutants effective
consumption to accelerate The
is widespread). the effect
degradation
of iron of
2- 2+ 2- 2+
study, the use of citric acid
valence (0, 2 and 3) and particle (CA)-chelated ferrous NPX in the S O /Fe and H O /S O /Fe
2- size of Zero-Valent Iron (ZVI) was studied in a batch isothermal
2 8 2 2 2 8
ion as an at
reactor activator for H2O2, S2O8 and combined systems at the studied pH values For the Fenton
2-20C. The efficiency of the process was evaluated in terms of pollutant and TOC removal, as
2O2/Sas
Hwell 2O8oxidant
oxidation of NPX
and iron was investigated.
consumption. process, standard
Moreover Microtox the positive procedure effectwas of employed
the chelated in
Additionally, transformation
ecotoxicity measurements. products were activator application on NPX removal was
identified by LC-MS analysis in all studied observed at pH 5, 7 and 9. In the studied
When Fe2+ was employed as PS activator, an undesired
systems. reaction
processes, the consumed
mineralization both Fe was2+
and
considerably .
2+2+
However,
Firstly, the in case of ZVI,
efficacy of the release of FeFe
non-chelated to to
the media
less occurs
effective at the
thanparticles surface through
NPX removal. Irrespective acid of
corrosion
activate H2Oand O82-, andwith
2, S2reaction PS. This
combined O2/S2Oa82-controlled
H2allows production
the activator used,rate of
the performance throughof thea studied
slow
2+
release
was of FeThebyFenton
studied. selecting the proper
process particle size,
demonstrated a which helpsinminimizing
processes this undesirable
NPX mineralization was as reaction
follows:
increasing
high oxidationthe efficiency
efficacy, of the
resulting oxidant. Better
in complete NPX results were obtained
the activated H2O2 > with ZVI thanH2with
the activated O2/S2Fe O82+ 2-
>
3+ 2+2+ 2-
especially
removal when
in less regeneration
than 1 h at a NPX/H of Fe2O2to /FeFe molarthrough oxidation intermediates
the activated S2O8 . did not occur.
ratio of 1/10/1 (pH 3). In the case of the S2O82- To sum up, the findings in this study strongly
A 2+kinetic
/Fe and model
combined capable
H2Oof describing
2- 2+ the evolution of pollutant, oxidant, and iron concentrations
suggested that Fe2+-CA-activated persulfate(atand
2/S2O8 /Fe system, a
the different oxidation stages)
fast decomposition of NPX and oxidant was as well as the mineralization was proposed and validated.
combined hydrogen peroxide/persulfate oxidation
observed during the first minute and then the could be a promising technology for groundwater
target compound along with oxidant was gradually remediation contaminated by the NPX.
degraded within the remaining reaction time.
Acknowledgements When ZVI is employed, the production rate of
Oxidation
The of Diuron
financial support (D),
provided Caffeine (C)
by institutional andfunding IUT (1-7) of the Estonian Ministry of Education and
research can be controlled by changing the particle
Ibuprofen (I), was
Research is gratefully performed by persulfate
acknowledged. size, since this can modulate the release of Fe2+ to
activated with iron, in order to evaluate the
influence of iron valence (Fe2+, Fe3+, ZVI) and
particle size on the effectiveness of the process, at
88
the media because reaction takes place at the ZVI
surface. 1
 R O O M C - C A TA L Y T I C R E D OX P R O C E S S E S

HIERARCHICALLY-STRUCTURED CuBi O COMPOSITE FOR SULFANILAMIDE

2 4 will be filled
Hierarchically-Structured CuBi2O4 Composite for Sulfanilamide
REMOVAL VIA PEROXYMONOSULFATE ACTIVATION in by C1-3
Removal via Peroxymonosulfate Activation
EAAOP4
W.D. Oh1, T.T. Lim1,2, Z.L. Dong1,3.
(1) Nanyang Environment and Water Research Institute (NEWRI), Interdisciplinary Graduate School, Nanyang
Technological University, 1 Cleantech Loop, CleanTech One Singapore, 637141, Singapore,
woh001@e.ntu.edu.sg.
(2) Division of Environmental and Water Resources Engineering, School of Civil and Environmental Engineering,
Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore.
(3) School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue,
Singapore 639798, Singapore.
A facile hydrothermal synthesis protocol was employed to prepare
hierarchically-structured CuBi2O4 composite by controlling the (i)
ratios of Cu2+:Bi3+:Co2+, and (ii) amount of ethylene glycol. The
composite was employed to generate sulfate radicals from
peroxymonosulfate (PMS) activation for sulfanilamide (SA)
removal. The influence of different pHs, catalyst loadings and
PMS dosages was studied. Investigation of the dominant radical
revealed that sulfate radical was responsible for the degradation of
SA. Indirect technique based on the reaction rate was successfully
employed to quantify the concentration of sulfate radical at various
conditions. The catalyst can be reused multiple times without
severe deterioration to its performance.

reactive radical was identified and quantification

Water pollution
MAGNETIC due to pharmaceuticals
CORE-SHELL MnO2 NANOCATALYSTS is of the FOR AQUEOUS
concentration ofORGANIC
radical was
Magnetic becoming
Core-Shell a MnO 2 Nanocatalysts
to their for Aqueous Organic willconducted
be filled
increasingly
DEGRADATION IN ADVANCED concern due
OXIDATION PROCESSES
using indirect technique based on the reactioninrate. by C1-4
Degradation
adverse effect to in Advanced
human health Oxidation
and aquaticProcesses
life.
EAAOP4
One particular class of the pharmaceuticals, i.e. The FESEM characterization revealed that the
Shaobin Wang, Yuxian Wang, Hongqi Sun, Ha Ming Ang, Moses O. Tad, Department of Chemical Engineering
sulfonyl drugs, are antibiotics that are difficult to Co-EG has sphere-like hollow core morphology.
and CRC for Contamination Assessment and Remediation of the Environment (CRC CARE), Curtin University,
be degraded and thus, pollution due to these The catalytic performance increases at higher pH,
GPO Box U1987
compounds could ,Perth,
resultWA in 6845, theAustralia,
emergenceshaobin.wang@curtin.edu.au.
of catalyst loading and PMS dosage. Radical
antibiotic resistance bacteria. Sulfate Magnetic quenching
radical-based core/shellstudy MnOgave2 nanoparticles
evidence that including
the main
1.0
advanced oxidation process is increasingly gaining Fe3O4/C/Mn and radical
reactive ZnFe2responsible
O4/Mn were for synthesized
the degradation andof
Phenol Degradation (C/C0)

attention
0.8 as an efficient and effective technology demonstrated
SA to wasbe highly effective
the sulfate in peroxymonosulfate
radicals at all pH. The
for organic pollutant abatement. Sulfate radical (PMS) activation to generate
contribution sulfate
of hydroxyl radicals
radical wasforfound
catalytic
to be
can 0.6
be generated from Mn/N MCS+PMS
2
the heterogeneous
Mn/Air MCS+PMS
oxidation
transition of a typical
negligible. For organic
the firstpollutant
time, the of phenol.
concentration Theof
metal activation ofCommercial Activated MnO +PMS
peroxymonosulfate2 (PMS) catalysts
for can be easily
sulfate separated
radical in thefromreaction
the aqueous solutions
system was
0.4 Commercial Fe O +PMS
the treatment of sulfonyl drugs. 3 4
by an external magneticquantified
successfully field. Theusing
generation and evolution
an indirect technique
0.2
of sulfate based
radicalsonandthephenol oxidation
reaction rate. were
The studied usingof
production
The objectives of this study are to (i) prepare both competitive radicalattests
sulfate radical and pHs
various electron paramagnetic
was compared. The
characterize a novel CuBi2O4 composite resonance
and 0.0 with (EPR). This
Co-EG can study provided
be reused a feasible
multiple timesapproach
without
0 20 40 60 80 100 120 140
hierarchical architecture, (ii) investigate forthe 160 180
removal of organic
severe pollutants by
deterioration to magnetically
its catalyticseparable
activity
performance of Time the(min)as-prepared CuBi catalysts.
2O4 indicating that it is stable.
composites for sulfanilamide (SA) removal via
PMS activation and (iii) identify and quantify the In summary, the CuBi2O4 composite was
synthesized via a modifiedusing hydrothermal method
Background
dominant generated reactive radical. successfully-prepared
and calcined in air or N
a facile hydrothermal
2. MCS supported
synthesis protocol to activate PMS for SA
Due
The to the2Otoxicity
CuBi 4 composite and (Co-EG)
resistancewas to prepared
natural manganese
degradation.catalysts
The effects wereofprepared by redox
several operational
degradation,
by using a facileorganic contaminants
one-step such
hydrothermal as phenol
protocol reaction with KMnO 4, which were labelled as
parameters, namely pH, catalyst loading and PMS
and chlorophenols
by controlling of Cu2+
in water
the ratio :Bi3+long
have :Co2+ been
and thea Mn/Air-MCS
dosage on SA Mn/N2-MCS,
anddegradation wererespectively.
investigated. For
serious
amountissue to the environment
of ethylene glycol. Theeven at a low level.
characteristics of
ZnFe2O4 nanoparticles were synthesized
the first time, sulfate radical was via a
successfully
Advanced
Co-EG were oxidation
examinedprocessesusing FESEM, (AOPs) XRDhave and
modified
quantifiedhydrothermal
using an indirectmethod and
approach then
basedloaded
on the
demonstrated to be effective for complete removal
porosimetry. The performance of Co-EG for SA
with MnO
reaction 2 using KMnO4 and HCl reacted at
rate.
ofremoval
organicsviain PMS wastewater,activation and become
in waterhighly was
different temperatures, which were labelled as
favorable
investigated overinothera batchphysical processesThe
experiment. suchmainas mMn-100 and mMn-140, respectively.
adsorption, extraction and flocculation. Recently,
sulfate radicals generated from peroxymonosulfate
(Oxone, PMS) or persulfate (PS) have been
89PMS activation and catalytic oxidation were1
carried out in a 500 mL reactor containing 20 ppm
applied as an alternative to hydroxyl radicals. For phenol solution. The concentrations of withdrawn
 O R A L P R E S E N TA T I O N S - 1 st D A Y

KINETICS OF SULFATE RADICAL-MEDIATED OXIDATION OF BISPHENOL A will

CATALYZED
be filled
Kinetics of Sulfate Radical-mediated Oxidation of Bisphenol A
BY CUBIC CuFe2O4-Fe2O3 CATALYST in by C1-5
Catalyzed by Cubic CuFe2O4-Fe2O3 Catalyst
EAAOP4
W.D. Oh1, T.T. Lim1,2, Z.L. Dong1,3.
(1) Nanyang Environment and Water Research Institute (NEWRI), Interdisciplinary Graduate School, Nanyang
Technological University, 1 Cleantech Loop, CleanTech One Singapore, 637141, Singapore,
woh001@e.ntu.edu.sg.
(2) Division of Environmental and Water Resources Engineering, School of Civil and Environmental Engineering,
Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore.
(3) School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue,
Singapore 639798, Singapore.
A novel CuFe2O4-Fe2O3 magnetic catalyst with cubic morphology
was prepared via a facile low temperature (90 C) co-precipitation
method. The catalyst was employed to generate sulfate radical via
peroxymonosulfate (PMS) activation for bisphenol A (BPA)
removal. The effects of initial pH, PMS dosage and catalyst
loading on BPA degradation was investigated and correlated with
the BPA degradation by-products. At acidic pH, the pseudo-first
order model fail to describe the BPA degradation curves attributed
to the interfacial repulsion between the catalyst surface and PMS.
For the first time, a mechanistic kinetic model taking into account
the initial pH, PMS dosage and catalyst loading was developed and
successfully employed to describe the BPA degradation. The
CuFe2O4-Fe2O3 catalyst could be reused for multiple cycles
without significant deterioration to its performance.

THE ROLES OF POLYCARBOXYLATES IN Cr(VI) REDUCTION

However, INDUCED
it is inadequate as theBY SULFITE:
pseudo first-order
The roles of polycarboxylates
Background
INVOLVEMENT OF ACTIVE RADICALSin Cr(VI) reduction modelinduced
does not bytake
sulfite:
into account the influence of C1-6
Involvement
Environmental ofpollution
active radicals
due to bisphenol A initial pH, PMS dosage and catalyst loading. In
Bo Jiang
(BPA) and Jingtang
is known to causeZheng
harmful effect to human this regard, a more robust kinetic model is
health and aquatic lives [1]. Many BPA treatment warranted.
In this study,
methods the effectssuch
were proposed of polycarboxylates
as ozonation andon both Cr(VI) reduction and S(IV) consumption
Objectives
were investigated
activated in acidic solution.
carbon adsorption. However, Study of the Cr(VI) reduction mechanism unprecedentedly
these

indicatesrequire
methods that under aerobic
high conditions,
energy the formations
and generate of highly
Herein, CuFeactive
2O4-Feradicals,
2O3 catalystsuch as SO 4cubic
with
and OH accounted for the excess consumption of sulfite and these produced radicals can low-
secondary pollution. morphology was prepared via a facile
temperature co-precipitation method. It was used
successfully oxidize otheradvanced
Sulfate radical-based pollutants,oxidation
i.e., RhB and As(III). Sulfite-induced reduction of Cr(VI)
for treating BPA in water via PMS activation. The
can be significantly
processes promoted
are gaining attention as by
an the addition of polycarboxylates,
eco-friendly whichpHs,
effects of various initial are catalyst
greatly influenced
loadings and
by solution
and efficient pH and regent
method concentrations.
for removing Surprisingly,
recalcitrant PMS dosages on BPA removal enhanced
only Ox can induce the were also studied.
productions
organics. of active
Sulfate radicalradicals
has a accompanying
relatively highwithAthemechanistic
fast depletion of S(IV).
kinetic model Contrarily,
taking into inaccount
additionpotential
oxidation to scavenging theV)
(Eo = 2.7 active
withradicals, other three
longer half- tested of
the effects polycarboxylates,
initial pH, catalysti.e., malicand
loadings acid,
PMS
life compared
tartaric acid and withcitric
the acid
hydroxyl radical. This
can effectively play as dosages
sacrificialwas
regents for Cr(VI)
proposed reduction
to describe theviaBPA
allows better utilization of the reactive sulfate
intramolecular electron transfer, leading to the retrenchment degradation of byS(IV) and
sulfate retarded
radical via productions
catalytic PMS
radical for pollutant degradation [2]. An efficient
of active species. This electron transfer
way to generate sulfate radical is by heterogeneous
capacity is governed
activation. by the energies of the highest
occupiedmetal
transition molecular orbital
activation of and chemical structuresMethods
peroxymonosulfate of sacrificial polycarboxylates. In general,
this is the first study that an explanation
(PMS)[3]. Current trend of study involves the use for the variant reactivity pattern of Cr(VI) reduction
ofinduced
Co-basedby materials
specific polycarboxylates
as PMS activatorsis whichreported. The CuFe2O4-Fe2O3 catalyst was synthesized via
suffers from the dissolution of highly-toxic Co a low temperature co-precipitation method at 90
ions during treatment thus making it less attractive C. The characteristics of the catalyst were studied
[4, 5]. One appealing transition metal which is using XRD, FESEM, BET and FTIR. Batch
relatively less toxic than Co is Cu. experiment was conducted to study the catalytic
activity of the catalyst for BPA removal in water
Investigation of the kinetics of sulfate radical via PMS activation. The performance of the
oxidation is relatively limited [6]. In most cases, catalyst was compared with other heterogeneous
the pseudo first-order kinetics was employed to catalysts, namely Fe2O3, Cu-based spinels
describe the degradation of pollutants over time. (CuX2O4, X = Bi and Al) and ferrospinels

90 1
 R O O M C - C A TA L Y T I C R E D OX P R O C E S S E S

THE UNPREDICTABLE EFFECT OF CHLORIDE AND CARBONATE will

RADICAL ANIONS
be filled in by EAAOP4
The unpredictable
DURING ADVANCED effect of chloride
OXIDATION and carbonate
PROCESSES C1-7
radical anions during advanced oxidation processes
A. Bianco, A. B. Tour, G. Mailhot, M. Brigante*, Clermont Universit, Universit Blaise Pascal, Institut de
Chimie de Clermont-Ferrand, UMR CNRS 6296, BP 10448,F-63000 Clermont-Ferrand (France). Corresponding
author: marcello.brigante@univ-bpclermont.fr
F. Author1, S. Author2, T. Author1,2. (1) Institution, Address, Town, Country, Institution, Address, Town, Country.
Naturally occurring ions such as chloride and
hydrogencarbonate/carbonate are considered as scavengers
during application of radical degradation via advanced
oxidation processes.
In this research project, we investigate the reactivity of
different organic pollutants using the UV/H2O2 system to
generate hydroxyl radical in the presence of inorganic
compounds. The main results underline a possible degradation
enhancement in the presence of chlorine ions due to a better
selectively of the process.

In wastewaters, the concentration of Second order rate constants between HO, Cl2- or
hydrogencarbonate (HCO3-) and chloride (Cl-) ions CO3- and pollutants are determined by using a
is variable and the assessment of their impact on competition kinetics with Laser Flash Photolysis
Removal
REMOVAL
AOPs of METHYLENE
OF
processes Methylene
mediated Blue by radical,
BLUE
by hydroxyl Fenton Like Oxidation
BY FENTON
the Process using
LIKEtechnique.
(LFP) OXIDATION
will be filled
PROCESS USING in by
nano-Zero-Valent-Iron supported
NANO-ZERO-VALENTIRON SUPPORTED Pumice stone-STONE -
PUMICE C1-8
most important oxidant involving in AOPs [1, 2], Cl2 and CO3 are less reactive than EAAOP4
HO but
needs to 1, be
D.I.ifi deeply
S.Meri 1 investigated
. (1) Department of Environmental could beorlu
[3]. The Engineering, more selective Faculty,
Engineering and could react
Namk directly
Kemal
University, of
degradation orlu 59860- Tekirda,
different TURKEY
pollutants is followed with pollutant while HO can be partially
This study investigated the treatment of methylene blue (MB) dye
under UV/H2O2 process and in the presence from or inaqueousscavenged byFenton
solution by other like
species in solution.
oxidation process using Nano-
the absence of Cl- or HCO3- ions. Up to now, zero-valent-iron
these (nZVI) supported pumice stone as catalyst in the
In conclusion, chloride and carbonates ions could
presence of hydrogen peroxide. The effect of process conditions such
anions are considered as inhibitors of the oxidation have
as initial dye and Hdifferent effects nZVI-Pumice
2O2 concentrations, on the disappearance
dosage and pHof
of the solution were investigated on the removal efficiency of MB in
process because they react with hydroxyl radical pollutants
the nZVI-Pumice/H during AOPs applications and these
2O2 system. Concentrations of MB (50-250 ppm,
- H2O2 (1.47-7.35 mM), nZVI-Pumice (0.2-10 g/L) were varied at the
(HO ) to give chlorine radical anion (Cl2 ) and effects should be elucidated using a chemical
reasonable amounts and the initial pH was kept in the interval of 2-7
carbonate radical anion (CO3-) generally during less batchkinetic approach
experiments whichtowere
findconducted
the best indecontamination
a 100 mL flask
(active volume 50 mL) placed on a rotary shaker at 200 rpm and at
reactive than HO [4]. process for a selected media. Moreover, kinetic
room temperature. Initial MB concentration, pH value, nZVI-Pumice
dosage,
In this work, batch irradiations experiments were and H O concentration were found to influence
data2 2will improve the description ability of reaction
parameters. Degradation kinetics were improved 3-4 times in nZVI
performed for different compounds: degradation advanced
supported Fenton Likeoxidation processes models.
oxidation system.
rates (Rd, M s-1) are determined to evaluate the References
Keywords: Fenton like oxidation, Methylene blue, Nano-composite,
Pumice
positive or negative effect due to the presence of stone,
[1] nano Zero
I. Oller, S.Valent
Malato,Iron
J.A. Sanchez-Perez, Science of the
Total Environment, 409 (2011) 4141. [2] W. Huang, M.
inorganic ions toward a large range of physico- Brigante,
volcanic F.stone
Wu, with
C. Mousty, K. Hanna,
a large surface G.area
Mailhot,
and
Dyes
chemicalare conditions.
widely usedForininstance,
differentthe
industries
presencefor
of Environmental Science and Technology, 47 (2013) 1952.
founded easily and cheaply in the environment and
textiles, pulp mills, leather, dye synthesis, printing, [3] Y. Yang, J.J. Pignatello, J.Ma, W.A. Mitch,
Cl -
ions enhances the photoinduced degradation of has been used as an effective adsorbent [12], as well
Environmental Science and Technology, 48 (2014) 2344
painting, photography, food and plastics etc. [1]. as catalyst
Resistance towhileremoval by inhibition
biologicaleffect
treatment [4] P. Neta, for different
R.E. oxidation
Hule, A.B. methods
Ross, Journal of [13].
Physical
Ethoxyquin, plays an in the
and Chemical Reference Data.17, (1988) 1027. [5] A. B.
systems of the most dyes have cause a severe The main objective of this study is to evaluate the
case of Benzenesulphonic acid. Toure,, A. Bianco, G. Mailhot, M. Brigante, Journal of
problem due to toxicity for the ecosystems. treatment of and
Photochemistry methylene blueA, under
Photobiology (MB)revision.
dye from
aqueous solution using Nano-zero valent iron
In recent years, Advanced Oxidation Processes supported pumice stone in the presence of hydrogen
(AOPs) which are based on the generation reactive
hydroxyl radicals have become most popular 91 1
peroxide. The effect of of process conditions such
as initial dye and H2O2 concentrations, nZVI-
processes for the destruction of non-biodegradable Pumice dosage and pH of the solution were
 O R A L P R E S E N TA T I O N S - 1 st D A Y

AN INTENSIFIED FENTON PROCESS IN A CONTINUOUS FIXED BED REACTORwill

USING
An Intensified Fenton Process in a Continuous Fixed Bed Reactor be filled
LOW COST Fe/SiO2 CATALYSTS in by C1-9
using Low Cost Fe/SiO2 catalysts
EAAOP4
R. Molina1, M.I. Pariente1, J.A. Siles2, J.A. Melero1, F. Martnez1. 1Department of Chemical and Environmental
Technology, Universidad Rey Juan Carlos, 28933, Mstoles, Spain, raul.molina@urjc.es. 2Department of Inorganic
Chemistry and Chemical Engineering, University of Crdoba, 14071, Crdoba, Spain.

Treated Effluent
Different iron-containing catalysts were prepared by simple
Off Gas
direct synthesis routes and low cost reagents and tested in a
Fenton system for the treatment of phenol aqueous solution.
PC
FC AIR
The activity of the iron containing catalysts in terms of TOC
TC
conversion and oxidant efficiency is almost not affected by
TC

LC
Autoclave
Catalytic
the type of silica support. The iron incorporation in the
FC PI
QA
TC Fixed Bed
Reactor
iron/silica matrix using sodium silicate as silica source
provides higher stability of the supported iron species.
Pressure
ump
TC
Interestingly, higher iron contents promote higher stability
PI
in the catalyst during the reaction. Fe/SiO2 catalyst prepared
FC
QR

High Flow via sol-gel in absence of organic template and using a

Pump
cheaper silica source, was considered an interesting
alternative for its application in industrial Fenton processes.

Background sol-gel method reported in literature [3]. This is a

simple direct synthesis route in with a control of
The heterogeneization of Fenton catalytic the iron content in the material can be achieved in
system has been of great interest in the field of a shorter synthesis route. Additionally, this method
industrial wastewater treatments based on avoids the use of expensive reagents, such as the
Advanced Oxidation Processes.
DECONTAMINATION The combination
OF ANTIBIOTICS AND INACTIVATION
organic templates OFinvolved
ANTIBIOTIC-RESISTANT
in the preparatiton
Decontamination of antibiotics and inactivation of antibiotic-resistant will be filled of
of that powerful
BACTERIA IN URBANprocessMBR for WASTEWATER
hydroxyl radical USING NOVEL GRAPHENE-BASED
mesostructured catalysts, being the mesostructured
in by
bacteria with
generation
COMPOSITES
in urban
a solid MBRcatalystwastewater
is a desirable using novel graphene-based
EAAOP4
C1-11
material a 43 % expensive, taking into account
composites
alternative avoiding the main drawback of the only the2 cost in reactives. Moreover, sodium
P. Karaolia1, E.
conventional Hapeshi1, I. Michael
homogeneous 1
system., C. That 2
Drosouis, theXekoukoulotakis
, N. , D. Fatta-Kassinos1.
silicate has been employed as silica source instead
generation
1 of metallicWater
Nireas-International sludges that need
Research to be
Center, also ofof
University Cyprus, P.O. Box
expensive 20537, 1678 Nicosia,
organosilicates Cypruswith
(as TEOS), . an
treated.
2 Several
Department of studies have been
Environmental addressed
Engineering, to the University
Technical of Crete,
additional 19 % GR-73100 Chania, in
of reduction Greece.
the cost. The
incorporation of active and stable iron species over
The degradation of properties
catalytic three antibiotics
were evaluated(sulfamethoxazole,
in the oxidation
different supports [1]. The most clarithromycin promising ofand erythromycin),
phenol aqueous solutionsthe disinfection
in an intensified and
materials in terms of activity andinactivation stability of
Fentonantibiotic-resistant
system consists of abacteria, continuousnamely catalytic
(zeolites, mesostructured solids, etc.) usually need
Pseudomonas aeruginosa and Escherichia
fixed bed reactor coupled with coliainstirred
a pilot-scale
autoclave
expensive reactants and complex MBR synthesis
effluent [4].
by heterogeneous
This system (TiO 2) photocatalysis
is considered were
an innovative
methods, with a strict pH and temperature control, inprocess
investigated this which
study. can Twobring novel graphene-based
significant benefits in
and synthesis periods up to 3-4 days. Therefore, composites, its using hydrothermal
terms (HD) and
of the efficiency photocatalyticcatalysts
of heterogeneous (PH)
industrial application seems to be uncertain methodsand of synthesis were evaluated,
for wastewater treatmentalong the commercially
by Fenton-like processes.
difficult to achieve. That is the case of theAeroxide
available ThisP25. The results show
intensified-Fenton an effective
process removal of
takes advantage
Fe2O3/SBA-15 material [2] which isofa highly antibiotics thewith the newly
iron dissolved from thesynthesized
heterogeneous catalysts
catalyst
active and stable catalyst for the treatment of a
(clarithromycin = 86%,
for erythromycin
further oxidation =by84%). There was Fenton
homogeneous a 1-
wide range of pollutants but it must belogprepared removal of reactions
bacteria using
in theallstirred
catalysts while there
autoclave. was a a
Moreover,
following a long and complex synthesis route (>70%)
high removal of antibiotic-resistant
mesostructured Fe2O3/SBA-15 P. aeruginosa
material after (a
involving a costly template reagent. 60 minutes of treatment
composite withmaterial
the PH catalyst.
that contains crystalline
Objectives hematite embedded
The following on a mesostructured
aspects were examined:SBA-15 i) the
matrix) and an
investigation of unsupported
the presence crystalline
of 2 typeshematiteof ARB
TheTheoccurrence
aim of this of antibiotics
work is toand of antibiotic
study different were tested for comparison.
(Pseudomonas aeruginosa, Escherichia coli) in the
approaches(AR)
resistance for thehaspreparation of iron-containing
risen in recent years as an absence (NO) or in the presence of:
emerging concern
catalysts with in aquatic
simplified synthesisenvironments.
routes, low cost The Methods
sulfamethoxazole (SMX), clarithromycin (CLA),
pressure
reagents which is applied iron
and different onto content,
bacteria inbut aqueous
with Several powder
erythromycin (ERY)iron-silica
and a mixture materials
of all were three
environments by the extensive
appropriate catalytic properties use (activity
of antibiotics,
and prepared
(MIX), ii)following a sol-gel
the reduction of method
antibioticsbased on
(spiked
stability)
leads to for
an the degradation
increase of organicofpollutants.
of prevalence antibiotic acid-catalyzed
concentrration hydrolysis
of 100 g -1
and Lbasic ) and antibiotic
condensation
resistant
The new bacteria
materialsandhavegenes (ARB & following
been prepared ARG) [1], a resistance
with ammoniumremoval efficiencyusing
hydroxide of a TEOS
combination
(samples of a
causing a rise in prevalence of nosocomial pilot-scale Membrane BioReactor (MBR) (capacity
diseases. 92
of 10 m3 day-1) and an advanced wastewater post- 1
Despite the acknowledgment of AR as an issue of treatment technology, namely bench-scale
 R O O M C - C A TA L Y T I C R E D OX P R O C E S S E S

MECHANISTIC MODEL FOR BACTERIA PHOTO-INACTIVATION IN WATER USING will beSOLAR

Mechanistic model for bacteria photo-inactivation in water using filled
RADIATION
solar radiation in by C1-12
EAAOP4
P. Fernndez-Ibez1, M.Castro-Alfrez1, M.I. Polo-Lpez1, J.Marugn2. (1) Plataforma Solar de Almera
(CIEMAT), Carretera Sens, Km 4, 04200 Tabernas, Almera, Spain. (2) Department of Chemical and
Environmental Technology, ESCET, Universidad Rey Juan Carlos, Mstoles, Madrid, Spain.
This work aims at developing a mechanistic model to describe
the kinetics of the basic phenomena involved in the solar water
disinfection process, so-called SODIS. This process consists on
the solar exposure of small volumes (<2L) of polluted water to
sunlight in transparent plastic containers for at least 6 h,
producing significant bacterial inactivation due to the action of
sunlight and mild thermal heating. This paper proposes a
mechanistic approach of the solar radiation effects over bacteria
cells, considering the UV part of the spectrum, which is the
primary cause of the bactericidal action. The photo-inactivation
of catalase by UV is considered to induce accumulative ROS
inside the cell and enhancing the damage on it.

(H2O2) and hydroxyl radicals (HO). Bacteria have

Introduction a defensive mechanism to regulate the amount of
Solar disinfection treatment (SODIS) is a house- ROS inside cells through some enzymes. Catalase
hold water treatment technique approved by the is one of these enzymes that cause the
World Health Organization in those areas that decomposition of H2O2 and maintain the
have no access to safe drinking water. Disinfection concentration of HO at not toxic levels [1].
efficiency against several microorganisms has Intracellular catalase activity decreases when it
been proved.
VISIBLE LIGHT However, the mechanisms that
PHOTOLYTIC/PHOTOCATALYTIC DISINFECTION
is exposed to UV, whichOF WATER
leads to the SAMPLES
accumulation
Visiblethe
govern
USING Light Photolytic/Photocatalytic
process are still TITANATE
Cu-DEPOSITED Disinfection
unknown. NANOTUBE-BASED of ROSof inside
Water Samples
CATALYSTS
cells. In the model this inactivation C1-13
Using Cu-deposited Titanate Nanotube-based Catalysts
SODIS consists in the solar exposure of the is considered by the following reaction (1):
T. Tiler,
water B. Erjavec,
usually M. Plahuta,
in plastic bottlesA.without
Pintar adding any h
Laboratory
reactive orfor Environmental
catalysts. Among Sciences and main
this, the Engineering,
factor NationalCAT
Institute of CAT
Chemistry,
i (1)
Hajdrihova 19, SI-1001
Ljubljana, Slovenia. E mail: tatjana.tisler@ki.si
in the process is the solar radiation. The solar
ROS can cause damages in several sites of the
spectrum ranges from UV-B (280 nm) to infrared
(1000 m), being the most harmful Onepartof thethepromising alternative
bacterial cell, i.e.methods for water
DNA lesions, disinfection
pyrimidine dimer
UVA&B ranges. No direct damages on cells are is photocatalytic oxidation.
formation In
or this study
proteins the removal
oxidation. of
Afterbacteria
all these
reported by solar radiation, in contrary Escherichia
UV-C does. coli most from water
damages, samples
bacteria was studied
inactivation in photolytic
finally occurs. The
and photocatalytic disinfection
reactive ROS runsisby HO, which
themeans of visible light.
is considered
The objective of this work is to For findthis
outpurpose
a different
as the main Cu-deposited
lethal factor.titanate nanotube-based
Also, the model proposes
suitable mechanistic description ofcatalysts the main were three
developed
stages of using advanced
bacteria according photoreduction
to their viability
phenomena that govern solar disinfection. method, in ordertotorepresent
In line deposit cluster-size
the progress Cu on of the
the nanotube
inactivation
with this, a mechanistic kinetic model surface. The as-prepared
is proposed process by photocatalysts were further
generated hydroxyl subjected
radicals, these are,
to predict how bacterial concentration to thechange
heat-treatment in oxidative
undamaged (Bu), or reductive
damaged (Bdatmosphere, in
) and inactivated
along the time of exposure to solar radiation.order to anchor Cu on the(Bsupport.
bacteria i). The obtained results clearly
showed that the presence of reduced Cu-deposited titanate
B HO Bd (2)
nanotubes enabled theu most rapid inactivation of E. coli in water
Mechanistic model samples. Bd HO Bi
(3)
This model suggests that bacterial inactivation in Kinetics and mass balance equations of each
BACKGROUND
water by solar radiation is mainly produced by the OBJECTIVES
compound or component involved in the process
generation of Reactive Oxygen Species (ROS) and have been taken into account for this model.
Accordingbytothe
eventually thephoto-inactivation
WHO report [1],of1.1 billion
the catalase The aim of this study was to synthesize and
people
enzymelack
thataccess
preventsto the
safe drinkingaction
oxidative waterof and
ROS assess
The disinfection
solution forpotential of modified
the couple set of Cu-two
consequently
inside cells. every year about 2.2 million people deposited
differentialTNT-based
equations catalysts
(4 and in5) visible light a
will give
died, mostly children under the age of five due to photo(cata)lytic
predictive model oxidation process the
that describes using bacteriaof
behavior
diarrhea.
In theFor this reason,
electron transport effective
chain disinfection
during cell E.viable
coli. bacteria concentration, changing with solar
technology
respirationshould
cycle, be used toROS
different remove pathogenicas
are generated exposure time, at different UV-A irradiances, and
microorganisms and (O organic pollutantsperoxide
from METHODS
-
superoxide radicals 2 ), hydrogen different initial bacteria concentrations.
drinking water supplies.
Traditional disinfection methods are effective in
controlling pathogens; however, the formation of
93
Titanate nanotubes (TNTs) were prepared via1
alkaline hydrothermal synthesis route in a teflon-
 O R A L P R E S E N TA T I O N S - 1 st D A Y

EFFECT OF H2O2/SUNLIGHT PROCESS IN THE SIMULTANEOUS INACTIVATIONwill OF

Effect of H2O2/sunlight process in the simultaneous inactivation of be filled
MULTI-DRUG RESISTANT BACTERIA AND REMOVAL OF ANTIBIOTIC RESISTANT GENES
multi-drug resistant bacteria and removal of antibiotic resistant genesin by C1-14
EAAOP4
G. Ferro1, F. Guarino2, S. Castiglione2, L. Rizzo1. (1) Department of Civil Engineering, University of Salerno, via
Giovanni Paolo II, 132, 84084, Fisciano (SA), Italy, gferro@unisa.it (2) Department of Chemistry and Biology,
University of Salerno, via Giovanni Paolo II, 132, 84084, Fisciano (SA), Italy

H2O2/solar-simulated process was carried out at lab scale in order

to assess the simultaneous inactivation of an indigenous multi-drug
resistant E.coli strain and the removal of ampC, qnrS and tetW,
which have been selected as target antibiotic resistant genes
(ARGs). DNA was extracted from both E.coli bacterial cells grown
on selective culture media and wastewater samples. The
investigated disinfection process was effective in the inactivation
of the tested multi-drug resistant strain (detection limit reached
after 90 min), but not in the removal of ARGs, which were still
present in the treated samples. On the base of the obtained results,
the disinfection process may contribute to the release into the
environment of antibiotic resistance determinants and mobile
genetic elements.

Materials and Methods

Introduction
Multi-drug resistant E. coli strain was selected
Urban wastewater treatment plants (UWTPs) are from UWTP of Salerno, Italy, from the effluent of
regarded as one of the main anthropogenic sources the activated sludge process, by membrane
for antibiotic resistant bacteria (ARB) and genes filtration and subsequent cultivation onbeselective
Comparative
COMPARATIVE Evolution
(ARGs) spread intoEVOLUTION Between
the environment BETWEENOxidation
[1]. UWTPs Processes
OXIDATION Used
PROCESSES For USED will
FOR BACTERIAL filled
Bacterial
INACTIVATION Inactivation
AFTER After
THREE Three Different
DIFFERENT medium supplemented
Secondary
SECONDARY Treatment
TREATMENT withMETHODS
a mixture ofin three by
C1-15
and conventional disinfection processes may be antibiotics (ampicillin, ciprofloxacin EAAOP4 and
Methods
not successful in the removal of ARB [2, 3] and tetracycline). The antibiotics concentrations were
antibiotic
C. Pulgarin resistance
1
, M. Voumardmay 1
spread into the
, S. Giannakis 1
chosen according toLausanne
the respective minimum
1
SB, ISIC, Group
environment. Theof occurrence
Advanced Oxidation
of ARBProcesses,
and ARGs cole Polytechnique Fdrale de (EPFL), Station 6,
inhibiting concentrations for E. coli listed in
in1015
UWTP Lausanne,
effluentSwitzerland,
can alsocesar.pulgarin@epfl.ch
pose a serious risk to Clinical and Laboratory Standards Institute
human health if an effective tertiary treatment is In thisdocumentation
work, disinfection [9]. by 5 oxidation processes was
not applied before wastewater reuse, especially for preceded by 3 different secondary treatment systems at
agricultural purposes [4]. Wastewatertreatment
the wastewater samples were plantfreshlyof collected
Lausanne, from
UWTP 5ofAOPs
Switzerland. Salerno, Italy,
after two then autoclaved
biological (15 min
treatment
Screening campaign of selected antibiotic at 121
resistance determinants and mobile genetic methods and C) to remove indigenous
a physiochemical process bacteria
were tested and in then
spiked
laboratory with
scale. The theinactivation
selected E. and coli strain.ofBacteria
regrowth total
elements in UWTPs have been carrying out in count were
was performed by spread plate disinfection
method.
Europe [5,6,7] and scientific literature is starting to coliforms monitored and the
focus on disinfection processes in order to capabilities were correlated with the physicochemical
H2O2/solar-simulated experiments were carried
minimize ARB and ARGs release into the characteristics
out in 2.2 of Lthecylindrical
previous. Finally,
glass batch the changes
reactor (13.0of
environment [8]. long term survival of total and fecal coliforms
cm in diameter) filled in with 500 mL wastewater after
secondary
sampletreatment
(5.0 cm andwater
solar height).
exposureThe wasreactor
assayed, was
Advanced oxidation processes (AOPs) have by simulating the discharge of the effluents
placed in a water at room temperature (roughly in lake25
been successfully investigated for the removal of water. a C) during the experimental procedure. The
wide range of emerging contaminants and wastewater solution was continuously stirred
microorganisms. Due to the possibility to save duringtendency
the experiments.
In this work, effluents
money of energy costs, solar driven AOPs are an of activated The in the longSolar term irradiation
survival study was
sludge/secondary sedimentation, supported provided abyrequired
revealed a wide timespectrum
of higher 250than W4 lamph to
attractive option for wastewater treatment in small equipped with a UV filter (Procomat, Italy),
activated
communities. sludge/moving bed bioreactor and a completely inactivate the total coliform load.fixedThe
physicochemical treatment (coagulation- at 40 cm from
necessary dosethetoupperensurewater
totallevel in the reactor.
inactivation was
In this light, aim of the present study
flocculation) were collected and treated by AOPs is to assess A spectrometer model HR-2000
linked to the efficiency of the pretreatment. from Ocean
the lab
in efficiency
scale. Theof H2link
O2 (20 mg L-1AOPs
between )/solar efficiency
simulated Optics (Florida,
Dilution of the treatedUSA),samples
equipped with Geneva
in Lake cosine
treatment
and in the(pre)treatment
secondary simultaneouswas inactivation
assayed by of corrector
water with Spectralon
determined shorter diffusing
survival material,
times, linked was
multi-drug resistant E. coli and removal
estimating the bacterial concentration i) before of ARGs used to measure irradiance spectra
with predation and unfavorable osmotic conditionsof UV lamp. 20
from real urban
secondary wastewater.
treatment, ii) after the secondary for the microorganisms. Finally, samples that were
treatment methods and iii) after the AOPs. exposed for an extended period never presented
Disinfection and regrowth of the total coliform
content were the evaluation indicators. Also, a
94
regrowth, regardless of the pretreatment methods
and the dilution conditions, verifying an energy
1
combination of cheap methods, potentially threshold after which bacteria are permanently
 R O O M C - C A TA L Y T I C R E D OX P R O C E S S E S

INACTIVATION AND MUTAGENICITY OF ANTIBIOTIC RESISTANT SALMONELLA AFTER

Inactivation and mutagenicity of antibiotic resistant Salmonella after will be filled
DISINFECTION BY UV-C RADIATION AND TiO2 PHOTOCATALYSIS in by C1-16
disinfection by UV-C radiation and TiO2 photocatalysis
EAAOP4
A. Fiorentino1, C. Merlin2, L. Rizzo1. (1) Department of Civil Engineering, University of Salerno, Via G. Paolo II,
132, 84084 Fisciano (SA), Italy, afiorentino@unisa.it. (2) Laboratoire de Chimie Physique et Microbiologie pour
l'Environnement, University of Lorraine, 405 rue de Vandoeuvre - 54600 Villers-ls-Nancy.

UV-C radiation and TiO2 photocatalysis were evaluated in the

Salmonella inactivation of antibiotic-resistant Salmonella Typhimurium
Typhimurium TA102 and formation of mutants. Experiments were performed
TA102 with different initial bacterial cell densities (109, 108 and 107
CFU mL-1) and samples were taken at different irradiation
SolarUV/TiO2 UVCRadiation times). In UV-C tests a total inactivation was reached in 45, 15
and 10 min, respectively, while in photocatalytic tests total
inactivation was reached after 60, 30 and 15 min, respectively.
Formationofmutant
However the mutation rate increased compared to background
speciesduringtreatment mutants value (21, 1868 and 26 fold for 109, 108 and 107 CFU
mL-1 initial bacterial density, respectively) as UV-C dose
increased. In photocatalytic tests a fold increase of 41, 1469 and
42 compared to background level was reached respectively.

TiO2 photocatalysis on the inactivation of

1. Introduction and Objectives
Salmonella serovars are increasing in
importance in bacterial infections, as significant
pathogens to both humans and animals (Turki et
al. 2012). Moreover, the increased frequency of
MDR Salmonella strains in human infections is an
emerging issue of major health concern too
(Lightfoot, 2004; Rahman et al. 2014).
Different studies have investigated the
inactivation of Salmonella strains by disinfection
processes in water and wastewater. The effect of
different disinfection processes on Salmonella
strains in synthetic wastewater effluent was
studied by Koivunen and Heinonen-Tanski (2005).
In particular, the treatment with peracetic acid and
UV radiation, has been shown to be faster than UV
radiation alone and chlorine processes in the
inactivation of Salmonella enteritidis. Moreover,
Salmonella has been found to be more resistant to
chlorine and UV radiation than others indicator
bacteria, including total coliforms and
Enterococcus, (Li et al. 2013; Sciacca et al. 2011).
However conventional disinfection by either
chlorination or UV radiation may be not effective
in controlling antibiotic resistance spread (Rizzo et
al., 2013), therefore new disinfection methods,
such as Advanced Oxidation Processes (AOPs)
have been recently investigated (Rizzo, 2011;
Sannino et al., 2013; Murcia et al., 2013). Among
AOPs, TiO2 photocatalysis is an effective water
disinfection option, due to its capacity to inactivate
a wide range of pathogens in water; however, to
the best of our knowledge, the effectiveness of
Salmonella strains and/or its possible effect on
mutagenicity has not been investigated so far.
The objective of the present work was to
investigate the effects of the TiO2 photocatalysis
process in terms of inactivation and mutagenicity
on a model antibiotic resistant microorganism.
Salmonella was chosen as target/model organism
(its genus belongs to the same family as
Escherichia, which includes the species E.coli)
because of (i) its spread in aqueous matrices
(particularly in natural water and wastewater), (ii)
the related concern for human health (it can cause
illnesses such as typhoid fever and paratyphoid
fever), (iii) its role in antibiotic resistance spread
and (iv) the availability of a well-established test
(Ames test) to evaluate the formation of mutants.
Moreover, the effect of TiO2 photocatalysis on the
inactivation and mutants formation of Salmonella
was compared with a conventional disinfection
process such as UV-C disinfection.
2. Material and Methods
S. Enterica serovar Typhimurium strain TA102
was used as tester strain for general mutagenicity
testing according to Maron and Ames (1983).
Briefly, TA102 colonies were unfrozen and
reactivated by streaking on minimal glucose agar
and incubated at 37 C for 48 h. A single colony
from the plate was inoculated into 10 mL sterile
Luria Bertani broth (LB, Sigma-Aldrich, USA)
and incubated at 30C for 18 h under agitation
(160 rpm) in a rotating shaker to obtain a

95 1
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

ABATEMENT OF PHARMACEUTICAL POLLUTANTS UNDER UVA LIGHT BY Wil2l be filled

Abatement Of Pharmaceutical Pollutants Under UVA Light by
MAGNETICALLY SEPARABLE TiO2 PHOTOCATALYST A2-1
in by
Magnetically Separable TiO2 Photocatalyst
EAAOP4
P. Ghute1, S. Sable1, A. Rey2, F.Beltrn2, F.Medina1, S. Contreras1, (1) Departament d Enginyeria Quimica,
Universitat Rovira i Virgili, Av. Pasos Catalans, 26, Tarragona 43007, Spain. email: Pallavi.ghute@gmail.com
(2) Departamento de Ingeniera Qumica y Energtica, Facultad de Ciencias, Universidad de Extremadura, 06071
Badajoz, Spain.

The photocatalytic efficiency of bimetallic Fe3O4Pd NPs

light
decorated on commercial TiO2 (P25), synthesized NT-WO3 and
P25-WO3 catalyst has been investigated in the oxidative removal
Pd of Ibuprofen (IBP) by photocatalysis and PhotoFenton-like
process through in-situ generated H2O2 from formic acid and
oxygen under UV/Visible light. This work aims to investigate the
Fe3O4 enhancement in Fenton-like process with introduction of light.
IBP
Magnetically separable and improved activity under UV/Visible
with addition of little amount of Pd and WO3 on semiconducting
H2O + CO2 TiO2 material could be a promising catalyst in photocatalytic
TiO2 support
application.

Background and objective:

In recent years, concern regarding the presence of processes (AOPs) are considered as a promising
environmental xenobiotics such as technology for the treatment of wastewaters
pharmaceuticals and personal care products containing PPCPs. With high oxidation potential
(PPCPs)in surface and groundwater has been they are considered capable of oxidizing and
growing on due to their adverse effects on aquatic mineralizing almost every organic molecule into
life and potential
MAGNETIC impact on humanPHOTOCATALYSTS
SEMICONDUCTOR health[1,2]. CO2 FOR and THEinorganic
DEGRADATIONions. In this OF context,
EffluentsMagnetic
RECALCITRANT from Semiconductor
wastewater
CHEMICALS Photocatalysts
treatment
FROM plants BACK
FLOW For The
application
WATER Degradation
of heterogeneous photocatalyst with A2-2
(WWTPs) are Of Recalcitrant
considered a Chemicals
major source Fromof Flow theBack
use ofWater
semiconducting materials is an efficient
pharmaceutically 1 active compounds 1 (PhACs), 2 method1 for the purification of wastewater.
A. Zieliska-Jurek , I. Wysocka , Z. Bielan , J. Strychalska , J. Hupka , (1) Department
1
of Chemical Technology,
since
Facultytheof efficient
Chemistry,removal of numerous
Gdansk University PhACs is(GUT),Research
of Technology studies
Narutowicza 11/12, states
80-233thatGdansk,
use ofPoland,
nanoscale TiO2
difficult to accomplish
annjurek@pg.gda.pl. by conventional
(2) Department wastewater
of Solid in treatment
State Physics, Faculty of Appliedof Physics
waste and water limits its (GUT)
Mathematics, widespread
techniques. This has led to their occurrence In in the present
applicationstudyas ittreatability of persistent
involves additional organicstep
separation
wastewater effluents, surface water, and more compoundsfor itsfrom the flow
efficient back water
recovery after hydrauling
[5]. Magnetic separation
rarely
40 in groundwater[3].2-[3-(2-methylpropyl) fracturing was investigated.
provides a convenientThe combination
approach of TiO2and
for removing
phenyl propanoic acid, commercially available photocatalyst
Fe O /TiO 2:1
3 4 2 as recyclingandof magnetic oxide nanoparticles by
magnetic particles/composites
Fe O /TiO 1:1
Ibuprofen
20 (IBP), a Non-Steroidal Anti-
3 4
Fe O /TiO 1:2
2
enhanceapplying
the separation and recoverable
an appropriate property
magnetic field. On ofother
Inflammatory Drug1:4 (NSAID) is one of the most nanosizedhand,TiO photocatalyst.
the2photo efficiency ofFe 3O42@SiO
TiO 2/TiO2
is substantially
3 4 2
Fe O /TiO
M (emu/g)

nanocomposites were shows prepared by

3 4 2
consumed
0 drug against muscular pain and limited as it usually fast electron-hole
inflammatory disorders and has been detected heteroagglomeration.
in recombination and All presence
prepared ofsamples were
large band-gap
effluents
-20 from wastewater treatment plants characterized
exhibitingby XRD,
photoVSM, SEM/EDS,
efficiency DR/UV-Vis
in ultraviolet region
(WWTPs). Several recent studies have reported and BET [6].analysis.
Also TheTiO2prepared
WO3 coupled composites contained
semi-conductors
-40 presence of the NSAID (IBP), in effluents TiO of 2 and haveFebeen
the 3O4 successfully
crystal phases. The tomagnetization
applied the degradation
wastewater
-3
treatment
-2 -1
plants.
0 1
Although
2
the
3
removalhysteresis loop for
of different Fe3O4contaminants
organic /TiO2 indicated that through
in water the
rate by biological Hoxidation
(T) 0 in some cases has hybrid photocatalytic
photocatalyst ozonationshowed superparamagnetic
under visible light
been reported upto 70%, the ecological risk still characteristics.
radiation. WO3 and TiO2 semi-conductors can
remains high, due to the generation of byproducts extend the absorption of radiation to the visible
like hydroxyl-IBP and carboxy- IBP during the region as a result of the lower band gap energy of
Introduction
biological oxidation [4]. Thus an efficient Table WO3 1.andCharacteristics
also allow ofa obtained wide electronhole
An innovative approach to the degradation Fe3O4/TiO2
destruction of IBP and its degradation by-products and separation
Fe3O4@SiO2/TiO2 nanocompositesto some extent
avoiding recombination
possibility of organic compounds in the flow back
needs to be carried out for achieving its complete [7]. Towards this prospective, development of
water using titanium dioxide photocatalysis was Degradation constant rate
removal from wastewaters. Currently most of the photocatalystMolar Molar
with enhanced activity in visible
investigated. The flow back fluid contains Sample no.
ratio ratio [min1]10-2
research work is focused on development of light regionFeand efficient recovery is desired. 4-
chemicals added to the fracturing fluid, part of 3O 4 TEOS
Phenol Pyridine
innovative and efficient technologies which can be Bimetallic Fe/TiO 3O42Pd /Fe supported
3O 4 TiO2 could act as Heptanone
a
which return gradually via the wellhead to the
applicable in complete removal of such type of Fe 3O4/TiO2_
promising 1:1
material - in the 1.01 removal
0.18 1.36
of
surface when stimulation is complete. In order to 1pharmaceutical contaminant. This work investigate
emerging organic pollutants. Advanced oxidation
reuse it or return into the environment, it requires Fe3O4/TiO2_ 1:2 - 1.34 0.94 1.21
appropriate treatment. 2
Heterogeneous photocatalytic oxidation of
organic pollutants occurred to be a promising
96
Fe3O4/TiO2_
3
1:4 - 3.02 0.26 2.10
1
Fe3O4/TiO2_ 2:1 - 0.85 0.15 1.46
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

EFFECT OF SINTERING TEMPERATURE AND TIME ON ANATASE AND RUTILEwill

PHASES
Effect of Sintering Temperature And Time On Anatase and Rutile be filled
OF TiO2 PREPARED BY SOL-GEL METHOD in by A2-3
Phases of TiO2 Prepared By Sol-Gel Method.
EAAOP4
J. Morales-Meja, Y. M. Vargas-Rodrguez, R. Almanza. Universidad Nacional Autnoma de Mxico, Av.
Universidad 3000, Universidad Nacional Autnoma de Mxico CU, 04510, Coyoacn, D.F., Mxico,
jmoralesm@iingen.unam.mx.
A set of thick TiO2 films were prepared by conventional Sol-gel
process. Precursors were based on Titanium Isopropoxide,
organic solvents, at acidic conditions. Sintering temperature and
time were modified in order to find a suitable set of sintering
conditions that produce a catalyst with crystalline phases having
the higher ratio of anatase to rutile. Sintering time varied from
0.5 to 24 hours and sintering temperature ranged from 500C to
675C. The results indicate that the temperature effect on
anatase/rutile ratio is small in the range of 500-600C with 2
hours of sintering. For higher temperatures, anatase content
decreased fast. Sintering time of 60 minutes resulted on films
with high anatase content. Longer sintering periods did not
increase anatase content. On the other hand, particle size was
proportional to sintering temperature.

Significant
SIGNIFICANT Enhancement
ENHANCEMENT of PhotocatalyticACTIVITY
OF PHOTOCATALYTIC Activity OVER Pt-TiO2
PHOTOCATALYSTS FOR PHENOL DEGRADATION A2-4
over Pt-TiO2 Photocatalysts For Phenol Degradation
A.Zieliska-Jurek1, M. Janczarek1, Zhishun Wei2, Ewa Kowalska2 (1) Gdansk University of Technology,
Department of Chemical Technology, Narutowicza 11/12, Gdansk, Poland, annjurek@pg.gda.pl (2) Hokkaido
University, Catalysis Research Center, 21-10 Kita-ku, Sapporo, Japan

A considerable increase of the photocatalytic activity was

reported with respect to platinum deposited on TiO2 particles.
Platinum nanoparticles were deposited on different TiO2 matrix
such as decahedral anatase NPs, mesoporous spheres, titania
nanotubes and commercial ST-01 (Ishikara), P-25 (Evonik) by
sol-gel or microemulsion method. The effect of platinum
nanoparticles size and TiO2 template on photocatalytic activity
was investigated. Obtained nanoparticles were characterized
using XRD, STEM, XPS, DR/UV-Vis absorption spectroscopy
and BET surface area analysis. It was found that size of platinum
was decisive for the photocatalytic activity under visible light
irradiation, i.e., the smaller Pt NPs were the higher was
photocatalytic activity.

absorption spectroscopy and BET surface area

Introduction
Photocatalytic properties of TiO2-based
nanomaterials greatly depend on their
morphology, chemical composition and surface
modification. Nanotubes, hollow spheres and
mesoporous NPs possess large surface. Both
surface adsorption as well as photocatalytic
reactions can be enhanced by development surface
area of the photocatalyst as more reactive sites for
degradation of organic compounds is available.
Nevertheless, due to large band gap of pure TiO2
analysis.
Experimental
Platinum nanoparticles were deposited on
different TiO2 matrix such as decahedral anatase
NPs, mesoporous spheres and titania nanotubes by
sol-gel or microemulsion method.
Microemulsion offers a unique
97
microenvironment in which monodispersed,1
ultrafine nanoparticles with a narrow size
distribution can be obtained. This method has
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

Morphosynthesis of
MORPHOSYNTHESIS TiO22/METAL
OF TiO /Metal OXIDE
Oxide NANOSTRUCTURES
Nanostructures for FOR OXIDATION OF
AIROxidation
POLLUTANTS
of Air Pollutants A2-5
Christos Trapalis1*, Maria-Veronika Sofianou1, Nadia Todorova1, Tatiana Giannakopoulou1, Tilemahos
Georgakopoulos2, Katerina Pomoni2.
1
NCSR Demokritos, Institute of Nanoscience and Nanotechnology, Patriarchou Grigoriou E & Neapoleos, 153 43,
Ag. Paraskevi, Greece. *c.trapalis@inn.demokritos.gr.
2
University of Patras, Department of Physics, 26504, Patras, Greece

Ag on anatase {001} facet In the present work, synthesis of anatase nanostructures

with dominant {101}, {001} or {010} facets in different
shapes and scales is presented. Hydrothermal treatment in
various solvents, experimental conditions as well as in
presence of metal salts was employed. Ag nanoparticles
were selectively deposited on chosen crystal facets.
Furthermore the crystal structure, the morphology and the
photocatalytic activity of Ag-, Mg-, Mn-, Zn-containing
TiO2 powders in NOx and acetaldehyde oxidation were
examined. Selectivity towards the two oxidation processes
was observed depending on the dominant crystal facets in
Ag Nanoparticles the synthesized anatase and the level of the metal loading.

nanocrystals was examined by XPS. Photocurrent

Morphosynthesis of anatase TiO2 crystallites, as measurements in vacuum and air were performed in
well as coupling of titania with various metal/metal order the photocatalytic activity to be enlightened.
oxides are two powerful strategies widely applied The photocatalytic activity was evaluated by
for enhancing the photocatalytic performance of the oxidizing inorganic nitrogen oxide (NO) and
semiconductor [1, 2]. organic acetaldehyde (CH3CHO) IN air pollutants
ANATASE-TiO2 VERSUS RUTILE-TiO2- TO UNDERSTAND THE DIFFERENCE
Anatase-TiO2 versus
PHOTOCATALYTIC Rutile-TiO2 to Understand
ACTIVITY under UVA irradiation. in
the Difference A2-6
In the present work, synthesis of anatase
Photocatalytic Activity
nanocrystals with dominant {101}, {001} or {010} It was demonstrated that the oxidation of NO is
Wojciech
facets Macyk,1 Marta
in different shapesBuchalska,
1
and scalesMarcin
is presented. higher
Kobielusz,1 Anna when 1,2{101}
Matuszek, Michacrystal
Pacia,1facets
Szymonare dominating
Wojtya 1
.
(1) Jagiellonian University in Krakw,
Hydrothermal treatment of inorganic/ organic Faculty of whereas
Chemistry, Ingardena the
3, decomposition
30-060 Krakw, of
Poland,acetaldehyde is
macyk@chemia.uj.edu.pl.
titanium precursor applying (2) University of Auckland,
various solvents andDepartment
enhanced of Chemistry,
when the Private Bag 92019,
{001} crystalAuckland,
facets are
New Zealand conditions yielded anatase with
experimental dominating in the anatase nanocrystals. As a
different dominant crystal facets. The addition The rutileof consequence
form of TiO all2 theis anatase
usually crystals that had
considered as
metal salts of Mg, Mn and Zn in the solution dominant
photocatalytically
system inactive.{101} facets exhibited
A number of studiesaproves
high photonic
that this
resulted in preparation of metal-dopedhypothesis efficiency Superoxide
TiO2 or is incorrect. regarding the NO are
radicals oxidation whereas
photogenerated
metal oxide-TiO2 composites. with a higher those crystals
efficiency withsurface
at the dominant {001}due
of rutile facets
to ashowed
better
a highatphotonic
oxygen adsorption efficiency
the surface. The for the decomposition
anatase form of titania of
Ag nanoparticles were also deposited on can be used asthe
selected acetaldehyde gas.
a photocatalyst in the degradation processes of
crystallographic facets in order enhanced various
e- - horganic
+ pollutants
Doping to inorganic
the anatase crystalsproducts (a complete
with magnesium ions
separation and utilization to be achieved.mineralization,
The size leading
or/and to CO2, H2O).silver
photodeposing On the other hand,onrutile
nanoparticles the
of the TiO2 crystallites, the shape of the micro-,efficient
is more {101}in afacets
partialofoxidation of organic
the anatase crystalscompounds
enhanced
nano-structures were tuned [3]. when mild reaction conditions
significantly thearephotocatalytic
required. activity of the
samples under UVA irradiation in comparison to
The produced
The differencescrystal morphologies
between were studied
rutile (r-TiO 2) and
the pure anatase.
negligible. This Theobservation
nanocystals points
doped with at a
as for to (a-TiO
anatase their structure
2 ) and
structuresphotocatalytic
of titanium activity.
dioxide manganese
significantly ions exhibited
more photocatalytic
efficient oxygen activity
reduction
The structure
have a strongofinfluence
the nanocrystals
on their was investigated
physicochemical under
takingvisible
place light.
at r-TiO2 than at a-TiO2. This
using XRD, Rutile-TiO
properties. SEM, TEM, isRaman. a moreThe stable
BET SSA and observation is 8,
consistent
and porosity
2
were investigated by liquid form N2 The Zn (2, 4, 10, 20, 50withandthe higher oxygen
70 %)-modified
usually less photoactive (or even non-active) availability at the surface of rutile.
TiO2 with dominating {001} facets were in the form
adsorption/desorption.
of titanium dioxide [1]. The The adsorption
energy of gap
O2 atwasthe of spheres with the size to depend on the acidity of
surface of the material is associated with an the The
determined with DRS measurements and Kubelka- measurements of redox properties of r-TiO2
initial solution.using Among them, the one
interfacial electron transfer from the surface containing 28made
Munk function. The chemical composition, i.e. and a-TiO a spectroelectrochemical
% Znsignificantly
exhibited better
the reduction
highest
doping with metal ions and photodeposition III of method [7] revealed
defects (i.e. oxygen vacancies, Ti centers) and photocurrent values and the best photocatalytic
silver nanoparticles on selected facets of the properties of r-TiO2 than a-TiO2 (Figure). These
results in formation of superoxide anion [2,3]. O2
adsorption at r-TiO2 is usually much better than at measurements, described in detail during the
a-TiO2. Unusually high photocatalytic activities of conference, confirm a better photoactivity of1 r-
TiO2 have been reported for anatase/rutile TiO2 in the reduction processes (here reduction of
composites. A good example is P25 (Evonik) 98
oxygen), while a-TiO2 appears a significantly
stronger oxidant (here oxidation of water to
offering a very high activity in photocatalytic
hydroxyl radicals). This difference has serious
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

DEGRADATION OF FLAME RETARDANT TRIS (1-CHLORO-2-PROPYL) PHOSPHATE

Degradation of flame retardant Tris (1-chloro-2-propyl) phosphate
will be filled
(TCPP) BY TiO PHOTOCATALYSIS: KINETIC AND MECHANISTIC STUDY in by A2-7
(TCPP) by TiO22 photocatalysis: Kinetic and mechanistic study
EAAOP4
M. Antonopoulou1, P. Karagianni1, I.K. Konstantinou1
(1)Department of Environmental and Natural Resources Management, University of Patras, 30100, Agrinio,
Greece. E-mail: mantonop@upatras.gr; iokonst@upatras.gr

The application of heterogeneous photocatalysis for the oxidation

of aqueous Tris (1-chloro-2-propyl) phosphate (TCPP), a widely
used flame retardant, under simulated solar irradiation has been
investigated. Complete degradation of TCPP (C=25-500 g L-1,
CTiO2=50 mg L-1 and I=250 W/m2) takes place in 20-180 min.
Liquid chromatography time-of-flight mass spectrometry (LC/MS-
TOF) was used for the elucidation of the main transformation
products (TPs) and following a photocatalytic degradation pathway
is proposed including mainly dechlorination, demethylation and
hydroxylation reactions. The roles of reactive oxygen species and
h+ were completely investigated by adding appropriate scavengers
to the reaction medium. Toxicity assessment revealed the
efficiency of the photocatalytic treatment.
1. Introduction identified TPs showed a maximum concentration
The global use of Tris (1-chloro-2-propyl) within 15-60 min and they completely disappear
phosphate (TCPP), an effective halogenated flame quickly after 90-120 min. photocatalytic
retardant, and its incomplete removal by degradation pathway was proposed, including
conventional wastewater treatment plants has led mainly dechlorination, demethylation and
to its accumulation throughout the environment hydroxylation reactions. Based on the
[1]. As a consequence, there is a growing interest luminescence of Vibrio Fischeri bacteria, complete
MODIFIED
inModified
developing PPeffective
PP SURFACE byBY
surface methods PECVD
PECVD forFORuse USE
for removing ASdetoxification
SUPPORT
asit support for TiOFOR 2of
TiO
inthe
the IN THE
solution was achieved of
photodegradation
2
at 120
from aqueous phase. Heterogeneous
PHOTODEGRADATION OF FORMALDEHYDE photo- INmin of irradiation.
GASEOUS PHASE A2-8
formaldehyde
catalysis, in gaseous
represents an examplephase of advanced
oxidation processes, capable of achieving
M.C. Canela 1
*, M.S. Curcio ,
1 2
, W.R.Waldman 3 4. ConclusionsEstadual do Norte Fluminense -UENF,
, E.C. Rangel4,(1)Universidade
Campos dosmineralization
complete Goytacazes RJ, Brazil, organic (2)Results
*mccanela@uenf.br,
of various Instituto of the present
Federal study
Fluminense clearly point out that
- IFFluminense,
Quissam - RJ, Brazil, (3) Universidade Federal
pollutants [2-3]. The present study focuses for the de So TiO
Carlos - photocatalytic
UFScar,
2 Sorocaba treatment
SP, Brazil. is
(4) suitable
Universidadefor the
Estadual Paulista - UNESP, Sorocaba SP, Brazil
first time on the detailed kinetic and mechanistic elimination of TCPP from the aqueous phase. The
investigation of the TiO2 photocatalytic photocatalytic oxidation is mainly explained by
Formaldehyde is a volatile organic compound with high the emission in indoor
participation of environments
HO. On the basisdue toofitsidentified
origin
degradation of TCPP under simulated solar light.
in building materials, furniture and cleaning products. It productsis directly and
associated withasick
radicals, building pathway
proposed syndromeof
(SBS). The use of advanced oxidation process (AOP), inphotocatalytic particular heterogeneous
degradationphotocatalysis, is used
of TCPP is presented.
2. Irradiation procedure- Analytical methods
to address the incidence of this and other pollutants characteristic
Toxicity assessment fromrevealed
SBS. Thealso heterogeneous
the efficiency of
Photocatalytic experiments were carried out in a
photocatalysis works under room temperature and pressure, the and converts organic
photocatalytic pollutants
treatment to to CO2almost
achieve and
solar simulator Atlas Suntest XLS+ (Heraeus,
H2O. complete detoxification of the irradiated solution.
Germany). TCPP concentration and the
This work aims to build a catalytic device to degrade formaldehyde gas by heterogeneous photocatalysis.
identification of TPs, were determined by a LC-
It is made with TiO supported on polypropylene (PP) References coated by organosilicon. The organosilicon film
MS/ TOF instrument.2
deposited by plasma enhanced chemical vapor deposition [1](PECVD),
E. Schreder, is located between
M. J. La PP and
Guardia, TiO 2 and
Environmental
has the function of protecting the polymer from the radicals formed
Science and during photodegradation
Technology, 48 (2014) by TiO 2.
11575.
3. Results
Complete degradation of TCPP (C=100 g L-1, [2] M. Antonopoulou, V. Papadopoulos, I.
-1 2
CTiO2=50 mg L and I=250 W/m ) takes place in Konstantinou, Journal of Chemical Technology
20-180 min. Cl- and PO43- ions reach about 88% and Biotechnology, 87 (10) (2012) 1385.
and 55% of the expected stoichiometric Cl and P [3] I. K. Konstantinou, T.A. Albanis, Applied
amount respectively. According to scavenging Catalysis B: Environmental, 49 (1) (2004) 1.
study, oxidative species, in particular HO, formed Acknowledgments
at TiO2 valence band were predominantly This research has been co-financed by the European
responsible for TCPP degradation in water. A Union (European Social Fund ESF) and Greek
smaller contribution was associated with O2 and national funds through the Operational Program
1
O2 and h+. The parent compound was easily "Education and Lifelong Learning" of the National
degraded under photocatalytic treatment and Strategic Reference Framework (NSRF) - Research
Funding Program: THALIS. Investing in knowledge
transformed into numerous species. All the
society through the European Social Fund.

99 1
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

DETERMINATION OF PHOTOCATALYTIC ACTIVITY OF SELF-CLEANING PAINTS USING

Determination of photocatalytic activity of self-cleaning paints using
SMART INKS
will be filled
A2-9
in by
smart inks
EAAOP4
J.Krsa, M.Baudy, A. Mills2
(1)Dept. of Inorganic Technology, University of Chemistry and Technology Prague, Technick 5 166 28 Praha
6,CZ, krysaj@vscht.cz
(2) Queens University Belfast, School of Chemistry and Chemical Engineering, David Keir Building, Stranmillis
Road, Belfast, BT5 9AG, UK
New method of photocatalytic assessment based on smart
inks was applied on several paints exterior, interior and
laboratory acrylic formulation with TiO2 photocatalyst.
Attention was paid to the influence of accelerated
weathering on paint photocatalytic activity and stability.
Smart inks were proved to be suitable and rapid indicators
of paint photoactivity. Resazurin ink is convenient only for
unexposed paint with low photocatalytic activity while
Acid Violet 7 ink for most of the paints, especially those
exposed to weathering test. Furthermore it has been shown
that self-cleaning paints need some time of weathering to
develop full photocatalytic activity.

Ttb90 values for each ink are summarized in Table

Self-cleaning paint contain besides usual pigments 1. Exterior paint shows the lowest photocatalytic
and fillers also particle of photocatalytic material activity. The Ttb90 for Rz ink was about 4000 s (66
mostly TiO2 of anatase modification. The current min), and for AV7 no measurable photocatalytic
commercial photocatalytic paints are manly with activity (no colour change) was observed even
regard to exterior facade paint which, via the after 70 minutes of UV irradiation. In the case of
SOLAR PHOTOCATALYSIS
photocatalytic TREATMENT
processes treatment
are not susceptible USING
to IMMOBILIZED NF-TlO2 COMPOSITE
Solar photocatalysis using immobilized NF-TiO
exterior composite
paint 2the situation is opposite and paint
WITH
soiling MONODISPERSE
and so help to keep the NANOPARTICLES
TlOexterior of building OF INDUSTRIAL WASTEWATER
with monodisperse TiO2 nanoparticles
2 of industrial
exhibitswastewater
very high activity. The reduction of A2-10
CONTAINING
clean. 1,4 DIOXANE Resazurin to Resorufin is very quick and
containing 1,4-Dioxane
3 Resorufin
This work is a 1,2
D. Hermosilla continuation
, H. Barndkof2,aC.previous
Han 3, D.report [1]
D. Dionysiou , C. Negro2, is A.than reduced
Blanco 2 to another
. (1) Institution, form which is
Address,
from this group
Department which focused
of Agricultural and Forest onEngineering,
the effect University
of colourless. ForSoria,
of Valladolid, determination
Spain, of photocatalytic
dhermosilla@iaf.uva.es.
weathering of acrylic (2) Institution, Departmentactivity
Address,paints,
photocatalytic of Chemicalwe had to use AV7
Engineering, Universidad the Ttb90 was
ink andComplutense
de Madrid, TiO
containing Madrid,
2 andSpain.
ZnO (3) Institution,
on their Address,
photocatalytic about
Environmental 360 s.
Engineering The
and possible
Science explanation
Program, of high
University of
Cincinnati,asCincinnati,
activities, assessedOH, USA.a test based on the
using activity could be in the higher amount of the
bleaching of Acid Orange 7 (AO7) in Non-metal
solution. doping photocatalyst
was usedbuttothis is onlythe
enhance speculation because
photocatalytic
The objective of this work is an application propertiesof aof TiO the2. composition
Optical and ofphysicochemical
the paint was notproperties
provided.ofFor
new method of photocatalytic activity NF-TiO assessment
2 filmslaboratory
were acrylic
improved paintbyit was possible
adding to obtain
P25-TiO 2
based on smart inks. This method nanoparticles.
recently Ttb90 values for both inks. For Resazurin ink the
published in papers [2.3] is based on irreversible Ttb90 value was about 80 s while for Acid Violet 7
Industrial wastewater Ttb90 was contaminated
about 2770 with s (46 1,4-Dioxane
min). It means was
that
colour change of the dye in ink on photocatalytic
successfully treated by solar light applied to immobilized
Ttb90 values for AV7 ink are about 35 times higher films
surface. Excited positive holes are trapped by
of NF-TiO composite than Ttb withvalues
monodisperse
for Rz ink TiO2.
sacrificial electron donor mostly glycerol which is2 90
than oxidized to glyceric acid and excited
The main reaction pathways for the degradation of 1,4-dioxane
electrons reduce dye in ink which is then wereTable
by oxidation 1. Photocatalytic activity unexposed paints
elucitated.
connected with colour change. Compared to Resazurin Acid Violet 7
oxidative bleaching of dyes this process is due to Paint
TiOcharge
good 2-basedseparation
nanotechnology
very quick for and
photocatalytic
the colour active and mechanically Ttb90stable
/s photocatalytic
Ttb90/sfilms
water remediation
change offers various
take few seconds. benefits
The result duetest
of this to its
is [3]. Moreover,
Interior the optical
too fast and physicochemical
36040
highcalculation
the decomposition
of time in efficiency
which 90%and green
of overall properties of NF-TiO2 films were improved by
characteristics
colour of TiO
change occurs 2, e.g.,
(Ttb low toxicity, inert
90). The aim of this work
adding
ExteriorP25-TiO2 nanoparticles
4000600 into thetoo sol-gel
slow [6].
nature,
is and relatively of
the determination lowphotocatalytic
cost [1]. Using sunlight
activity of The incorporation 8015
Laboratory of lab-made monodisperse
2770200
instead of
various UV using
paints radiation allows (Rz)
Resazurin decreasing
and Acid the titania nanoparticles [7] layer-by-layer on NF-
treatment
Violet cost by
7 (AV7) ink.minimizing
Results of the electricity
photocatalytic TiO2, instead of the direct addition of P25-TiO2,
expensesof two
activity [2]. commercial
The immobilization
paints exterior of andthe further improved its photocatalytic performance
photocatalyst
interior would greatly
are compared withenhance the process
laboratory acrylic [8].The However,
next objective thewas immobilized NF-TiO2
to evaluate the influence
engineering containing
formulation by straight-forward
8% of TiO2 separation
P25. and composite
of accelerated withweathering
monodisperse on paint 2 (NF-TiO2-
TiOphotocatalytic
recovery of the catalyst [3] even though it could monodisp.TiO2) has not been tested on industrial
restrict the reactant mass transfer [4], which is the
main obstacle in the ongoing research in 100 effluents. Therefore, in the current research, the
treatment of industrial wastewaters containing 1,4- 1
immobilized photocatalysis. Among the different dioxane by solar photocatalysis was studied using
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

OPTIMIZATION OF TTIP THIN-FILMS FOR REMOVAL OF METHYLENE BLUE will

AND
Optimization
AMPICILLINE ofINACTIVATION
AND TTIP thin-films for
OF E. removal
COLI of methylene
BACTERIA
be filled
in by A2-11
blue and ampicilline and inactivation of E. coli bacteria EAAOP4
Can Burak ZKAL1*, Sreyya MER1 , Dionissios MANTZAVINOS 2
(1) Envrionmental Engineering, Namk Kemal University, Faculty of Engineering, Tekirdag, Turkey;
(2) Dept. of Chemical Engineering, University of Patras, GR-26504 Patras, Greece
* cbozkal@nku.edu.tr
Solar driven photocatalysis defined very competetive for bacterial
inactivation among many disinfection methods. Thin-film structure
is important for an effective disinfection system. This study attempts
to determine the photocatalytic efficiency of immobilized thin-films
produced by TTIP (Titanium Tetra isopropoxide) based sol-gel
methodologies for removal of methylen blue azo dye and for
inactivation of E.coli bacteria under UV-A irradiation following
ISO-27447 & ISO methods. Process efficiency and thin-film
regeneration capacity were followed by TOC, UV-vis absorbance,
SEM, EDX, AFM and FTIR analyses. Bacteria inactivation was also
attempted by Cu and Mn doped thin-films in comparison with the
pure thin-films both under UV-A and UV-visible spectrum. Both
bacteria inactivation and color removal results urge that surface
modifications on thin-films and the need for regeneration during the
photocatalysis process should be addressed particularly to better
represent a real system consisting of both microbial and chemical
constituents.
Keywords: Ampicilline, E.coli, bacteria inactivation, color removal,
photocatalysis, thin film, regeneration
copper nitrate (CAS # 10031-43-3, and manganese
Background nitrate (CAS # 15710-66-4) were purchased from
Advanced oxidation processes (AOPs) are described Aldrich.
THEtheINFLUENCE
with mechanism ableOF INERToxidant
to produce INGREDIENTS
species with IN FORMULATIONS
Preparation of thin ON THE RATE will
films OFbe filled
Theoxidation
Influence of Inert Ingredients as in Formulations on the Rate of
high
PHOTOCATALYTIC potentials. Photocatalysis,
DEGRADATION aOFpotent
PESTICIDES METHOMYL AND CARBOFURAN in by A2-12
Photocatalytic
AOP, Degradation
is also able to provide acceptableof Pesticides
levels of bacteriaMethomyl andsol-gel
3 different Carbofuranmethodologies were implemented EAAOP4
1
inactivation under both 1 artifical and1 solar irradiation 1[10]. The TTIP based sol-gels with acetic acid (A1) and
Anelka Tomaevi
conditions. , Slavica surface
In photocatalysis, Gai , Rada urovi-Pejev
interactions and , Duan
with Mijin2, Aleksandar
PEG+TiO Marinkovi2.
2 additive (A3), TTIP sol-gel with HNO3
(1)Institute of Pesticides and Environmental
attractive/impulsive forces are predominating factors onProtection,Banatska 31b,11080 Belgrade-Zemun,Serbia,
(B1) and with PEG+TiO2 (B3) were coated on glass
Andjelka.Tomasevic@pesting.org.rs.
direct hole+ mechanisms mainly promoting (2) University
formationofofBelgrade, Faculty of
substrates. Technologyaddition
PEG+TiO and Metallurgy,
were carried out
2
Karnegijeva
oxidation 4, 11000
species. Belgrade,
The main Serbia.
advantage of a fixed bed or following the hydrolysis step (with 1 hour intervals
immobilized-thin film (TF) surface application is the between each, at continious mixing in the dark
non-requirement for recovery of the catalyst following
Photocatalytic conditions). TFs
degradation of the were
twoexposed to PCactive
pesticides activityingredients
assessment
treatment, but the longevity of the photocatalyst activity tests (ISO 10678:2010). The
(methomyl and carbofuran) and their commercial products amount of TiO 2 deposited
should be revelaed with standart tests and the target
(Lannate-90 andonFuradan TFs was estimated via gravimetric analysis and
35-ST) in aqueous suspension of ZnO
pollutant removal studies [1,2,3,4]. correlated to the results of suspended photocatalytic
and TiO2 were investigated.
system to remove TheAMP objective of the
(data not investigation
shown). A total number was
Karnegijeva
In 4,11000
this study TTIP basedBelgrade,
TFs were Serbia.
producedto and
study and compare
tested of 6 TFsthe rate glass
coated of photochemical degradation
substrates (representing of
0-30-60-
forAndjelka.Tomasevic@pesting.org.rs.
their photocatalytic activity and bacteriapure inactivation
active ingredients
120-180 and commercial
minutes products with
of photocatalysis and 180 them min in
potentials. Deactivation of TF surface order duringto thefind out the impact
adsorption of inert
conditions) were ingredients
prepared for each and set type of
of the
continous flow circulating system, methylene blue (MB) on experiments.
formulations the degradations process. of
Regeneration It was found out
TF surfaces wasthat the
carried
color removal was examined in parallel to surface out with H2O
photochemical degradation of2/UV
pure process
methomyl according
was to methodology
slower than the
characterisation of TF by means SEM, EDX, AFM, described elsewhere
FTIR analyses. Regeneration requirement isdegradation determined of inactivation
commercial product[5]. To increase
Lannate-90, the bacteria
otherwise the
after a certain cycle of photocatalytic treatment. photochemical degradation capacity of TF, MnNO3 and CuNO3 were
of pure carbofuran was faster than the
added into the sol-gel following the hydrolysis step and
degradation of product
PEG+TiO Furadan 35-ST.
addition. Molar ratios of Mn and Cu were set
Materials/Methods 2
as %0,5-1-2 dopant/TiO2 on w/w basis [6] Isopropanol
Chemicals was used as solvent for the nitrate solution. 3 times of
coating was selected to achieve optimum TF thickness
Ampiciline (AMP) (CAS # 7177-48-2), were on the basis of yielding better photocatalytic activity [7].
Methomyl
purchased from and carbofuran
and used belong
as obtained. to the
TTIP solution 99% after one hour, but only 70% of carbofuran
(CAS# 546-68-9), Titanium dioxide
chemical group of the carbamate insecticides (TiO 2 ) ( # CAS
and from Furadane
Photocatalytic and35-ST
Bacteriawas degraded
Inactivation at the same
Assesment
1317-70-0)
they have was been kindly provided
in use by Aldrich.
for many NuveBefore
years [1]. ND12 time. It should be pointed out that first indication
distilled waterthose
systemactive
was used for the preparation of the Photocatalytic activity tests of TFs coated glass
application ingredients are formulated of decomposition
substrates were made of the product
according to ISO Furadan
10678: 35-ST
2010 for
fresh solutions. Nitric acid(%70 reagent grade), acetic
and come on the market as different products. The was
an disappearing
initial MB concentrationof redof 10 colour
umol/L which
at pH is 10. inert
ISO
acid(%99 reagent grade), isopropanol(%99,7 grade),
products contain
polyethylene beside600
glycol(PEG methomyl
CAS and carbofuran
# 25322-68-3), ingredient inmethod
27447:2009 the formulation.
was followed This tophenomenon
determine
techical variety of inert ingredients which could was registered after one hour.
have different impact on photochemical
degradations of active ingredients. It is a very 101On the basis of those results it can be concluded
that inert ingredients from commercial products
1
important to investigate the degradation of and probably the type of applied formulations can
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

PHOTOCATALYTIC OXIDATION OF SWEETENERS SACCHARIN AND ACESULFAME K.

Photocatalytic oxidation of sweeteners Saccharin and Acesulfame K. will be filled
EFFECT OF INITIAL pH AND PERSULFATE CONCENTRATION in by A2-13
Effect of initial pH and persulfate concentration.
EAAOP4
J. Morales-Meja, D. Lpez, S. Silva, R. Almanza. Universidad Nacional Autnoma de Mxico, Av. Universidad
3000, Universidad Nacional Autnoma de Mxico CU, 04510, Coyoacn, Mxico DF. jmoralesm@iingen.unam.mx

Two synthetic organic sweeteners have been oxidized by TiO2

Saccharin photocatalytic oxidation
at different initial pH values
photocatalysis inside a solar simulator that provided UVA
irradiance. Each sweetener has been treated separately from the
other. We have modified initial pH and persulfate concentration
in order to find an optimal set of conditions for the pollutant
removal under sunlight. Results for each organic molecule
indicate that there is a suitable range of pH and oxidant
concentration that can produce removal with efficiencies of
90% or higher. Kinetics is also analysed and it fits properly the
conventional L-H reaction model. Best conditions we have
found are: acidic pH and low persulfate initial concentration
(lower than the conventionally adopted value of 1x10-3M.

A NEW SUPPORTED TiO2 FILM DEPOSITED ON STAINLESS STEEL FOR THE will be filled
A new supported TiO2 film deposited on stainless steel for the
PHOTOCATALYTIC DEGRADATION OF EMERGING ORGANIC CONTAMINANTS
photocatalytic degradation of emerging organic contaminants in by A2-14
EAAOP4
G. Mascolo1, S. Murgolo1, 2, D. Nasuhoglu1, R. Gerbasi3, Francesca Visentin3, Naida El Habra3, V. Yargeau1
(1) CNR, Water Research Institute, Via F. De Blasio 5, Bari, Italy, giuseppe.mascolo@ba.irsa.cnr.it.
(2) McGill University, Department of Chemical Engineering, University Street, Montreal, Quebec, Canada.
(3) CNR, Institute for Energetics and Interphases, Corso Stati Uniti 4, Padova, Italy.

A new supported catalyst based on TiO2 film deposited on a

stainless steel net by Metal Organic Chemical Vapour
Deposition technique was developed for UV photocatalytic
treatments of a mixture of emerging organic pollutants in
water. Consecutive cycles of organic pollutants degradation
demonstrated that the catalyst can be conveniently re-used for
several photocatalytic treatment batches. Treatments were also
performed in a real secondary municipal effluent to evaluate the
possible application of the developed catalyst for the removal of
emerging organic contaminants from wastewater. Toxicity
investigation on treated water was performed by Microtox
Scanning electron microscope of the
stainless steel coated with TiO2
analysis to evaluate the toxic nature of transformation products
and their chemical structures were investigated employing
liquid chromatography coupled to high-resolution mass
spectrometry (LC-HRMS).

Organic Chemical Vapour Deposition technique

Conventional wastewater treatment processes do
not generally efficiently remove a wide variety of
pharmaceuticals and personal care products
(PPCPs), which consequently end up in receiving
water bodies. Such organic pollutants, classified as
emerging contaminants, have been found in the
aquatic environments with concentrations ranging
from ng L-1 to g L-1 and their adverse effects on
was employed in photocatalytic experiments. In
addition, the photocatalytic performance was
compared to the conventional Degussa P25,
employed as a suspension (50 mg/L).
102The structural characterisation of the supported
1
catalyst was carried out by X-ray diffraction. The
film thickness was determined by using a surface
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

UV-LED TlO2 PHOTOCATALYSIS FOR THE DEGRADATION OF BISPHENOL-A: LED

will VS
UV-LED TiO2 photocatalysis for the degradation of bisphenol-A: be filled
BLACK LIGHT FLUORESCENT LAMP & INVESTIGATION OF KEY PARAMETERS
LED vs black light fluorescent lamp & investigation of key parametersin by A2-15
EAAOP4
K. Davididou1, R. Nelson1, E. Chatzisymeon1. (1) Institute for Infrastructure and Environment, School of
Engineering, The University of Edinburgh, Edinburgh EH9 3JL, United Kingdom, K.Davididou@ed.ac.uk.

A light emitting diode (LED) was compared with a black

light fluorescent lamp (BL) as illumination source for the
TiO2 photocatalytic degradation of bisphenol A (BPA).
LED-photocatalysis was able to remove up to 99.9% of the
initial BPA while the highest removal rate was 66.8 % when
the BL lamp was used for the photo-excitation of TiO2. The
effects of BPA (2.5-10 mg/L) and TiO2 concentration (100-
500 mg/L) on the performance of LED driven
photocatalysis were also assessed. 250 mg/L TiO2 was
proved to be the optimal dosage of catalyst being able to
breakdown 98.9% of BPA in 45 minutes. Increase of BPA,
from 2.5 to 10 mg/L, resulted in removal decrease from 99.9
to 79.7% due to depletion of TiO2 active sites for the BPA
adsorption.

temperature and pressure and catalyst itself

1. Introduction features outstanding properties such as long-term
Endocrine disrupting compounds (EDCs) photostability, chemical inertness, low cost and
regenerate considerable academic and public environmentally friendly nature [7]. To increase
attention due to their widespread occurrence and process sustainability, solar or light emitting
ASSEMBLING
potential impact CELLULOSE
on human health MEMBRANES
and wildlife.WITH GO-TiO COMPOSITES
diodes 2(LED)-based FOR THE can be
photocatalysis
Assembling
TREATMENT cellulose
OF substancesmembranes
ORGANICS INbeen withWATER
SALTY GO-TiO2employed.
compositesInforthis the direction, considerable A2-16
Various chemical have identified
treatment of organics in salty water
as potential EDCs including pharmaceuticals and attention has been drawn to optimize process
J.L. Faria, L.M.
personal carePastrana-Martinez,
products (PPCPs), S. Morales-Torres, efficiencyA.M.T.
pesticides, J.L. Figueiredo, for water
Silva treatment applications [8].
LCM Laboratory
industrial chemicals, of Catalysis and Materials
heavy metals Sunlight driven
Associate Laboratory
and recently photocatalysis
LSRE-LCM, Faculdademakes use of the
de Engenharia,
Universidade do Porto, Porto,
artificial sweeteners (ASs)Portugal.
[1, 2]. jlfaria@fe.up.pt
Bisphenol-A UV band of solar spectrum for the photo-
(BPA), a listed EDC, is used extensively excitation of catalysts in an economic and
GO-TiO Flat in the ultrafiltration
sheet (UF) membranes with photocatalytic
plastic industry
2 for the manufacture of polymers ecological way without the high operating cost of
properties were prepared with lab-made TiO2 and graphene
membrane
(polycarbonates and epoxy resins), flame (GOT).
oxide-TiO 2
the artificial photon generation [8]. LEDs in
These membranes were tested in continuous
retardants and rubber Pollutant
chemicals [1,operation
3], andmode for contrast to low pressure mercury-vapour UV
the degradation of water pollutants under
receives considerable attention as itboth is highly lamps present significant advantages such as
near-UV/Vis and visible light irradiation. The effect of
abundant in water environment [3]. NaCl was also narrower emission spectra, higher output light
investigated considering simulated brackish
efficiency, lower energy consumption, extended
Advanced oxidation processes (AOPs) water and are seawater. A hierarchically ordered membrane was
life time, smaller environmental footprint and are
attractive technologies for EDCs and also PPCPs
prepared by intercalating a freestanding GO membrane in
free of the toxic mercury [9].
treatment due to their ability the structure
of mineralizing them of the M-GOT membrane (M-GO/GOT). The
CO 2 + H2O
completely [1, 4]. Additionally, results key
AOPs feature showed considerably higherLED
In light of this, pollutant removalforinthe
photocatalysis
advantages the economic point ofdarkness
fromphotocatalytic
Ultrafiltration view andand good BPA photocatalytic
removal from activity under near-UV/Vis
aqueous solutions was
disposal of the effluents and
the safe membranes [4].visible
The light irradiation
investigated in continuous modeExperimental
in this study. experiments. series
processes of this category follow the same were conducted comparing the efficacy of LED
reaction
Water way; highly
shortage reactiveissue,
is a critical species,as mainly
clean free
and and BL
visible lightlamp as illumination
irradiation. The effectsources and was
of salinity the
hydroxyl radicals
consumable fresh water (OH),isarebecoming
formed and attack
a scarce effect of key
investigated operational
considering parameters,
simulated brackishnamely
water
non-selectively
resource. refractory
Hence, efficient organic pollutants
purification methods are by catalyst
(SBW, 0.5 load,
g L1initial
NaCl) BPA concentration
and simulated and
seawater
their subsequent
required for producing conversion CO2 and
cleantowater andinorganic
also for treatment
(SSW, 35 g time, on the photocatalytic performance
L1 NaCl).
ions [1]. wastewaters
reclaiming Heterogeneous TiO2 atphotocatalysis
aiming subsequent was assessed.
holds a unique position between other
usage. In recent years, membranes prepared with AOPs due
2.(a) Materials and methods
to its demonstrated
photocatalytic efficiency
nanoparticles haveinattracted
degrading and
a great
finally
deal mineralizing
of attention bio-recalcitrant
due to their organic
superior characteristics 2.1 Chemicals
compounds
(e.g., [5, 6].
anti-fouling andFurthermore,
photocatalyticit isproperties)
chemical
stable, inexpensive, operatesmembranes
in ambient BPA (CAS No: 80-05-7) was obtained from
when compared to conventional [1].
Hereby, the preparation of graphene oxide
(GO)TiO2 composite photocatalysts for solar
applications is described. For instance, by using
103 1
the liquid phase deposition method and subsequent
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

DIPHENHYDRAMINE DEGRADATION BY PHOTO-FENTON UNDER DIFFERENT willLIGHT

Diphenhydramine Degradation by Photo-Fenton under Different be filled
SOURCES
Light Sources in by B2-1
EAAOP4
S. Esplugas, A. Afkhami, P. Marco, J. Gimnez. Department of Chemical Engineering, Faculty of Chemistry,
Universitat de Barcelona, C/Mart i Franqus, 1, 08028, Barcelona, Spain. email: santi.esplugas@ub.edu

Diphenhydramine hydrochloride (DP) is a first-generation

antihistamine widely used in human and veterinary drugs. As
pharmaceuticals are persistent organics in the environment,
utilization of advanced treatment methods is appropriate.
Among them, photo-Fenton is an advanced oxidation process
(AOP) able to eliminate many hazardous organic compounds. In
this work, degradation of DP by photo-Fenton under different
light sources (UV-C, UV-A and Xenon lamp) has been
investigated. From the results it can be seen than, in terms of
efficiency (energy supplied to the lamp/DP removed), the UV-C
source gives the best values in degradation and in
mineralization.

classic H1 receptor antagonist mainly used for

Nowadays the occurrence of persistent and treatment of allergies. Berninger et al. studied the
emerging organic micropollutants - including effects of DP on selected aquatic organisms giving
pharmaceuticals, pesticides, steroids, surfactants, for Daphnia magna a LC50 value (in 48h) of 0.374
flame retardants - in natural waters has raised a mg/L [9].
concern
EFFECT about their impact
OF WATER on environment
COMPOSITION ONandIRON CHELATE BASED PHOTO-FENTON
Effect
public of Water
healthEFFICIENCY Composition on Iron
[1]. Although pollution of surface Chelate Based
The aim Photo-Fenton
of this work focuses on the will be filled
degradation
PROCESS in by B2-2
and ground
process waters is strictly regulated by
efficiency and mineralization of Diphenhydramine in
EAAOP4
Dangerous 1Substances 2 Directive (76/464/EEC), aqueous solution by photo-Fenton treatment with
A. De Luca , R.F. Dantas , S. Esplugas1. (1) Dpt. of Chemical Engineering, Universidad de Barcelona, C/Mart i
substances such
Franqus, 6th as 08028,
floor, pharmaceuticals and personal
Barcelona, Spain, different (2)light
antonelladeluca@ub.edu. School sources.
of Technology, Additionally,
University of the
care products are increasingly detected in the
Campinas, Paschoal Marmo 1888, 13484332, Limeira, Brazil. importance of photolysis and UV-C/H2O2
environment [2]. In Europe, more than 4000 active treatment were also studied.
pharmaceutical ingredients (APIs) are suspected to
reach every environment compartment due the Solutions of 50
In this study photo-Fenton likemg/L of DP (total
at neutral volume 1 by
pH catalyzed o2
human and veterinary drugs use [3]. Fe(III)-NTA L) werewas
Many chelates prepared
appliedand fortreated by photo-Fenton
Sulfamethoxazole (SMX) by
removal.
advanced technologies have proved to be suitable The using
effect three
on the different
treatment devices based
efficiency due ontoUV-C,
the UV-
water
for the removal of persistent organics found in
composition was A andevaluated.
Xe lamps. Thus,
During SMX the experimentation,
was spiked the in
concentration of
treatment plants effluents. Among them, advanced temperature
0.079 mMofintheMilli-Q solution was
water, constantly
tap water,kept riverat
oxidation processes (AOPs) seem to bewater, 25 C and
well water
the most by controlling
secondarytheeffluent
temperature
from ofmunicipal
the jacket
appropriated technologies [4]. AOPs wastewater of the reservoir
are treatment tank by an
plant. Depending of ultra-thermostat
the aqueous matrix bath
considered,
environmentally friendly methods based on in situ The
different information
efficiencies of
as the
SMX experimental
removal wereinstallations
obtained
production of hydroxyl radical (OH) as main
by adding 0.089 maymMbeoffound elsewhere
Fe3+, NTA [10]. aIt1.5:1
to ensure is important
NTA:Fe3+to
oxidant. Hydroxyl radical is able to react ratio andindicate
molar non- 0.29 mM that
of the
H2O installation
2. The highest basedSMX in Xe lamp
removal
selectively with most organic compounds [5] andwas obtained incorresponds
Milli-Q to
water a
(84%)Solarbox
while (SB)
75%, giving
55.4%, a good
21.3%
constitute a good alternative to remove and kindwere simulation
these8.2% of the
the efficiency sun spectra
obtained radiation
in river water, tap water,
wastewater and well water respectively.
of pollutants. One of the efficient AOPs is photo- Concentration of DP was monitored using a
Fenton, which is very effective in degradation of High Performance Liquid Chromatograph (HPLC)
many hazardous organic pollutants [6]. from Agilent (Agilent 1260 Infinity). Total
reactionCarbon
Organic as well (TOC)as thewas effectiveness
measured with of athe
Photo-Fenton is a combination of Fenton reagent
1. Introduction treatment on SMX removal and solution
and Advanced
UV/Vis radiation ( <processes
oxidation providingare Shimadzu
500 nm) (AOPs) mineralization
TOC-VCSN analyzer. Hydrogen
were then evaluated.
extra OH via two additional reactions: photo- peroxide consumption was monitored by a
treatment technologies globally recognised
3+ to Fe2+ and photolysis of
as spectrophotometric method during photo-
reduction
suitable offorFerecalcitrant contaminants removal degradation reactions (Hach Lange DR 3900).
2. Material and methods
hydrogen peroxide [7, 8].
[1,2]. Among them, Fenton and photo-Fenton Ferric ion solution 17.91 mM was prepared
processes are particularly
Diphenhydramine hydrochloridepowerful
(DP) isforthethe The changes
freshly dailyindissolving
concentration of ironFeCl
anhydrous in the form
3 in 0.1 M
achievement of this purpose. Even though, some HCl. Iron chelate solution (0.089 mM of Fe3+) was
modifications in the conventional treatments are
required in order to make them applicable for real 104
prepared by directly mixing in the aqueous matrix
the ferric ion solution with NTA (1.5:1 NTA:Fe 1 3+
applications. In this regards, the scientific molar ratio)[7]. The pH was adjusted to allow the
 ROOM B - FENTON & FENTON LIKE PROCESSES

DEGRADATION OF A NAPHTHENIC ACID MODEL COMPOUND BY NITRILOTRIACETIC

Degradation of aFENTON
ACID-MODIFIED Naphthenic Acid Model Compound by
PROCESS B2-3
Nitrilotriacetic Acid - Modified Fenton Process
Y.Zhang1, N. Klamerth1, M. Gamal El-Din1. (1) Department of Civil & Environmental Engineering, University of
Alberta, 116 St. And 85 Ave., Edmonton, T6G2R3 Canada, yz5@ualberta.ca.

Cyclohexanoic acid (CHA) as a naphthenic acid model

compound at 0.39 mM was chosen to investigate the efficiency
120 of a nitrilotriacetic acid (NTA) - modified Fenton process at pH
0.27 mM Fe
CHA removal (%)

100 0.45 mM Fe * 8. Degradation of CHA was greatly influenced by H2O2 dose,

80 0.89 mM Fe but not influenced by mode of dosing, while Fe-NTA complex
concentration influenced the degradation time mainly. The
60 process achieved CHA degradation of 95% with 5.88 mM H2O2
40 and 0.45 mM Fe-NTA (NTA:Fe = 1:1) in 5 hours.
20 Although the Fe:NTA complex is a 1:1 stoichiometric complex,
0 higher H2O2 decomposition rate were achieved with a Fe:NTA
0.29 1.47 2.94 4.41 5.88 ratio of 1:2 than 1:1. The OH radical was the main responsible
H2O2 (mM) radical for CHA degradation, as tested by radical scavenging
experiments.

The oil sands industry in northern Alberta, [4] for the decomposition of H2O2 and 2,4-
Canada produce large amount of oil sands process- dichlorophenoxyactic acid among 50 chelating
affected waters (OSPW). These waters are basic agents.
(pH 8) and a complex mixture of inorganic (silts, Although several chelate driven Fenton
sands, salts, heavy metals) and organic processes have been described in the literature,
(naphthenic acids, residual bitumen, BETX, there is no report of these processes for the
Acrylic Textile
ACRYLIC
phenols) TEXTILE Dyeing
contaminants. Wastewater
DYEING
OSPW WASTEWATER
is acute Treatment by
and TREATMENT Combination
treatment of BY
OSPW ofor NAs model will
COMBINATION OF be filled
HETERO-
compounds
in by so
Heterogeneous
GENEOUS Fentons
FENTONS Oxidation
OXIDATION
chronic toxic to numerous organisms. Due to the in
IN Aa CSTR
CSTR and
AND Biological
BIOLOGICAL DEGRADATION
far. To further advance the knowledge IN A SBR
of these B2-4
EAAOP4
Degradation restrictions
environmental in a SBR and the self-proclaimed processes and eventually promote their
Brunodischarge
zero M. Estevespolicy
1
, Carmen S.D.industry,
of the Rodriguesthese
1
, Rui A.R. Boaventura
waters 2
, F.J. Maldonado-Hdar
applications 3
for the degradation, Lus M.ofMadeira
NAs and 1,
. other
(1) LEPABE,
are stored Department of Chemical
in large ponds. TheEngineering
naphthenic(DEQ), Faculty of organic
acids Engineeringcontaminants
University of Portoin (FEUP),
OSPW, R. Dr.this
Robertostudy
Frias, 4200-465 Porto, Portugal. (2) LSRE, Associated laboratory LSRE/LCM, DEQ, FEUP, R. Dr. Roberto Frias, 4200-465 Porto,
(NAs) present in OSPW of concentrations up to assessed the degradation of CHA
Portugal. (3) Department of Inorganic Chemistry, Faculty of Sciences, University of Granada, Avenida de Fuente Nueva, 18071
in the NTA-
100 mg/L
Granada, aremmadeira@fe.up.pt.
Spain. thought to be the main culprits for modified Fenton processes at pH 8 and ambient
the OSPW toxicity. NAs are a group of aliphatic temperature. The parameters investigated in this
and alicyclic compounds with a general The treatability
formula of of an
study were acrylic textile the
as follows: dyeing
dosewastewater
of H2O2 and by Fe-
CSTR
CnH2n+zOx, where n represents the carboncombination number, of heterogeneous
NTA, the ratio of NTA Fentons
to Fe, theoxidation and
redox potential
z the hydrogen deficiency number (0 or biological negative degradation
of Fe-NTA was solution.
evaluated To in this work. the oxidant
determine
even integer) and x the number of oxygen atoms In the oxidation stage, performed in a
species responsible for the degradation catalytic continuous
of CHA,
present (x = 2 for classical NAs, x 3 forstirring oxidizedtank reactor
two different(CSTR), it wasscavengers
radical evaluated were the effect
used, of TBA
NAs)[1]. Additionally several aromatic some andoperating as conditions,
a scavenger namely
of OHthe type andofchloroform
catalyst usedas a
heteroatomic groups of NAs have been (Fe-containing found in zeolite, activated
scavenger carbon impregnated
of O2-. Through the analysiswith of the
OSPW [2,3]. Due to the toxicity and recalcitrance iron acetate and iron nitrate), hydrogen
species in the reactions, we proposed peroxide feed
the reaction
of NAs to biodegradation, their removal concentration,
from contact time
mechanism of and temperature.Fenton
NTA-modified Underprocesses.
the best
OSPW has been attracting attentions operating
from conditions it was reached,
Experiments at steady-state,
were conducted using CHA62.7 and as one
SBR
researchers since 1980s. 39.9% of color of and TOC removal,
the simplest cyclic NAsrespectively;
as a model moreover,
compound
AOPs are attractive options to degrade the NAs effluent
into biodegradability
to study the degradation was significantly
mechanismimproved of NAs by
biodegradable degradation products, and among (BOD 5 :COD was raised from <0.001
NTA-modified Fenton processes. to 0.29 and specific
these AOPs the Fenton process is a particular oxygen specificTouptake rate (SOUR)
investigate the impact from < 0.2 toand
of Fe-NTA 11.1 H2O2
potent application, because it is fast, low mgO /(gSSV h))concentration
cost,2and and the toxicity on (towards inhibitionofof Vibrio
the degradation 0.39 mM
easy to handle at room temperature. The onlyreduced
fischeri) CHA from 92.1-94.0
in the to 6.9-9.9.%.
buffer solution at pHThese results
8, several doses
down side of the Fenton process is the need allowed
for a the ofapplication
H2O2 (0.29,of1.47, the2.94,subsequent
4.41 and 5.88 biological
mM) and
degradation in a sequential
three different dosesbatchofreactor
Fe-NTA(SBR). (0.27, Upon
0.45 and
pH 3, so research has been conducted on chelate
combination of 0.89these mM) twowere
processes
tested. highThe overall
removal treatment
of CHA
modified Fenton processes, which can remove
performance was increasedreached withandincreasing
an effluent H2Othat meets the
contaminants at neutral pH. Among the potential 2 dose. Removal
legislated discharge
rates were valuesaround
was obtained.
20% for 0.29 mM H2O2 and
chelating agents, NTA has been proven to be one
of the most active chelates by Sun and Pignatello around 95% for 5.88 mM H2O2. The difference in

1. Introduction 105
important disadvantage, heterogeneous Fentons
oxidation has been used, where different forms to1
Effluents produced by textile dye-houses are attach the iron species to a porous solid matrix
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

OXIDATIVE AND REDUCTIVE DEGRADATION OF AN AZO DYE, AMARANTH, USING ZERO

Oxidative
VALENT andNANO
IRON reductive degradation of an azo dye, amaranth, using Zero Valent Iron
PARTICLES B2-5
Nano Particles
V.A. Sijumon1,3, U.K. Aravind1, C.T. Aravindakumar2,4. (1) Advanced Centre of Environmental studies and
sustainable Development, Mahatma Gandhi University, Kottayam, Kerala-686560, India,
sijuabraham7@gmail.com (2) School of Environmental Sciences (3) School of Chemical Sciences (4) Inter
University Instrumentation Centre, Mahatma Gandhi University, Kottayam, Kerala-686560, India.

Oxidative and reductive degradation of an azo dye, amaranth,

The Graphical Illustration (Figure,
Scheme, etc.) should not exceed
the size of this area.
using zero valent iron nano particle and its potential application in
coir factory waste water was investigated. A complete
decolourization and reasonable mineralization was observed using
nano scale zero valent iron treatment. Four major stable
intermediates were identified using LC-Q-TOF-MS analysis and
this allowed us deducing a complete reaction mechanism.

identified using Waters Acquity, UPLC system

INTRODUCTION coupled with a Waters Xevo G2 Quadrupole
Textile industry is one of the major sources of Time-of-Flight (Q-TOF) high resolution mass
environmental pollution and azo dyes are the spectrometer.
major class of colorants used in textile and coir
RESULTS AND DISCUSSION
industry. Azo dyes are among the prominent
pollutants present in the textile effluent. Amaranth It is observed that synthesized zero valent iron
is one of the azo dyes used in textile
SYNTHESIS AND EVALUATION OF A NEW Fe/ALGINATE and coir nano particles can effectively remove
HETEROGENEOUS the color and
CATALYST
Synthesis
industry
FOR [1].and
Costevaluation
PHOTO-FENTON
of a new
effectiveness, Fe/alginate
environmental
AND SIMULATED SOLARTOC
heterogeneous
of amaranthcatalyst
PHOTO-FENTON under optimized will
AT NEUTRAL
be filled
condition.
pH in by A B2-6
for photo-Fenton
friendly nature, and itsand simulated
unique ability solar photo-Fenton
to activate complete at decolourization
neutral pH and 51% TOC reduction
EAAOP4
peroxides made iron as a transition metal of choice was observed within 15 minutes of treatment. The
C. Sans1, A. Cruz1, S. Esplugas1. (1) University of Barcelona, Department of Chemical Engineering, C/Mart i -1
for environmental applications. Oxidative and
Franques 1, 08028, Barcelona, Spain, carmesans@ub.edu
ideal operational conditions were 1.5-2.5gL of
reductive mechanisms are possible with this ZVINP, 15-30 minutes of reaction time, stirring
catalyst [2]. In this study the oxidative and speed of 150-200 rpm and pH of 3-9 for initial dye
reductive degradation of an azo dye, Photo-Fentonamaranth, concentration
is a well-known of AOP mgL-1.efficiency
50-70 which The complete
and
using zero valent iron nano particleapplications and its have decolourization was resulted
been limited because of the from the substantial
low solubility and
potential application in coir factory waste azo link
water activity
non-catalytic cleavage.
of most iron ESI-MS(-ve)
species at neutralmonitoring
pH. To of
were investigated. overcome this stable
handicap,intermediates afterheterogeneous
a Fe/alginate nano scale zero valent
catalyst
has been iron treatment
synthetized and led for
tested to the
this identification
reaction by of stable
using a
MATERIAL AND METHODS intermediate products such as 4-
UVA batch reactor and a simulated solar light reactor.
Amaranth, ferric chloride hexahydrate aminonaphthalene-1-sulfonic
(Loba activity
Its catalytic has been proved for bothacid (m/z on
processes = the222),
chemie, India), sodium borohydride (Merck, India) of a2,2'-(3-amino-5-sulfobenzene-1,2-diyl)diacetic
degradation reference emerging pollutant.
were used as received. Nano scale zero valent Resultsiron acidproved
have also (m/z the= dependence
288), 4-[2-(3-sulfonaphthalen-1-
of catalyst stability
particles (ZVINP) were chemically synthesized in pH,
with sample yl)hydrazinyl]naphthalene-1-sulfonic
turning the homogeneous reaction acidinto
(m/za =
the laboratory as per the reported method [3]. 443), {3-hydroxy-4-sulfo-2-[2-(4-sulfonaphthalen-
second reaction pathway of degradation if pH reduces under a
Experimental variable such as reaction time, which
limit value 1-yl)hydrazinyl]phenyl} acetic acid
depends of alginate carboxylic groups (m/z
pKa=467).
.
ZVINP dosage, initial dye concentration, pH and The results obtained using UV/Vis, TOC, HPLC
stirring speed were considered. Absorbance and LCMS techniques confirmed that these
measurements were carried out by UV-visible compounds degraded by several pathways; initial
spectrophotometer (Shimadzu UV-2450). Total step was azo bond cleavage and subsequent
Organic Carbon (TOC) values were obtained by solid catalyst.As the ZVINP dosage increases, the
degradation.
Introduction
Thermo Scientific Hiper TOC analyser with IR surface
Materials areaandforMethods
reaction also increases but
Photo-Fenton
detector. is an advanced
Degradation of parentoxidation
compound process
and dissolution of iron may retard the efficiency after
(AOP)
formationbased on the catalytic
of intermediates werereaction
determinedproduced
using certain limit. As seen
A homogeneous from(m/m)
2.5% results,sodium
at pH = 3; the
alginate
when
HPLChydrogen
coupled peroxide
with a isDiode
irradiated
Arraywith UV-A
Detector treatmentsolution
aqueous was most effective
was due Sodium
prepared. the added effect
alginate
light in presence
(Shimadzu of someStable
LC-20AD). iron species.
intermediates after of Fenton
solution was reaction
warmed toin40C addition
for 24 htoto reductive
decrease
nano mechanism
the solution [4,5]. Application
viscosity of theseairoptimised
and to eliminate bubbles
Due scale
to thezero
low valent Ironandtreatment
solubility were
low catalytic formed during the mixing process. The solution
activity of most iron species at neutral pH, the
efficiency and application of this process has been
limited to been usually applied at acidic pH, which
106
was introduced on syringes on the top of a vacuum
chamber, and a 0.05M FeCl3 hardening solution 1
was placed inside.
 ROOM B - FENTON & FENTON LIKE PROCESSES

TREATMENT OF REAL EFFLUENTS BY NANOFILTRATION AND SOLAR PHOTO-FENTON:

Treatment of Real Effluents by Nanofiltration and Solar Photo-
ANALYTICAL AND TOXICOLOGY ASSESSMENT
will be filled
B2-7
in by
Fenton: Analytical and Toxicology Assessment
EAAOP4
S. Malato1,3, S. Miralles1,3, J.A. Snchez-Prez3, Isabel Oller1,3, A, Agera,3, M. Llorca,4(1) Plataforma Solar de
Almera-CIEMAT. 04200 Tabernas (Almera), Spain, sixto.malato@psa.es. (2) Dep. Chem. Eng., University of
Almera, 04120, Almera, Spain. (3) CIESOL, Joint Centre of the University of Almera-CIEMAT, 04120, Almera.
(4) Catalan Institute for Water Research (ICRA), University of Girona, Emili Grahit 101 Girona, Spain
Combined nanofiltration/solar photo-Fenton process at pilot
plant scale at low iron (<0.2mM) and H2O2 (<2mM)
concentrations for the treatment of effluents of municipal
wastewater treatment plant (MWWTP). Effluent was directly
WW + ECs
or reuse AOP For reuse treated and compared with the treatment of membrane rejection
under different conditions. A QTRAP MS/MS system
ntrate
combined with solid phase extraction was used to evaluate
Permeate

Concentrate
Biotreatment

+ ECs micropollutants (MPs) degradation and >90% degradation took

less than 12 minutes. Acute and chronic toxicity has been also
evaluated by Vibrio fischeri and Daphnia magna. Treated
NF/RO Pre-treatment NF/RO
effluent by solar photo-Fenton showed insignificant acute
toxicity by both bioassays. Chronic toxicity in Daphnia magna
was observed in untreated effluents that did not increase during
the treatment but did not reach harmless conditions.

Membrane technologies have emerged as a solar photo-Fenton assays were carried out in this
significant innovation for treatment and study: (i) Direct treatment of water or MWWTP
reclamation of water, as well as a leading process effluent; (ii) water or MWWTP effluent spiked
for upgrading and expanding wastewater treatment with model MPs (at 15 g L-1 each), NF and
HETEROGENEOUS FENTON-LIKE
plants. The main drawback of the membrane DEGRADATION OF NAPHTHENIC
treatment of the concentrate ACIDSbyMODEL solar photo-
Heterogeneous
COMPOUNDS BYFenton-like
ACTIVATED Degradation of Naphthenic Acids Model will be filled
technology applied to MWWTPAND MESOPOROUS
effluents is Fenton;CARBON (iii) NF IMPREGNATEDof MWWTP WITH effluent Fe,
in byand
FeCompounds
O
probably
2 3
AND the by Activated
-FeOOH.
discharge of the and Mesoporous
concentrate with Carbon
treatment Impregnated
of with by photo-Fenton,
concentrate EAAOP4 B2-8
Fe, This
MPs. Fe2Oconcentrate
3 and -FeOOH. must be treated to minimize evaluated by QTRAP MS/MS. MWWTP effluent
1 1
N. Klamerth
MPs , M. Meshref
environmental , M. Gamal
impact, El-Din1 to the
or returned was pretreated by conventional filtration in which
(1) University
biological of Alberta,
system whereDepartment
they would of Civil & Environmental
accumulate. Engineering,
mainly suspendedEdmonton, Canada,
solids T6G 2W2,turbidity
(62-88%
klamerth@ualberta.ca
MPs in MWWTP effluents are in the hundreds of reduction) were removed. Second, the pretreated
g L-1 range as a whole of all. Degradation and adsorptioneffluent
MWWTP of three was different naphthenic by
concentrated acidsNF
An Advanced Oxidation Process (AOP) as a (NAs) was investigated on activated
maintaining a cross-membrane pressure (CMP) carbon (AC) andnot
polishing step could solve these problems, mesoporous and Carbon
higher meso)5-bar,
(Cthan impregnated
with a with -FeOOH,
through-flow rate Fe
of O3
2500
may therefore be a viable option for and membrane Fe0 respectively.
700 L h-1. These NAs were
The concentrate stream 1,3-Adamentane
was returned to
concentrate treatment. Although dicarboxylic chemical the acid
feed tank(ADA), while the Methyl-octahydro-3-
permeate stream was
pollution of MWWTP effluents is low, methylpentalene-1-carboxylic
flow rates purged. Once theacid concentrate(MOPCA) was preparedand 2,2- a part
3 Dicyclohexylacetic acid (DCHA). High decomposition rates of
are very high (tens of thousands of m per day per of it was transferred to a solar CPC photoreactor
plant) making optimized treatment essential. H2O2Solarin the presence of carbon- iron
for photo-Fenton composites were observed.
treatment.
photo-Fenton has been demonstrated to Experiments be a good were conducted at neutral pH with a mixture of
option for the removal of MPs from water three NAs at a total of 45Natural
systems mg/L. water
Removal a
of over NF82% of model
concentrate b
25

[1]. Thus mild photo-Fenton conditions (natural compounds in 48h15 was achieved
spiked with using
MPs 200150 mg/L H O
2 2 although
pH, low H2O2 and low iron concentrations) individual are naphthenic acids had Ofloxacindifferent removal rates.
sulfamethoxazole
consumed HThis
2
O 2
20

required to improve treatment competitiveness might and be attributed to thecarbamazepine chemical structure of these
Concentration (g/L)

Flumequine

maximizing the reaction rate is an important compounds.

issue.
H2O2 (mg/L)

Ibuprofen
10 100 15

Therefore, combination with NF could make

sense, because photo-Fenton is governed by first degradation products, and among these AOPs the 10
Overkinetics,
order 169 billionand barrels of recoverable
the concentration of bitumen
MPs is Fenton process is a particular potent application,
5 50
are available
higher in theinNF theconcentrate
Athabasca oil thansands deposits,
in the feed because it is fast, low cost, and easy to handle 5at
making
stream. Canada the country with the third largest roomDarktemperature. However, the optimum pH for
oilPhoto-Fenton
reserves in the world. isThe
efficiency poorsurface mineable
at neutral pH FentonFenton
reactions is 3, thus the requirement 0of
bitumen Fe(III)
is extracted
is infrom the sands formby a caustic
0 0

because its insoluble (ferric

3 large-25 amounts
0 25
of acid
50 75 100
before-25
and
0 25
alkaline
50 75
after
100

hot water method,

oxides), but whichpolycarboxylates
generates about 2.5 mand of illumination time, min
treatment
Figure for neutralization
1. Degradation of five MPswill resultwater
in natural in athighpH
oil sands process-affected
aminopolycarboxylates form water (OSPW)
strong per m3
complexes 3+
5costs.
by Besides, the
photo-Fenton slow conversion
(0.1mM Fe(II), 25 of Fe
mg/L H O to Fe2+
).
oil sands
with processed.
Fe(III), keepingThis OSPW
it soluble is Three
[2]. sent totypes
tailingsof
2 2
required large amounts of ferric salts to maintain
ponds, where the water is separated from solids
the concentration of Fe2+ during the reaction.
and recycled back into the extraction process.
About 80% of OSPW is recycled and due to the
107
Additionally, the Fe3+ containing sludge following 1
9 3 the Fenton reaction after neutralization is a serious
zero discharge practice there are about 10 m of
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

TOWARDS AN ENHANCED BIODEGRADABILITY OF AN ACTUAL

PHARMACEUTICAL WASTEWATER
Towards an Enhanced Biodegradability of an Actual Pharmaceutical B2-9
Wastewater
F. Martnez, M.I. Pariente, Y. Segura, R. Molina, I. Rodrguez, J.A. Melero. Department of Chemical and Energy
Tech., Chemical and Environmental Tech., Mechanical Tech. and Analytical Chemistry, ESCET, Universidad Rey
Juan Carlos, 28933, Mstoles, Spain. fernando.castillejo@urjc.es.

This work is focused on the treatment of a pharmaceutical

wastewater by different strategies in order to achieve an optimal
pre-treatment to decrease the high organic loading (COD of 7 g/L
and TOC of 1.5 g/L) and increase its biodegradability, promoting
a further biological treatment in a cost-effective approach.

Fenton-like processes based on dissolved Fe/Cu salts and solid

zero-valent iron (ZVI) have been studied. ZVI treatment led to
remarkable TOC removal (65%), whereas homogeneous Fenton
process achieved the highest biodegradability value (74%).
.

The effective removal of substances included in Table 1 summarized the main results obtained for
pharmaceutical residual effluents is a challenging all the catalytic runs, in terms of TOC removal,
task due to the wide variety of chemicals produced H2O2 consumption, biodegradability and toxicity of
in drug manufacturing plants, which lead to the treated effluents.
wastewaters of variable composition and refractory
Catalytic removal of binary mixturecost-of dyesTable
with opposite
1. Resultsand will beFenton
filled in and
by EAAOP4
to biological degradation. In this sense, the Fenton of homogeneous
CATALYTIC processREMOVAL OF BINARY
to be aMIXTURE OF DYES WITH OPPOSITE AND SIMILAR
similar charges of inPRESENCE
the presence OFof ceria/H O2FENTON-LIKE
Fenton-like system
oxidation has been found heterogeneous ZVI experiments.
CHARGES
effective IN THE
treatment organic compounds from 22O
CERIA/H 2
SYSTEM
XTOC XH2O2 Biod. Tox.
B2-10
different sources [1]. In order to overcome the
H. Issa of
Hamoud, B. Azambre, G. Finqueneisel
(%) (%) (%) (%)
production large amounts of metal sludge in the
Universit
finaldeneutralization
Lorraine - Laboratoire de Chimie et Physique Approche Multi-chelle des Milieux Complexes (LCPA2MC)
a 100 47 7
necessary step of homogeneous ZVI-50% 38
EA n 4632, Institut Jean Barriol Rue Victor
Fenton processes, zero-valent iron (ZVI) could be Demange, 57500 Saint-Avold,
ZVI-100% a France. 60 100 65 < 2
usedHoueida.issa-hamoud@univ-lorraine.fr
as an alternative way to induce Fenton-like ZVI-200%a 63 100 44 <2
oxidation [2]. Fenton-50-300% b 35 58 67 37
In this work, different Fenton and ZVI systems Among the Advanced
Fenton-100-300% c Oxidation
42 100Process 54 (POA), 16 the systems
were evaluated as pre-treatments of a based on Fe(III)/Fe(II)
Fenton-50-100% b 41as the100 active 74Fenton7.5 species were
pharmaceutical wastewater characterized by a found
Reactionto bea120
time: efficient
min, b24 h,for
c
180the
min.treatment
Code: Fentonof heavily-charged
type-
Chemical Oxygen Demand and Total Organic wastewaters containing
temperature in case dye Fenton-
of homogeneous mixtures. [1]. In the search of
H2O2 concentration
Carbon of 7.0 and 1.5 g/L, respectively. Moreover, novel effective solid catalysts, ceria has attracted some interest
low biodegradability (26 %) and partial toxicity (13 because
In all of its unique
systems, structuralTOC
a remarkable properties
removal andwas high oxygen
%) was also established by respirometric tests. mobility.
obtained, Oxygen
especially vacancy
for the defects
ZVI.can be rapidly
However, theformed and
Homogeneous Fenton experiments were eliminated
results showed on thethatsurface TOC ofdegradation
ceria, in relation
is not with the
4+
performed in a batch reactor, using FeSO4 and Ce /Ce3+ redox
necessary correlatedcycle. to Recently, the mechanism
high biodegradability and of Fenton-
CuSO4 as catalysts and temperatures of 50 and like
low reaction
toxicity, catalyzed
probably by nanoceria
due to has the been reported. It was
different
100C. The ZVI runs were performed in an aerated proposed
intermediatesthat itformed
involved duringin athe
first step theThus,
reaction. the of H O
activation 2 2
(5 LAIR/min) batch reactor at room temperature. In by Ce4+/Ce3+ sitesallowed
Fenton-50-100% to generatea lowersurface
valueperoxide
of XTOCspecies [2].
both cases, initial H2O2 concentration was The
withlatter decomposed
a higher into highly
biodegradability, reactive hydroxyl
appropriate for a radicals
calculated according to the reaction 1 for the allowing
subsequent the treatment
sequential in degradation
a biological of organic dyes. However,
depuration
theoretical total carbon mineralization contained in no particular attention was devoted to the adsorption and
system.
the wastewater. The hydrogen peroxide was varied discoloration of binary mixtures of dyes in the presence of
CeO 2/H2O2 system.
[1] P. Bautista, A.F. Mohedano, J.A. Casas, J.A. Zazo, J.J.
between half to triple stoichiometric concentration, Rodrguez, Journal of Chemical Technology and
coded as 50% to 300%, respectively. The present study
Biotechnology, focuses
83 (2008) 1323.on the adsorption and discoloration
of
[2]binary
Y. Segura,mixtures of dyes
J.A. Melero, R. with
Molina,similar (Orange
R. Chand, D.H. II & Acid
C + 2H2O2  CO2 + 2H2O (1) Green
Bremmer. 25) and opposite
Applied charges
Catalysis B: (Orange II & Malachite
Environmental, 113 green)
by a CeO
(2012) 100.2 catalyst in presence of H2O2. First, ceria was
characterized by XRD, Raman spectroscopy and N2
physisorption at 77 K. Then, the thermodynamic and kinetic
108
adsorption behavior, including the pH effect, as well as the
discoloration rates were studied using UV-Vis spectroscopy. It
1
was shown that the adsorption of dyes is highly pH-dependent
 ROOM B - FENTON & FENTON LIKE PROCESSES

EFFECT OF HYDROXYL GROUPS SUBSTITUTED IN THE CHANGES OF SOLUTION

TURBIDITY DURING THE OXIDATION OF AROMATIC CONTAMINANTS

B2-11

This work analyzes the turbidity generated in aqueous samples
containing several kinds of contaminants, able to be degraded by
OH H O
photoFenton treatment. Paracetamol has been considered as a
model compound for this study, because its internal structure is
constituted by a benzene ring substituted by a hydroxyl group,
OH HO
similar to phenol.
We present the effect of the substituent groups in the turbidity
generated in aqueous solutions of aromatic contaminants, phenol
and paracetamol like, degraded by photochemical oxidation. A
A possible structure mechanism is proposed of degradation of paracetamol, enhancing
generator of turbidity the currently accepted, showing that its decomposition can proceed
through intermediates like those of phenol decomposition

Keywords: resorcinol, turbidity, phenol

2. Materials and methods

1. Introduction
The experimental assays of this work are carried
Advanced Chemical Oxidation Processes out with synthetic solutions of 500.0 mL. The
(AOPs) are utilized to degrade
Adsorption-oxidation toxicfor
processes andremoval
highly of specific
organiccatalyst
contaminants
dose for each will beisfilled
experiment added
ADSORPTION-OXIDATION PROCESSES FOR REMOVAL OF ORGANIC CONTAMINANTS
refractory pollutants in the wastewater of in by
by
BY heterogeneous
HETEROGENEOUS Fenton-like
FENTON-LIKE process
numerous industrial processes. Studies reported in
using
PROCESS Pd/Fe-zeolite
asUSING
ferrous based
ions (FeSO4 2H
Pd/Fe-ZEOLITE 2O Panreac, 80%).
BASEDCATALYSTS
EAAOP4
B2-12
catalysts These reagents are mixed in a photocatalytic
the literature show
1
that some1 parameters2 of reactor 1equipped with a1 cooled quartz sheath,
Shailesh S. Sable
organoleptic , Pallavi
nature P. Ghute
(color, , Anett Georgi
turbidity) can , Francesc
be Medina , Sandra Contreras
(1) Department dEnginyeria Quimica, URV, Av. Pasos Catalans, inserting a UV Spain.
26, Tarragona, lamp (Heraeus TQ150, Hg
regarded as indicators of water quality [13]. medium pressure, 87.4V, 167.3W, 2.20A), with
Email: shailesh.sablepatil@gmail.com, sandra.contreras@urv.cat
(2)Department of Environmental
This paper presents a studyTechnology, 95% 15,
UFZ, Permosertrasse
on the nature of transmission between
04318, Leipzig, 300570 nm. The
Germany.
organoleptic parameters, including turbidity, to In this reaction
studymixture is homogenized
the degradation by a magnetic
and mineralization of
analyze their suitability to be efficiency indicators phenol stirrer at 500 rpm,by while
was investigated acidity
Fenton-like adjusted
process usingat
of the water treatment containing pharmaceuticals. two pH=3.0,
Adsorption types pouring NaOH=0.2M
of Pd/Fe-ZSM5 (Probus, 99.9%)
(hydrophilic and
Specifically, the study focuses on the application hydrophobic)with an catalysts
automaticat buretteconditions
ambient (Dosimatand665at
CO2 Metrohm), andwith
temperature stabilized at 25.0C,
of photoFenton Technology to degrade pollutants nearly neutral pH, and without in-situ generation
acetaminophen typePd Pdin aqueous medium
Pd Pd Pd Pd Pd Pd
[4].
OH of Husing a cryothermostat bath (Selecta Frigiterm
2O2. Fe-ZSM5 (236) showed excellent adsorption
of 10,
phenol 1150
from watts),
aqueousrecirculating refrigeration
solution. The best resultwater
for
Oxidation

In order to performPd the study, some Pd pollutants of through the cooled sheath. The solution turbidity is
various kinds Pd
are selected, which Pd are usually phenol degradation and mineralization was observed
. Pd Pd Pd
overmeasured
0.1 wt% with a Nephelometric
Pd/Fe-ZSM5(26/236) using turbidimeter
commercial
present HO in the wastewater
Pd
Pd produced by a
Pd Pd (2100Qis Hach).
significant segmentPd of urban society. Due to their H2O2, achieving total conversion of phenol in 2h and
common use, pharmaceuticals such as analgesics 60-63% mineralization degree in 6h. This study
(paracetamol), antiinflammatories (ibuprofen) and shows 3. that Fe-ZSM5 are promising catalysts for a
Results andofdiscussion
antibiotics (flumequine) are increasingly H2O2 found in combined approach adsorption/oxidation of phenol
H O Pd/Fe-ZSM5
municipal2 sewage and even drinking water. Once by commercial H2O2 andpathway
3.1. Chemical also Pd/Fe-ZSM5(236)
proposed for
decomposed by the body organisms, these drugs shows better
paracetamol (acetaminofen)generated
activity by in-situ oxidationH2O2.
generate metabolites that are excreted together
with their residual active ingredients. As a result, The degradation mechanism proposed in this
work (Fig.
they often reach the wastewater treatment plants. commercial
Introduction: H2O21)andis also
based on the breaking
hydrophobic of the
Pd/Fe-ZSM5
The increasing
These organic
substances, even pollution in water sources
in low concentrations, can interesting alternative in order to achieve the
showsparacetamol
better molecule
activity by through
in-situ bonds
generated linking
hydrogenan
in
belast decades promoted
as they the
aredevelopment
accumulatedof in
water amino group
peroxide.
improved to theofbenzene
degree ring, ofandHthe
utilization bond
dangerous, the 2O2 for
treatment
receiving environment [5]. Phenolic compounds
technologies. linking the degradation
contaminant amino group with the
compared to itssubstituted
parasitic
removal is a very active research field due to the methanol group. The selectivity of
decomposition and also lowering the relevant the reaction
cost
occurrence and toxicity of phenolic pollutants in mechanism
of is favored
transportation, by and
storage hydroxylation
handling. of the
Also,
industrial wastewaters. Wastewater originated
from many industries likes paper and pulp, resin 109
Fenton-like process has shown good performance
with catalytic in-situ generated H2O2 using Fe-Pd1
gas and coke manufacturing, tanning, textile, bimetallic catalytic system [7-8]. Zeolites are
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

PHOTOCATALYTIC REDUCTION OF Cr(VI) OVER Fe(III)-CITRATE COMPLEXES willIN

beAfilled
Photocatalytic Reduction of Cr(VI) over Fe(III)-Citrate Complexes in
SIMULATED SOLAR SYSTEM in by B2-13
a Simulated Solar System
EAAOP4
B. A. Marinho, R. O. Cristvo, J. C. Lopes, R. A. R. Boaventura, V. J. P. Vilar, LSRE - Laboratory of Separation
and Reaction Engineering - Associate Laboratory LSRE/LCM, Faculdade de Engenharia, Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. belisamarinho@fe.up.pt
Toxic hexavalent chromium reduction to less toxic trivalent
chromium was evaluated using a solar driven photocatalytic
system, Fe(III)/UVA-Vis, with citric acid addition. The
photocatalytic reduction experiments were conducted in a lab-
scale tubular photoreactor with compound parabolic collectors
under simulated solar radiation (graphical abstract). The effect
of solution pH and Cr(VI):citric acid molar ratio on the Cr(VI)
CPC Compound Parabolic Collector photoreduction kinetics was evaluated. For a Cr(VI):citric acid
MS Magnetic Stirrer
MSB Magnetic Stirrer Bar molar ratio of 1:3 the reduction was complete in 15 min (0.72
pH pH-meter - PP Peristaltic Pump kJ L-1). pH values between 3 to 5 are in the optimal range to
SP Sampling Point - SS Solar System promote Cr(VI) reduction. The Fe(III)/UVA-Vis/citric acid
TC Temperature Controller
TM Temperature Meter system showed also good results in the treatment of Cr(VI)
containing wastewaters from a galvanization process.
cess.photocatalytic reduction in a real effluent was achieve
in 45 minutes.
Introduction both Cr(VI) photocatalytic reduction and BPA
In nature, chromium exists in two major forms, degradation rates were higher in the
Cr(III) and Cr(VI). The last one has high aqueous Fe(III)/Cr(VI)/BPA system.
solubility and toxicity [1, 2]. In this work, the photoreduction of hexavalent
Fe(II) is one of the dominant Cr(VI) reducing chromium present in synthetic aqueous solutions
DESIGN
agents. InOF TWO-COLUMN PHOTO-ELECTRO-FENTON and in a REACTOR effluentFOR
wasTHE TREATMENT
Design ofthis process, the Cr(VI)
two-column is reduced to
Photo-Electro-Fenton reactor for real
the treatment investigated using
will be filled
Cr(III)
OF (Eq. 1),
WINERY
of winery
that can be then precipitated as
WASTEWATER
wastewater
Fe(III)-citrate complexes irradiated by simulated
in by B2-14
Cr(OH) 3 (Eq. 2), at neutral pH[3, 4]. solar light. EAAOP4
M. Pazos1, A.Dez1, E. Rosales1, M. A. Sanromn1. (1) Department of Chemical Engineering, University of Vigo,
Isaac4 (aq)
HCrO Newton 2+
Building,
+ 3Fe 7H + (aq)As Lagoas, Marcosende 36310,Methods
(aq) +Campus Vigo, Spain, mcurras@uvigo.es.
Synthetic Cr(VI) solutions were prepared from
Cr 3+ (aq) + 3Fe3+ (aq) + 4H2 O (1) K2Cr2O7 (Merck, purity 99.9%). Cr(VI)
concentration
The management was determined
and treatment of winery by colorimetry
wastewater is
Cr 3+ (aq) + 3OH (aq) Cr(OH)3 (solid) difficultusing
(2) 1,5-diphenylcarbazide
to carry (Merck,
out as result of effluent purity 98%).
properties as
well asIron the(III) chloridegeneration.
seasonal hexahydrateRecently,
(Merck), and citric
Photo-
The main drawback of this process is the great acid monohydrate
Electro-Fenton (VWR Prolabo,
(PEF) technology purity 98%)
has become an
amount of iron required, leading to the generation werealternative
attractive used in the for photocatalytic
the treatment experiments.
of this
of high quantities of sludge, that need further Acetic acid (Panreac, 99.5%) and 1,10-
wastewater.
treatment. Since the early 19th century it has been In thisphenanthroline (Fluka, 99%)
study, an innovative weredesign
reactor employed
was to
reported the Fe(III) reduction to Fe(II) with the evaluateddetermine
for the dissolved
treatment iron concentration.
of winery Sulphuric
wastewater by
generation of some reactive species (OH) using by a acid (Pronalab,
sequential 96%, 1.84
PEF. Initially, g/cm3) and ofsodium
the performance the
photochemical dissociation of hydroxylated Fe(III) hydroxide
two-column reactor(Merck) were with
was studied used respect
for pHtoadjustment.
various
complexes [5]. This way, the Fe(II) generated may processAll samples using
parameters were simulated
filtered through
effluents.0.45
Afterm
reduce the Cr(VI), and the hydroxyl radicals that, thecellulose
treatmentacetate membranes
of a real (Sartorius)
effluent from before
the winery
produced can oxidize, at the same time, the industryanalysis.
was efficiently accomplished.
organic compounds present in the aqueous Total chromium concentration was determined
solutions. Actually, inorganic pollutants usually by atomic absorption spectrometry (current/ of
coexist in the natural environment with organic 6.0 mA/357.9 nm) with a detection limit (DL) of
matter
1. or organic pollutants, being possible the
Introduction 0.08 mg L-1. The hexavalent chromium
elimination of both pollutants simultaneously [6]. concentration was measured by molecular
LiuWinery
et al.wastewater
[6] studiedis theoriginated
use of in washing
Fe(III)OH In this study,
absorption a sequential (PEF
spectrophotometry = 540process
nm, DwasL =
operations during grape harvesting, pressing
complexes to promote the reduction of Cr(VI) and, and selected for
-1 carrying out the remediation of winery
2.05 g L ).
first fermentation the
simultaneously, phases of wine of
oxidation processing.
bisphenolAs A a wastewater. Initially, an innovative reactor design
The photocatalytic experiments were carried out
consequence of the working period
(BPA) in a photocatalytic system. The results and the was evaluated for its application for PEF
in a lab-scale photoreactor (Graphical abstract)
winemaking technologies,
showed a synergic effect volumes and pollution
in the ternary system: treatment. After that, the performance of the
comprising: (i) a solar radiation simulator (ii) a
loads vary greatly over the year [1]. The designed reactor was studied with respect to
composition of the produced effluent is
heterogeneous including various contaminants 110
various process parameters using simulated
effluents. Finally, the treatment of a real effluent 1
such as nitrogen, phenolic compounds, ethanol, from the winery industry was carried out.
 ROOM B - FENTON & FENTON LIKE PROCESSES

THE USE OF ULTRASOUNDS FOR OXIDATION OF WATER POLLUTANTS

The Use of Ultrasounds for Oxidation of Water Pollutants B2-15
M. Vinatorua, M. Dukkancib, M. Shestakovac, T. J. Masona
a
Coventry University, Faculty of Health and Life Sciences, Sonochemistry Centre, CV1 5FB Coventry, United
Kingdom, email: m.vinatoru@coventry.ac.uk
b
Ege University, Faculty of Engineering, Chemical Engineering Department, 35100, Bornova, zmir, Turkey
c
Laboratory of Green Chemistry, Faculty of Technology, Lappeenranta University of Technology, Sammonkatu 12,
FI-50130 Mikkeli, Finland

The presentation will show the effect of ultrasound on the

removal of dyes from aqueous solution as a model for effluent
treatment for the textile industry. Orange II and methylene blue
were selected as case studies. Both have a high visual impact
even at low concentrations (sometimes under the pollution
limits). Some aspects of the ultrasonic wave action in different
sections of collapsing acoustic cavitation bubbles have been
studied For this chlorobenzene removal from water was used as
a model system (see attached figure).

One of the main discovery from the very pollution limits) is enough to produce an
beginning of the uses of ultrasounds was its unpleasant impression on the environment.
influence on chemical reactions [1, 2]. It was A range of methods are reported for the
BIO-RECALCITRANT POLLUTANTS REMOVAL FROM WASTEWATER WITH
shown that the
Bio-recalcitrant hydrolysis
Pollutantsof dimethyl
Removal sulphate treatment
from Wastewater of Orange II (O-II) in aqueous solution
with
COMBINATION
was accelerated OF
under THE
the FENTON
influence ofTREATMENT
ultrasonic AND aBIOOXIDATION
with variety of ultrasonic equipment in the B2-16
Combination of the Fenton Treatment and Biooxidation
irradiation. 1One of 2the very 1
early experiments
1 1
absence
2
of other
1
oxidants.
2
Four different types of
M. Trapido
using , T. Tenno
ultrasonic , A. Goi
irradiation , N. Dulova
showed , E. Kattel , A. Kivi
that ultrasound , D. Klauson
ultrasound , K. Kleinwere
equipment Viisimaa1. (1) Tallinn
, M. used:
University
are able to ofdarken
Technology, Ehitajate plates
photographic tee, 5, Tallinn
submersedEstonia, marina.trapido@ttu.ee (2) University of Tartu, Ravila
20 kHz low frequency probe system (Sonics
14a, Tartu, Estonia.
in water (the plates were enclosed in a sealed and Materials Model, CV 26) with tip diameter
copper
Waste-foil envelope allowing the sonic waves to of 12.5 mm dipped into 200 cm3 of aqueous
The main aim of the study was to develop strategies for
travel through but to CHEM exclude the light) [3]. The dye solution in a beaker.
water implementation of combined chemical (CHEM) and biological
authors noted that it is possible that ultrasound 40 kHz ultrasonic cleaningorganic
bath (Langford
(BIO) treatment for removal of recalcitrant pollutants
enhance the oxidation reduction processes. Ultrasonic, Model 475TT) using 200 cm3 dye
from wastewater from different sources.
There are many studies relating to solution in a beaker with fromdiameter
differentof 80 mm.
ultrasonically assistedBIO
Three heavily polluted wastewaters sources
oxidation, most of them
containing significant amount of recalcitrant organics were at
Multi-frequency ultrasonic bath operating
being at laboratory level. In addition to known three different
studied and the treatment schemes frequencies, 380, 1000
for their purification wereand
effects of ultrasound when water is sonicated 1176 kHz (Meinhardt Ultraschaltechnik).
developed. Wastewaters were subjected to combined chemical
(production of free HOCHEM radicals) there are other 850andkHz reactor supplied by with
Meinhardt
(the Fenton) treatment aerobic biological treatment the
associated phenomena, e.g. sonoluminescence [4], Ultraschaltechnik (K8). scheme.
The diameter
final aim of establishing an optimal treatment The cost of
surface cleaning [5, 6], enhanced natural products
effectiveness of the transducer is 69.6 mm.
treatment schemes was The
alsovolume of aqueous
evaluated.
extraction
Effluent [7], chemical syntheses [8], etc. dye solution is 200 cm3 placed directly in the
Coloured effluentsBIO cause visual impact on the reaction vessel.
environment even at very low concentration. Such The most effective decolourization of Orange II in
pollution impedes light penetration and thus terms of power using ultrasound alone was
The biological
reduces photosynthesistreatment where only
in aquatic plantshighly
and organic
achieved loadat 850and kHz improve
and increasedotherfrom
wastewater
4.1% to
biodegradable contaminants
affects their growth [9-11]. are removed is used characteristics at least 50%; whereas
49.0% with increasing ultrasonic power from a lot2.04
of
nowadays
This as conventional
presentation willapproach
show the in wastewater
effect of attention
W to 22.07 wasW paid to the
over cost-effectiveness
2 hours. This trend was of the
in
treatment
ultrasoundinstallations.
on some dye However,
removal somefromwastewater
aqueous proposed schemes.
good agreement with the corresponding production
flows may
effluents contain
from compounds
the textile industry. thatOrange
are toxic to
II and of H2O2 during the sonication of water in the
biological community.
methylene blue Whenever
were selected thestudies.
as case wastewaterBoth Table
absence of 1. Orange
Main II [12].
characteristics of studied
contains
have a high recalcitrant
visual impact or in poorly
waste biodegradable
water, even a wastewatersa
compounds,
small amount the (sometimes
latter are not degraded
under neither
the allowed PW
during the biological treatment nor by Parameter MLL SCL
W
microorganisms present in the water environment.
Recalcitrant compounds accumulate in water and
bottom sediments and may affect aquatic biota and
111 COD, mg/L
5900-
15700
5100-
7800
1000
-2100 1
3100- 1600- 175-
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

PHOTOCATALYTIC HYDROGEN PRODUCTION FROM DEGRADATION OF GLUCOSE

will be filled
Photocatalytic Hydrogen Production From Degradation of Glucose
OVER FLUORINATED Pt-TiO2 CATALYSTS in by C2-1
Over Fluorinated Pt-TiO2 Catalysts
EAAOP4
G. Iervolino1* , V. Vaiano1 , D.Sannino1, L.Rizzo2, J.J Murcia3, M.C Hidalgo4 and J. Navo2. (1) Department of
Industrial Engineering, University of Salerno, Italy, (2) Department of Civil Engineering, University of Salerno,
Italy (3) Universidad Pedaggica y Tecnolgica de Colombia, Boyac Colombia, (4) Instituto de Ciencia de
Materiales de Sevilla (ICMS), Consejo Superior de Investigaciones Cientficas (CSIC), Universidad de Sevilla,
Amrico Vespucio 49, 41092 Sevilla - Spain
e-mail: giiervolino@unisa.it*

The present work reports the renewable hydrogen

production by photocatalytic degradation of glucose over
Pt loaded on platinum, the crystalline structure of F-TiO2,
and of the solution pH were investigated. In particular, the
photocatalysts are activated with UV-LEDs used as a light
source.
The results show that the photocatalytic H2 production
from the glucose solution can be significantly enhanced in
the presence of Pt on Fluorinated TiO2.
The hydrogen evolution rate increased by decreasing the
initial pH of solution reaching the highest value of about
590 mol h-1 g-1 after 3 hour of irradiation time.

suspension for 120 min with an Ultra-Vitalux lamp

Background and objective (300 W).The final amount of Pt was 0.5 wt%. All
The generation of H2 via semiconductor is a the prepared photocatalysts are reported in Table
UNEXPECTEDLY HIGH ACTIVITY OF SUPPORTED NOBLE METALwere TiO2 characterized
IN
Unexpectedly
promising route for the high activity
production ofofa sustainable
PHOTOCATALYTIC H2 PRODUCTION FROM PROPAN-2-OL
supported noble metal
1. The TiO2 in
photocatalysts will be filled
using
C2-2
greenphotocatalytic in by
fuel. With respect H2 production
to commercial fromtitania
propan-2-ol different techniques: XRD, S BET, UV-Vis DRS,
samples, TiO12 modified 1 with fluorine (F-TiO ) XRF and XPS. Photocatalytic experiments EAAOP4
were
21
J. Hidalgo
inhibites , A. Marinas , F.J.
the recombination rateTenllado
of holes
1
, V.and
Montes
free, F.J. carried
Urbano1,out
J.M.with
Marinas 1
, L. Ilieva
a pyrex 2
, T. Tabakova
cylindrical 2
reactor., F.Reid
The1
(1) Organic Chemistry Department, University of Cordoba, E-14014 Crdoba, Spain, alberto.Marinas@uco.es
photoreactor was irradiated by a UV-LEDs strip.
electrons, enhancing the photocatalytic activity
(2) Institute of Catalysis, Bulgarian Academy of Sciences,0.12 1113gSofia, Bulgaria was suspended in 80 ml of
of catalyst
[1]. F-TiO2 was effective in the photocatalytic
removal of not biodegradable contaminants (such Two different C-3 alcohols (glycerol
aqueous solution containing and 2000propan-2-ol)
mg/L were of
as phenol)[2]. However no article reports thetested use as glucose.
sacrificial
Theagents
initialfor
pHHof 2 production
solution through
was changed photo-
by
of F-TiO2 as support for noble metals in reforming the on M/TiO
adding 2 solids.
nitric acid orThe effect of metal
Ammonium of choiceThe
Hydroxide. (Pt,
photocatalytic production of hydrogen from Pd and Au) and the incorporation method, the catalyst
analysis of gaseous phase was performed by
aqueous samples. For this reason, in the present reductioncontinuous
pretreatment and and
analyzer the concentration
reaction temperature of glucose on
work, Pt on F-TiO2 photocatalysts were usedcatalytic to performance
was measured by were studied. Propan-2-ol
a spectrophotometric method led[3].to
reform biomass, such as glucose to hydrogen. unexpectedly The higher H2 productions than glycerol and did not
Results
effects of the presence of Pt, the crystalline result in catalyst deactivation. Results were explained in terms
structure of F-TiO2 and the initial pH of solution of differentBy XRDreaction
it wasmechanisms:
observed that purehpphoto-reforming
TiO2 contain
on the hydrogen evolution and degradation(glycerol) of or isopropanol
rutile and anatase oxidation
phases, into afteracetone. In contrast,
fluorination only
glucose were investigated. propan-2-ol oxidation
anatase was seemed
observed. to be a more structure-sensitive
Characterization results is
process. presented in Table 1. Fluorination or Pt addition
Methods did not induce any significant changes on P25
TiO2 was prepared by hydrolysis of titanium properties; in the case of the hp TiO2, the
tetraisopropoxide in isopropanol solution. fluorination leads to the increase of the SBET and
Commercial TiO P25 was used as received. evaluatedsize
crystallite theofeffect
anatase; of this
Pt oxidation state and
can be explained
Background 2
particle sizeaccount
on photocatalytic activity.onIt was found
Fluorinated samples were prepared by adding 10 taking into that F species surface
mMThe NaFsocial
to an and political
aqueous concernofabout
suspension a more prevent
uncalcined that withthe
Pt inrutilization
the oxidationprocess 0, activity was
state of Ptduring the
sustainable
home preparedfuture,
TiO2 (hp together
TiO2) orwith
P25.thePrecipitate improved, but
increasing calcination at for samples
higher with the sameAfraction
temperatures. slightof
energy
was demandbyhave
recovering resulted
filtration, in aand
dried significant
calcinedneed
at metallic Ptof(Pt
decreasing 0), particle size was also influential
band gap value was observed after
for technologies and raw materials
650 C for 2 h. Platinum was deposited on the more benign to on activity.
fluorination The
of hp problem
TiO2. By is that
XPSthe initial oxidation
analyzes it was
the environment
surface than the currently
of the fluorinated samples by existing
a state and
detected thethepresence
metal particle size can
of fluoride change
species onduring
the
alternatives. Hydrogen
photodeposition method isbyan illuminating
important energy the the reaction.
surface fluorinated samples, indicating that Ti-
molecule whose combustion produces only water, An additional factor to consider is the different
thus resulting in a clean and non-polluting energy
process. However, hydrogen is not readily available 112
rates on hydrogen production and byproducts
obtained depending on the molecules used as
1
in sufficient quantities and the production cost is sacrificial agent [2-3]. Therefore, for instance,
 ROOM C - AOPS FOR ENERGY PRODUCTION

INFLUENCE OF PROCESS PARAMETERS ON PHOTOCATALYTIC HYDROGEN will be filled

Influence Of Process Parameters on Photocatalytic Hydrogen
PRODUCTION C2-3
in by
Production
EAAOP4
M. Gmurek1, K. Bednarczyk2 and M. Stelmachowski2.
(1) Lodz University of Technology, Faculty of Process and Environmental Engineering, Department of Bioprocess
Engineering, ul. Wlczaska 213, 90-924 d, Poland, marta.gmurek@p.lodz.pl
(2) Lodz University of Technology, Faculty of Process and Environmental Engineering, Department of Safety
Engineering, ul. Wlczaska 213, 90-924 d, Poland.

160
Hydrogen is considered as the fuel of the future. The greatest
140 advantage is the lack of CO2 emissions during combustion.
Since over twenty years, in many research centers, intensive
H2 production efficiency,

120

studies have been conducted in order to find of the energy-

[mmol/h g ]
cat

100
efficient and economical methods of hydrogen production
80
using renewable sources of energy. Currently, many studies
60 have focused on the processes using photocatalysts, which
40 could be applied for water splitting or to convert organic
20
waste into hydrogen.
The paper presents the results of the studies that were
0
0.07 0.03 0.015 0.003 0.005 0.0015 performed in order to find the optimal conditions of
amount of Pt/TiO2, [g] photocatalytic production of hydrogen in the system glycerol-
water.

Background Modified photocatalysts based on TiO2, which

Biofuels are produced by processing of by- have a higher activity under the visible light can be
products animal of or vegetable origin. One of the prepared by metals or sensitizer dyes (absorbing
PRODUCTION
liquid biofuels OF is ENERGY-RICH
biodiesel obtained GASES by the VIA CATALYTIC
visible light)DECARBOXYLATION
doping. The application OF of the
Production of energy-rich gases via catalytic decarboxylation of will be filled
FORMIC AND ACETIC
transesterification ACIDoils.
of vegetable IN AThe TRICKLE-BED
result of REACTOR
modified OVER Ru/TiO
photocatalyst gives possibility in by of C2-4
formic
the and aceticofacid
implementation the EUin aDirective
trickle-bed2009/28 reactor
/ over Ru/TiO
efficient
2
use 2of sunlight, without EAAOP4 generating
ECA. was essential
Pintar 1,2 increasing
, I.G. Osojnik the ,amount
rnivec 1 of biofuels
P. Djinovi 1,2
, B. Erjavec additional pollutants [3,5].
1,2

in(1)the fuel market.

National InstituteOne of the major
of Chemistry, barriers19,toSI-1001
Hajdrihova the Ljubljana, Slovenia, albin.pintar@ki.si. (2) Centre of
Excellence
further for Low Carbon
development Technologies,
of this industry is Hajdrihova
the surplus19, SI-1001 Objectives
Ljubljana, Slovenia
of glycerol, which is obtained during Herein we present results of the photocatalytic
Catalyticthedecarboxylation
production isof ahydrogen
novel and prospective
under simulated pathway
sunlight.
production of biodiesel. Therefore, forintensive continuous and efficient conversion of organic wastewaters.
studies have been carried out to find a new method The paper presents the results of the studies that
In this study, stable
were and completeinconversion
performed order to offind acetic theacid to
optimal
or modify one of known methods that would allow
CH4 and CO2 mixtures (T225
for profitable use of large quantitiesdemonstrated. of waste conditions of the C, Sp>80for%,the
process 70system
h TOS) was
glycerol-
On the The
water. othercatalysts
hand, accompanied
based on by unwanted
TiO - doped by
glycerol. Traditional methods of gas-phase disposal side reactions and thermally-stable deposition 2
of
(reforming, fermentation, dehydration, gold, palladium and platinum (0.1, 0.5%, 1% by
carbonaceous-residues, operation with formic acid feed resulted
in lower weight)(S have
Hopesselectivities been used in the performed
hydrochlorination, etc.) are ineffective. CO2<60 %) and catalyst deactivation.
have been placed on bio- or photocatalytic The presented experiments.
exploration ofThe an research
alternativeaimed
low at selecting a
temperature
conversion of waste glycerol into hydrogen indirect approach
or photocatalyst
for valorization of highly oxygenated organic as
with high yield and selectivity
other energy carriers (methane, methanol) compounds [1-3]. intowell CH4finding
and H2anshows optimal concentration
a promising routeofforthe
There are known other methods of hydrogen utilization of catalyst
acetic in
acid. the glycerol
Efficient solution.
decarboxylation of formic
production (e.g. via steam reforming, splitting of acid, however, faces further challenges in the fields of catalyst
Methods
water by electrolysis) but they require design and reactor engineering.
energy, Photocatalytic reactions were carried out in the
which has to be probably produced from fossil semi-batch quartz reactor (40cm3). The external
fuels. xenon lamps (3-4 lamps Xe-arc XBO 75W each)
Introduction TiO h (1) were used todecarboxylation
temperature simulate sunlight. The reactor
of aqueous was
solutions
C3 H8O3 (lq ) 3H 2O (lq ) 7 H 2 ( g ) 3CO2( g ) 2

Carboxylic acids offer high potential for waste- charged with the mixture of glycerol
containing acetic and formic acid in a three-phase aqueous
As a result
to-energy of the photocatalytic
or waste-to-product conversion
conversion, as they of solution and
trickle-bed photocatalysts.
reactor with the aim Thetovolume
produceofCH the
4,
glycerol
can be tosourced hydrogen from (eq.1) 7 hydrogen
various industrialmolecules
waste reaction
H solution was 16 cm3. The temperature of
2 and CO2 was examined. The window oof
and three
streams (e.g. molecules
wastewatersof carbon dioxide
of textile, couldand
polymer be the reaction
relevant mixture
operating was in the
conditions was range of 35-55and
established C.
generated.
food and beverageThis reaction does asnotwell
industries) require
as in high the Argon
the was used
network of ascompeting
a carrier gas,sidewith the flow was
reactions rate
energy
form if the photocatalyst
of intermediates could beof active
during treatment complex in 30 cm3/min.
analyzed and The suspension has been obtained by
discussed.
visible range
organic [4].
substances by means of advanced stirring with argon (inert gas) prior and during the
Experimental
oxidation processes [1]. However, due to low
energy content (5.4, 13.5 and 44 MJ/kg LHV for 113
The 3 wt. % Ru/TiO2 catalyst [4] was prepared
by means of incipient impregnation of TiO2 P25
1
formic, acetic acid and gasoline, respectively) as
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

WASTEWATER SLUDGES PRE-TREATED BY DIFFERENT OXIDATION SYSTEMS TO

Wastewater sludges pre-treated by different oxidation systems to will be filled
MAXIMIZE THE BIOGAS PRODUCED IN A SUBSEQUENT ANAEROBIC PROCESS in by C2-5
maximize the biogas produced in a subsequent anaerobic process
EAAOP4
Y. Segura, L. Ballesteros, F. Martnez, J.A. Melero. Rey Juan Carlos University, ESCET, 28933 Madrid, Spain.
yolanda.segura@urjc.es

The effect of pre-treatments on the change of

wastewater sludge properties was investigated using
-3
different Advanced Oxidation processes (AOPs).
x10
2000 350 350 Ultrasound is a very effective mechanical pre-
1800
300 300 treatment method to enhance solubilisation of the
organic matter. It was compared to other AOPs such
1600

1400 250 250

as Fenton and combined systems sono-fenton, photo-

polysaccharides (mgL )
-1
SCOD (mgL )
-1

1200
proteins (mgL )
-1

200 200
1000 Fenton and sono-photo-Fenton. The pre-treatment
processes break-up sludge flocs, destroying cell walls
150 150
800

and membranes and resulting in the release of

600 100 100
400

200
50 50 organics in liquid phase. The aim of this study is to
0
Raw US F US/F UV/F US/UV/F
0 0 maximize the production of biogas in a subsequent
Pre-treatments
anaerobic process by means of the evaluation of the
properties, composition and the biochemical methane
potential (BMP) assays of pre-treated sludges.

The sludge management is one of the major the yield of OH produced during the combined
issues of wastewater treatment plant and their systems is higher than when only applying a
disposal legislation is becoming increasingly individual system, as a results of a snynertetic
stringent. The treatment and disposal of sludge increase in the generation of hydroxyl radicals. It
accounts of 50-60% of the operational costs in a might be that, the highly oxidative Fenton-based
NOVEL
wastewater PHOTOCATALYTIC
treatment plant MATERIALS
(WWTP). Various FOR SOLAR DRIVEN COcouldREDUCTION
Novel photocatalytic materials for solar drivencoupled processes,
CO2 reduction 2 degradewill thebe filled
soluble
C2-6
technologies, including chemical, thermal and organic matter released towards mineralization, in by
mechanical methods, have been proposed to observing lower values of SCOD after 60EAAOP4 minutes.
J.A. Byrne,1the
minimize J.W.J., Hamilton,
excess
1
P.K. Sharma,
sludge
1
A. Brown,
production. In
1
P.S.M. Dunlop,1 M. Nolan,2 K.A. Gray,3 K.
of theSchool ofProteins and Ulster
polysaccharides increased with all
3 3 3
Schwartzenberg,
addition, increasing J. Notestein, E. Weitz , (1) NIBEC,
the biodegradability Engineering, University, Newtownabbey,
BT37 0QB, U.K j.byrne@ulster.ac.uk
sludge can be an economically favourable (2) Tyndall National the pre-treatments
Institute (TNI), Lee studied
Maltings, Dyke hereby,
Parade, realising the
Cork,
Ireland (3)Northwestern University, Evanston, IL, USA
alternative due to its revaluation by biogas maximum concentration when ultrasound was
production. In this study, the sludges were treated applied (ca. 0.150 and 320 mg/L, respectively), in
The solar efficiency
accordanceofwith photocatalytic
the solublematerials is limited
COD obtained. It is
by different methods including ultrasonication
due to the knownuse of wide
that band semiconductor
augmentation materials
of nutrient such
availability
(US), Fenton (F) and combined systems sono-
as TiO which can utilise only UV photons. Much
fenton (US/F), photo-Fenton (UV/F) and sono- 2 (increase in solubilization) and amelioration of
research has massbeenandfocused
oxygenontransfer
the development
(decrease of in novel
particle
photo-Fenton (US/UV/F).
materials mainlysize) arebased on doping
the main reasonsTiO withenhancement
for2 the metals and of
The effect of ultrasound is mainly attributed non-metals.
to An alternative approach
biodegradability observed toafter the development
the US pre-
hydro-mechanical shear forces that of can novel visible lightBiochemical
treatment. active photocatalytic materials
methane potential is
(BMP)
disintegrate sludge aggregates and disrupt surface cells, modification
assays were of carried
titania with
out tomolecular
measure clusters
the methaneof
breaking the microbial slurry and resulting otherin metalyield oxides.
of allComputational
pre-treated sludge modelling
samples indicates
studied
reduced floc strength. As a chemical process, that small hereby.
clusters Itofis metal oxides on
an important test TiO canknown
as it2 is inducethat
Fenton oxidation caused sludge small particle bandtonarrowing and therefore
increased lead to
solubilisation doesvisible light activity.
not hundred percent
flocculate and form larger particles. It implies This apaperinduce will present
an initial
improvedresults anaerobic
investigatingdigestion
TiO2
partial oxidation (hydroxyl radical production) modified
of with MnOx The
efficiency. clusters
idealwith the aim of
comparison of pre-treatments
developing
cells and organic matter leading to enhancedphotocatalytic lysis systems in
effectiveness foranaerobic
carbon dioxide
digestionreduction
besides Sto COD,
or disintegration of sludge cells. As it can befuels seenusingare solar energy.
other key factors as type of method applied,
in the figure above, the effect on solubilization composition of soluble organics released, etc. that
(SCOD) was observed to be more pronunced after should
as also be takenorinto
recombination account.
visible light activity, the
The
US global
(ca. 1600 potential
mg/L) of solar
comparedenergytois the vast;other
for ultimate goal is the rational design of a
example, Acknowledgements
oxidation more of theThe
systems. sunssoluble
energy COD hits theobtained
face of multifunctional
Financial support catalyst
of RegionalwithGovernment
optical, electronic,
of Madrid
the
afterearth
the inUS/UV/F
two hourssystem
than is consumed
(ca. 180 mg/L)globallywas in and
providedchemicalthroughproperties
project tailored to CO2
S2013/MAE-2716-
alower
year. than
Yet, thewe currently
values oftap bothonlycoupled
minor amounts
systems REMTAVARES-CM
adsorption, activation,co-financed
and reduction. withIdeally,
structural
the
of
US/Fthisandenergy
UV/F to(ca.meet
800 an ever-growing
mg/L). It is known world
that funding of the
moieties European Community
responsible for theseare functions
acknowledged. are
demand. The artificial photochemical fixation of independently tunable and the catalyst can couple
CO2 to energy rich hydrocarbons for solar energy
storage, or potential feedstock chemicals for
the reduction of CO2 to the oxidation of water. 1 114
industry, is an attractive, albeit daunting, challenge One promising group of materials is metal oxide
ROOM C - AOPS FOR ENERGY PRODUCTION

115
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

PEROXO-GOLD MODIFIED TITANIUM NANOTUBES FOR EFFECTIVE REMOVAL willOF

Peroxo-gold modified titanium nanotubes for effective removal of
METHYL ORANGE WITH CWPO UNDER AMBIENT CONDITIONS
be filled
C2-7
in by
methyl orange with CWPO under ambient conditions
EAAOP4
N. Drainac1, B. Erjavec1, A. Pintar1. (1) Laboratory for Environmental Sciences and Engineering (EnviroEng),
National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia, nina.drasinac@ki.si.

Titanium dioxide based nanotubes (TN) were prepared via

alkaline hydrothermal synthesis method, treated in the different
temperature ranges and modified with hydrogen peroxide (TNp)
and gold (TN/Au). The obtained catalysts were used for the
degradation of methyl orange (MO) in the catalytic wet
peroxide oxidation (CWPO) process under ambient conditions.
The experimental results showed that more than 70 % of 100
ppm MO aqueous solution can be removed in the 1.0 g/L
suspension of the catalyst with the usage of the stoichiometric
amount of hydrogen peroxide under mild operating and reaction
conditions.

radicals is obtained through the decomposition of

Background hydrogen peroxide in the presence of an
Water pollution represents one of the most appropriate heterogeneous catalyst. Application of
pronounced environmental risks nowadays. The the proper catalyst in the CWPO process not only
main problem in water pollution is presented reduces the severity of reaction conditions, but
POLYMER-BASED
through the existence NANOCATALYSTS of highly toxicFORand WETalsoAIR OXIDATION
enables moreOFfacile PHENOL decomposition of
Polymer-based Nanocatalysts for Wet Air Oxidation of Phenol C2-8
refractory organic pollutants, which can cause refractory pollutants under ambient conditions [3].
severe problems for the environment. One of the
V. Doluda, N. Lakina,
representatives of these V. Matveeva, pollutants E. Sulman, V. Molchanov, V. Bykov, A. Stepacheva.
are synthetic
Tver state
dyes. Theytechnical are widely university, used Dep. in differentof biotech. and chem., Nab.Objectives
branches A. Nikitina 22, 170026, Tver, Russia;
tel. +74822 449317, e-mail: doludav@yandex.ru
of industry (i.e. textile, painting, leather etc.) and
enter easily in the environment where they can In the present study, TN were synthesized via
cause aesthetic and biologic problems. The The special alkaline
attention hydrothermal
is paid method followedcatalysts
to use of nanocomposites by heat-
greatest OHthreat
OH O
is presented O
through for environmental
usage of azo protection.
treatment CWAO oftemperatures
at different phenols is anranging
importantfrom
process of 300
environmental to 700 C.
catalysis, Non-treated
allowing one TN
to were
reach nearlyalso
[O] O

dyes whose functional OH

OH HO
Hgroup HO contains double
nitrogen
OH
catechol bond [O] (-N=N-).
o-benzoquinone
C C C
O Their
complete
products of subjected
oxidation of to
phenols chemical
to treatment
non-hazardous with hydrogen
compounds.
Catalysts based on peroxide to form nanoparticles
Ru-containing surface peroxo(NPs) groups and used
formed in
O O H [O]
[O]
degradation, aromatic amines, COare 2 + H2O mutagenic and
maleic acid malonic acid
OH O
HO HO

carcinogenic [1]. oxalic acid CH C OH

phenol
O
C C
O O the pores of hypercrosslinked
further as a support polystyrene
for the (HPS)
deposition were
of gold
[O]
3
HO
acetic acid
synthesized. nanoparticles.
C H
Degradation OH O
of above
O mentioned and similar
pollutants
hydroquinone p-benzoquinone
demands
Heavy CWAO intermediates
formic acid
Easily biodegradable CWAO high
intermediates and efficient The obtained catalysts were used in the CWPO
decomposition what sometimes isnt possible to of aqueous MO solution under ambient conditions.
accomplish with the utilization of simple and It has been observed that the formation of peroxo
conventional methods, such as adsorption and groups on the surface of TN highly influences the
biological degradation decomposition of hydrogen peroxide and
The purification of [2]. wastewaters from phenol application
consequently of the CWAO
mineralization process
of MO. is the
More than 70
compounds
One of the(phenol, most promising chlorophenols, techniques m-, p-, for
andthe
o- heterogeneous
% removal of MO catalysis
was due to stability
accomplished of such
during the
cresols, pyrocatechin,
removal of organic pollutants resorcin, etc.) from is one of the
water are catalysts
four hourcompared
treatment.toWithhomogeneous
the usageorofcolloidal
TN/Au
most essential
advanced oxidation tasksprocesses of green chemistry
(AOPs). They ones. Platinum
solid more and%ruthenium
that 50 removal ofmetalsMO wasandachieved
cerium,
considering
include different the types hazardousness of chemical of treatment
phenols. titanium,
in the acidicmanganese
solutionand
what ironis oxides deposited
40 % more than onin
Although
proceduresnumerous designed to methods removeare organicknown for the
pollutants zeolites,
neutral pHalumosilicates
region. The size and ofalumina have been
gold nanoparticles
elimination
through oxidation of phenols reaction from water, with highly the majority of
reactive employed
should still as catalysts,
be variedhowever,
to achievethey all use higher
even a high
them
and nonselective are physical hydroxyl methods radicals. that Catalytic
preserve wetthe content (up to 25%)
mineralization extent of MO. of the active metal in the
phenol
peroxidemass oxidation balance, (CWPO) i.e., lead represents to theonepollutant
of the catalyst and they are often unstable due to metal
redistribution/concentration
AOPs, in which the generation without
of hydroxyl its leaching. These problems can be solved by the use
transformation to non-hazardous substances. of more efficient catalysts requiring less active
Nowadays there is a large amount of phenols in metal and by its stronger interaction (or enclosing)
the environment, hence, novel technologies for the
conversion of phenols to non-hazardous or useful
116 with support.
Here we report the synthesis of nanocatalysts
1
 ROOM C - W E T A I R A N D S U P E RC R I TI C A L OXI DA TI ON

SURFACTANT ENCAPSULATED HETEROPOLY-ANION WITH BIOLOGICAL MEMBRANE will be filled

Surfactant encapsulated heteropolyanion with biological membrane-
LIKE STRUCTURE FOR CATALYTIC WET AIR OXIDATION in by C2-9
like structure for catalytic wet air oxidation
EAAOP4
S.K. Lua,1,2, T.T. Lim2,4, Z.L. Dong3. (1) Interdisciplinary Graduate School, Nanyang Technological University, 50
Nanyang Avenue, Singapore 639798, Singapore, luas0005@e.ntu.edu.sg. (2) Nanyang Environment and Water
Research Institute,Nanyang Technological University, 1 Cleantech Loop, CleanTech One, Singapore 637141,
Singapore. (3) School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang
Avenue, Singapore 639798, Singapore. (4) Division of Environmental and Water Resources Engineering, School of
Civil and Environmental Enginnering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798,
Singapore

A series of surfactant encapsulated heteropolyanion (SEH-n)

based on molybdovanadophosphates with biological membrane-
like structure was prepared and used as a wet air oxidation
catalyst for removal of bisphenol-A. The as-prepared materials
were characterised by TEM, XRD, FTIR and TGA. The
performance of SEHs as wet air oxidation catalysts for the
removal of bisphenolA under ambient conditions was
evaluated, showing promising potential. The hydrophobic
property of the nanosized SEHs provides good aqueous
stability and allows excellent recoverability of the catalyst from
the aqueous solution after treatment.

been applied extensively as the cationic modifier

ORANGE
Background II DYE DEGRADATION BY WET PEROXIDE OXIDATION USING AN Au/Al be2O
Orange II Dye Degradation by Wet Peroxide Oxidation in the past using an The amphiphile
decade. will is filled
able
3 to
CATALYST
Au/Al2O3 Catalyst
Wet air oxidation usually require a combination conform to a biological membrance-like in by C2-10
of high temperature and high pressure for the structure[3] and this property will EAAOP4 allow
Carmen S.D.
removal Rodrigues1, Snia
of recalcitrant A.C. Carabineiro,
organic F.J. Maldonado-Hdar
pollutants from improvement 3
, Lus M. Madeira
in surface 1
properties in addition to
(1) LEPABE, Department of Chemical Engineering (DEQ), Faculty of Engineering
the catalytic properties
University of of
Porto (FEUP),
POM. TheR. organic
Dr. Robertopart
waste water.[1] However, such processes are
Frias, 4200-465 Porto, Portugal. (2) LCM, Associate Laboratory LSRE/LCM, DEQ, FEUP, R. Dr. Roberto Frias, 4200-465 Porto,
Portugal. (3) Department of Inorganic Chemistry, Faculty of Sciences, University of Granada, Avenida de Fuente Nueva, 18071the
energy intensive and thus results in high operating of the hybid formed by the combination of
Granada,
cost Spain. mmadeira@fe.up.pt.
which imposes a limit on practical amphiphile would provide hydrophobic
application. Catalytic wet air oxidation allows the microenvironment for the trapping of organic
degradation
TOC Dye
H2O2 of organic pollutants
In this study pollutants
XTOC/XH2O2 under milder
the degradation of a model
in wastewater compound
while the POM (Orange II
part will
100
conditions making it an effective 0.5 processdye) was evaluated
for the be able tobyactwet peroxide
as the catalyticoxidation
centre. using gold
80 of wastewater highly0.4concentrated with on alumina (Au/Al2O3) as catalyst, in a slurry batch
supported
Removal (%)

XTOC:XH2O2

treatment
60 pollutants. The use 0.3 reactor. It wasPOMsconcluded
withthat hasthebeen
process is predominantly
extensively used for
organic of heterogeneous
40 0.2
catalytic, via hydroxyl radicalsoxidation
photocatalytic formation.ofThe catalyst
organic proved to
pollutants[4].
be stable during
Theat least five consequent runs (seeacid Fig. 1), with no12-
catalysis in catalytic wet air oxidation would be molybdovanadophosphoric (H3+x PMo
highly20 desirable, allowing 0.1 Au being
of leached into
40) the
(x solution,
= 1, 2, putting in evidence the major
easy recovery
xVxO 3) type of transition metal
0 from the treated wastewater.0
catalyst advantage of substituted
such materials their high stability. A parametric
heteropolyacid/heteropolyanion (HPA),
1st 2nd 3rd 4th 5th
Polyoxometalate Run(POM) is a molecular study
metal was carried outand
is stable to can
assess the influence
be easily of by
reoxidized the oxygen.
main
Figure 1. TOC and dye removal, hydrogen peroxide
oxide with fascinating properties, they operatory
have been variables;
They arein thesuitable
best operating conditions
candidate found,for
of choice highthe
consumption and its efficiency of use after 4 h of wet efficiencies were reachedcentre
catalytic (dye removal
in the~100%, TOC removal
aforemention of
organic-
peroxidationmainly
applied in five consecutive runs (pH=3.0,
as catalyst dueT=30 to their multiple
C, [H2O2] = 6 mM and [catalyst] = 2.0 g/L). 50.3% and XTOC :XH2O2 = 0.53).
inorganic hybrid to study their feasibility in
electron redox properties and the stability under
application as a wet air oxidation catalyst. The
such redox processes.[2] A major difficulty in the The catalyst stability was also evaluated. Five
Some dyes
application of are
POM toxic,
for wetcarcinogenic
air oxidationand isnon-
the stability of POM and the activation of POM with
consecutive runs were performed, being observed
biodegradable,
solubility in aqeous thereforemedium
they have to be makes
which removedit oxygen in air makes it an inherantly green catalyst.
a maximum variation of only 5.4, 1.3 and 0.3% for
from
difficultwastewaters.
for post treatmentThe wet peroxide
recovery. An oxidation
emerging dye and TOC removals and H2O2 consumption,
(WPO)
methodologyis a possible treatment technology
of heterogenization of POMthat is can
the respectively, between cycles, as shown in Fig. 1.
be
useapplied, where hydroxyl
of amphiphilic cations for radicals are generated
the formation of an The gold leaching in all runs was negligible; BET
Objective
by the hydrogenhybrid
organic-inorganic peroxidewhichdecomposition
imparts a degree in surface areas after 1st (210 m2/g) and 5th (207 by
m2/g)a
presence of a metal.
of hydrophobicity to theGold
catalyst.catalysts have been Molybdovanadophoshate
runs were similar to that of
encapsulated
the fresh Au catalyst.
recently used for removal of water pollutants by model amphiphile forming a biological membrane-
Results obtained
this process [1, 2]; however, to the
Dimethyldiocatadecylammonium best of our
(DMDOA) has like structure is allowed
prepared tousingconclude that the
a simple ion
catalyst is quite stable, which is a crucial aspect
knowledge, Au on Al2O3 was never tested yet. The for industrial application.
main goal of this study is thus using this material
in the degradation of the Orange II dye. 117 Then a parametric study was carried out, aiming 1
evaluating the effect of different variables and
 O R A L P R E S E N TA T I O N S - 2 nd D A Y

YDROLYTIC HYDROGENATION OF CELLULOSE IN SUBCRITICAL WATER

ydrolytic Hydrogenation of Cellulose in Subcritical Water C2-11
E.M. Sulman, V.G. Matveeva, O.V. Manaenkov, O.V. Kistlitsa, A.E. Filatova, V.Yu. Doluda, A.I. Sidorov,
M.G. Sulman Tver state technical university, Dep. of biotech. and chem., Nab. A. Nikitina 22, 170026, Tver,
Russia;tel. +74822 449317, e-mail: sulman@online.tver.ru.

In this paper Ru-containing catalysts based on hypercrosslinked

polystyrene (MN-270) and its functional analogues (MN-100
and MN-500) were studied for the first time in cellulose
hydrolytic hydrogenation. The catalysts were characterized using
transmission electron microscopy (TEM), high resolution TEM,
and porosity measurements. Catalytic studies demonstrated that
the catalyst containing 1.0% Ru and based on MN-270 is the
most active. The total yield of sorbitol and mannitol was 50% on
the average at 85% cellulose conversion.

The purification of wastewaters from phenol Subcritical water, in particular, contributes to the
Cellulose is one of the wide-spread organic acceleration of acid- and base-catalyzed reactions
structures in nature. It has been estimated that by approximately 400 times higher ions H3O+
11 12
10 10 tons of cellulose are synthesized OH- concentrations; the decrease of diffusion
annually. It is mostly combined with hemicellulose limitation, connected with low viscosity of
and lignin in the plants cell walls [1]. A lot of subcritical water; the increase in gas solubility
PHOTODEGRADATION
scientists consider cellulose OF BISPHENOLS:
a prospective MECHANISTIC ASPECTS the increase will
and, in consequence, in be
hydrogen
Photodegradation of bisphenols: mechanistic aspects filled
alternative to fossil fuels as its renewable concentration on the catalyst surface. in by C2-13
resources can provide production of raw material In this paper a new type of Ru-containing EAAOP4
for
V. the chemical
Salomatova 1 industry and
, I. Pozdnyakov 1,2 second-generation catalysts
, V.Grivin1,P. Sherin3, V. Plyusnin 1,2 on the
, N. Bazhin 1 basisVoevodsky
(1) V.V. of hypercrosslinked
Institute of
biofuels
Chemicalon a large
Kinetics scale [2, 3].Institutskaya
and Combustion,3 Moreover,St.,atNovosibirsk,
polystyrene
Russia,(HPS) is suggested(2)
salomatova@ngs.ru forNovosibirsk
the process of
present, chemicals
State University, obtained
2 Pirogova from cellulose
St., Novosibirsk, cellulose Tomography
Russia, (3) International hydrolytic hydrogenation in a subcritical
Center, 3a Institutskaya St.,
Novosibirsk,
biomass can Russia
be cheaper than those obtained from water medium. The use of rhutenium catalyst
oil [4]. A large number of hydroxyl groups part of (1.0 % Ru) on the basis of HPS allowed achieving
cellulose composition account for theInoptimum the total sorbitol
this work steady-state and mannitol
and nanosecond laseryield
flashabout 50 % on
photolysis
way of its conversion hydrolytic hydrogenation were used to average
study that is comparable
mechanistic aspectswith of the results
aqueous
to sorbitol (mostly) and other polyols. This process
photochemistry obtained
of three with widelymore
usedcomplex
bisphenolsand(BPs)
therefore more
- bis(p-
was first carried out by A.A. Balandin and his expensive catalytic
hydroxyphenyl)methane (BPF), systems. Being reused this
bis(4-ydroxyphenyl)ethane
colleagues in the USSR. They (BPE) conducted catalyst was stable.
and 4,4-Bis(4-hydroxyphenyl)valeric acid.
hydrolytic hydrogenation of cellulose Forinallthestudied Fig. 1 presents
systems the maintypical chromatographs
primary photochemical of the
presence of mineral acids and Ru, Pdprocess and Pt- liquidtoand
was found begas phases obtained
photoionization withafter the reaction
formation of
containing catalysts. Now great attentionphenoxyl with
is paid toradical. 1%Ru/MN-270.
Phenoxyl radical decays The main products
in recombination and of
supercritical fluidic technologies in the reaction chemistrywith cellulose
superoxide hydrolytic
anionhydrogenation
radical formed are sorbitol
during (S),
of wood and its components [5]. One mannitolelectron
of the of hydrated
scavenging (M), asby well as 1,4-sorbitan
dissolved oxygen. The (1,4-S),
main
prospective media is sub- and supercritical primarywaterproductxylitol
for given(X),BPs
erythritol (E), glycerol
was determined (G), propylene
as hydroxylated
[6, 7]. For example, there were studies BP. discussing glycol
Also, tentative scheme (PG),of BPs
ethylene glycolwas(EG)
photolysis and some
proposed.
the possibilities of cellulose hydrolytic glucose which has not been hydrogenated
hydrogenation in a subcritical water medium [8]. It (Fig. 1a). Chromatography-mass spectrometric
allowed excluding mineral acids from the process analysis also shows trace amounts of cellobiose,
and solving the problems of their disposal and the hexane-1,2,5,6-tetrols, hexane-1,2,3,4,5-pentol and
corrosion of (BPs)
the equipment. Subcritical water spectral products
other and kineticofproperties
glucose of and excitedsorbitol
states
Bisphenols are
o
widely used in production and primary intermediates and their further
(temperature
of polycarbonate < 350 , pressure < 221 bar)
plastics, epoxy resins, adhesives, is a hydrogenolysis in a liquid phase. In a gas phase
universal transformation products.
coatings formedium
drink packagesfor performing
and food cans.chemical
As a there are methane and trace amounts of ethane,
reactions.
consequence It can
BPsservehave asbeena non-toxic solventinwith
widely detected the propane,
For all and isobutane
studied BPs (Fig. 1b).
the main primary
well variable physical
environment and foodchemical products properties (due to
[1]. However, photochemical process was observed to be
the
many change in temperature
(e.g. well-known bisphenol A) andof them
pressure).
refer photoinization with formation phenoxyl radical
to endocrine-disrupting chemicals (EDCs) and hydrated electron pair. It was found that phenoxyl
were reported to possess acute toxicity and
estrogenic activity. Conventional treatment
118
radical decays in recombination and reaction with
superoxide anion radical formed during
1
ROOM C - W E T A I R A N D S U P E RC R I TI C A L OXI DA TI ON

119
Cellulose is one of the wide-spread organic acceleration of acid- and base-catalyzed reactions
structures in nature. It has been estimated that by approximately 400 times higher ions H3O+
11 12
10 10 tons of cellulose are synthesized OH- concentrations;n dthe decrease of diffusion
annually. It is mostly combined O Rwith A Lhemicellulose
P R E S E N Tlimitation,
A T I O N connectedS - 2 D A Y low viscosity of
with
and lignin in the plants cell walls [1]. A lot of subcritical water; the increase in gas solubility
PHOTODEGRADATION
scientists consider cellulose OF BISPHENOLS:
a prospective MECHANISTIC ASPECTS the increase will
and, in consequence, in be
hydrogen
Photodegradation of bisphenols: mechanistic aspects filled
alternative to fossil fuels as its renewable concentration on the catalyst surface. in by C2-13
resources can provide production of raw material In this paper a new type of Ru-containing EAAOP4
for
V. the chemical
Salomatova 1 industry and
, I. Pozdnyakov 1,2 second-generation catalysts
, V.Grivin1,P. Sherin3, V. Plyusnin 1,2 on the
, N. Bazhin 1 basisVoevodsky
(1) V.V. of hypercrosslinked
Institute of
biofuels
Chemicalon a large
Kinetics scale [2, 3].Institutskaya
and Combustion,3 Moreover,St.,atNovosibirsk,
polystyrene
Russia,(HPS) is suggested(2)
salomatova@ngs.ru forNovosibirsk
the process of
present, chemicals
State University, obtained
2 Pirogova from cellulose
St., Novosibirsk, cellulose Tomography
Russia, (3) International hydrolytic hydrogenation in a subcritical
Center, 3a Institutskaya St.,
Novosibirsk,
biomass can Russia
be cheaper than those obtained from water medium. The use of rhutenium catalyst
oil [4]. A large number of hydroxyl groups part of (1.0 % Ru) on the basis of HPS allowed achieving
cellulose composition account for theInoptimum the total sorbitol
this work steady-state and mannitol
and nanosecond laseryield
flashabout 50 % on
photolysis
way of its conversion hydrolytic hydrogenation were used to average
study that is comparable
mechanistic aspectswith of the results
aqueous
to sorbitol (mostly) and other polyols. This process
photochemistry obtained
of three with widely more
usedcomplex
bisphenolsand(BPs)
therefore more
- bis(p-
was first carried out by A.A. Balandin and his expensive catalytic
hydroxyphenyl)methane (BPF), systems. Being reused this
bis(4-ydroxyphenyl)ethane
colleagues in the USSR. They (BPE) conducted catalyst was stable.
and 4,4-Bis(4-hydroxyphenyl)valeric acid.
hydrolytic hydrogenation of cellulose Forinallthestudied Fig. 1 presents
systems the main typical chromatographs
primary photochemical of the
presence of mineral acids and Ru, Pdprocess and Pt- liquidtoand
was found begas phases obtained
photoionization withafter the reaction
formation of
containing catalysts. Now great attentionphenoxyl is paid toradical.with 1%Ru/MN-270.
Phenoxyl radical decays The main products
in recombination and of
supercritical fluidic technologies in the reaction chemistrywith cellulose
superoxide hydrolytic
anionhydrogenation
radical formed are sorbitol
during (S),
of wood and its components [5]. One mannitolelectron
of the of hydrated
scavenging (M), asby well as 1,4-sorbitan
dissolved oxygen. The (1,4-S),
main
prospective media is sub- and supercritical water
primary productxylitol
for given(X),BPserythritol (E), glycerol
was determined (G), propylene
as hydroxylated
[6, 7]. For example, there were studies BP. discussing glycol
Also, tentative scheme (PG),of BPs
ethylene glycolwas(EG)
photolysis and some
proposed.
the possibilities of cellulose hydrolytic glucose which has not been hydrogenated
hydrogenation in a subcritical water medium [8]. It (Fig. 1a). Chromatography-mass spectrometric
allowed excluding mineral acids from the process analysis also shows trace amounts of cellobiose,
and solving the problems of their disposal and the hexane-1,2,5,6-tetrols, hexane-1,2,3,4,5-pentol and
corrosion of (BPs)
the equipment. Subcritical water spectral products
other and kineticofpropertiesglucose of and excitedsorbitol
states
Bisphenols are
o
widely used in production and primary intermediates and their further
(temperature
of polycarbonate < 350 , pressure
plastics, < 221adhesives,
epoxy resins, bar) is a hydrogenolysis in a liquid phase. In a gas phase
universal transformation products.
coatings formedium
drink packagesfor performing
and food cans. chemical
As a there are methane and trace amounts of ethane,
reactions.
GATIFLOXACIN It can
consequence BPs have serve as a
DEGRADATION non-toxic
been widely detected solvent with
BY HYDROXYL
in the propane, and isobutane
RADICALS:BYPRODUCTS
For all studied BPs (Fig. 1b).
the AND main
Gatifloxacin degradation by hydroxyl radicals: byproducts and will beprimary
filled
well variableTOXICITY
environment
RESIDUAL physical
and foodchemical products properties (due
[1]. However, to photochemical process was observed intoby be C2-14
residual
the change toxicity
in temperature
many (e.g. well-known bisphenol A) of them refer and pressure). photoinization with formation phenoxylEAAOP4 radical
toC. endocrine-disrupting
Rodrigues-Silva2, M. Caianelo chemicals
1
, M. G.(EDCs)
Maniero1and hydrated
, J. R. Guimares 1 electron pair. It was found that phenoxyl
(1) School of Civil Engineering, Architecture
were reported
and Urban Design, to University
possess acute toxicityP.O.
of Campinas, andBox 6021,
radical decays inCampinas,
13083-852, recombinationBrazil.and (2) reaction
Institute with
of 1
estrogenic activity. of Conventional
Chemistry, Department Analytical Chemistry, treatment
University ofsuperoxide
Campinas, POanion Box 6154, radical
13084-971formedCampinas,during
SP,
techniques arecaio.rodrigues@iqm.unicamp.br.
Brazil. E-mail: not effective enough for the scavenging of hydrated electron by dissolved
removal of majority of EDCs, while photochemical oxygen with formation of one main product which
and photocatalytic processes haveGatifloxacin, proved anwas determined drug
antimicrobial by LC-MSfrom the method as product of
fluoroquinolone
themselves as perspective methods family, for water BP hydroxylation. In present
currently used in the control of human bacterial work quantum yields
purification and disinfection from thesehave already
infection, of primary intermediates
been reported formation and
in the environment matrix. BPs
compounds. Besides the broad number This study of isphotodegradation,
dedicated to investigate rate constants the of gatifloxacin
intermediates
investigations devoted to decomposition of BPs by
degradation disappearance
hydroxyl and their spectral
radicals, generated properties
by the were
using photochemical approaches, thereUV is 254nm
almost determined.
/H2O2 process Also, on= the
(CH2O2initial 0.4basis
2.4ofmmol
all obtained
L-1), anddata,
no information about mechanisticevaluate aspectstheir scheme
capabilityof toBPs reducetransformation
the solutionin toxicity. aqueous
regarding the photochemistry of BPs. Approximately solutions was proposed
97% of degradation was(Figure
observed 1). when applied
Using combination of pulsed photochemical 2.4 mmol L-1 of initialUV-method H2O2 was
concentration
found to be and 20 min ofeffective
sufficiently UV-
techniques with stationary methods is comparable C254nm irradiation. way for Two BPsmajor
removal degradation
from water,products
nevertheless werethis
rarely used but very informative approach identified forand the molecules
method structures
is needed in were
furtherproposed.
improvements and
construction full and reliable model of modifications to reach endurable results.
photodegradation of organic pollutants. Cyclodextrin complexation has recently emerged
INTRODUCTION as a new catalytic technology complement to the
In this work aqueous photochemistry of three 280 nm) withtreatment
photochemical hydrogenapproaches.
peroxide Ittowas
generate
found
bisphenols (4,4-hydroxyphenylmethane (BPF), hydroxyl radical, whose generation in the
for all studied compounds that inclusion of BPs 4 in
4,4-hydroxyphenylethane
Antimicrobial (BPE)used
drugs are widely andfor4,4-Bis(4-
infection UV 254m/H2O2 process
cyclodextrin is shown
cavity leads to in reaction
great 1.
increase of
hydroxyphenyl)valeric
control and therapeutic acid
uses.(DPA)) was studied
The majority by
of these photoionization and fluorescence quantum yields
means areof stationary (XeBr excimer lamp, 282 nm) H2O2 + h ! 2 "OH Reaction (1)
drugs not fully metabolized due to their low as well as fluorescence lifetime due to decreasing
and laser flash photolysis (6 ns,
DEGRADATION OF 17-ETHINYL ESTRADIOL IN
absorption in the digestive tract.1 Nd:YAG laser,
Therefore, these TheWATER
of By
solvent BYofHYDRODYNAMIC-
objective the of
quenching present study excited
the singlet was to state
submitof
Degradation Of 17-Ethinyl Estradiol In Water Hydrodynamic- will be filled
266
drugs nm).
canMain attention
be excreted
ACOUSTIC-CAVITATION: was paid
in natura viatofeces
determination
FREQUENCY and urine
EFFECTS
gatifloxacin
BPs. solution (Cinitial = 500 g L -1
in by) to C2-15
ofAcoustic-Cavitation
in primary
their non-metabolized Frequency
photochemical processes,
form or asEffects
nature,
active UV/H2O2 process and evaluate its degradation,
EAAOP4the
metabolites, thereby contaminating surface residual acute toxicity and the degradation
F. Anschuetz, M. Franke, P. Braeutigam, A. Stolle, B. Ondruschka.
waters. 1,2
120
products formation. Jena, Lessingstr. 12, Jena,
Institute for Technical and Environmental Chemistry, Friedrich-Schiller-University
Germany, franziska.anschuetz@uni-jena.de
1
Gatifloxacin, anInstitute
(2) BAM Federal antimicrobial agent
for Materials of and
Research theTesting,
METHODS
Richard-Willstaetter-Str. 11, Berlin, Germany
 280 nm) with hydrogen peroxide to generate
hydroxyl radical, whose generation in the
Antimicrobial drugs are widely used for infection UV254m/H2O2 process is shown in reaction 1.4
ROOM C - RADIATION PROCESSES
control and therapeutic uses. The majority of these
H2O2 + h ! 2 "OH Reaction (1)
drugs are not fully metabolized due to their low
DEGRADATION OF 17-ETHINYL ESTRADIOL IN
1
absorption in the digestive tract. Therefore, these WATER
TheBy BYofHYDRODYNAMIC-
objective the present study was to filled
submit
Degradation Of 17-Ethinyl Estradiol In Water Hydrodynamic- will be
drugs can be excreted in naturaFREQUENCY
ACOUSTIC-CAVITATION: via feces and urine
EFFECTS gatifloxacin solution (Cinitial = 500 g L -1
in by) to C2-15
Acoustic-Cavitation Frequency
in their non-metabolized form or as active Effects UV/H2O2 process and evaluate its degradation,
EAAOP4the
metabolites,
F. Anschuetz, M. thereby
Franke, P.contaminating surface
Braeutigam, A. Stolle, residual acute toxicity and the degradation
B. Ondruschka.
1,2
waters. products formation. Jena, Lessingstr. 12, Jena,
Institute for Technical and Environmental Chemistry, Friedrich-Schiller-University
Germany, franziska.anschuetz@uni-jena.de
Gatifloxacin,
(2) BAM Federal anInstitute
antimicrobial
for Materials agent
Research of and
theTesting,
METHODS
Richard-Willstaetter-Str. 11, Berlin, Germany
fluoroquinolone family, is commonlyThe used
entryin of different contaminations (esp. pharmaceuticals)
human medicine to treat infection originated into 3thebyaquatic environment is a growing problem. One
Gram-positive and Gram-negative bacteria. The to solve
possibility Working
this problemsolutionsis the(Capplication
GAT = 500 of L-1) were
goxidation
available technology in the conventional agents (ozone,prepared hydrogenfrom a stockorsolution
peroxide) advanced of gatifloxacin
oxidation
wastewater treatment plant is not efficient processesto(AOP) (Sigma Aldrich).
in sewage The batch
treatment reactor
plants. Theis cavitation-
composed of
remove or degrade this pollutant, causing its
based degradation a reservoir
of micro (h pollutants
= 39 cm, dcan be=classified
internal 10 cm andasVan net =
continuous reintroduction into the environment. AOP due to the1.0 in-situ L)generation
jacketedof to maintain
oxidative species. thePrevious
solution
The occurrence of gatifloxacin residues studies have been temperature stable during the reaction,
of Hydrodynamic-Acoustic-Cavitation (HAC) prove and a
detected and reported in aqueous environments synergism (41 compared
quartz tube
with (h
the = 32.5
single cm and
methods, d but they
external = 2.5
were cm)
ng L-1), and its presence can contribute to thedownwith
narrowed to the autility closed
of lowbase, which
frequency was installed
ultrasound (US).
2
development of resistant bacteria. This Aim fact brings concentrically
of this study was the transfer to ofthethereservoir,
HAC-concept beingto higher
used as
the need to apply advanced processes that USarefrequencies
able support
and the for investigation
a UV-lamp 254 nm (Philips,
of other influencing16W).
to mitigate the deficiencies that the parameters. traditional TheHsynergy2O2 from Synth
effects wasbeused
could as oxidant. Mineral
confirmed.
WWTP are facing today in eliminating these water was used as acquired (Supplied by
drugs. Bonafont: CHCO3- = 29.23 mg L-1, CK+= 1.93 mg
The hydroxyl radical excels amongst the other L-1, CNa+= 3.12 mg L-1, CNO3-= 0.85 mg L-1, CCl-=
The cavitation-based
0.13 mg L-1, CSO42- = 0.09 degradation
mg L-1, C is another class-
Background.
oxidants due to More its and more anthropogenic
capability to destruct F-= 0.08 mg L
1of AOPs. Cavitation, which is defined as the
substances organic
recalcitrant from contaminants
usage of pharmaceuticals, in water and its , pH = 7.6) without any correction.
formation, growth and collapse of gas- or vapour-
disinfectants, diagnostics
disinfection properties. It is also reported in the and personal care Gatifloxacin
filled micro bubbles, sample leadspreparation prior to the
to the generation of
products asreach
literature the environment
a non-selective oxidant.2,4by different quantification
hydroxyl radicals wasupondone theby homolytic
solid phasecleavageextraction of
pathways of diffuse DEGRADATION
AMICARBAZONE entry [1]. The inability of
BY UVA-ACTIVATED (SPE); PERSULFATE
quantification INthe THE PRESENCE
Amicarbazone
The
commonapplicationsewageoftreatment degradation
the advanced plants by UVA-activated
oxidation
ORtoFehold
process
micro
water
persulfate moleculesin thedue towas done will by
release high
beoffilled
OF HYDROGEN PEROXIDE 2+
2+ performance
temperatures liquid
and chromatography
pressures and with
without in byUV
any C2-16
presence
UV/H 2O2 involves
pollutants of hydrogen
such the use peroxide
as pharmaceuticals of UV radiation or Fe back,
entirely ( <
additives [6]. EAAOP4
leads
CtiatoGraa an increasing
1
, Adriana Correia pollution of the1, hydrologic
de Velosa Antonio Carlos S. C. Teixeira1. (1) Universidade de So Paulo, Avenida
cycle. Especially,
Prof. Luciano the consequences
Gualberto, tr. 3, 380 Sofor Paulo,the Brazil, Objectives. Cavitation can be generated by
aquaticcatia.graca@usp.br 1
fauna and human beings is difficult to assess. different methods. This study focuses on the use of
Already discussed are the formation of resistances Abstract ultrasonic waves with different frequencies (AC)
of microorganisms by the entry of antibiotics [2]
U V Lam p
In this and
studythe the hydrodynamic generation with
degradation of amicarbazone (AMZ, orifice
a
and the feminization 4 x P h ilip s T L 8 W
of fish populations by platesfor(HC).
substitute Both methods
atrazine), driven have by the advantages
UVA/PS, and
hormones such as the contraceptive pill ingredient UVA/PS/H disadvantages
2O2,
due to main
Fe(II)/PS andfactors, which affect
UVA/Fe(II)/PS
17-ethinyl estradiol (EE2) [3]. processesthe degradation
is described(collapse for the conditions
first time. and bubble
The
density), but
UVA/Fe(II)/PS also regarding
system has shown the toscale-up,
be the costs
most and
Moreover, EE2 among 17-estradiol and energy efficiency. AC as ofathemore energy-
T h e r m o m e te r
diclofenac were the first pharmaceuticals added toR e a c to r effective, achieving total degradation pesticide in
less thanconsuming and therefore
30 min reaction. Results alsomoreindicated
cost-intensive
that
the first watch list of the C o o lEuropean
w a te r b a th water process leads not to better collapse conditions
framework directive (WFD). WFD includes a list
S tir r e r b a r adding H 2O 2 does affect significantly the
comparedofto HC,
performance PS/UVAwhich issystem.
in turn able Underto generate
the
of priority substances and deals with the definition a higherconditions,
amount of bubbles. In the literature HC is
of environmental quality standards to improve the experimental AMZ degradation showed
water quality and finally the protection of aquatic pseudodescribed
first-order as kinetics.
more energy efficient and
Nevertheless, thisthestudy
scale-
revealed up that
of HC-reactors
UVA/PS is easier
is a to implement
promising technique[7]. for
organisms and consequentially human beings [4].
decontamination of water containing the pesticide.
5 6 5 6
4 7 4 7

The combination of both methods as

8 8
3 3

2 9 2 9

C lo s e d
1 11 1 10

The investigation of more efficient C o n ta in e r treatment

Hydrodynamic-Acoustic-Cavitation (HAC) could
M a g n e tic s tir r e r
technologies is a broad field of research and it can lead to a synergism by merging the benefits and
be divided in separation techniques (e.g. filtration/ distinguishing the drawbacks. Few publications
adsorption) and degradation processes (e.g. prove this potential benefit [7, 8], but there is a
INTRODUCTION
chemical oxidation). The advanced oxidation scavenged by other water constituents. [4].
lack of research concerning the interaction of
processes (AOP) deal with the in-situ generation ultrasound (US) frequency and other parameters.(1)
Amicarbazone (AMZ) is a triazolinone herbicide
of oxidative species by different methods for
used in place of atrazine. Although AMZ presents
instance Fenton-, photo-Fenton-process or photo (2)
low toxicity, it is moderately persistent in the
catalysis [5].
environment due to its slow degradation by
(3)
photolysis, hydrolysis and anaerobic aquatic
metabolism [1]. Due to its low vapor pressure
(9.75 10-9 mm Hg at 30 oC) and its high water 121 In addition, persulfate is cheaper than H2O2 and
(4)
1
solubility (4600 ppm at 20 oC) AMZ can be
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

HETEROGENOUS AND HOMOGENOUS CATALYSIS IN PHOTOCHEMICAL DEGRADATION

Heterogenous and Homogenous Catalysis in Photochemical will be filled
OF CORTISOL in by A3-1
Degradation of Cortisol
EAAOP4
S. Klementova, L. Doubkova, Faculty of Science, University of South Bohemia, Branisovska 1760, Ceske
Budejovice, Czech Republic, sklement@jcu.cz

Cortisol heterogeneous photocatalytic degradation on

immobilised TiO2 and homogenous photocalytic degradation
with Fe as the catalyst was investigated. The rate constant in
heterogeneous photocatalytic reaction was 0.020 min-1, in
homogenous degradation with just traces of the metal present
in the reaction system (less than 1*10-7mol/l) the rate constant
was 0.046 min-1; addition of ferric ions accelerated the reaction
enormously with metal ions at the concentration 1*10-5mol/l
the degradation was completed in less than two minutes.
Quantum yield of the homogeneous reaction is 6.839*10 -3.

aphical Illustration (Figure,

Scheme, etc.) should not exceed
the size of this area. The aim of our study was to determine the
Background kinetics of cortisol photocatalysed degradation on
Cortisol is a steroid hormon of the family of immobilised TiO2 and compare it with the
glucorticoids produced by adrenal cortex of the degradation in the homogeneous phase in the
adrenal gland. Cortisol stimulates presence of ferric ions as the catalyst in the
PROCESS INTENSIFICATION IN THE PHOTO-CATALYTIC
concentrations SPINNINGinDISC REACTOR: THE
Process Intensification
gluconeogenesis, in the of
i.e. the formation Photocatalytic
glucose, and Spinning Disc common
Reactor: natural waters. will be filled
EFFECT
activates OF PHOTOCATALYST
anti-stress and MACRO-STRUCTURE
anti-inflamatory pathways
The Effect of Photocatalyst Macro-Structure on Treatment Efficiency
ON TREATMENT EFFICIENCY in by A3-2
in organisms. EAAOP4
Wan Salida Wan Mansor1,2, Emma A.C. Emmanuelson1, Darrell A. Patterson
Methods
1
.
Hydrocortisone
(1) is the name
Bath Process Intensification of cortisol
Laboratory, when of Chemical Engineering, University of Bath, Claverton
Department
used
Down,asBath
medication for skin
BA2 7AY, United irritation,
Kingdom, allergic
wswm20@bath.ac.uk, The light source Phillips
wansalida@umt.edu.my (2) SchoolTLD 15 W 08 lamp
of Ocean
Engineering,
reactions and Universiti Malaysia Terengganu,
other pharmaceutical 21300 Kuala Terengganu,
applications. (light with theTerengganu,
wavelength Malaysia.
range of 350 410 nm)
The thin was used for irradiation of reaction mixturesiswith
Runnals et al.1 analyzed a comprehensive U.K.film photocatalytic
TiO2. Homogeneous
spinning disc
mixtures
reactor (pSDR)
were irradiated in
a
database covering all new
prescriptions process
of intensification reactor for supported photocatalysts.
This work the Rayonet the reactor
use ofwith lamps ofRPR 3000
pharmaceuticals to determine the annual usage of investigates
(emitted light 254(meshes
a range
350 nm), light
different
belowin300
photocatalyst
all steroid and anti-steroid pharmaceuticals. They macro-structures and grooves thenm
photocatalyst was filtered
disc) in order out
to toincrease
imitate theshort-wavelength
micromixing tosun
found that glucocorticoids are used in much radiation.
greater amounts than estrogens. All these increase the overall degradation rate in the pSDR.
pharmaceuticals are likely to be Results have shown
constantly that degradation
Actinometric rate can was
measurements be optimised
performed
entering the aquatic environment viathrough identification
effluents of the
according optimal7. rotating speed, disc surface
to Murov
from sewage treatment plants.structure
River (meshes/grooves/smooth), oxidant input and
concentrations of these pharmaceuticals are very flowrate.
volumetric HPLC,The HPLC-MS
optimal wasand found to be was
ICP-MS at 300 rpmfor
used
low, probably in the ng or sub-ng/l and 20 (no
range mL/s forreaction
a disc with square
mixtures grooves. Overall, this work
analyses.
precise data are available). However, shows that reactor and photocatalyst surface macrostructure and
even such
low concentrations may still pose adesign threatalso
to plays an important role in increasing photocatalytic
aquatic organisms. treatment efficiency.
Results and Discussion

Advanced oxidation procedures have been The spectrophotometric analysis of degradation

Introduction.
investigated Processdegradation
for possible intensification can be
of xenotiotics
properties.used
progress e.g. inet plasma
Boiarkina al. [3] degradation
found that theof
photocatalytic
cortisol 8 surface rate of reactionprecise
does not provide sufficiently was
described
in as
the aquatic any chemical among
environment; engineering
those independent of these flow regimes. However, and
this
development that
techniques, leads to a substantially
heterogeneous smaller,
photocatalysis on results, the comparison of spectrophotometric
pSDR thin film photocatalytic
HPLC analyses is visualised in Fig. 1. system has
cleaner and morehas
semiconductors energy efficient
attracted attention2,3,4,5,6
muchtechnology. The. disadvantages if a thin film catalyst is coated
spinning disc reactor (SDR) has been shown to be directly onto the disc [3], then the catalyst amount
a process intensification technology that can and surface area is largely limited to the surface
increase reaction rate and photonic efficiency
Objectives area of the disc. This past work on the pSDR also
compared to conventional reactors [1]. The found that with the smooth disc used, oxygen mass
principle of SDR technology is based upon the
formation of a thin liquid film (20300 m) on a
122transfer is the rate limiting step at higher initial 1
concentrations [5].
rotating disc induced by centrifugal and shear
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

PHOTOCATALYTIC NO DEGRADATION: MECHANISTIC AND KINETIC ASPECTS

Photocatalytic NO Degradation: Mechanistic and Kinetic Aspects
will be filled
in by A3-3
EAAOP4
R. Dillert , Gottfried Wilhelm Leibniz Universitt Hannover, Callinstr. 3, 30167
Hannover, Germany.

Air pollution by nitrogen oxides represents a serious

environmental problem in urban areas where numerous sources
of these pollutants are concentrated. One approach to reduce the
concentration of these air pollutants is their light-induced
oxidation in the presence of molecular oxygen and a
photocatalytically active building material using titanium
dioxide as the photocatalyst. Possible mechanisms of the
photocatalytic transformations of nitrogen oxides will be
discussed. It will be shown that the observed transformation of
NO in the presence of visible-light irradiated titanium dioxide
might be due to a ligand-to-metal charge-transfer process.

Air pollution by nitrogen oxides represents a References

serious environmental problem in urban areas [1] J. Freitag, A. Dominguez, T. A. Niehaus, A.
where numerous sources of these pollutants are Hlsewig, R. Dillert, T. Frauenheim, D. W. Bahnemann,
concentrated. One approach to reduce the J. Phys. Chem. C 119 (2015) 4488-4501.
concentration of
EFFECTIVE these air pollutants
TREATMENT is their light-
OF ACRYLIC [2] R. Dillert, J. Sttzner, WASTEWATER
FIBRE MANUFACTURING A. Engel, D. W. Bahnemann,
USING
Effective
induced
ADVANCED treatment
oxidation of presence
in the
OXIDATION acrylic fibre manufacturing
of molecular
PROCESSES wastewater
J. Hazard. Mat. 211-212 using
(2012) 240-246. A3-4
advanced
oxygen and oxidation processesactive building
a photocatalytically [3] T. Giannakopoulou, N. Todorova, G. Romanos, T.
material 1 using 2 titanium 3 dioxide 1 as the Vaimakis, R. Dillert, D. Bahnemann, C. Trapalis, Mater.
W. Szeto , J.T. li , H.B. Huang , Y.C. Leung . (1) The University
Sci.ofEng.
Hong
B:Kong, Pokfulam,
Adv. Func. Hong Kong,
Solid-State Mater.China,
177 (2012)
photocatalyst. Based on own
u3003605@connect.hku.hk experimental
(2)FRIPP, results & Chemical
China Petroleum Corporation, Fushun, China (3)School of
1046-1052.
[1] possible mechanisms will be discussed
Environmental Science and Engineering, Sun Yat-sen University,[4] R.China
Dillert, A. Engel, J. Groe, P. Lindner, D. W.
involving both, the photocatalytically generated Bahnemann, Phys. Chem. Chem. Phys. 15 (2013) 20876-
holes as well as the respective electrons as To destroy the biorefractory organics laden in
20886.
initiators of the process. It will be shown that the [5] acrylic
. ngel,fibre
. l manufacturing
, . H l e ig, J.wastewater,
Groe, R. Dillert,
a
observed transformation of NO in the presence of D.W. Bahnemann,
series of UVChem. basedEng. advanced
J. 261 (2015)oxidation
88-94.
visible-light irradiated titanium dioxide might be [6] processes
A. Engel, J. Groe,
wereR. Dillert, D. W. Bahnemann,
attempted. ExcellentJ.
due to a ligand-to-metal charge-transfer process. Adv. Oxid. Technol. (2015) accepted.
TOC/COD reduction was observed for the
Moreover, results of an investigation concerning UV + TiO2 + Persulfate process. Instead of
the influence of the photon flux, the humidity and the typical TiO2 nanoparticles, a novel
the pollutant concentration on the rate of the photocatalyst with hedgehog-like Fe2O3 @
photocatalytic oxidation of nitrogen(II) oxide in SiO2 @ TiO2 microparticle morphology and
the presence of molecular oxygen and UV(A) magnetically separable property has been
irradiated titanium dioxide powder will be developed used in this work.
presented [2-6].

Acknowledgements
Background UV/Persulfate and their combination are
The work was funded in part by the German Federal promising technologies of destroying the residual
Ministry fibres
Acrylic of Education and fibres
are synthetic Research
mainly(contract
used in no non-biodegradable organic matters laden in the
03X0069F,
textile industryHelioClean manufacturing
and carbon fibre Nanotechnologisch acrylic fibre manufacturing wastewater. A novel
funktionalisierte Baustoffe zurof solarkatalytischen
made from polymerization acrylonitrile (AN)Luft- photocatalyst with hedgehog-like Fe2O3 @ SiO2 @
und Oberflchenreinigung).
mainly. Depending on the manufacturing TiO2 microparticle morphology and magnetically
technology, solvent used in the polymerization and separable property, namely magnetically separable
spinning processes can be sodium thiocyanate spiny TiO2 (MSST) has been developed and used
(NaSCN), dimethylacetamide (DMAc) or in this work instead of the typical TiO2
dimethylformamide (DMF). Large amount of nanoparticles.
wastewater (> 10 tons per ton acrylic fibre) is
generated from various washing and the solvent
123 1
Objectives
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

FLUIDIZED-BED PHOTOCATALYTIC REACTOR: INFLUENCE OF OPERATING will be filled

Fluidized-Bed Photocatalytic Reactor: Influence of Operating Conditions
CONDITIONS ON THE ELIMINATION OF PERSISTENT EMERGING MICROPOLLUTANTS
on the Elimination of Persistent Emerging Micropollutants in by A3-5
EAAOP4
N. Pronina1, D. Klauson1, S. Kamenev1, T. Rudenko1, K. Knnis-Beres2, A. Moiseev3, J. Deubener3, M.
Krichevskaya1. (1) Dept. Chem . Eng., (2) Inst. Marine Syst., Tallinn Univ. Technol., Ehitajate tee 5, Tallinn,
Estonia, natalja.pronina@ student.ttu.ee. (3) Inst. Non-Metallic Mater., TU Clausthal, Zehntnerstr. 2a, Germany.

The implementation of TiO sol-gel-coated expanded clay

2

granules for aqueous photocatalytic degradation of four

persistent pharmaceuticals and their mixture in larger lab-scale
fluidized-bed reactor was evaluated. The proneness of drug
molecules to photocatalytic oxidation is increasing with the
increase in their adsorption affinity towards TiO coatings. The 2

optimization of operating parameters, such as air superficial

velocity and catalyst bed loading, allowed performing the
photocatalytic degradation with higher removal rate at lower
mechanical stress put on the coated granules. The photocatalytic
oxidation was accompanied by the significant decrease in the
toxicity to several bacterial strains allowing the process
application as a pre-treatment prior to biodegradation.

growth of the solutions turbidity. Within the

Among the photocatalytic reactors designs, studied bed loadings range the higher loadings
recent advances in environmental chemistry have resulted in the significant increase in the turbidity
focused on the implementation of fluidized-bed of the treated solutions with the marginal increase
concept for the oxidation of pollutants benefitting in photocatalytic oxidation rate. The mechanical
from the high light utilization and reactant-catalyst stress placed on coatings even at optimized
contact. However,
REMOVAL despite all
OF ARSENIC FROM the advantages,
AQUEOUS bedSOLUTIONS THROUGH A COUPLED SYSTEM
Removal of arsenic fromlevels aqueous solutions through operatinga coupled
conditionssystem
caused up to 40 % be filledOF
decrease
will in
material is subjected
PHOTOCATALYSIS toANDhigh ZERO-VALENT of mechanical IRON coatings photocatalytic activity after 3 cycles A3-6
in byof
of photocatalysis
stress and zero-valent
causing photocatalyst detachment. This ironis the
use due to the detachment of catalyst. EAAOP4
fluidized-bed concepts main limitation that should
M.J. Lpez-Muoz, A. Arencibia, Y. Segura, J.M. Arsuaga, J.M. Raez. Environmental and Chemical Engineering
beGroup,
overcome by theRey
Universidad appropriate
Juan Carlos, choice
C/ Tulipnof support s/n, Mstoles,The photocatalytic
Madrid, degradation of the individual
Spain, mariajose.lopez@urjc.es.
material and attachment method as well as reactor compounds in a mixture proceeded as follows:
operating conditions. 2
doxycycline > prednisolone > sulfamethizole >
1,0
Theamoxicillin.
removal of arsenic
At thefrom aqueous solutions
optimized reactor has been
operating
The
0,9
aim of this study is to optimize the fluidized- studied by using photocatalysis
conditions at least 70 with % TiO 2, zero valent
decrease iron
in initial
bed0,8reactor operating conditions having the highest (ZVI) and a mixedconcentration
doxycycline process combining (25 mg both Lsystems.
-1, 3 h)The was
impact
0,7
on photocatalystAs(III) coating As(V) abrasion influence
achievedof pHdueand the concentration
to adsorption and particle
on coated expanded size clay
of
resistance, i.e. air superficialAs(III)velocity, bed loading ZVIand was investigated. The presence of ZVI in the coupled
As(III) As(V); [ZVI] = 0,1 g/l
As(V); [nZVI] = 0,1 g/l
photocatalytic oxidation.
and photocatalyst coating modifications. The system, improved not only the oxidation of As(III) to As
0,6
[As]/[As]0

by (V) but Thealso the further uptake of thesolution

latter. The removal
0,5
reactor performance was evaluated toxicity of doxycycline to the model
photocatalytic degradation of pharmaceuticals of As(V) was enhanced by increasing the concentration of
0,4
and environmental bacterial strains has noticeably
0,3 ZVI, up to 0.1 g L , being favored in acidic conditions
-1
doxycycline, amoxicillin, prednisolone and most decreased during the experimental runs in the
likely due to the formation of iron oxide/hydroxides
sulfamethizole
0,2
on TiO2 sol-gel-coated lightweight on following the surface of order: E. coli
the metallic (80
iron. %) > P.
Moreover, putida >
the addition
expanded
0,1
clay granules under UV-A irradiation. bacterium isolated
of nanoparticles ZVI in thefrom activesystem
coupled > S. aureus
sludgeenhanced the
0,0
oxidation
(33 rate
%). and
Theled to the total
toxicity removal
reduction of As(V)
profilefrom in
Photocatalytic
0 15 30 45 fluidized-bed
60 75 90 105 120 135 reactor
150 165 180 (see theexperimental
aqueous solution
runs even in alkaline
indicated the conditions.
absence of toxic by-
Graphical Illustration) of 2 L volume was operated
Time (min)
products. The photocatalytic oxidation in fluidized-
in semi-batch mode, where pre-humidified air bed reactor with TiO2 sol-gel-coated expanded clay
superficial velocities were varied between 0.04 and granules as a bed material could be suggested as a
0.08 m s-1. Titania sol-gel-coated expanded clay
In this context,stage
pre-treatment the oxidation
prior to of As(III) to As(V)
pharmaceuticals
Arsenic is were
granules a toxic prepared
and carcinogen usingelement dip widely coating
inbiodegradation.
aqueous solutions and the subsequent uptake of
distributed
technique.in the aquatic systems by a combination
the later, has been evaluated in the present work by
of natural processes and anthropogenic activities. Acknowledgements
The study of reactor performance demonstrated three approaches:
supportphotocatalysis with TiO2,Council
ZVI
The World Health Organization (WHO) has The financial from the Estonian Research
that the increase in air velocity led to the increase in and and the coupledForschungsgesellschaft
Deutsche system. The aim has (DFG) been to
(grants
classified this element as one of the ten chemical
doxycycline photocatalytic oxidation rate followed optimize G8978, DE the598/26-1,
removalproject
of arsenic from aqueous
SF0140022s10) is greatly
species of greatest concern to public health, setting
by its decrease, accompanied by the constant solutions using the coupled system by studying the
appreciated.
a limit value of 10 g L-1 in drinking water [1]. influence of i) the concentration of ZVI in the
Inorganic arsenic in water mainly exists as arsenite, solution, ii) the initial pH of the solution and iii) the
As(III), and arsenate, As(V), being the former
species more toxic, mobile and less efficiently
124 size of the iron particles. 1
removed than arsenate. The photocatalytic reactions were performed in a
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

PHOTOCATALYTIC REMOVAL OF TOXICITY AND ESTROGENICITY OF WATER

Photocatalytic removal of toxicity and estrogenicity of water dissolved
DISSOLVED BISPHENOLS (BISPHENOL A, F AND AF) IN BR AND CSTR
will be filled
A3-7
in by
bisphenols (bisphenol A, F and AF) in BR and CSTR
EAAOP4
B. Erjavec1, P. Hudoklin2, K. Perc2. T. Tiler1. M. Sollner Dolenc2. A. Pintar1 (1) National Institute of Chemistry,
Hajdrihova 19, SI-1001 Ljubljana, Slovenia, bostjan.erjavec@ki.si. (2) Faculty of Pharmacy, University of
Ljubljana, Akereva 7, SI-1001 Ljubljana, Slovenia.
Glass fiber-supported TiO2 photocatalyst was synthesized by a
OH
novel preparation procedure, thoroughly characterized and
HO
F3 C
subsequently applied in a UV-irradiated three-phase batch
(BR) and continuous stirred-tank reactor (CSTR) for removal
CF
3

HO

HO
HC
3
CH
3
OH
of toxicity and estrogenicity of water dissolved bisphenols
OH
(bisphenol A, F and AF). Bioassays of treated aqueous samples
showed no estrogenic activity and complete removal of
Liquid
inlet toxicity. These results were in accordance with high
Air
mineralization extent of BPs and their derivatives attained after
Liquid
outlet 4 h of illumination. Photolytic reactions demonstrated that
Catalyst
CO2 BPAF with two CF3 groups attached to the central C atom was
+ the most stable under UV light irradiation. Finally, an excellent
H2O stability of immobilized TiO2 photocatalyst was confirmed
after 25 h of continuous photocatalytic oxidation.

subsequently apply it in a UV irradiated three-

BACKGROUND phase batch (BR) and continuous stirred-tank
Bisphenol A (BPA) and its analogues (BPF and reactor (CSTR) for removal of toxicity and
BPAF) are a class of chemicals that are proven to estrogenicity of water dissolved BPs (bisphenol A,
elicit endocrine disrupting effects [1]. Purification F and AF). In addition to chemical analysis,
ESR
ofESR INVESTIGATION
water samples containingOF THEthese PHOTOCATALYSIS
endocrine MECHANISM
bioassays were used OF CYANOTOXINS
to assess the UNDER
will estrogenic
VISIBLE
Investigation
LIGHT
of the Photocatalysis Mechanism of Cyanotoxins be filled
A3-8
disrupting chemicals (EDCs) is necessary, since activity and toxicity of stock and treated aqueous in by
Under Visible Light
many studies have reported harmful effects of samples, using yeast estrogen screen (YES) EAAOP4 assay,
A. Hiskia, T.
bisphenols Fotiou
(BPs)
1
at ,very
T.M.low
Triantis 1
, T.Kaloudis2, N. Ioannidis
concentrations. and
1
marine
, (1) bacteria
Institute Vibrio
of Advanced fischeri and water fleas
Materials,
Physicochemical Processes, Nanotechnology & Microsystems,Daphnia Nationalmagna,
Center for Scientific Research
respectively. Finally, we focused
Heterogeneous
Demokritos, photocatalytic
Neapoleos 25, 15310oxidation is one of
Agia Paraskevi, a.hiskia@inn.demokritos.gr
on the photocatalyst (2) stability
Water Qualityin aDepartment,
continous-flow
Athens
the Water
most Supply and
promising Sewerage
methods forCompany (EYDAP
degradation ofSA), Oropou 156, 11146
UV irradiated Athens,
reactor forGreece
25 h on stream.
such chemicals, due to its high mineralization Titanium dioxide based materials were used under UV-A
efficiency, low toxigenicity, ideally producing and visible light and elucidation of the reaction
carbon dioxide, water and inorganic mineralmechanism ions was attempted. In order to identify the main
EXPERIMENTAL
as end products [2]. Among the photocatalysts reactive oxygen species formed during the process,
used, titanium dioxide (TiO2) is consideredelectron as a paramagnetic
TiO2 was immobilized
resonance (EPR) by impregnating
methodology thewasglass
very efficient one because of its photoactivity, employed.fiber The (GF) cloth used
approach with was
titanium oxysulfate
throughspin solution,
trapping
physical and chemical stability, low cost andagents. easy Also, followed by drying and
identification andannealing
comparisonat 500ofC.the The
access. Usually, it is found in a powdered intermediate form textural,
products surface
formed andduring
morphological properties
photocatalysis under of
and applied as a slurry catalyst, i.e., titanium UV-A andnewly visibledeveloped photocatalyst
light was performed, were
using investigated
LC-MS/MS.
dioxide powder suspended in the water to be showed
Results using that SEM-EDX, XRD,light
during visible UV-Vis-DR, FTIR,theetc.
photocatalysis
treated. However, the post-treatment separation main of reactive
analyticaloxygen techniques.
species isPhotolytic/photocatalytic
superoxide radical,
TiO2 powder from the treated water inevitably whereas duringdegradation
UV light runs of solutions containing
photocatalysis BPsand
both hydroxyl (C0 =
increases the cost of water purification process, superoxide44radicalsM) were were carried out in
present. It awas
250also
mL reactor
found thatunder
therefore, immobilized photocatalysts seem under to be visibleirradiation of UV
light singlet oxygenhigh-pressure
is formed. mercury lamp.
more prosperous in light-assisted water treatment The continuously collected particle-free samples
technologies were further analyzed for residual BPs and total
Water pollution has become an environmental neurotoxin that has been reported in water
organic carbon (TOC) content, using HPLC, UV-
issue of ever increasing importance. In addition to reservoirs and lakes worldwide. Geosmin (GSM)
Vis, IC and TOC analyzer, respectively. The
conventional technologies used for purification of and 2-methylisoborneol (MIB), even though they
OBJECTIVES estrogenic activity (EA) of feed and treated
water, another type of treatment processes, are not considered as toxic, they give unpleasant
samples was determined by yeast estrogen screen
commonly referred
In the present study,aswe advanced oxidation
aimed to synthesize taste and odor in water (structures shown in Figure
(YES) assay, which is based on human estrogen
processes
immobilized (AOPs)
TiO2 isphotocatalyst
emerging. Among by a AOPs,
novel 1). Although the degradation of these compounds
receptor-transfected yeast strain Saccharomyces
TiO 2 photocatalysis
preparation procedure,isthoroughly
considered to be very
characterize and has already been studied under TiO2/UV-A , the
cerevisiae. The toxicity tests were performed with
promising. The process efficiency is based on the studies concerning their degradation under visible
ability of TiO2 to generate highly reactive oxygen light photocatalysis are limited.
species (ROS) upon illumination with UV-A light, 125 1
with hydroxyl radicals (HO) being the main
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

AQUEOUS PHOTOCATALYTIC DEGRADATION OF SELECTED MICROPOLLUTANTS BY

will be filled
Aqueous Photocatalytic Degradation of Selected Micropollutants by
Pd-MODIFIED TITANIUM DIOXIDE
Pd-modified Titanium Dioxide in by A3-9
EAAOP4
Deniss Klauson1, Marko akaravili1, Natalja Pronina1, Marina Krichevskaya1, Erki Krber2, Valdek Mikli2 . (1)
Dept. Chem. Eng., Tallinn Univ. Technol., Ehitajate tee 5, 19086 Tallinn, Estonia, deniss.klauson@ttu.ee. (2) Dept.
Mater. Sci., Tallinn Univ. Technol. Ehitajate tee 5, 19086 Tallinn, Estonia.
250
Aqueous photocatalytic oxidation of three widely used broad
spectrum antibiotics, doxycycline (DC), sulphamethizole
200
(SMZ), and amoxicillin (AMO), was conducted with sol gel-
E, mg W-1 h-1

Pd-TiO2 synthesised anatase Pd-TiO2 under UV-A radiation.

150 Photocatalytic activity of the new material was tested in open
P25
batch slurry reactor, with additional experiments undertaken in
100 in semi-continuous fixed and fluidised-bed reactors. Testing the
1h capabilities of the Pd-TiO2 in batch reactor showed results
significantly surpassing those obtained previously with
50
6h 4h 6h Aeroxide P25 TiO2. Removal and adsorption of doxycycline
were analysed and mathematically described, with the observed
0 differences explained largely by adsorption of the pollutants on
DC SMZ AMO the photocatalysts surface.

step is required. At the same time, fluidized-bed

Currently, micropollutants are among the most systems provide highly efficient mass and heat
studied pollutant classes, with specific attention transfer, resulting in better contact between
paid to antibiotics. The main sources of antibiotics pollutants and irradiated photocatalyst surface, and
in wastewater are household, medical and potentially higher photons transfer efficiency [14-
veterinary
HATR-FTIR wastes;
ONLINEas antibiotics
ANALYSIS areOFrefractory
SURFACE SPECIES ON P25 ANDoptimal Au MODIFIED
HATR-FTIR
substances[1-3], online
they passanalysis
throughof surface
the species
biological
17].
on P25 However,
and Au will beTiO
photocatalyst 2
filled
DURING PHOTOCATALYTIC OXIDATION OF NITROGEN
immobilisationMONOXIDEprocedure should be a compromise in by A3-10
wastewater
modified treatment
TiO2 during plantsphotocatalytic
into the environment
oxidationbetween
of nitrogen monoxide
the coatings performance and
EAAOP4
[4, 5]. There,1 they pose a serious threat to micro- mechanical stability [17]. The expected efficiency
K. Skalska . (1) Faculty of Process and Environmental Engineering, Lodz University of Technology, Wolczanska
flora
213, and fauna,
90-924 Lodz,accumulate
Poland. in food chains[6, 7], decrease when substituting photocatalyst slurry by
and accelerate the development of resistant micro- immobilised photocatalyst may be not too drastic,
organisms, including pathogens[8-11]. while it is coupled
The photocatalytic oxidation withof dramatic
NO on P25 decrease
and goldin the
Photocatalytic oxidation could be a very modified photocatalyst
TiO 2 (Au amount
0.1) under [18].UV, Vis and UV+Vis
promising solution for the selective removal irradiation of was studied using Horizontal Attenuated
Second(HATR) limitation
micropollutants from water. Its performance Total is Reflection FTIR.ofReaction
photocatalysis
substratesisand that
despite
adsorbed at photocatalysts surface werecan
its potency, it is relatively slow. This
based on the creation of electron-hole pairs on products the be accelerated by two ways: - the decrease - of
surface of illuminated semiconductor (mostly identified. NO, H2O, NO 2 and NO2 and NO3 in
differentelectron-hole
surface recombination
arrangements were rate,
present and
at TiO the
TiO2), producing numerous reactive oxygen 2
species (ROS), including powerful hydroxyl surface.broadening
It was proved of utilisable
that Au 0.1 fraction of the
material exciting
possesses
better radiation.
sorption Both of these
properties. It was targets
also can bethat
proved achieved
Au 0.1by
radicals [12]; direct decomposition of pre- doping titania with metal nanoparticles, which
adsorbed pollutant molecules can also take place was more active material and enabled NO
serve asinto
transformation charge
HNO carrier traps, prolonging electron-
on holes, which are the strongest oxidants known 3, which was adsorbed at the
hole recombination,
surface finally leading to its deactivation. and thus Au 0.1increasing
higher
[13].
activity photocatalyst
was attributed performance
to higherefficiency
amount [19, 20], and
of peroxo
Presently, successful implementation species of at the )same
(Ti(O time can provide the red shift in the
2 and TiOO-) present at the surface.
photocatalytic processes at larger scale is hindered excitation spectrum.
by two main factors, connected with mass transfer The goal of this research was the
The oxidative properties of TiO can be used in The obtained results enabled to synthesis
explain the of
and the photocatalyst performance.2 TiO2, testing
the process aimed at selective NO oxidation into Pd-modifiedobserved
behaviour overitsP25performance
and Auunder 0.1
NOFirstly, there
2. At first thisare complications
idea arising when
might seem unreasonable, UV-A in batch
photocatalysts slurry
during photocatalytic 1 g L-1
reactor (0.2NOL,oxidation,
tryingNO
since to2 is
design
more atoxichighly
than efficient and cost-
NO. The concept is photocatalyst)
i.e. photocatalyst withdeactivation.
three different Thewidely
gas phaseused
effective
that NO can large-scale
be oxidized photoreactor.
into NO2 andWith fixed
afterwards pharmaceuticals
composition during(doxycycline,
all processes amoxicillin
showed and no
photocatalyst,
removed fromproviding
flue gaseshigh either
surface by
areaSCR
coupledor sulphamethizole),
difference when P25 andandtesting
Au 0.1itswere
applicability
used. It was in
with efficient
absorption mass transfer
processes. It thisand light penetration
approach PCO could is semi-continuous
determined fixed (0.13
that addition L, photocatalyst
of water vapour intofixed gas
notaan
be easy task,
method while
for the no photocatalyst
intensification of NOseparation
x removal upon glass
stream has plate,
a strongtreated solution
influence circulated
on the at 2 to
NxOy surface
from flue gases both by SCR and absorption 5.3 mL s-1formed
species ) and fluidised-bed (2 L, expanded
at photoactive clay
materials.

126
process. Usually flue gases contain up to several Furthermore, it was showed that even under dark
hundred ppm of NOx. Previous studies [1] conditions the species observed on P25 and Au 0.1 1
revealed that in NO PCO of high NO differ. During irradiation these differences become
 R O O M A - P H O T O C A TA L Y T I C OX I D A T I O N

GAS-PHASE PHOTOCATALYTIC OXIDATION OF MIXTURES OF REFRACTORY ORGANIC

Gas-Phase Photocatalytic Oxidation of Mixtures of Refractory will be filled
COMPOUNDS: THROUGH THE NET OF PROCESS LIMITATIONS
Organic Compounds: Through the Net of Process Limitations in by A3-11
EAAOP4
M. Krichevskaya1, A. Moiseev2, S. Preis3, J. Deubener2. (1) Tallinn University of Technology, Ehitajate tee 5,
19086 Tallinn, Estonia, marina.kritsevskaja@ttu.ee. (2) TU Clausthal, Zehntnerstrasse 2a, 38678, Clausthal-
Zellerfeld, Germany. (3) South China University of Technology, Guangzhou 510006, P.R .China

Mixtures of volatile organic compounds of different adsorption

100 14 affinity to TiO2 including toluene, styrene, acrylonitrile and
(CIN - COUT)/CIN, %

12 acrylic acid were treated photocatalytically in air. The effect of

Content, ppm
80
10
60 8 low doses of ozone on the pollutants conversion was studied.
40 6 The introduction of ozone to the deactivated catalyst
4
20 2 restoration resulted in the energy and time savings. The
0 0 optimum conditions, providing entire degradation of initial
10 20 30 40 50 60 70
substances along with the absence of unfavourable by-products
Experimental run time, min
in the reactor outlet, could be ascertained for P25 and novel
Toluene Acrylic acid
Acrylonitrile HCN (P25) nanosized pyrogenic F3 photocatalysts, although F3 shows
HCN (F3) higher photocatalytic activity.

was compared with that of P25.

The photocatalytic indoor air treatment has a
potential for its implementation in the field of
environmental engineering surpassing that of
water treatment if considering the number of
patents [1]. However, process limitations, such as
relatively low rate of pollutants oxidation,
formation of toxic oxidation by-products and
catalyst deactivation should be overcome by the
optimization of process parameters and synthesis
of highly active catalytic materials.
The study of the gas-phase photocatalytic
oxidation process of mixtures of styrene,
acrylonitrile, acrylic acid, toluene and ozone was
undertaken. These volatile organic compounds are
considered as hazardous air pollutants by
environmental agencies of OECD countries.
The mixtures consisting of catalyst-deactivating
styrene, toluene and acrylonitrile with the content
of individual component of 10 or 25 ppm were
photocatalytically treated using the annular reactor
with the photocatalyst fixed at its walls in absence
and presence (40-80 g L-1 or ca. 20-40 ppm) of
ozone. The regeneration of deactivated Aeroxide
P25 (Evonik) photocatalyst coating by ozone was
also studied as an alternative to UVA irradiation
with or without heating.
The mixture of acrylonitrile, toluene and acrylic
acid was chosen to evaluate the activity of
pyrogenic TiO2 nanopowder F3 [2, 3]. The
performance of this flame-synthesized titania
(average particle size of 13 nm, anatase content 97
wt% and the specific surface area of 102 m2 g-1)
The use of ozone in the catalyst regeneration
resulted in the energy and time savings: the
restoration of the photocatalyst activity with 15
min ozonation at 170 20 g L-1 of ozone with
simultaneous UVA was equal in its performance to
15 h of UVA radiation in humid air or 2 h heating
at 130 C combined with the UVA radiation.
The presence of ozone during the photocatalytic
degradation of styrene-toluene-acrylonitrile
mixture did raise the toluene conversion, only
slightly influencing that of other compounds. The
outlet content of CO and CO2 significantly
increased indicating accelerated pollutants
mineralization processes. These levels of ozone,
however, did not prevent the P25 photocatalyst
deactivation (11.5 s contact time, 25 ppm content
of pollutants).
The contact time exhibited the strongest
influence to the degradation of toluene,
acrylonitrile and acrylic acid and the quantities of
oxidation by-products on P25 TiO2. The contact
time extension from 11.5 to 23 s enhanced the
conversion of all pollutants more than an increase
in reactor temperature from 60 to 130 C or in air
relative humidity from 6 to 30 % (Fig. 1).
The use of the novel material F3 demonstrating a
better photocatalytic performance [3] in
degradation of sole air pollutants, shows also
superior performance oxidising the mixtures. This
is particularly seen in the formation of hydrogen
cyanide, the photocatalytic oxidation by-product

127 1
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

APPLICABILITY OF ELECTROCHEMICAL OXIDATION USING DIAMOND ANODES TO THE

Applicability of Electrochemical Oxidation Using Diamond anodes to will be filled
TREATMENT OF A SULFONYLUREA HERBICIDE in by B3-1
the treatment of a Sulfonylurea Herbicide
EAAOP4
C. Sez1, F. Souza2, S. Quijorna1, M.R.V. Lanza2,P. Caizares1, M. Rodrigo1 (1) Department of Chemical
Engineering, Universidad de Castilla - La Mancha, Campus Universitario s/n, 13071 Ciudad Real, Spain,
cristina.saez@uclm.es. (2)Instituto de Qumica de So Carlos, Universidade de So Paulo, P.O. Box 780, CEP
13560-970, So Carlos, SP, Brazil.

In this work, the removal of the Chlorsulfuron, a

1,0
-2
30 mA cm Na2SO4
100
sulfonylurea herbicide, was studied by electrooxidation
process using boron doped diamond (BDD) anodes in a
-2
30 mA cm NaCl
-2
100 mA cm Na2SO4
-2
100 mA cm NaCl

0,8 80 flow reactor. Operation parameters such as current

density, support electrolyte and initial concentration of the
% TOC removal
Conc/Conc0

0,6 60
herbicide were investigated. Results showed that the
0,4 40 performances of the process slightly depend on the
0,2 20
applied current being more efficient at lower current
applied. Complete removal of the pollutant is obtained in
0,0
0 1 2 3 4 5 6 7
0 all cases; however for attaining complete mineralization
Q / A h dm
-3
more electrolysis time is required. This technology was
capable of depleting this pollutant in a wide range of
initial concentrations being very fast in chloride medium.

mediated electro-oxidation processes due to the

In the recent years, herbicides are the object of effect of peroxosulphates in sulfate medium. In
growing environmental concern of agencies and chloride salts the removal is very fast, due to the
scientific community. Sulfonylureas, a group of electrogeneration of the HOCl and Cl2 species.
highly selectiveELECTROCHEMICAL
SELECTIVE herbicides, are used worldwide for
DEGRADATION OF 4-CHLOROPHENOL
However, in atthe higher 2current AT Adensities
Ti/RuO -
2 the
Selective electrochemical degradation of 4-chlorophenol a Ti/RuO - will be filled
weeds
IrO and grasses
ANODE control and
IN CHLORIDE RICHin some crops.
WASTEWATER efficiency decreases due to generation of ClO in- and
by B3-2
IrO2 them,
Among
2
anodeChlorosulfuron
in chloride rich wastewater.
(ClSF) has great
3
ClO4- species and due to the competitionEAAOP4 between
phytotoxicity
J. De Costereven
1 at low concentration,
, W. Vanherck 2
, L. Appels1, R.and thus
Dewil 1 it
. (1) KU the
Leuven, Department
reactions of Chemical
of oxygen Engineering,
evolution and Process
chloride
is classifies by EPATechnology
and Environmental as toxixity
Lab, J.class III (low 5, B-2860
De Nayerlaan Sint-Katelijne-Waver,
oxidation. Belgium,
It can also be seen that there is a decrease
toxicity). Likewise, its bio-refractory
jonas.decoster@cit.kuleuven.be. character
(2) UC Leuven Limburg, Herestraat 49, B-3000 Leuven, Belgium.
in the mineralization efficiency for the largest
makes necessary the development of new treatment current density independently of the supporting
technologies to eliminate this type of pesticides The electrochemical degradation
electrolyte used. In fact,of at4-chlorophenol in the
lower current densities
from contaminated water and soil[1]. presence of chlorides by the
the process use of
seems more2-IrO
to abeTi/RuO 2 anode was
efficient, with a
investigated under different
concomitant operational
decrease in theparameters suchWith
intermediates. as
Electrochemical oxidation have demonstrated to
applied currenthigher
density (J) and chloride concentration.
current densities (100 mA cm-2) The effect
be a very efficient technology for the removal of
of the presence of glucose
intermediates reachasa plateau
a model with component
softer decay.for
organic pollutants [2]. The hydroxyl radicals and
biodegradable substrates on the degradation profile of 4-
many other mediated oxidants produced at high Acknowledgements
chlorophenol (4-CP) was determined. The results show a fast 4-
concentrations on the surface of diamond are The authors with
acknowledge funding support
CP degradation combined only a limited decrease in from
glucose the
responsible for the harsh oxidation conditions
concentration EU forand Spanish
each Government
condition applied. through
This the MINECO
indicates a
attained [3]. For this reason, the purpose of the Project ofCTM2013-45612-R, FEDER 2007-2013
selective degradation the phenolic compound, independent of
present study is to evaluate the applicability of the PP201010 andparameters.
INNOCAMPUS. Foundation for
the values of the operational
oxidation of chlorsulfuron with diamond Research Support of the State of So Paulo
electrodes. The effect on results of the supporting (FAPESP) by grant 2014/02580-7 is gratefully
electrolyte, current density and initial herbicide acknowledged.
concentration are going to be studied.
References
Results showThethatpresence
Background. the herbicide
of variousis types
rapidly
of organic components in the wastewater (reaction 4) [3].
oxidized andindepleted [1] Rodrigo, M. A.; Oturan, N.; Oturan, M.A. Chemical
chlorophenols industrialduring the is
wastewater electrochemical
problematic for Indirect oxidation with chlorides provides a much faster
Reviews, 114 (2014) 8720.
oxidation
its in NaCl
purification. and Na2SOsuch
Chlorophenols, 4 media, although the
as 4-chlorophenol oxidation than indirect oxidation with OH-radicals, but
[2] Sirs, I.; Brillas, E.; Oturan, M. A.; Rodrigo, M. A.;
herbicide
(4-CP) are decay
widelyisproduced
softer inasthe presence of
intermediates in the
the chlorinated organics (e.g., AOX) can be produced as
Panizza, M. Environmental Science and Pollution
production
sodium sulfate. of Furthermore,
insecticides, there
herbicides, wood
is an increase of intermediates throughout the oxidation pathway. Several
Research, 21 (2014) 8336.
preservatives,
the removal as bodices, pharmaceuticals
the current and dyes This
density increases. [1]. studies, however, indicate that these chloro-organics are
[3] Rodrigo, M. A.; Canizares, P.; Sanchez-Carretero, A.;
Some specific chlorophenol types are listed as top priority further degraded by oxidation at increased reaction time
can be explained in terms of great generation of the Saez, C. Catalysis Today, 151 (2010) 173.
pollutants by the United States Environmental Protection [3, 4].
hydroxyl radicals and to an additional effect of
Agency (US EPA) [1]. 2Cl Cl2 + 2e (reaction 1)
Advanced (electrochemical) oxidation processes (AOP) Cl2 + H2 O HClO + H+ + Cl (reaction 2)
are mostly used to decrease the concentration of this type
of components in wastewaters, because of their
128
HClO ClO + H+ (reaction 3)
R + ClO RO (reaction 4)
1
recalcitrant properties towards traditional biological This paper aims to investigate the degradation of 4-
R O O M B - ELECTROCHEMICAL/PHOTOELCTROCHEMICAL PROCESSES

TRANSITION METAL MODIFIED CATHODE FOR HETEROGENEOUS ELECTROwill FENTON:

Transition metal modified cathode for heterogeneous electro-Fenton:
PREPARATION AND PERFORMANCE
be filled
B3-3
in by
Preparation and performance
EAAOP4
M. Zhou1, F. Yu1, Y. An1
(1) Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, College of
Environmental Science and Engineering, Nankai University, Tianjin 300071, China, zhoumh@nankai.edu.cn
Electro-Fenton (EF) technology is one of the powerful
advanced oxidation processes (AOPs) for the treatment of
industrial wastewater containing non-biodegradable organic
pollutants. However, homogeneous EF requires an optimum
pH < 3. In this work, we reported some transition metal
carbon composite catalysts (M = Co, Fe, Ce and Cu), which
were synthesized and tested for methyl orange (MO)
degradation in acidic and neutral condition. It was observed
that the presence of transition metal on GF cathode
demonstrated a more stable performance over a wider pH.
Thus it was promising as potential cathode material for high
performance of heterogeneous electro-Fenton process.

Electro-Fenton (EF) technology is one of the performance over a wider pH. Thus it was
powerful and widely used advanced oxidation promising as potential cathode material for high
processes (AOPs) for the treatment of industrial performance of heterogeneous electro-Fenton
wastewater containing non-biodegradable organic process.
pollutants [1, 2]. However, homogeneous EF
requires an optimum pH < 3 circumstance, large 100 (A)
Co
2+
AVOIDING
amounts of FeTHE FORMATION
addition, OF CHLORATES
and the effluent must be DURING THE ELECTRODISIFECTION
Fe OF
Avoiding the formation of chlorates during the electrodisifection of will be filled
B3-4
80 Ce
URBAN WASTEWATER
neutralized after disposal WITH
which BDD ANODES
results in the Cu
in by
urban wastewater with BDD anodes

0%
generation of abundant sludge [3].
60
GF EAAOP4
S. Cotillas, J. Llanos, P. Caizares, M.A. Rodrigo 40
University of Castilla-La Mancha. Department of Chemical Engineering, Avenida Camilo Jos Cela 12, 13005,
This work focuses on constructing
Ciudad Real, Spain, Salvador.Cotillas@uclm.esa highly 20

catalytic cathode of an EF system, to overcome the

0
defects of low activity and pH limitation.
In Some
this work, the simultaneous production of chlorine
power supply

compounds
transition metalcarbon composite catalysts (M = and hydrogen peroxide is evaluated for the
20 40 60 80 100 120

Time (min)
electrochemical
Co, Fe, Ce and Cu) have been synthesized and disinfection of urban
Indirect
wastewater with BDD
anodes. First, the electrodisinfection has been carried out with
Disinfec. disinfection
Red

tested for methyl orange (MO) degradation in

E. coli
Figure 1. The MO removal efficiency on different
E. coli
e- Direct
e-

BDD as anodecathode.
and SS as cathode. The results show that the
disinfection ClO- + NH4+ NH2Cl + H2O
Ox
Disinfec. ClO- + NH2Cl NHCl2 + OH-

acidic and neutral condition. E.coli is completely removed at a current density of 6.37 A m-2
ClO- + NHCl2 NCl3 + OH-

e-
H2O
and applied electric charges lower than 0.01 A h dm-3.
ClO- + H2O2 2e- Cl- + 3/2 O2 + 2H+
H2O
e-

The transition metal/GF was characterized

Anode H+ + O2 Acknowledgements
by X- the presence
However,
2 ClO- 4 ClO3- + 2 Cl-
of chlorates during the process has been
H2 + OH-
Cathode

The authors thank Natural Science Foundation of China

ray diffraction (XRD), scanning detected, electron limiting
2 ClO3- + H2O2 + 2 H+ ClO2 + 2 H2O + O2
the application of this technology. Next, it
(Nos. 21273120 and 51178225), National High
Cl-

microscopy (SEM), X-ray was observed

photoelectron that the formation of hydrogen peroxide on
Technology Research and Development Program of
e- E. coli O2
E. coli

carbon felt cathodes limits the concurrence of these compounds

e-
ClO- Indirect

spectroscopy (XPS). The transition metalcarbon China (2013AA065901 and 2013AA06A205).

Disinfec.
Indirect disinfection H2O2

(chlorates) at current densities around 7 A m-2. These results

disinfection Disinfec.

composite catalysts presented good catalytic

BDD Carbon felt

broaden the application of BDD for wastewater disinfection.

activity for the MO degradation (Fig. 1), much References
higher than that in the EF with GF cathode. And
Although the lack of water resources in to E.
[1] human
Brillas,health
I. Sirs,and Oturan, Chemical
M.A.therefore, Reviews,
their generation
the Co-based
countries as catalysts
Spain showed
means the highest
a very activity
important 109 (2009)
should be6570.
avoided during disinfection processes.
towards
problem MO to beremoval
solved,andreclaimed
H2O2 formation.
water isThea In L.this
[2] Zhou,context,
M. H. Zhou, hydrogen
Z. X. Hu, Z.peroxide can be
H. Bi, K. G.
MO removal
resource remained
that has not been over 90% after
extensively 10-times
used so far. considered an alternative
Serrano, Electrochimica Actato140
reduce
(2014)the
376.potential
In this case,
reuses. a wastewater
The maximum effluent, which
accumulation of H2Ohas been
2, up to
formation of chlorine
[3] S. Garcia-Segura, compounds
J. A. Garrido, in high
R. M. Rodriguez, P.
previously treated by a conventional treatment,
544.5 mg/L was obtained, which was much higher is oxidation state due to its oxidative
L. Cabot, F. Centellas, C. Arias, E. Brillas, Water
and/or
further purified in order to fit the requirements for reductive capacity.
than GF. Moreover, the presence of transition Research 46 (2012) 2067.
its use in irrigation (agriculture or gardens) or With this background, the main aim of this work
metal on
drinking. GF cathode demonstrated a more stable is to study the simultaneous production of chlorine
For the case of urban wastewater, the compounds and hydrogen peroxide during the
reclamation of a previously treated water effluent 129
electrodisinfection 1
of urban wasterwater with
may imply the reduction of the microbiological BDD anodes.
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

SYNERGETIC TREATMENT OF PESTICIDE CONTAMINATED DRINKING WATER willBY

Synergetic Treatment of Pesticide Contaminated Drinking Water by be filled
COMBINED RO SEPARATION AND ELECTROCHEMICAL DEGRADATION in by B3-5
Combined RO Separation and Electrochemical Degradation
EAAOP4
J. Muff1, H.T. Madsen, E.G. Sgaard, (1) Section of Chemical Engineering, Department of Chemistry and
Bioscience, Aalborg University, (1) Niels Bohrs Vej 8, DK-6700 Esbjerg, Denmark, jm@bio.aau.dk

This project studied the electrochemical removal of the

pesticide transformation product 2,6-dichlorobenzmide (BAM)
in Danish drinking water produced from groundwater at two
different anode materials. The influence of the electrolyte
composition on the degradation kinetics and pathways of BAM
was clarified. Although chloride is present in small
concentrations in the groundwater, persistent chlorinated
intermediates were not found. The quantity of intermediate
products with and without chloride was at the same level or
lower compared to inert electrolyte. Integrating electrochemical
removal with RO pretreatment significantly reduced the overall
energy consumption of the process by 95%; 0.96 kWh/m3
compared to 18.5 kWh/m3 (EO alone).

This project demonstrated that BAM can indeed

Pesticides and pesticide residues are the most be removed from Esbjerg tap water (DK) by an
important micropollutants found in Danish EO treatment process. Detailed model solution
groundwater aquifers and responsible for large studies in inert and electroactive electrolyte
quantity of groundwater currently being unusable solutionsCONTRAST
elucidated theMEDIAdegradation pathways and
ELECTROCHEMICAL DEGRADATION OF IODINATED ANDwillOTHER
Electrochemical
for drinking water Degradation
production. One of Iodinated
very good Contrast Media
the quantity of and Other during
DIs formed
be filled
the treatment at
PERSISTENT
example is the ORGANIC
pesticide CONTAMINANTS
transformationbyproduct BY ELECTROCHEMICALLY ACTIVATED in by
Persistent organic Contaminants Electrochemically
two Activated
electrode materials; Ti/Pt-IR and Nb/BDD. B3-6
SULFATE
(PTP) AND PERSULFATE
2,6-diclorobenzamide IONS AT
(BAM) thatBORON DOPED DIAMOND ANODES
is a Diamond EAAOP4
Sulfate and Persulfate Ions at Boron Doped EspeciallyAnodes the presence of chloride in
daughter product
1 1of the commonly
1 used 2pesticide
A. Farhat , S. Tait , J. Keller , J. Radjenovic , (1) Advanced Watergroundwater,
Management although in University
Centre, The small amounts,
of has
dichlorobenil. Of the total
Queensland, Queensland number
4072, of groundwater
Australia, a.farhat@awmc.uq.edu.au
caused (2)initial
Catalanconcerns
Institute for related
Water Research
to harmful
aquifers that are
(ICRA), Scientific included inParkthe
and Technological of theDanish
University ofbyproduct
Girona, 17003 Girona, but
formation, Spain.
our study revealed that
groundwater monitoring programme, 50% have even though the degradation pathways was much
been found to be contaminated with pesticides and
Electrochemical oxidation
more complex ofinhalogenated
a chloride rich persistent organic
electrolyte (Figure
PTPs, and in 18.820.2% of these contaminants cases, the such as the
1), the iodinated
quantity in DIs diatrizoate
were at theandsame
iopromide
level or
primary contaminant was BAM. and the chlorinated lower triclopyr and triclosan
than in inert were investigated
sodium sulphate electrolytes
Electrochemistry offers a potentially efficientusing a boron-doped
(Figure diamond
2). All (BDD)
DIs anode.
formed Electrooxidation
during the treatment
alternative to AC adsorption a well-known in sulfate
wateranolytewhereyielded removal
removed rates thattreatment
at prolonged are 1117times
times and
treatment technique with pros and cons - for higher compared to
completenitrate
TOC as well
removal as perchlorate
was obtained. anolytes at
pesticide removal at Danish water works. various
In recentoperating conditions, suggesting the contribution of
years, electrochemical oxidation (EO) technology sulfate-based oxidizing agents such as sulfate radicals (HSO4,
-
has developed from fundamental research SO4 ) and/oron non-radically activated persulfate. In an attempt to
synthesis of new electrode materials aimed segregate
at high the effects of HO radicals and SO4- radicals, typical
oxidation power, resistance and durability HO radical
and probe compounds were examined and provided
laboratory studies of treatment efficiencies evidence
further of for the presence of SO4- radicals.
various polluted aqueous matrices into commercial
available products. However, concurrent to the
incipient market dissemination of the technology, sulfate in EAOPs by investigating the rates of
Background
much more research is still needed in order to fully electrooxidation of iodinated contrast media (ICM)
understand
The incomplete the effect
removalof theof technology on the
persistent organic such as diatrizoate and iopromide at BDD anode in
water matricessuch
compounds, and the as produced effluents. One
pharmaceuticals and sulfate anolyte and electrochemically inert nitrate
challenge
pesticides, isinelucidating
conventional contaminant
water and degradation
wastewater anolyte. Several other persistent organic
pathways
treatment plants,andhas raised
identifying
the interestdegradation
for novel contaminants (e.g., triclosan, triclopyr, and
intermediates (DIs) of
technologies capable with the aimdegrading
effectively of ensuringsuch tribromophenol) were also investigated.
discharge of an environmentally
organic contaminants. safe anddiamond
Boron-doped healthy
effluent.
(BDD) electrodes have attracted a lot of interest
for wastewater treatment due to their high electro-
catalytic activity towards organic oxidation [1] and 130Methods
Experiments were performed in a laboratory-scale
1
their ability to accomplish significant degradation
electrolytic cell, at applied current densities in the
 R O O M B - ELECTROCHEMICAL/PHOTOELCTROCHEMICAL PROCESSES

ELECTROCATALYTIC AND PHOTOASSITED DEGRADATION OF PERFLUOROOCTANOIC will be filled

Electrocatalytic and photoassited degradation of perfluorooctanoic
ACID
acid in by B3-7
EAAOP4
A. Urtiaga, B. Gmez, I. Ortiz, Department of Chemical and Biomolecular Engineering. University of Cantabria.
Av. de Los Castros s/n, Santander, Spain, urtiaga@unican.es

CO2 F-
The scientific community is facing the challenge of
developing clean technologies for the treatment of the
emissions of highly persistent perfluoroalkyl substances
e-
(PFASs) and for the abatement of the existing water
CxFyCOO polluted sites. In this work, efficient PFOA degradation
-
e-
and mineralization was achieved by means of
electrooxidation with boron doped diamond anodes. Direct
photolysis using a wide spectrum lamp could also degrade
PFOA
CATHODE

PFOA, although conversion into shorter chain PFASs,

ANODE

OH -
accompanied by a low mineralization rate, was observed.
+
Comparison of energy consumptions was also in favor of
the electrochemical process.

of destructive technologies enabling their

Introduction conversion into compounds of lower toxicity, and
Among emerging water contaminants, if possible their complete mineralization. For this
perfluoroalkyl substances (PFASs) are particularly reason, presently the research is oriented to
problematic because they are highly persistent, promote the activity of the hydroxyl radical using
PHOTOCATALYTIC and DEGRADATION
Photoelectrochemical
bio-accumulative Degradation
have OF SODIUM
Of
been detected Sodium DODECYL
substrates
Dodecyl SULPHATE
that either
Sulphate
debilitateBASED
On
the C-F -Feor
ONbond, O
2 3
NANOSTRUCTURE
ubiquitously in the abiotic environment, biota, introduce more energy, such as photo-Fenton [4], B3-8
-Fe2O3 Nanostructure activated persulfate, UV photolysis [5], alkaline
food items and humans, all over the planet [1]. The
Hoang Nguyen,
wide-spread use Chiof Phan*,
PFASTushar has Sen. email: in
resulted minhhoang.nguyen1@postgrad.curtin.edu.au,
an ozonation and sonolysis. However, these
Curtin University,
important release of Kentthese
Street,compounds
Bentley, Australia
into the technologies are still limited by the slow
environment, which was estimated at 32007300 mineralization kinetics, and by the formation of
tons during the period 19502004 by direct and persistent intermediate fluorinated compounds.
indirect emissions [2]. The electrochemical oxidation is a technology that
has demonstrated its capacity to mineralize PFASs
Taking into account their potential toxicity Sodiumand
Sodium Dodecyl Sulfate
Dodecyl Sulphate
[6,7]. On the (SDS)
otherwas successfully
hand, degraded
photocatalysis by
is one
the extent of their environmental distribution,photoelectrochemical (PEC)
alternative process
method for onthe-Fe 2O3 nanostructure
degradation of these
PFASs have started to be regulated by SO3-
anode with applied
various
Na+ voltage from
very persistent 1 to 3 V. The
compounds. SDSefficiency
was completely
of pure
international bodies. Perfluorooctanesulfonate removed after TiO
MOX(*OH)
a 2first
has hour
been infound
all testing
MOX(*OH)
conditions,
to be quite low [8].while
The
(PFOS) and its salts are included in thegenerated
Annex B intermediates continued
of the toTiO
be2degraded. The proposed
MOX(*OH)
MOX(*OH)
MOX(*OH)) iates
MOX(*OH) Intermed
H2O CO2 combination
-Fe2O3
catalyst with graphene
of the Stockholm Convention on model
e-
well fitted
Persistent
Reference
oxidethe
electrode
Pt
experimental
is one data.
of the latest The results
innovations can beto
oriented
Organic Pollutants. PFOS is also listed appliedas toa decompose synthetic anionic
the enhancement of thesurfactants
TiO2 in wastewater
photocatalytic
priority substance in the field of European to lesswaterharmful substances,
activity or light
in the visible to carbon
spectrum dioxide
[9]. before
policy according to Directive 2013/39/EC. discharging into the environment.
U.S.EPA has also set guidelines of 0.3 g/L for Objectives
perfluorooctanoic acid (PFOA) and PFOS, in This study will report the experimental
drinking water supplies. assessment on the degradation and mineralization
Sodium dodecyl
The scientific sulphate (SDS)
community is athe
is facing major anionic
challenge ofphotodegradation
perfluoroctanoicof organics
acid in using
wastewater [3]
both
ofsurfactant
developinginclean technologies for the treatment electrochemical and photocatalysis processes. The
commercial detergents, soaps, owing to its affordability, and large response to
of the emissions of PFASs and for the abatement performance of boron doped diamond anodes will
ofshampoos, shower
the existing watergels. It is also
polluted sites.one
Manyof the
of main
the bevisible lightand
assessed [4].the effect of the main operation
already published variables, e.g.: applied current, concentration,
ingredients of otherstudies emphasize
daily using products thesuch
lowas The objective of this work is to oxidize SDS to
efficiency of the conventional water treatment flowrate, temperature, on PFOA removal and
paper, polymer,
technologies andremoval
for the cosmetics. Due to [8].
of PFASs its The
wide harmless intermediates
mineralization by PEC
will be studied. processPFOA
Secondly, on -
degradation of PFASs requires of the application degradation under direct photolysis and TiO2-
application, SDS has been considered as major Fe2O3 thin film. Accordingly, the sol-gel method
pollutant in wastewater and environment. The was used to deposit -Fe2O3 thin film on the
presence of SDS in water can cause dangerous 131 1
Stainless Steel substrate. Field Emission Scanning
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

DEGRADATION OF MICROCONTAMINANTS IN WASTEWATER BY PHOTO-ASSISTED

Degradation of microcontaminants
ELECTROCHEMICAL OXIDATION in wastewater by Photo-assisted B3-9
Electrochemical Oxidation
Salatiel Wohlmuth da Silva1, Marco Antnio Siqueira Rodrigues2, Andra Moura Bernardes1 (1) Federal
University of Rio Grande do Sul, Bento Gonalves Avenue, 9500, Porto Alegre, Brazil, salatielws@gmail.com. (2)
Feevale University, Campus II ERS-239, 2755, Novo Hamburgo, Brazil.
In this work the hybrid process Photo-assisted Electrochemical Oxidation
(PEO) was applied in the degradation of microcontaminants e.g.
antibiotics. The synergistic effect of the processes that composed the
PEO process was evaluated. The cyclic voltammetry experiments, UV
photon fluxes, UV/Vis and Total Organic Carbon (TOC) were also
evaluated. The reaction kinetics and energetic consumption were
calculated. The results show that the azithromycin (AZI) degradation
occurs probably by oxidizing agents generated by the Photocatalytic and
Electrocatalytic processes that formed the hybrid process PEO. On the
other hand, the amoxicillin (AMX) and norfloxacin (NOR) can be
degraded by Direct Photolysis and by the oxidizing agents generated by
the hybrid process. Moreover the PEO process achieved a mineralization
of AMX (74.6%), NOR (76.4) and AZI (52%), respectively.

Background and NOR. The synergistic effect of the hybrid

The Photo-assisted Electrochemical Oxidation process was also evaluated.
(PEO) use a mixed metal oxide anode such as (70- Methods
30%)TiO2RuO2-Ti that enables the The stock wastewater was prepared by dilution
electrochemical oxidation to be photoassisted by of the AMX, AZI or NOR in distilled and
heterogenous photocatalysis, increasing the deionized water to a final concentration of 100
IRRADIATED-ASSISTED
degradation pathway of theELECTROCHEMICAL microcontaminants PROCESSES
mgL -1 and pH FORwasTHE REMOVAL OF
Irradiated-assisted electrochemical processes for the of adjust to 4.willThe
removal URBAN initial
be filled
PERSISTENT POLLUTANTS
[1]. That is, it is the application of a potential or FROM BIOLOGICALLY TREATED
wastewater was prepared WASTEWATER
by diluting theinstock by B3-10
persistent pollutants from biologically treated wastewater
current density in combination with an ultraviolet
urban wastewater
to a final concentration of EAAOP4 200 gL-1.
radiation
M.J. Martn source, which radiates
de Vidales, C. Sez, theP.anode surface.
Caizares, This concentration was chosen based on the
M.A. Rodrigo.
InDepartment
this process, the photon
of Chemical and electron
Engineering, areofthe
Faculty literature
Chemical Sciences [3,&4]. Na2SO4 2 gL
Technologies, -1 was added
University of as a
Castilla
only - La Mancha.
reactants. Campus Universitario
In the photocatalytic process,s/n,the
13071 support
Ciudad electrolyte.
Real, Spain.mariajose.mcalvo@uclm.es.
semiconductor species are photoexcited by Cyclic voltammetry (CV) experiments were
promoting an electron from the valence band Conventional
(VB) wastewater
performed treatments are not
with the stock able to completely
wastewater. The work
to Anode
the conduction
Anodic electrochemical
reaction zone band (CB).
Chemical
reaction zone degrade Persistent Organic
electrode was Pollutants.
the DSA However,
type composedConductive
by (70-
With promotion of the electron to the Diamond
CB and Electrochemical
30%) TiO2RuO Oxidation
2-Ti, with (CDEO)area andof 1.5electro-
cm2.
the generation
e- Si
Direct oxidationof the gap (h ) in the VB, reducing
i S + irradiated technologies
Platinum have counterdemonstrated
electrode and to beAg/AgCl
robust and as a
and oxidizingS i+1
sites areS created, which are
i+1 efficient
capabletechnologies
referencefor electrode
treating wastewater
were used. polluted
The with cyclic
of
S
catalyzing
i i+1 S

Indirect
chemical UV/US irradiation
these
reactions. pollutants.
The Results
voltammetry show that
experimentCDEOwas attains
carried an
out efficient
between -
degradation a of 2.0
persistent
and 2.0pollutants
V startingin and
urban wastewater.
at theThe
Oxidant
electrochemical process is based on applying finishing open
e-
oxidation
agent

to reduce efficiency
or oxidize achieved
circuitis potential.
even higher Theinpotentiostat
real systemsused thanwasin athe
Indirect
current density
Initial
oxidant or a potentialoxidation
the substrates
Oxidant
of interest.
i

Oxidant
i+1 S
The
S
electrolysis synthetic
and the medium,
EG&G which is Applied
Princeton due to Research
the contribution
Model 273A.of
processeselectrogenerated oxidant
reactor species suchPEOastrialshypochlorite.
Activated radical
heterogeneous
e- agent
photocatalysis
agent
involve The used in the was a jacket
the generation Initial
oxidant of hydroxyl radicals (HO) Irradiated
[2]. The technologies
borosilicateinfluence on the process
glass reactor efficiencyofand
with a capacity 3 L,
oxidation of organic compounds, represented the profiles
by of concentration
operated in batch modeof ionic species to(nitrate,
and connected an ultra-
RH, RX e PhX, by the HO occurs through ammonium,
three chlorate and perchlorate).
thermostatic bath to control the temperature. The
basic mechanisms: proton abstraction, electron anode was dimensionally stable (DSA) and
transfer and radical addition, which are described composed of (70-30%) TiO2RuO2-Ti and the
by equations 1, 2 and 3, respectively. cathode was composed
Electrochemical of TiO(CDSPEO),
Oxidation 2-Ti. The electrodes
paying
Introduction
HO + RH R + H2O (1) were placed concentrically
close attention to the ionic species aroundformedthe during
lamp,
HO + RX RX + OH - (2) remaining
the treatmentunder (sulphate,
UV irradiation. 250 Wnitrate,
ammonium, high-
Persistent Organic Pollutants (POPs) have been
HO + PhX OH PhX (3) pressure commercial mercury
hypochlorite, chlorate and perchlorate). vapor lamps,
detected in ground and drinking water, indicating
Objectives without the glass bulb and inside a quartz tube,
that the conventional treatments performed in
The objective of this work was to apply the were
Results used
andasdiscussion
source of UV radiation. 5 L of the
Municipal Wastewater Treatment Plants (MWTP)
Photo-assisted Electrochemical Oxidation process initial wastewater were placed in the reservoir that
failed to completely remove them from the The thetreatment
in the degradation of the antibiotics AMX, AZI feeds reactor ofat wastewater
an average coming
flow ratefromof 1theL
wastewater. However, Advanced Oxidation secondary treatment of a MWTP intensified with
Processes (AOPs) and, especially, Conductive
Diamond Electrochemical Oxidation (CDEO) are 132 caffeine, sulfamethoxazole, progesterone or
metoprolol (selected as model of POPs) has been 1
considered as a good alternative for the treatment studied by CDEO, CDSEO, CDPEO and
R O O M B - ELECTROCHEMICAL/PHOTOELCTROCHEMICAL PROCESSES

STUDY OF METHANOL REFORMING USING DIFFERENTIAL ELECTROCHEMICAL MASS

Study of methanol
SPECTROMETRY reforming using differential electrochemical mass
(DEMS) B3-11
spectrometry (DEMS)
J. Vakros, B. Hasa, A. Katsaounis. University of Patras, Department of Chemical Engineering, Patras, Greece,
vakros@chemistry.upatras.gr.

The electrochemical reforming of methanol using differential

electrochemical mass spectrometry (DEMS) was studied using
commercial carbon and home-made titanium supported PtRu
anodes. It was found that hydrogen production is feasible in a
polymer electrolyte membrane (PEM) electrolysis cell. TiO2
modified PtRu anodes supported on titanium gave the best
performance. Using DEMS it was found that a small fraction of
CO2 is periodically produced at the cathodic side. In addition
methanol crossover through the proton exchange membrane is
taking place during the electrolysis process.

Hydrogen is probably the most promising energy surface of Pt and/or PtRu based electrocatalysts. It
carrier for providing a clean, reliable and was found that the presence of TiO2 in a molar ratio
sustainable energy system [1,2]. The global CO2 1:1 with respect to the metal loading (Pt or PtRu)
balance could be affected using hydrogen as fuel results in more stable and active anodes. In this
since the only product during oxidation processes study the performance of commercial carbon
would be water. Hydrogen can be produced supported PtRu electrodes (PtRu/C) were evaluated
Removal of
REMOVAL
chemically, OF Iopamidol,
via various an
IOPAMIDOL, Iodinated
AN
catalytic IODINATED X-RayX-RAY
reforming Contrast Media,
CONTRAST
and compared by
with Zero- BY titanium
MEDIA,
home-made will be filled
ZERO-VALENT
supported
2- in by
Valent Aluminum-Activated
ALUMINUM-ACTIVATED
processes and electrochemically H2O via H
AND O and
S O
electrolysis
2 2 2-S O
OXIDATION
of
2 8 Oxidation
PtRu (PtRu/Ti) and TiO 2 modified PtRu B3-12
2 2 8 EAAOP4
water or electrochemical reforming of light (PtRuTiO2/Ti) electrodes during electrochemical
alcohols such as methanol,
I. Arslan-Alaton 1
ethanol,
, T. Olmez-Hanc 1
, glycerol
G. Korkmaz C. Sahinreforming
etc.1, [3- 1
of methanol.
. (1) Istanbul In all cases
Technical University, carbon
School cloth
of Civil
5].Engineering,
One of theDepartment
advantagesofof methanol reforming
Environmental Engineering,is 34469 wasMaslak,
used asIstanbul,
gas diffusion
Turkey, layer (GDL).
arslanid@itu.edu.tr
the lower energy demand ascribed to the Figure 1 shows the effect of applied potential at 5
electrolytic production of hydrogen [3]. H2O2 and S2O82-different activation temperatures on the
with zero valent current (ZVA)
Aluminum and the
In this study the reforming was carried out in a has
nanoparticles normalized by the totalfor
been investigated mass theoftreatment
Pt and Ruofcurrent
the
CO2 + H2O
polymer electrolyte membrane (PEM) commercially
cell using important density for all samples.
X-ray contrast media Iopamidol in pure
PtRu based electrodes as anodes and carbon
water, real surface water and tertiary treated wastewater.
supported
H2O Pt based electrodes as
2- cathodes.
Results Anhave demonstrated that in particular oxidation with
S O8
aqueous
2
solution of methanol2 was usedS2as O82-
anode
can be activated via ZVA addition resulting in a dramatic
fuel while pure He was fed to the cathode. enhancement of aqueous Iopamidol removal rates and
During the electrolysis process protons are The remarkable capacity of the proposed redox
efficiencies.
produced according to equation (1) after application systems in the removal of Iopamidol indicates their potential
of a constant potential and transferred to the in the treatment of micropollutant-contaminated
application
cathode through the proton exchange membrane. water or wastewater if shortcomings including costs and mass
-
TheHO latter plays also the role SO4of the separator of
transfer limitations can be solved appropriately.
hydrogen from the anode gas mixture. Hydrogen is
then evolved at the cathode via equation (2):
Increasing attention has been paid to the presence acting as hydroxyl (HO ) and sulfate (SO4 -)
of pharmaceutical compounds in aquatic radical promoters as shown in the below reactions;
CH3OH + H2O CO2 + 6H+ + 6e- (1)
environments due to their widespread use and ZVA/HP oxidation system:
2H + + 2e- H
2 (2)
incomplete removal during water/wastewater 2Al0 + 3O2 + 6H+ 2Al3+ + 3H2O2 (1)
treatment. Among the pharmaceuticals, Iodinated Al0 + 3H2O2 Al3+ + 3HO- + 3HO (2)
The cathodic
X-ray contrast gas
mediamixture wascomposed
(ICM), followed by of awater-
mass Figure oxidation
1. Effectsystem
of applied potential on the
ZVA/PS (tentative):
spectrometer
soluble (Extrel,
iodinated MAXcompounds,
aromatic 300-LG). The areeffect
widely of current and2- the +
normalized current density for 3 M
2Al0 + S2O 3+ -
8 + 6H + 1.5O2 2Al + 2SO4 + 3H2O (3)
temperature
used (20-60the
to enhance C)imaging
and methanol
of organs concentration
or blood methanol solution at 5 different temperatures.
IOPA removal was examined in three different
(0.5-3 M) was examined
diagnosticduring this study.iodinated Higher matrices;
current densities
vessels during tests. Recently, effluent namelyare observed
distilled at elevated
water (DW),
In previous papers [6,7] we reported
disinfection by-products have also drawn TiO2 can
that concerns temperatures in allwater
cases. The TOC:6.5
performance of and
the
untreated surface (SW; mg/L)
affect
as theysignificantly
are potentially themuch
electrochemically
more cyto-genotoxic active 2 anode
PtRuTiOtreated showseffluent
the best performance,
tertiary sewage (WW; TOC:10.1
than brominated-chlorinated DBPs. Among the
ICM, iopamidol (IOPA) is the most frequently 133 mg/L) to assess the effect of water and wastewater
constituents on IOPA removal with the 1
detected ICM in the aqueous environment with ZVA/H+/HP and ZVA/H+/PS oxidation systems.
carrier for providing a clean, reliable and was found that the presence of TiO2 in a molar ratio
sustainable energy system [1,2]. The global CO2 1:1 with respect to the metal loading (Pt or PtRu)
balance could be affected using hydrogen as fuel results in more stable and active anodes. In this
since the only product during O oxidation
R A L Pprocesses R E S E N Tstudy A T I the S - 3 r d D of
O Nperformance A Ycommercial carbon
would be water. Hydrogen can be produced supported PtRu electrodes (PtRu/C) were evaluated
Removal of
REMOVAL
chemically, OF Iopamidol,
via various an
IOPAMIDOL, Iodinated
AN
catalytic IODINATED X-RayX-RAY
reforming Contrast Media,
CONTRAST
and compared withby Zero- BY titanium
MEDIA,
home-made will be filled
ZERO-VALENT supported
2- in by
Valent Aluminum-Activated
ALUMINUM-ACTIVATED
processes and electrochemically H2O via H
AND O Sand
O
electrolysis
2 2 2-S of
2 O
OXIDATION
8 Oxidation
PtRu (PtRu/Ti) and TiO 2 modified PtRu B3-12
2 2 8 EAAOP4
water or electrochemical reforming of light (PtRuTiO2/Ti) electrodes during electrochemical
alcohols such as methanol,
I. Arslan-Alaton 1
ethanol,
, T. Olmez-Hanc 1
, glycerol
G. Korkmaz C. Sahinreforming
etc.1, [3- 1
. (1) Istanbulof methanol. In all cases
Technical University, carbon
School cloth
of Civil
5].Engineering,
One of theDepartment
advantagesofof methanol reforming
Environmental Engineering, is 34469 wasMaslak,
used asIstanbul,
gas diffusion
Turkey, layer (GDL).
arslanid@itu.edu.tr
the lower energy demand ascribed to the Figure 1 shows the effect of applied potential at 5
electrolytic production of hydrogen [3]. H2O2 and S2O82-different activation temperatures
with zero valenton the current (ZVA)
Aluminum and the
In this study the reforming was carried out in a has
nanoparticles normalized by the totalfor
been investigated mass theoftreatment
Pt and Ruofcurrentthe
CO2 + H2O
polymer electrolyte membrane (PEM) commercially
cell using important density for all samples.
X-ray contrast media Iopamidol in pure
PtRu based electrodes as anodes and water,carbon real surface water and tertiary treated wastewater.
supported
H2O Pt based electrodes as 2- cathodes. Results An have demonstrated that in particular oxidation with
S2O8 2-
aqueous
2
solution of methanol was used S 2as
O 8 anode
can be activated via ZVA addition resulting in a dramatic
fuel while pure He was fed to the cathode. enhancement of aqueous Iopamidol removal rates and
During the electrolysis process protons efficiencies. are The remarkable capacity of the proposed redox
produced according to equation (1) after application systems in the removal of Iopamidol indicates their potential
of a constant potential and transferred to the in the treatment of micropollutant-contaminated
application
cathode through the proton exchange membrane. water or wastewater if shortcomings including costs and mass
TheHO latter plays also the role SO4of- the separator of
transfer limitations can be solved appropriately.
hydrogen from the anode gas mixture. Hydrogen is
then evolved at the cathode via equation (2):
Increasing attention has been paid to the presence acting as hydroxyl (HO ) and sulfate (SO4 -)
of pharmaceutical compounds in aquatic radical promoters as shown in the below reactions;
CH3OH + H2O CO2 + 6H+ + 6e- (1)
environments due to their widespread use and ZVA/HP oxidation system:
2H + + 2e- H
2 (2)
incomplete removal during water/wastewater 2Al0 + 3O2 + 6H+ 2Al3+ + 3H2O2 (1)
treatment. Among the pharmaceuticals, Iodinated Al0 + 3H2O2 Al3+ + 3HO- + 3HO (2)
The cathodic
X-ray contrast gasmedia mixture
(ICM),wascomposed
followed by of awater-
mass Figure oxidation
1. Effectsystem of applied potential on the
ZVA/PS (tentative):
spectrometer (Extrel, MAX 300-LG).
soluble iodinated aromatic compounds, are widely The effect of current and 2- the + normalized current density for 3 M
2Al0 + S2O 3+
8 + 6H + 1.5O2 2Al + 2SO4 + 3H2O (3)
-
temperature
used (20-60the
to enhance C)imaging
and methanol
of organs concentration
or blood methanol solution at 5examined
different temperatures.
IOPA removal was in three different
(0.5-3 M) was examined
diagnosticduring this study.iodinated Higher matrices;
current densities
vessels during tests. Recently, effluent namelyare observed
distilled at elevated
water (DW),
In previousby-products
disinfection papers [6,7]have we reported
also drawn TiO2 can
that concerns temperatures in allwater
cases. The TOC:6.5
performance of and
the
Degradation of ethyl paraben by untreated surface
heat-activated (SW; willmg/L)
be filled
affect
as theysignificantly
DEGRADATIONare potentiallyOF theETHYL
electrochemically
much PARABEN
more cyto-genotoxic active
BY HEAT-ACTIVATED 2 anode
PtRuTiOtreated PERSULFATE:
showseffluent
the best STATISTICAL
performance,
in by
tertiary sewage (WW; TOC:10.1
than persulfate:
EVALUATION statistical
OF OPERATING
brominated-chlorinated DBPs.evaluation Among the of operating
FACTORS mg/L) to assess factors.
the effect of water and wastewater EAAOP4 B3-13
ICM, iopamidol (IOPA) is the most frequently
1 2
constituents on IOPA removal with 1
the
Z. Frontistis
detected ICM, M. in Antonopoulou
the aqueous, N. Potakis1, A. Michailidi
environment with
1
,ZVA/H
B. Mathaiou
+ 1
/HP ,and I. Konstantinou
ZVA/H+/PS, D.
2
Mantzavinos
oxidation
1
. (1)
systems.
Department of Chemical
concentrations up to 2.7 Engineering,
g/L in University
raw water, of Patras,
15 GR-26504, Greece (2)Department of Environmental
Experimental results have indicated that PS
and Natural Resources Management, University of Patras, Agrinio, Greece; zfrontisis@chemeng.upatras.gr
g/L in treated sewage, 2.4 g/L in groundwater
Department of Environmental and Natural Resources Management, (optimum concentration:0.50
University mM) was much
In this work, Ethyl of Patras, Agrinio,
Paraben (EP) was Greece
chosen as a
and 0.49 g/L in rivers. Studies on the treatment more effective in IOPA degradation than HP
representative model compound of the EDCs family to
of ICM by advanced oxidation processes (AOPs) (optimum concentration:0.25 mM), resulting in
investigate its decomposition by heat-activated persulfate
such as -irradiation, H2O2/UV-C, TiO2/UV-A and more than 90% removal in the presence of ZVA
oxidation. The main scope was to evaluate the effect of
O3/H2O2 have been reported, but these various are onlyoperating after 120 min treatment. Without catalytic
conditions such as initial EP and SPS
few and incomplete regarding their potential for activation, no significant pollutant abatement was
concentrations, reaction time, pH, temperature and water
real-scale application and ecotoxicological risks.on kinetics.obtained (2-4%), and removal with the
matrix A factorial design approach was
Some researchers have demonstrated that in an ZVA/H+/O system remained at 8%. Removal
implemented to assess the2 importance of initial Ethyl Paraben
aerated environment, zero-valent aluminum (ZVA) rates dropped dramatically with increasing
concentration (0.5-1.5 mg/L), treatment time (2-30 min),
nanoparticles were capable of degrading complexity of the effluent matrix from 87%
Sodium persulfate (100 -500 mg/L), Temperature (40-60C),
chlorophenol, sodium dichloroacetate, phenol (PS/ZVA) and 41% (HP/ZVA) in pure water to
water and matrix (ultrapure water and secondary treated
nitrobenzene through the production of wastewater) HO via 7% (PS/ZVA) and 15% (HP/ZVA) in real surface
and initial pH (3-9) on the amount of ethyl
surface reactions on ZVA. Addition ofparaben oxidantsremoved. water. No IOPA degradation occurred in treated
Initial EP, temperature and SPS, as well as
such as hydrogen peroxide (HP) and persulfate wastewater, though TOC removals were obtained
their interaction resulted in the most important, positive effects
(PS)-enhanced redox (charge transfer) complexity. reactions The as 8% for activated HP and 16% for activated PS,
effect of water matrix is negative.
and free radical formation on the catalyst surface. speaking for the selectivity of the treatment
The objective of the present work was to explore systems on the basis of organic carbon type.
Parabens, esters of 4-hydroxybenzoic acid with concentrations,
Currently, acutereaction
toxicitytime, pH, temperature
changes being observed and
the degradation of IOPA with ZVA-activated HP
an alkyl or benzyl group, have been employed for water matrix on kinetics.
during application of the selected oxidative
and PS oxidation under acidic pH. It is believed
about a century as preservatives in foodstuff, treatment Oxidation
systems reactions were conducted
are in progress employing in a
that these two oxidants exert a positive effect on
cosmetics and pharmaceuticals and personal care 120 mL thermostated
battery bioassays. reactor made of pyrex glass.
IOPA and organic matter (TOC, DOC) removal by
products. Parabens in the aquatic environment are The vessel was open to the atmosphere without
typically present at the ng/L
HOTOVOLTAIC-DRIVEN UV-LED levelPHOTO-FENTON:
and are gas sparging
A NEW APPROACH since preliminary FORrunswill showed that
Photovoltaic-driven UV-LED photo-Fenton: thea effect
new approach of aerationforon degradationin by
be filled
suspected
MICROPOLLUTANTto behave as endocrine
REMOVAL disruptors [1]. was
1 B3-14
micropollutant removal
In recent years, various efforts are being 134 negligible. Certain volumes of EP and EAAOP4
solutions
SPS stock
J.L. Casas
made to Lpez
1,2
eliminate , G. Rivas
or Ibaez
1,2
effectively obra1,2, M. Prez
, I. de laremove Garcawere
1,3 mixed
, J. A. to aPrez
Snchez predefined
1,2
(1) Solarvolume
Energy of
ultrapure water in order to get the desired
 Parabens, esters of 4-hydroxybenzoic acid with concentrations, reaction time, pH, temperature and
an alkyl or benzyl group, have been employed for water matrix on kinetics.
about a century as preservatives in foodstuff, Oxidation reactions were conducted in a
cosmetics andRpharmaceuticals
O O M B - and F E personal
N T O Ncare& F 120 E NmLTO N L I K Ereactor
thermostated PRO madeC EofSpyrex
S E Sglass.
products. Parabens in the aquatic environment are The vessel was open to the atmosphere without
typically present at the ng/L
HOTOVOLTAIC-DRIVEN UV-LED levelPHOTO-FENTON:
and are gas sparging
A NEW APPROACHsince preliminaryFORrunswill showed that
Photovoltaic-driven UV-LED photo-Fenton: thea effect
new approach of aerationforon degradationin by
be filled
suspected to behave as endocrine
MICROPOLLUTANT
micropollutant removal
REMOVAL disruptors [1]. was B3-14
negligible. Certain volumes of EP and EAAOP4 SPS stock
In recent years, various efforts are being solutions were mixed to aPrez
predefined volume
J.L. Casas Lpez 1,2
, G.
made to eliminate or effectively remove Rivas Ibaez 1,2
, I. de la obra 1,2
, M. Prez Garca 1,3
, J. A. Snchez 1,2
(1) Solar Energy of
Research Centre CIESOL, Ctra de Sacramento s/n, ES04120, ultrapure
Almera,water in jlcasas@ual.es
Spain. order to get(2)the desired
Chemical
xenobiotics in the environment; among them, concentration of each reactant. SPS was added
Engineering Department, University of Almera, Ctra de Sacramento s/n, ES04120, Almera, Spain. (3) Chemistry
advanced
and Physicsoxidation
Department, processesUniversity (AOPs) are a Ctra
of Almera, viable after the
de Sacramento s/n, working EP solution
ES04120, Almera, Spain.had reached the
alternative option for water/wastewater treatment desired temperature (i.e. up to 60C).
[2]. The sulfate radical-AOP has recently been All experiments were performed un-
discussed in the literature as an efficientPhotovoltaic and (PV) technology has recently attained
buffered at their inherent pH. Samples periodically
affordable process. significant development regarding cost reduction and
18(High(power(UVA(LEDs((365,(385(&(400(nm)( drawn from the reactor were immediately cooled
energy production yield, achieving electric energy
Sodium persulfate (SPS) (Na2S2Oproductions (
((365((((((385((((((400
8) has
down at 4C in an 2ice bath for about 5 min to
Poten&ometer(
around 250 W/m . At the same time, low
attracted the attention of the scientific community quench the reaction and then analyzed to assess
energy consuming LEDs with a wide range of wavelengths
as a promising source of sulfate radicals because the degradation of Ethyl Paraben by means of
and radiant flux are currently available. In this work, the
of its moderate cost (i.e. the wholesale priceuse is of high performance liquid chromatography (Waters
in low-cost UVA-LEDs driven by photovoltaic energy
the order1L(PVC(cylindrical(reactor((
of 1000 USD/tn) and its high isredox Alliance 2695).
explored as radiation source for photo-Fenton process as
potential of 2.01 V [3].Other advantages
(5cm(depth)(
of water treatment. The main goal of the present study
tertiary
persulfate Magne&c(s&rrer(
over other oxidants include the fact Table 1 shows the tested variables of the 25
is that
to get some insight on the relationships among PV
it is solid at ambient temperature, thus facilitating factorial design, where each variable takes a low
energy supply, LED consumption, UVA irradiance and
its storage and transport, as well as itsreaction high rate. and a high value.
Scale-up has also been taken into account.
stability and aqueous solubility. 5
Table 1. Levels of variables of the 2
In this work, ethyl paraben was chosen factorial design.
as a representative model compound of the EDCs EP Time SPS Temp
A newtoLED photoreactor was used at bylab heat-
scale pH Matrix
family investigate its degradation
3+

(mg/L)
240 (min)
5.5 mg Fe /L
11 mg Fe /L
(mg/L) C 3+

to remove
activated the oxidation.
persulfate pesticides Theacetamiprid and
main scope was 16.5 mg Fe3+ /L
Volumetric Rate Photon Absorption (W/m )

= 365 nm
0.5 2 0.3 3 40 UP
3

thiabendazole, 100 g/L each, from

to evaluate the effect of various operating aqueous 200
solution at pHsuch
conditions 2.8. Three UVA wavelengths
as initial EP and (365, SPS = 385 nm
1.5 30 0.5 9 60 WW
385 and 400 nm) and three values of iron 160

concentration (5.5, 11 and 16.5 mg/L) were

assayed. Initial hydrogen peroxide concentration 120

was 50 mg/L to work in slightly excess conditions. = 400 nm

1
The experiments were carried out in a 1-L 80

cylindrical reactor with 5 cm liquid depth located 40

inside the LED box built with 6 high power UV
LED emitters (PW03UV3) for each wavelength 0
able to give UV irradiance up to 110 W/m2. The 0 3 6 9 12 15 18

LED array was equipped with a potentiometer Power consumption (W)

allowing the electrical intensity be set in the 0700
mA range to linearly change irradiance on reactor
surface. The volumetric rate of photon absorption
(VRPA, W/m3) was calculated [1] and kinetics of
micropollutants removal by photo-Fenton was
studied as a function of VRPA.
An increase in wavelength gave rise to a
decrease in the VRPA and a marked reduction in
the power consumption (Figure 1). A balanced
situation was reached at 385 nm where VRPA was
high and power consumption low.
Hydrogen peroxide followed saturation kinetics
with VRPA and micropollutants removal rate was
proportional to the oxidant consumption [1].
Figure 1. Variation in VRPA with electrical power
consumption as a function of iron concentration and
wavelength. Irradiance was 17.5 W/m2.
Preliminary results showed the potential of UVA-
LED driven photo-Fenton for micropollutant
removal and enhancement for process scaling-up
taking into account the treatment economy.
Reference
[1] G. Rivas, I. Carra, J.L. Garca Snchez, J.L. Casas
Lpez, S. Malato, J.A. Snchez Prez. Applied Catalysis
B: Environmental. 178 (2015) 210217.

Acknowledgements
This research was supported by the Junta de Andaluca (P10-RNM-05951 / P12-RNM-1437) and the European
Regional Development Fund (ERDF).

135 1
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

COMBINATION OF MEMBRANE TECHNOLOGY AND UV-LED/TiO2 FOR THE REMOVAL

will be filledOF
Combination of Membrane Technology and UV-LED/TiO2 for the
PATHOGENS AND VOCs FROM URINE in by C3-1
Removal of Pathogens and VOCs from Urine
EAAOP4
Olivier Autin, Sean Tyrrel, Elise Cartmell, Alison Parker, Leon Williams, Athanasios Kolios, Ewan McAdam.
Cranfield Water Science Institute, Cranfield University MK43 0AL
olivier.autin@cranfield.ac.uk
2.5 billion people lack adequate sanitation facilities
with devastating consequences for human health and
the development of new technologies is becoming a
matter of urgency for 40% of the worlds population.
As part of the Nanomembrane toilet project, we have
investigated the combination of an ultrafiltration
barrier and a LED-driven UV/TiO2 photocatalysis
system to remove odorous compounds from the
treated urine. The results revealed that this double
barrier was able to produce pathogen and odour free
water with reduced amount of energy compared to the
currently used membrane distillation option. The
study showed that the 14 volatile organic compounds
tested were removed below their odour threshold
within 600 mJ cm-2.

1. Background which converts them into ash and energy which

will power the membrane process (and eventually
2.5 billion people (40% of the worlds population) a secondary treatment).
lack adequate sanitation facilities with devastating
consequences for human health as well as the
OXIDATION
environment AND ADSORPTION
[1]. OF ARSENITE IN AQUEOUS SOLUTIONS USING Fe-DOPED
Oxidation and Poor sanitation
adsorption contributes
of arsenite to
in aqueous solutions using Fe- will be filled
SBA-15
about AND PERSULFATE
700,000 child deaths from diarrhea each in by C3-2
doped SBA-15 and persulfate
year. The toilets, sewers, and wastewater treatment EAAOP4
systems
W. Dingused
1
in the
, W. Zhou 1
developed
, F. Wu1, J. L1*world require vast
. (1) Department of Environmental Science, Wuhan University, 430079 Wuhan,
Hubei, P. R. China, 740082672@qq.com;ljj0410@163.com.
amounts of land, energy, and water, and are
expensive to build, maintain and operate. Existing
alternatives that are less expensive Iron are oxide
often has been anchored on SBA-15 to synthesize a stable
unappealing because they dont kill disease- catalyst-sorbent named Ace-FeMS. Ace-FeMS was
and active
causing pathogens, have impractical designs, characterized
or by XRF, XRD and TEM. The oxidation and
retain odors and attract insects. adsorption of As(III)
Figurein1:aqueous
Currentsolutions
design ofbythe Ace-FeMS
Nanomembrane with
persulfate as toilet.
oxidant has been investigated in different
In 2012, the Bill and Melinda Gates foundation conditions. The influencing factors (Fe/Si ratio, pH) and the
launched the Reinvent the toilet recycling challenge.of Ace-FeMS
During the were
firstinvestigated.
phase of theResults
project,showed
the work thathas
Cranfield University, one of the grantees, removal rateis of focused
As(III) reached
on membraneto the highest at pH as
distillation 5, as
thiswell as
unique
developing the Nano Membrane Toilet which is the catalytic oxidation efficiency.
nanostructured The
membrane removal
wall rate of As(III)
facilitates water
able to treat human waste on-site without could still reach
external up to in
transport 95%the for
vaporfivestate
recycling runsasfor
rather than the
a liquid
energy or water. The toilet is designed removal of 1000state
g Lwhich
-1 As(III) in five fresh persulfate solutions.
for single- yields high rejection of pathogens,
household use (equivalent to 10 people) This catalyst-sorbent
and inorganic might offer
salts, a potential
organic application
compounds and for most
accepts urine and faeces as a mixture. arsenic removalodorous
The toilet, from waters.
volatile compounds. Whilst the process is
still under development, works as follow: a toilet highly effective at producing water of a drinkable
flush using a unique rotating mechanism transports quality, a survey in Ghana demonstrated that the
the mixture into the toilet without demanding users would not be prepared to drink the water due
water whilst simultaneously blocking odour and to its origin,
oxidation however of
and adsorption most of from
arsenic the customers
waters.
Background
the users viewand ofObjectives.
the waste.Problematic arsenic
Solids separation confirmed that they would be willing to use the
contamination
(faeces) deserves world
is principally concerns because
accomplished through of Methods.
water for Particulate
irrigation or hydrated
washing. ironTherefore,
oxides colloidsuch
its carcinogenicity
sedimentation [2]. and toxicity.
Loosely boundThiswater
has promoted
(mostly was synthesized
high quality waterbymight Li etnot al be
[9].necessary,
Acetone and was
intensive
from researches
urine) on the removal
is separated using of membrane
arsenic in added into the
particulate, generated
odour colloid. free
and pathogen Afterwater
stirredwould
for 1
the environment[1].
technologies. Following Inrelease
naturalof waters,
unboundarsenic
water, h, the
be intermixture
sufficient for was
such at 60 oC. Then
driedapplications. As thea
exists in two main inorganic formsarsenite
the residual solids (around 20-25% solids) are and solid iron oxide was
consequence, a passive membrane produced. The solid iron
filtration
arsenate. It isbywell
transported recognizedscrew
mechanical that arsenite
into a is about
gasifier oxide and
system 4 g triblock rather
(ultrafiltration) copolymerthan P123
membrane were
60 times more toxic than arsenate[2]. Different dissolved in 150 ml deionized water. After that,
arsenic species have been widely found in the
surface and groundwater sources[3]. Therefore,
136
8.5 g tetraethyl orthosilicate (TEOS) was added in
the solution under stirring for 24 h at 40 oC. The
1
arsenic pollution requires more urgent attention to solution was aged at 100 oC for 24 h in an
ROOM C - COUPLING AOP WITH OTHER PROCESSES, PILOT-SCALE STUDIES AND FIELD APPLICATIONS

NOVEL PILOT SCALE CONTINUOUS PHOTOCATALYTIC MEMBRANE REACTOR FOR

filledTHE
Novel Pilot Scale Continuous Photocatalytic Membrane Reactor for the will be
REMOVAL OF RECALCITRANT MICRO-POLLUTANTS FROM WATER
Removal of Recalcitrant Micropollutants from Water in by C3-3
EAAOP4
A.J Karabelas, V.C. Sarasidis, K.V. Plakas, S.I. Patsios, A.M. Lekkas.
Chemical Process and Energy Resources Institute, Centre for Research and Technology - Hellas, P.O. Box 60361,
6th km Charilaou-Thermi Road, Thermi, Thessaloniki, GR 57001, Greece, karabaj@cperi.certh.gr
A novel, fully automated Photocatalytic Membrane Reactor (PMR)
pilot unit is presented and evaluated herein. PMR combines two
modern processes; i.e. heterogeneous photocatalysis and membra-
ne ultrafiltration, employing dispersed TiO2 nanoparticles with
UV-C irradiation and hollow UF fibers in a submerged module,
respectively. The PMR-pilot aims at the continuous photocatalytic
degradation/mineralization of recalcitrant organic compounds,
commonly encountered in natural waters at very low concentrati-
ons. The performance of PMR pilot was evaluated by studying the
degradation of the pharmaceutical diclofenac, a typical recalcitrant
micro-pollutant, at different operating process parameters. In the
specific conditions tested, it is shown that catalyst loading and UV-
C radiant power per unit volume significantly affect DCF removal;
however, hydraulic retention time has a rather insignificant effect.

The contamination of surface- and ground- conditions. The experimental results of continuous
waters from hazardous for the public health, toxic treatment of DCF with the pilot-scale PMR are
organic micro-pollutants [e.g. Pharmaceutically presented in this study.
Active Compounds (PhACs), herbicides, industrial Titanium dioxide (Aeroxide P25, Degussa),
chemicals, dyes, etc.] is a well-known problem. comprising 75% anatase and 25% rutile, with a
Therefore,
Tertiary pursuing
treatment theofdevelopment
wastewater of by
effective,
adsorption BET solar area 50 m2/g, average
andsurface will be primary
filled
economic andTREATMENT
environment-friendly technologies BYparticle ofsize 21 nm andSOLAR
an energy band gap of
TERTIARY OF WASTEWATER ADSORPTION AND PHOTO- in by
photocatalysis for decontamination and disinfection secondary
EAAOP4
iseffluents
an issue of great importance. Among such
CATALYSIS FOR DECONTAMINATION AND 3.18eV, was used as photocatalyst. However, in
DISINFECTION OF SECONDARY EFFLUENTS C3-4
technologies, Advanced Oxidation Processes aqueous dispersions, TiO2 nanoparticles tend to
(AOP) are 1,3,5
M. Brienza considered much
; S. Gutirrez promising
Alfaro 2
candidate
, G. Plantard 3
aggregate
, S. Nir4, S.A. Bufo5, V.and
Goetzform
3
and fairly large
S. Chiron 1
agglomerates of
methods to efficiently remove and simultaneously size depending on various parameters [4].
1
UMR HydroSciences 5569, Montpellier Universit, France, monica.brienza@unibas.it
destroy
2
Faculty aof Marine
wide spectrum of
and Environmental Sciences, University ofDiclofenac
non-biodegradable Cdiz, Spain sodium salt of analytical grade,
organic substances from water. AOP France
have many purchased from Sigma-Aldrich, was used as a
3
PROMES-CNRS, UPR 8521, Perpignan,
4
advantages compared to currently widely used representative toxic organic micro-pollutant in all
The Hebrew University of Jerusalem, The R.H. Smith Faculty of Agriculture, Food and Environment, Israel
5
conventional water treatment methods, such as experiments. DCF is a non-steroid, anti-
Department of Sciences, University of Basilicata, Potenza, Italy

coagulation/flocculation, activated carbon inflammatory drug, frequently encountered in

A tertiary treatment which combines adsorption and solar
adsorption, ion-exchange and membrane filtration. natural and surface waters in very low
photocatalysis was carried out. Adsorption was by a sequence of
In recent years, researchers at CERTH (Natural concentrations, affecting both human health and
two column filters; the first included granular activated carbon
Resources and Renewable Energies Laboratory- environment [5]. Tap water from a well (serving
(GAC) and the second included a granulated nano-composite of
NRRE) have gained significant experience in CERTH) was used as feed water; the feed solution
micelle-montmorillonite mixed with sand (20:100, w/w). The
AOP, mainly on heterogeneous photocatalysis. pH was natural, without any adjustment and all
Solar Advanced Oxidation Processes (SAOPs) applied were
Specifically, NRRE has specialized on design and reagents were used as received, without any pre-
heterogeneous, using suspended TiO2, and homogeneous Photo-
construction of laboratory scale hybrid photo- treatment. DCF concentration was determined by
Fenton Photocatalysis using peroxymonosulfate as agent oxidant.
catalysis/ultrafiltration systems, with novel reversed-phase HPLC (LC-10AD VP, Shimadzu
The aims were to remove faecal micro-organisms such as
characteristics. Continuous-mode Photocatalytic Co.) fitted with a XTerra MSC (Waters) column,
Escherichia coli and Enterococcus spp., and emerging
Membrane Reactors (PMR) of different (18.5 m, 150 mm x 2.1 mm (i.d)) at 40oC,
contaminants (ECs) present in wastewater (WW) secondary
configurations have been successfully tested, coupled with a UV/Vis detector (SPD-10A VP,
effluents. The final effluent presents an improved sanitary level
regarding the oxidation/degradation of Shimadzu Co.) at 270 nm, after pre-concentration
with acceptable chemical and biological characteristics.
recalcitrant micropollutants, including Sodium by solid-phase extraction (Discovery DSC-18
Alginate
The domestic(SA), andHumic Acids
industrial use (HA),
of largeDiclofenac
amounts SPE Tubes, of
disinfection 500wastewater
mg, 3 mL)secondary
[3]. Totaleffluents
Organic
(DCF)
of waterandin Atrazine
developed(ATR) [1-4].generates
countries Details on largethe Carbon (TOC) concentration was measured in a
(WWSE).
construction
amounts and the experimental
of wastewater. results of
The need to recuperate TOC analyzer
We proceeded(TOC-5000A,
through Shimadzu Co). (i)
several steps:
previous
this water PMR
for new systems can be practically
uses, makes found elsewhere
essential [1- A schematicofdiagram
identification of the pilot PMR
the micropollutants and unit
faecalis
4]. purification
the The laboratory results paved
of wastewater to the way the
achieve for provided in
coliforms Figurein1.the
present Thesecondary
main partseffluent;
of the unit,
(ii)
scaling-up
desired one of
degree of the aforementioned
quality. For this reason hybrid designed and
assessment of constructed
filtration andin(iii)
NRRE laboratory,
of solar advanced are
systems which
wastewater was plants
treatment tested (WWTPs)
under realshouldfiltration
be the cylindrical
oxidation processes.membrane vessel, made of
designed for achieving the removal of The efficiency of these processes was evaluated
micropollutants and pathogens in order to
minimize their sanitary and environmental
137 through:
1) the inactivation of faecal bacteria and removal
1
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

ASSESSMENT OF THE KEY PARAMETERS OF THE PHOTOCATALYTIC PROPERTIES will be FOR

Assessment of the key parameters of the photocatalytic properties for filled
CONSTRUCTION MATERIALS: LIFE-MINOX-STREET EUROPEAN PROJECT
construction materials: LIFE-MINOX-STREET European Project in by C3-5
EAAOP4
B. Snchez1, S. Surez1, I. Jansson1, O. Vilanova1, B. Cadavid2, J. Perez2, J. O. Marrn2, A. Moral2, M. Snchez2, M.
Palacios3, L. Nuez3, B. Artiano3, M. Pujadas3and D. Iglesia4 (1) CIEMAT-FOTOAir, Avda. Complutense 40, 28040
Madrid Spain e-mail:benigno.sanchez@ciemat.es; (2) CEDEX-CET, Madrid Spain; (3)CIEMAT-Dpto.
Medioambiente, Madrid Spain;(4)Alcobendas Council, Madrid Spain.

The MINOx-STREET project, funded by EU (Life12

ENV/ES/000280), aims to evaluate the strategies for the
abatement of traffic related NOx levels. It will offer to the
local authorities a guide to optimize the use of commercial
photocatalytic materials designed for air purification in
urban environments. The potential usefulness of a range of
commercial photocatalytic materials to act as NOx sinks
was studied. Facades, asphalts, sidewalks and roof covering
were analysed and more than 160 analysis (ISO 22197-1
standard) on 23 photocatalytic products distributed in the
European market were performed. The most promising
solutions will be implemented on urban surfaces in real
condition in the Alcobendas District next to Madrid.
the Alcobendas Council, two Research Centres
Nitrogen oxides (NOx) contribute to several key CIEMAT (Centro de Investigaciones Energticas,
atmospheric phenomena such as the Medioambientales y Tecnolgicas) and CEDEX
photochemical smog, greenhouse effect or acid (Centro de Estudios de Experimentacin y Obras
rain. Nowadays, and especially in big cities, there Pblicas) with a total budget of 1.982.619 are
is a great concern about the atmospheric pollution involved. In the first stage of the project,
provoked by nitrogen oxides.PROCESSES
SOLAR PHOTOCATALYTIC Heterogeneous FOR SOIL photoactive
WASHING materials already available
WASTEWATER TREATMENT in the
photocatalysis with solar irradiation
Solar Photocatalytic Processeshas forstarted to
Soil Washing market, such as concrete,
Wastewater Treatment asphalt, paints and roof C3-6
be considered a plausible, clean and low cost, coverings, were evaluated under the parameters
technology
M. Race 1, R. NOx 2,removal
forAndreozzi I. Di Somma[1,2,3].
3 TiO2 1, R. Marotta
, M. Fabbricino reported 2
, L.inOnotri
the 2,ISO22197-1 standard4 (1)
F. Pirozzi1, A. Siciliano (Table
DICEA,1,
commercial materials
Univ. di Napoli FedericoorII, precursors
via Claudio 21, ofNapoli,
titania total flow = 3 L min-1(2)
Italia, marcorace@gmail.com., , [NO] = 1,000
DICMAPI, Univ.ppb , R.H. =
di vNapoli
nanoparticles [4],V. are
Federico II, P.le included
Tecchio with
80, Napoli, different
Italia, (3) IRC-CNR,50 %,V.I Tecchio
P.le = 10 Wm 80,-2Napoli,
, irradiation
Italia, time = 300
(4) Dip.to min).
di Biologia,
formulations intoFederico
Univ. di Napoli construction materials,
II, via Cinthia e.g.Napoli, Italia.
ed. 7, 80126
asphalts, pavements, facades. Incorporated Table 1. Materials evaluated according to
materials (where the precursor is included ISO22197-1 standard
The use of biodegradable chelating agentsin(EDDS)
the for removing heavy metals from soils is a very promising
ex-situ process for the treatment of contaminated soils. TheISO
preparation of the block) or coated samples N main Testdrawback of the 228soilDescription
washing is the need of
(prepared by spray or dip coating techniques)
a successive treatment of the wastewater which containsFacadesare the extracted heavy metals and- Bricks
chelating agents. The
the studies
two most common procedures to incorporate Types 3
on the possibility to decontaminate EDDS containing soil washing effluents are- Rough restrictedconcrete
to synthetic
semiconductors into construction materials. The - Tile
solutions or real soil washing solutions but using Pavements exclusivelyTypes artificial 10 solar radiation. The present
photo-oxidation process can be described, in a - Paving stonesthe high
investigation proposes, for the first time, an integrated outdoor photocatalytic process for lowering
simple way, as a two-stage reaction occurring on -Porous/non
concentration of copper, iron and zinc and EDDS present
the surface of the photocatalyst [2]: Asphalts
in soil washing wastewaters3 to values below the
limits defined by the Italian legislation for discharge in civil sewers. The effluents were -Aged/non
produced through a
+
NO + OH
soil NO
washing 2 + H using EDDS as chelating
process (1)organic Acknowledgements
agent. The polluted soils were taken from the Land
of Fires, an area- in Campania region, Southern Authors are grateful to thefor
EUROPEAN UNION LIFE12
NO 2 + OH NO3 + H
+
(2) Italy, near Naples,
ENV/ES/000280
known
for the
its high incidence
finaltial support.
of cancer
mortality also due to a marked presence of toxic residues in the environment. The outdoorruns under
Therefore,
sunlightNO 2 iscarried
were the first oxidation
during product
the spring 2015 andat University of Naples (Italy, local latitude 40 5000 ,
References
the longitude
key precursor
1412for further
00 W) byoxidation
means of atosolar nitrate
tubular [1]collector
J. Chen,supported
C.-s. Poon,byBuilding
an aluminum structure. 44
and Environment The unit
ions.comprised
The nitrate
8 parallelspecies adsorbed
borosilicate glass tubeson (i.d.the 4 mm, (2009)
length1899.
34.6 cm and width 6 mm) connected by plastic
photocatalyst
junctions. surface are expected to be washed [2] G. Hsken, M. Hunger, H.J.H. Brouwers, Building
away from the surface as weak nitric acid. and Environment 44 (2009) 37.
In this context, the European Project LIFE [3] M.M. Ballari, M. Hunger, G. Husken, H.J.H.
MINOx-STREET arises in order to implement Brouwers, Applied Catalysis B-Environmental 95 (2010)
photoactive materials in a neighbourhood of the 24.
Alcobendas District (Madrid, Spain). Four entities, [4] F. Pacheco-Torgal, S. Jalali, Construction and
Building Materials 25 (2011) 582.
INECO (Transport Engineering and Consultancy),

138 1
ROOM C - COUPLING AOP WITH OTHER PROCESSES, PILOT-SCALE STUDIES AND FIELD APPLICATIONS

ELIMINATION
Elimination ofOF ANTIBIOTIC
antibiotic ACTIVITY
activity of watersOF WATERS CONTAMINATED
contaminated with WITH
OXACILLIN BY PHOTO-FENTON, TiO -PHOTOCATALYSIS,
oxacillin by photo-Fenton, TiO2-photocatalysis,
2
SONO-CHEMICAL
sonochemical and AND
ELECTROCHEMICAL PROCESSES - A COMPARATIVE STUDY ON
electrochemical processes - A comparative study on the effects ofTHE EFFECTS OF
ADDITIVES
C3-7
additives
R.A. Torres-Palma1, E. Serna-Galvis2, J. Silva-Agredo 1, A. Giraldo-Aguirre 2. O. Florez 2 (1) Grupo de
Investigacin en Remediacin Ambiental y Biocatlisis ricardo.torres@udea.edu.co. (2) Grupo de Diseo y
Formulacin de Medicamentos, Cosmticos y Afines , Universidad de Antioquia, Medelln, Colombia,

In this work the effect of several additives of the pharmaceutical

2.5 industry: Mannitol (MAN), tartaric acid (TA), calcium
carbonate (CC) and sodium lauryl ether sulfate (LES), is
evaluated in the degradation of oxacillin (OXA) by several
OXA + MAN
2.0
OXA + TA
OXA + CC
rk = kOXA + ADDITIVE / kOXA

1.5
OXA + LES
advanced oxidation processes (TiO2 photocatalysis (PC), photo-
Fenton (PF), sonochemistry (SC) and electrochemical oxidation
1.0
with DSA anodes mediated by chloride ions (EO). Depending
0.5
on both the process and the additive type, interesting enhancing
or inhibiting effects were found on the kinetic of the
0.0
PF PC SC EO antimicrobial activity removal of the treated solutions. The
results are the high relevance in the choice of the most suitable
technology to the treatment of waters containing -lactam
antibiotics such as oxacillin..

Antibiotics are among the therapeutic groups pharmaceutical wastewaters. Therefore, two well-
commonly detected in wastewaters. The pollution known excipients (mannitol. MAN, and tartaric
by antibiotics in the biosphere induces a bacterial acid, TA) in the preparation of antibiotics, a
selection and the production of microbial common active principle (calcium carbonate, CC,
resistance1. The
PILOT-SCALE resistance
SLURRY genes at SOLAR-PHOTOCATALYTIC
AND FIXED-BED the i.e. bicarbonate ion according REACTOR to theFORpH THE
of the
environmental
Pilot-scale Slurrybacteria
OF and can be transferred
Fixed-bed to solution) Reactor
Solar-Photocatalytic and one of forthe
themost popular surfactant
DEGRADATION
humans increasing
HERBICIDE
the risk andIsoproturon
ISOPROTURON
diminishing our (sodium lauryl ether sulfate, LES) used for
C3-8
Degradation of Herbicide
ability to1 treat the 1illnesses2. Consequently,2
cleaning proposes in pharmaceutical industries,
A.Verma *, N. T. Prakash and A.P. Toor . (1)School of Energy and Environment, Thapar University, Patiala,
processes able to eliminate the antibiotics in were considered in a concentration 10 times higher
Punjab [INDIA]. anoop.kumar@thapar.edu. (2) Dr. SSBU C E Technology, Panjab University, Chandigarh, India
polluted waters are a need. than the antibiotic. Then, the mentioned processes
Pilot-scale slurry and fixed-bed solar photocatalytic studies in the degradation of OXA infor
have been performed presence of mannitol
the degradation
As antibiotics in pharmaceutical wastewaters are (MAN), or tartaric acid (TA),
of herbicide Isoproturon (IPU). The degradation achieved was 84% using slurry batch recirculation or calcium carbonate
accompanied
reactor with allwith other process
optimized substances such For
conditions. as fixed-bed
(CC) orcatalysis,
sodium the
lauryl
TiOetherwas sulfate on
coated (LES) were
cement
2
excipients, active principles and surfactants used
beads, clay beads and subsequently used for checking the degradation of IPU. The catalyst coated as
studied. The progress of oxidative species such
for cleaning
beads proposes,enough
were durable their effect on both for
to be recycled the morehydrogen peroxideWith
than 35 cycles. or HClO upon the
this outcome, different
parabolic
efficiencies of thewas
trough collector antibiotic
employed degradation and the
using catalyst coated processes
beads andwas determined
degradation and the UV
efficiency spectrum
achieved was of
elimination of the associated biological activity
-1 solutions
91% with IPU flow rate optimized at 1.0 L min with total working volume of 6 L.was measured in order to provide a
should be considered. A special attention at the comprehensive understanding of the effects of the
antimicrobial activity (AA) must be paid, taking additives on both the OXA and AA elimination.
Photocatalytic
into account technologies
that in several (AOP) have
cases, although the The kinetic constants of the antimicrobial activity
shown
pollutant their potential removed,
is effectively for treating the
the treated removal were obtained and used to compare
water/wastewater
solutions can still containing
conserve the biorecalcitrant
antimicrobial quantitatively the action produced by the additives.
compounds. However,
activity. In spite of that,theinoperating cost fordealing
most of papers AOP Finally, the above information was used to depict
is always
about higher than
the treatment of conventional treatment
wastewaters containing the more appropriate oxidation process in function
technologies.
antibiotics the Thus future
evolution research
of the AA has would
been aim
not of the type of additive present in the wastewater.
towards the cost reduction in terms of efficient
considered.
catalysts along with investigating the effectiveness
pilot-scale
In this work reactors with better
we evaluated retention of
the potential time and
anodic Photo-Fenton and photocatalysis with TiO 2
techno-economic
oxidation mediated analysis,
by chloridewhich ions andcertainly
several processes were done in a homemade aluminum
improve
AOPs (TiO the2 photocatalysis,
commercial viability of solar
photo-Fenton and reflective reactor, equipped with 5 lamps Philips
photocatalytic
high frequency technology.
ultrasound) to Theremove
investigation
the AA in in (TL-D Actinic BL) of 30 W. For the two
the present
waters study demonstrates
contaminated successful
with the antibiotic use of
oxacillin. processes, 150 W of light were applied to 100 mL
pilot-scale reactorsisslurry Fig: 1 Pilot-scale slurry reactor
Special attention paid asto well
the as fixed-bed
influence of of OXA solutions (47.23 mol L-1) placed in
reactors for the degradation
substances that can also be present in of herbicide beakers, under constant stirring. In photo-Fenton
isoproturon (IPU).
Scale-up studies have been performed
using slurry batch reactor (Fig. 1) for the
photocatalytic degradation of IPU with working
139 1
 O R A L P R E S E N TA T I O N S - 3 rd D A Y
The health risk decrease with simultaneous elimination of VOCs and will be filled
in by
POPs containing particles emitted from electronic waste dismantling
THE HEALTH RISK DECREASE WITH SIMULTANEOUS ELIMINATION OF VOCs AND POPs
EAAOP4
workshop by an integrated technique of dedusting with
CONTAINING PARTICLES EMITTED FROM ELECTRONIC WASTE DISMANTLING WORK-
decontamination
SHOP BY AN INTEGRATED TECHNIQUE OF DEDUSTING WITH DECONTAMINATION
C3-9
J.Y. Chen1, D.L. Zhang1, G.Y. Li1, T.C. An1*
State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and
Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640,
China, antc99@gig.ac.cn
Integrated technology of dedusting with
decontamination possessed high removal
Photocatalysis
capacity and long stability for both volatile
Bag Filter
organic compounds and persistent organic
pollutants (POPs) removal higher than 83.0%
of detected pollutants emitted in a primitive
TSP,VOCs,
POPs
e-waste dismantling workshop were
Cleaner and
safer gas
simultaneously eliminated with a
E-waste Biotrickling dramatically decrease of their health exposure
Dismantling Filter
risks to the workers after the integrated
reactor treatment.

primitive e-waste dismantling workshop. Before

Electronic waste (e-waste) is one kind of treatment, it was found that the emitted gas from the
electrical and electronic products that no longer dismantling processes was highly polluted, where
used or discarded. About 20-50 million tons of e- the concentrations of VOCs, PAHs and PBDEs
waste has been produced each year worldwide and ranged from 47.50 to 924.00 g m-3, 937.35 to
it increases annually with a rate of 4% [1, 2]. 1235.61 ng m-3 and 853.01 to 4753.42 ng m-3 with
PILOT STUDIES OF A NOVEL ELECTRO-FENTON the dominated
FILTER FOR THE components
REMOVAL of toluene,
Therefore,
Pilot Studies the business for dismantling
of a Novel Electro-Fenton and
Filter for the Removalfluoranthene,
of willOF
be filled
ORGANIC MICROPOLLUTANTS
recycling of e-waste is growing rapidly in China FROM POTABLE phenanthrene,
WATER naphthalene and C3-10
in by
Organic
and millions Micropollutants
of tons of wastesfrom potable water
are dismantled and pyrene, and BDE-209, -99, and -47, EAAOP4 respectively.
recycled
K. Plakas1each year due1,toS.high
, A. Karabelas Sklariprofit.
1
, V. Zaspalis 1
, D. YiankakisHowever,
Unfortunately, 2 after 2the treatment by a home-made
, G. Sideropoulos
theChemical
(1) techniques usedandinEnergy
Process recycling
Resourcesof e-waste
Institute,are middle
Centre for scale
Research and reactor
Technologyintegrated bag Box
- Hellas, P.O. filter with
often primitive,
60361, such as open-air
6th km Charilaou-Thermi Road, incineration and
Thermi, Thessaloniki, photocatalytic-biotrickling
GR filter, about 83.7%, 87.3%
57001, Greece, kplakas@cperi.certh.gr
acidic
(2) TEMAKwashing
AETE,without considering
DA13 Street, 33B Block, environmental and 91.3%
Industrial Area Thessaloniki, of VOCs,
Sindos, PAHsGRand
Thessaloniki, PBDEs
57022, Greecewere
protection and human health. Many volatile organic removed. In addition, the health exposure risks
compounds (VOCs) and persistent from VOCs, PAHs and PBDEs to the workers were
Thisorganic
paper reports on the results obtained in pilot studies of
pollutants (POPs) including polycyclic aromatic also found to be decreased dramatically after the
continuous water treatment, to degrade diclofenac (DCF), a
hydrocarbons (PAHs) and polybrominated treatment with the integrated reactor.
typical recalcitrant micro-pollutant, by a novel electro-Fenton
diphenyl ethers (PBDEs) are producedfilter. inevitably
The latterAcknowledgements.
consisted of three pairs of anode/cathode
into air during these dismantling processes [3, 4].of 4.5gr
electrodes, Thistotalwork
masswasand anfinancially supported~49cm
effective volume by 3.NSFC
However, the chronic health effects such Allaselectrodes
cancer (41425015,41373102
were made of carbonand felt, 21077104), Cooperation
with the cathodes
risk of VOCs and other POPs such as PAHs beingas wellimpregnatedProjects of Chinese
with Academy of Science
iron nanoparticles (Fe3O4with
). The Foshan
as non-cancer risk of VOCs and PBDEs optimum can be currentGovernment
efficiency (2012HY100101) and Team
of the filter (>50%) wasProject
recordedof NSF,
resulted from the inhalation and long-time at exposure Guangdong,ofChina
an applied potential 2V (S2012030006604).
and low water superficial
of these gaseous pollutants [5]. In addition, velocitiesthe (~0.023 cm/s).
References Under these conditions, the
adverse impact of these emitted VOCs and POPs on current efficiency (MCE%), regarding DCF in
mineralization
human health should also be concerned.tap Therefore,
water, was >20% [1] M. under
Andersson, M.K.
steady Wedel,
state C. Forsgren,
conditions. J. Christeen,
Moreover,
it is highly urgent to develop efficient techniques to Minerals Engineering, 29 (2012) 105.
the degradation/mineralization efficiency of the filter was
[2] J.J. Fu, Y.W. Wang, L.J. Zhou, A.Q. Zhang, G.B.
reduce the concentration as well as the exposure
stable after multiple electrolysis cycles.
Jiang, Progress in Chemistry, 23 (2011) 1755.
risk of these organic pollutants to acceptable levels [3] W.J. Deng, J.S. Zheng, X.H. Bi, J.M. Fu, M.H. Wong,
in the polluted air. Environment International, 33 (2007) 1063.
treatment
[4] X.Z. Yu,efficiency.
Y. Gao, S.C. Wu, H.B. Zhang, K.C. Cheung,
Hence, in this work, the health risk deduction
Introduction
M.H. Wong, Chemosphere, 65 (2006) 1500.
with simultaneous elimination of VOCs and POPs In view of the above challenges, a novel
[5] N. Ramirez, A. Cuadras, E. Rovira, F. Borrull, R.M.
In recent years, electrochemical advanced
including PAHs and PBDEs were investigated in a electrochemical device has
Marce, Environment been developed
International, 39 (2012) in200.
the
oxidation processes (EAOPs) are considered form of a filter comprised of a stack of carbon
environment friendly emerging alternatives for the anodic and cathodic electrode pairs for operation
abatement of pollution caused by a multitude of in continuous mode [2]. The design and1
organic micropollutants in waters. Among EAOPs,
the electro-Fenton (EF) method is the most
popular one, forming the basis for a variety of
140
construction of such a novel filter is characterized
by the following main innovative features: a) the
impregnation of catalytic nano-particles in the
related processes [1]. EF involves the continuous
ROOM C - COUPLING AOP WITH OTHER PROCESSES, PILOT-SCALE STUDIES AND FIELD APPLICATIONS

Novel ADVANCED
NOVEL Advanced Oxidation Process
OXIDATION on a Chemically
PROCESS Modified MODIFIED GRAPHITE
ON A CHEMICALLY will be filled
in by
GraphiteWITH
SURFACE Surface with Nanometal
NANOMETAL C3-11
EAAOP4
Mohamed A. Morsy1, Abdel-Nasser M. Kawde1, Mohamed A. Daous2, Ahmet U. Dogan1,3. (1) King Fahd University
of Petroleum and Minerals, Dhahran 31261, Saudi Arabia, mamorsy@kfupm.edu.sa. (2) Aramco R&D Center,
Dhahran 31311, Saudi Arabia. (3) University of Iowa, Iowa City, Iowa, USA.
Few studies are found in the literature dealing with the photo-
oxidation (PO) process on graphite surfaces for wastewaters
treatment. The presented PO process work is a type of the
advanced oxidation process (AOP). It is use to mineralize
refractory pollutants on the graphite or its modified surface with
nanometals such as graphite/TiO2 nanoparticles (NPs). The
morphology and composition of these materials have been
investigated with SEM, EDX and TEM. Electron paramagnetic
resonance/Spin Trapping (EPR/ST) spectroscopic technique was
also utilized to trap the active radical intermediates of the PO
process and hence investigate the PO process kinetics. The
results show, in the presence of photocatalyst copare to the
Coated graphite rode unmodified graphite, a remarkable MTBE degradation
surface with TiO2 NPs enhancement within the near UV and the visible light regions.

The chemical industry generates wastewaters oxides, such as TiOx, and hence achieve the
characterized by high levels of chemical oxidation optimum parameters toward the MTBE
demand (COD), suspended solids, fats and oils, remediation from model ground water using
detergents and some other process [1,2]. The COD different classes of UV (UVA, UVB, and UVC) and
test is commonly used to indirectly measure the visible light sources.
amount
PESTICIDEof organic
Pesticide compounds
REMOVAL
removal and
AND in water. Inofthe
EVALUATION
evaluation last OF DISINFECTION-BY
disinfection-by product
PRODUCT FORMATION
formation will be filled
decades, advanced oxidation
WITH LED-BASED AOPs processes (AOPs) The results indicate a remarkable enhancement of C3-12
in by
with LED-based AOPs
have been developed and proposed for a number of MTBE miniralization in the presence
EAAOP4 of
cases [3].Carra, Bruce Jefferson, Peter Jarvis
Irene
photocatalyst but with near UV-light. Moreover,
InCranfield
recent years, carbonInstitute,
Water Science nanotubes have attracted
Cranfield due toMK53
University, Cranfield, the 0AL,
presence
UK of TiO2 nanorods as a
considerable attention due to its unique electronic
irene.carraruiz@cranfield.ac.uk photocatalyst under same conditions, the process
property. For example, nanotube/TiO2 composites Drinking was completely degraded with
water production visible
needs light. Further
to increasingly
were used as photocatalyst for phenol degradation consider study removal
on the of development
backgroundoforganic
other matter
metaloxide
and
photocatalysts is in progress
under irradiation of visible light, which showed trace micropollutants without increasing disinfection-to achieve a better
higher efficiency compared to pure TiO2 [4,5]. To by-product degradation
(DBP)with higher concentration
formation of MTBE
potential. In this study
and other organic compound under
the best of our knowledge, the catalytic activity of the efficiency of LED-driven AOPs was investigated, visible light.
graphite/TiO2 nanoparticles (NPs) under visible comparing their efficacy in terms of micropollutant
Acknowledgements
light has not been well investigated. Therefore, in removal as well
The authors as DBP
acknowledge formation
support potential
provided by a grant
this work, deposited TiO2 nanomaterials on a (DBPFP). from the KingMetaldehyde
Abdulaziz City for
wasScience
usedandas
Technology
target
(KACST), and The
surface of graphite road (see graphical illustration micropollutant. by theresults
Scienceobtained
& Technology Unit at that
indicated King
above and Figure 1 below). Fahd University
LED-driven AOPsofarePetroleum & Minerals
efficient for the (KFUPM)
removal thatof
is supported
trace pollutantsbyfrom
Project No. 13-WAT250-04
drinking water but theaschoice
part of of
the
National Science, Technology and Innovation Plan.
treatment should be linked to DBP formation
References
potential studies since their capability to generate
DBPs is different from one another.
[1] M. Klavarioti, D. Mantzavinos, D. Kassinos.
Environmental International, 35 (2009) 402-417.
1. Background [2] P. Bautista,
example, theA.F.
THMMohedano, J.A. Casas,
formation J.A. Zazo,
in synthetic water
Figure 1. TEM
Pesticides are images
one of ofthecommercial
pollutant (left)
groups andof J.J. Rodrguez.
with UV/TiO Journal of Chemical Technology, 83
2 was observed to increase after an
synthase
major (middle)
concernTiOin2 and its SEM water.
drinking image onOne
the surface
of the (2008)
initial1323-1338.
drop from 200 g mg-1 to 400 g mg-1 and
of graphite rod. [3] A. S. Stasinakis, A mini review, 3(2008) 376-385.
possible adaptations at a water treatment plant remained above 280 g mg-1 thereafter (Figure 1);
[4] Y. J. Xu, Y. Zhuang, X. Fu. J. Phys. Chem. C, 114
The AOPsinclusion
involves capabilitiesofof these materrials
advanced were
oxidation while
(2010) 2669in real water a decreasing exponential
investigated by EPRAt
processes (AOPs). spectroscopy to quantify
the same time, the last the
step function
[5] is observed.
V. K. Gupta, The full
Shilpi Agarwal, study
Tawfik will present
A. Saleh, J.
hydroxyl radical
in drinking generation
water treatmentonisnano-flakes graphite
disinfection, usually results for
Hazardous UV/TiO
Mat., 2, UV/H
185 (2011) 2O2, photo-Fenton and
17-23.
surfaces and its modified
using chlorine surfaces wiht
or chloramine. Thisnano-metal
process is UV/persulfate.
known to yield disinfection by-products (DBPs)
such as trihalometanes (THMs). Therefore, the
application of AOPs to drinking water production 141 1
needs to consider removal of background organic
 O R A L P R E S E N TA T I O N S - 3 rd D A Y

QUANTITATIVE DETERMINATION OF H2S GAS USING KMnO4

Quantitative determination of H2S gas using KMnO4 C3-13
Naeem Shahzad*1, Shahid Iqba1 l 1National University of Sciences and Technology, Pakistan

This study is an effort to suggest a new technique for quantitative analysis of Hydrogen sulfide by
oxidizing it using Potassium Permanganate KMnO4. In this research, very small quantity of H2S gas was
passed through KMnO4 because of the fast reacting nature of KMnO4. This technique can be used in
conjunction with other qualitative analytical techniques to measure H2S gas or to analyze the destruction
rate of this gas. The amount of KMnO4 was kept the same in order to get similar concentrations for the
analysis (0.3 gms/300 ml). The initial absorbance of KMnO4 using UV/Vis Spectrophotometer was taken
as a reference and corresponding readings were taken after fixed time intervals along with the H2S gas
analyzer readings. The procedure was found to be convenient for occasional as well as frequent use.

142
ROOM C - COUPLING AOP WITH OTHER PROCESSES, PILOT-SCALE STUDIES AND FIELD APPLICATIONS

143
SECTION

6
POSTER P R E S E N T AT I O N S

1 st DAY
Poster Session 1....................................................................................................146
Photocatalytic Oxidation..................................................................................146
2 nd DAY
Poster Session 2....................................................................................................172
Fenton And Fenton Like Processes Catalytic Redox Processes Coupling
Aops With Other Processes Pilot-Scale Studies And Field Application
Ozonation.........................................................................................................172
3 rd DAY
Poster Session 3....................................................................................................196
Disinfection Electrochemical Processes Aops For Energy Production
Radiation Processes.........................................................................................196
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

USE OF ZnO AND Nb2O5 IMPREGNATED WITH SILVER OR IRON FOR PHOTOCATALYTIC
Use of ZnO and Nb2O5 impregnated with silver or iron for will be filled
DEGRADATION OF CELLULOSE AND PAPER WASTEWATER in by PP1-1
photocatalytic degradation of cellulose and paper wastewater
EAAOP4
A. M. Ferrari-Lima1,2; R. G. Marques1, V. Slusarski-Santana1, M. L. Gimenes1, N. R. C. Fernandes-Machado1. (1)
Universidade Estadual de Maring, Av. Colombo 5790, 87020-900, Maring, Brasil. (2) Universidade Tecnolgica
Federal do Paran, Rua Marclio Dias, 635, 86812-460. ana_eq@hotmail.com.

The photocatalytic degradation of wastewater from an

integrated pulp and paper industry was investigated under visible
and ultraviolet lights. ZnO and Nb2O5 were impregnated with
Fe2O3 and Ag2O and applied as photocatalyst after calcination at
500 C. Photocatalysts were characterized by textural analysis,
XRD, NH3-TPD and photoacoustic spectroscopy. The
impregnation reduced the bang gap energy and increased specific
surface area. The shorter hal-life time for COD reduction was
found to be 4 h with Fe2O3/ZnO under visible light.

were applied as radiation source during 6 h.

Introduction
The pulp and paper industry is one of the most
important industries in the world [1]. However, this Results
industry presents
NOVEL a wastewater with a high organic
ANATASE/RUTILE/BROOKITE TiO2 NANOCOMPOSITE WITH SUPERIOR
Novel anatase/rutile/brookite TiO2 nanocomposite Thewith superior
photocatalytic degradation willwastewater
of be filled
load and elevated colour
MINERALIZATION POTENTIAL [2,3]. Conventional
FOR PHOTOCATALYTIC DEGRADATION OF WATER in by
mineralization potential for photocatalytic
treatments are effective to reduce Chemical Oxygen degradation
from an of water
integrated pulp and paper industry
EAAOP4
was PP1-2
POLLUTANTS
pollutants investigated under visible and ultraviolet lights.
Demand of wastewater, but even after biological
A. Pintar1, the
treatment, R. Kaplan 1
effluent, B. is
Erjavec 1
highly, G.coloured. GrdadolnikZnO
Drai1, J.Many 1
. (1) and Nb2O
National 5 wereofimpregnated
Institute with Fe2O19,
Chemistry, Hajdrihova 3 and
SI-1001 Ljubljana, Slovenia, albin.pintar@ki.si.
industries are already using techniques of tertiary Ag 2O and applied as photocatalyst after calcination

wastewater treatment, as ultrafiltration. Another at 500C . Photocatalysts were characterized by

alternative that is gaining space on the A novel textural
tertiary anatase/rutile/brookite analysis, TiOXRD, NH3-TPD wasand
2 nanocomposite

treatment field is heterogeneous photocatalysis [4].prepared that photoacoustic

enables efficient spectroscopy.
transformation of The impregnation
emerging water
pollutants to COreduced
2 and H2the O as bang gap
final energy and
products increased specific
of photo-oxidation.
In this way, the present work aimed toSol-gel study procedure
the surface
with aarea. The shorter
subsequent hal-life treatment
hydrothermal time for led COD
photocatalytic degradation of the wastewaterfrom to the formation reduction
of TiOwas found to be which
2 nanomaterial, 4 h with Fe2O3/ZnO
consists of
an integrated pulp and paper industry (43 %),under
anataseafter rutilevisible
(24 %) light.
andInbrookite
XRD analysis
(33 %); theindividual
zincit phase
biological treatment under visible and polymorphs ultraviolet for ZnO and
formed mixed monoclinic structure for
agglomerates. The Nb2OTiO5 were2
radiation. nanocomposite identified
was highly after calcination
active in terms at 500 C/5 h. Ag2O/ZnO
of omineralization,
since after 60 min Fe2O3/ZnOunder
andof irradiation catalysts
UV light showed
almost 60 the % same
of
water dissolvedcrystalline
pollutant phase as bare
bisphenol A ZnO
was (graphical
transformed abstract).
into
Methods CO2 and H2O. Only On the twoother
peakshand,
relatingthetobenchmark
silver were TiO identified
2 P25 in
Degussa catalyst O/ZnO, while
Ag2reached a lower the peaks
extentrelated to iron were not
of mineralization,
The following catalysts were synthesised whichby issoldue identified.
to significantlyAg2O/Nb 2O5expressed
less catalyst presented
resistance the same
to
gel technique: ZnO, Fe2O3/ZnO, Ag 2O/ZnO,
accumulation ofcrystalline
carbonaceous structure
deposits ason thethepure
catalyst O5, and no
Nb2surface.
Nb2O5, Fe2O3/Nb2O5 and Ag2O/Nb2O5. The crystalline phase referred to silver was identified.
catalysts were calcined at 500oC/5 h and Fe2O3/Nb2using O showed to pollutant
be amorphous.
Introduction
characterised by XRD, photoacoustic spectroscopy evaluated a priority bisphenolThis A
structure
(BPA), is
which consistent
is a toxicwith
and the literature
endocrine [5,6] for
disrupting
(PAS),
Titanium 3-TPD (TiO
NHdioxide and2) textural
is the most analysis.
widely used The catalysts in which
photocatalytic reactions compound knownniobium was modified
to interfere with withnormallow
semiconductor material, werewhichcarried
is due out
to awith the
variety metal concentrations (<5% w/w).
hormone functions thus causing a threat to aquatic
pulp
of and paper (PP)
its applications wastewater
in different fieldscollected
[1,2]. It isafter
an
biological treatment. The concentration of catalyst lifeTheas well
bandasgap, humans.
specific Its surface
widespread area (detected
and acidity in
abundant, cheap and non-toxic material, with a landfill leachates in concentrations ranging from
was 1.0
high g/L and thefor
prospective degradation
addressing wasenvironmental
monitored by are shown in table 1.
Chemical ItOxygen Demand (COD) anddifferent
colour non-detectable to 17 mg/l [10]) and harmful nature
concerns. can mainly be found in three makes it an appropriate candidate for tests in
reductions. 125 W ultraviolet and
crystalline forms: anatase, rutile and brookite. visible lights
advanced oxidation processes (AOPs).
Anatase is commonly known as the most active
phase and therefore extensively used in a variety
of photocatalytic applications [3,4]. Its high
146
Experimental 1
activity is directly connected to prolonged lifetime Anatase/rutile/brookite TiO 2 nanocomposite
 P H O T O C A TA L Y T I C OX I D A T I O N

SUNLIGHT PHOTOCATALYTIC PURIFICATION OF WATER WITH NOVEL

Sunlight photocatalytic purification of water with novel will be filled
HETEROSTRUCTURES in by PP1-3
heterostructures
EAAOP4
C. Belver, J. Bedia, M.A. lvarez-Montero, J.J. Rodriguez. Universidad Autonoma de Madrid, Facultad de
Ciencias, Madrid, Spain.

Novel heterostructures based on metal oxide semiconductors

assembled over layered silicates have been prepared by an
original approach based on sol-gel procedures. The samples were
prepared upon exfoliation of a layered clay by the incorporation
of TiO2 and Ce-doped TiO2 precursor. The photocatalytic
performance analyzed by the degradation of phenol in water
under sunlight. Remarkably enhanced activities were observed
depending on the Ce and TiO2 contents. A synergistic effect has
been observed among the textural properties, the amount of
anatase formed and that of Ce doping. With irradiation times of
24 h fairly high mineralization was achieved with almost
complete degradation of phenol and aromatic intermediates and
a decrease of the initial ecotoxicity.

TiO2/clay have been prepared via a modified sol-

Introduction gel route to control the anatase crystallization and
In recent years, semiconductor photocatalysts achieve enhanced efficiency towards the
have gained attention for many applications in photocatalytic purification of water upon sunlight.
environmental remediation [1]. Photocatalysts that In addition, we discuss the effect of the clay and the
SURFACE
active inRECONSTRUCTION
are Surface the visible light region OFcanTITANIA
bewith WITH
veryg-C TiOg-C2 and
N AND Ag FOR EFFICIENT
3 4 how the dopant amounts affect to the
ELECTRONS Reconstruction
MIGRATION of Titania
AND ENHANCED 3 4 and Ag for Efficient
N
VISIBLE LIGHT PHOTOCATALYSIS PP1-4
useful as they efficiently decompose harmful synthesis process and improve the performance of
Electrons Migration and Enhanced Visible Light Photocatalysis
these materials in the purification of water under
organic compounds under indoor or solar light.
ThatK.H. Leong , S.L.efforts
Liu1, M.are
Jang , S. Ibrahim , P. Saravanan . (1)light.
Environmental Engineering Laboratory,
1 1 1 1
is why many currently focused on solar
Department of Civil Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia,
the development of photocatalysts that show high
hon1285@gmail.com. Experimental
efficiencies upon sunlight. In that respect, a variety
In the present work the TiO2 was reconstructed with g-C3N4 and
of strategies have been reported to improve the In this work, we use a commercial organoclay as
Ag to form a ternary (g-C3N4)-Ag/TiO2. The g-C3N4 was
TiO2 efficiency, such as doping, metal starting material (Rockwood, USA). This one was
prepared through a facile pyrolysis of urea. Ag acted as electron-
nanoparticles deposition, surface sensitization or dispersed in alcohol and further treated with
conduction mobiliser in the ternary was synthesised through solar
coupling with an additional phase. Recently, a titanium isopropoxide alcoholic solutions, varying
photodeposition method. The synthesised ternary characteristics
suitable way is the design of visible-light-driven the titanium concentration. The titanium alkoxide
were investigated through various physical and chemical
photocatalysts by multicomponent heterojunction hydrolysis was controlled by the addition of cerium
analyses. The presence of g-C3N4 in the ternary promoted the
between different materials, looking for large aqueous solutions yielding to the creation of a
formation of interface between Ag/TiO2 and g-C3N4 and
surface areas, optimum electronic properties and viscous gel. By this way, we introduced Ce doping
stimulated the electron transfer between them. These electrons
remarkable adsorption capacities [2]. In that sense, varying their concentration up to. 3%. The final
migration acknowledged by the synergic effect prolonged the
recent advances have been also reported in the photocatalysts were obtained after calcination at
lifetime of charge carriers. The g-C3N4 also significantly tuned
application of layered clay-based materials for 550 C, removing the organic matter and achieve
the energy gap of conventional TiO2. The prepared ternary
photocatalytic applications. Its heterojunction with the titania and Ce-doped titania formation. The
exhibited significantly high visible light photocatalytic
semiconductors, including metal oxides, sulfides or physical-chemical properties of these
performance by degrading Amoxicillin (AMX) at highest rate.
silver compounds, yields photocatalysts with heterostructures were studied by several
enhanced efficiency that can be easily recovered characterization techniques (XRD, N2 adsorption-
from the solution.
Background desorption, UV-vis, FE-SEM). The final solids
The hunt for high performance visible light were evaluated efficiency
photodegradation as photocatalysts for TiO
to 1.7 times than the2.
Some investigations suggest that the use of clay photodegradation oftophenol in aqueous solutions.
responsive photocatalyst has becomes a vital in This was attributed the characteristics of g-C3N4
materials into photocatalysts heterojunctions can The experimental
order to sustainably address the burning which stimulatedrunsthewere carried
visible out absorption.
light in a batch
affect the phase of the semiconductor formed or slurry
environmental issues. The hunt resulted an Furtherreactor under simulated
a remarkable increase sunlight of high
of photocatalytic
improve the separation of charges. Herein, we
innovative carbon material; graphitic carbon nitride intensity,
degradation 450inW/mthe2. order
The degradation
of 3.2 times rate was
was
optimized a one-step method for synthesizing novel followed by achieved
UV-visible spectroscopy analyses
(g-C3N4) as a visible light enhancer and narrowing successfully for the ternary. This clearly
heterostructures with photocatalytic applications. HPLC and TOC measurements.
band gap energy. Hence, g-C3N4 emerged as a best established the addition of Ag NPs to the (g-C3N4)-
Photocatalysts based on TiO2/clay and Metal-doped
candidate to reconstruct the well-known TiO2 triggered the visible light absorption through
conventional TiO2 in order to overcome its setback;
poor visible light utilization and high 147 the surface plasmon resonance and simultaneously
extended repulsion of charge carriers. 1
recombination rate of charge carriers.
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

Photocatalytic degradation
PHOTOCATALYTIC of NOx OF
DEGRADATION in aNO
continuous
X bench-scaleBENCH-SCALE REACTOR
IN A CONTINUOUS
USING ACTIVE
reactor TILES,tiles,
using active EXPERIMENTAL
experimental DATA ANDsimulations
data and SIMULATIONS PP1-5
Claudia Bianchia,1, Marta Stucchia,1, Carlo Pirolaa,1, Federico Gallia,1, Stefania Vitalia,1,Valentino Capuccib. (a)
Universit degli studi di Milano, Dip. Chimica - 20133 Milano, Italy. (b) GranitiFiandre SpA, 42014 Castellarano,
Italy, vcapucci@iris-group.it. (1) Consorzio INSTM, Firenze, Italy.

In the present work we present a new kind of gas-flow reactor

able to test photocatalytic building materials in large size,
optimizing the reaction conditions in order to work both with
artificial conditions of irradiation (UV-A lamp) and under the
direct sunlight. In particular, industrial porcelain grs tiles were
tested towards the photodegradation of NOx in air in a
continuous experimental setup, either using UV lamps or using
the sunlight, studying the effect of different concentration of
NOx on the building material performances first, as the effect of
different light sources.

Background artificial conditions of irradiation (UV-A lamp)

Nowadays it is imperative to develop new and under the direct sunlight. In this latter case, the
strategies and new materials to clean the test can predict the real efficiency of the material
environment. Every year laws and regulations when this product will be used to cover a building.
become stricter with the aim to reduce the As testing sample, we chose a photocatalytic
greenhouse gases emissions and improve the porcelain-grs tile by GranitiFiandre SpA,
quality of the air. Among all the pollutants, available in the market, whose photocatalytic
IMPLEMENTATION OF TIO2 OXYGEN ADSORPTION CAPACITIES FOR THE EVALUATION
Implementation
nitrogen oxides (NO ofx),TiO
are2 Oxygen Adsorption
strictly monitored all Capacities
propertiesfor are the
well-known [7]. will be filled
OF
over PHOTOCATALYSTS
Evaluation
the world ofandPhotocatalysts
guidelines ACTIVITY
on the IN POLLUTANTS
Activity
alarm in Pollutants
levels TargetOXIDATION
Oxidation
of the experimentation was to verify in byboth PP1-6
of these molecules in air were published by WHO the reactor performance and the EAAOP4
efficiency of the
M. Krichevskaya
[1]
1
, A. Moiseev
and often recalled
2
in the, D. Klauson 1
, N. Pronina
legislations of the , G. Hauser
1 2
, A.P. Weber
photocatalytic tile, B.toLohrengel
2
reduce ,the
3
J. Deubener
pollution
2
. and
(1) Tallinn Univ. of Technol., Ehitajate tee 5, 19086 Tallinn, Estonia, marina.kritsevskaja@ttu.ee. (2) TU
single Country worldwide. Photocatalysis with maintain the NOx level under 40 g/m3 (value
Clausthal, Adolph-Rmer-Str. 2a, 38678 CLZ. (3) Heilbronn Univ., Max-Planck-Strae 39, 74081 HN, Germany.
titanium dioxide as semiconductor [2,3] seems to requested by WHO for a clean air) [1].
be a very promising technique toOxygen reduce adsorption
the capacities as material characteristics of 19
30
pollutants concentration#5 thanks toindustrial its very and lab-synthesised
Methods titania samples were obtained. The
Adsorbed oxygen, mol g-1

powerful oxidation property. activity of these photocatalysts

Sample preparation and wascharacterization
evaluated by the
25 of the main problems regarding
One mineralisationthe of Industrial
dichloroacetic acid and
porcelain-grs tiles 4-chlorophenol.
are manufactured
construction materials is#4to find a Photocatalysts
serious and could
under be pressure
high characterised
by by the fine
dry-pressing adsorption
processed
20 coefficient, g)-1, specified
reproducible way to test them and confirm theirk, mol O2 (mm
ceramic rawHg materials form proportions
with large the slope of of
15
photo-efficiency. Many #3 reactors with linear isotherms quartz,
different No strict linear and
feldspar, dependence of and
other fluxes k onfinally
specific
fired
configurations have been proposed and published surface area of titania
at high temperatures (12001300C) in aThe
of different origin was observed. kiln.
106], but in all cases, #2 Theby
[4, 5, very smallactivity
sizes ofofthe TiO2 increases
Commercial with the increase in
photoactive the samples
porcelain grs k.tiles
sample5 are tested. The#1ISO reactor requires a
highest activity GranitiFiandre
of pyrogenic TiO S.p.A2, despite their moderate
were subsequently covered k, at
sample of 5x5 cm in size, a dimensioncould so small bein attributed
the surfaceto withtheir specific
a mixture intrinsic
of pure bulk
Anatase-micro-
0
comparison to the real use of the final properties.
material. TiO2 (1077 by Kronos) and a commercial SiO2-
0 200
Moreover, 400conditions
testing 600 800 are often very far based compound. To ensure the requested product
from Absolute pressure,
the reality: too high mm NOx Hg concentrations and stability, at the end of the preparation procedure
levels of UV-A irradiation impossible to obtain on tiles were treated at high temperature (min 680 C)
earth. for 80 min and then brushed to remove the powder
present at the sample surface and not completely
The optimization of photocatalytic reaction
stuck 5(samples name: WGActive). Temperature
parameters
Objectivesresults in the more profound oxidation
was precisely chosen to maintain the anatase form
of organic pollutant;
In the present work however,
we present the adsorption
a new kindofof
of the semiconductor and allow the vitrification of
molecular
gas-flow oxygen
reactoras an acceptor is a determinative
0 2, mol O2 mm Hg -1g -1

able to test photocatalytic 4 surface [8].

the tiles titania with the highest
process
buildingstep. Nevertheless,
materials in largethere is no
size, information
optimizing the
available on the quantification
reaction conditions in order to work of bothoxygen
with non-selective activity
adsorption on catalytic materials. 3

In present study series of pyrogenic and wet-

synthesised titania samples were characterised 1482 1
with respect to their oxygen adsorption capacity,
 P H O T O C A TA L Y T I C OX I D A T I O N

Preparation of TiO2
PREPARATION and
OF TiO 2
graphene
AND film decorated
GRAPHENE TiO2 nano-tube
FILM DECORATED TiO2 NANO-TUBE ARRAY
array photoelectrodeAND
PHOTOELECTRODE and enhanced
ENHANCED visible light LIGHT
VISIBLE photocatalytic
PHOTOCATALYTIC MECHANISM PP1-7
mechanism
Huiling. Liu1, Xiuwen Cheng 1, Yu Tian1, Fuyi Cui1, Jun Nan1, Jie Yao1, Zhiqiang Chen 1. (1) School of Civil and
Environmental Engineering, Harbin Institute of Technology, huanghe road 73, harbin, China, hlliu2003@126.com
A graphene film decorated TiO2 nano-tube array (GF/TiO2 NTA)
photoelectrodes were prepared through anodization, followed by
O2- electrodeposition strategy. Morphologies and structures of the
H+ O2
H 2O 2
e-
e- e- e- resulting GF/TiO2 NTA samples were characterized by scanning
e-
e- electrons microscopy, XRD, XPS and Raman. In addition, the
CB e- hv
OH optical and photoelectrochemical properties were investigated
MB
MB through UVvis and MottSchottky analysis. Furthermore, the
TiO2 OH-+H2O
VB h+ photodecomposition performances were investigated through
CO2+H2O h+

Ti yield of hydroxyl radicals and PC degradation of MB under

CO2+H2O OH
visible light irradiation. PC performance was 65.9% for the
MB
degradation of MB. Moreover, the enhanced visible light PC
mechanism was proposed and confirmed in detail.

Highly ordered TiO2 nano-tubes arrays (TNTAs) both in UV light and visible region, higher
electrode was fabricated through anodization. The transient photoinduced current of 0.107 mA
effects of some experimental parameters
PHOTODEGRADATION OF SPIRODICLOFEN, SPIROMESIFEN on cm 2 and charge carrier concentrationINof
AND SPIROTETRAMAT
Photodegradation
photocatalytic of Spirodiclofen,
(PC) ANDactivity
Spiromesifen
and 0.84 and Spirotetramat
1019 cmAND 3, as inwell as will be filledPC
effective
WATER USING BINARY TERNARY OXIDES OF TITANIUM ZINC in by PP1-8
Water Using Binary(PEC)
photoelectrocatalytic and Ternary activityOxides
were of Titanium
performance andofZinc 65.9% for the degradation of MB.
EAAOP4
investigated in detail. It was found 1 that the Furthermore, contribution of several reactive
I. Garrido , J. Fenoll , P. Flores , P. Helln , N. Vela , S. Navarro .
1 1 1 2 3
optimum preparing conditions were as followed: species to the PC efficiency of GF/TiO2 NTA
(1) IMIDA. C/ Mayor s/n. La Alberca, 30150 Murcia. Spain, isabgmar@gmail.com.
the applied voltage, water content, fluoride
(2) Universidad Catlica de Murcia.Campus de Los Jernimos, photoelectrode
s/n, Guadalupe,was 30107,distinguished.
Murcia, SpainMoreover, the
concentration, anodization
(3) Facultad de Qumica. time de
Universidad and reaction
Murcia. enhanced devisible
Campus Universitario Espinardo. light
30100, PCMurcia.
mechanism
Spain. was
temperature was 20 V, 40 vol%, 0.5 wt%, 2 h and proposed and confirmed in detail.
40 oC, respectively. In addition, the TNTAs The photocatalytic degradation of spirocyclic
H3C O
CH3 O

H3C H2C C C O

electrode exhibited high PC and PEC activities, in tetronic/tetramic Acknowledgements acid derivatives (spirodiclofen,
O
CH3 O C
H2C
O H3C O
H
N

blue (MB) spiromesifen This work and was supported byand

spirotetramat) National
their Natural
main
H3C

e +O O
which 39.1% and 65.7 % of methyl
- -
O
O 2 2
Cl Cl

Science Foundation of China has (50978066, 51178138),

CH3

O + H O OH
metabolites in pure water been studied using
-
could be mineralized, respectively.
Spirodiclofen Spirotetramat 2 2

National
(TiO2 Creative
and ZnO)Research Groups of China
Then, graphene film decorated TiO2 nano-tube binary and ternary (ZnTiO 3 and
CH3 O

H3C C H2C C
O

(51121062) and State Key Laboratory of Urban Water

array (GF/TiO2 NTA) photoelectrodes were Zn2Resources
CH3

TiO4) oxides as photocatalysts under artificial

CH3
O

and Environment (2010DX03).

prepared through anodization, followed by light irradiation. Photocatalytic experiments showed
O

TiO
References
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Spiromesifen

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+
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h + OH OH
photoelectrochemical properties were investigated removal of the studied insecticides.
through UVvisible light diffuse reflection
spectroscopy, photocurrent response and Mott
Schottky
Spiromesifen, analysis.
spirodiclofenFurthermore,
and spirotetramat the standards were purchased from Dr. Ehrenstorfer
photodecomposition
are insecticides derivatives performances
from the tetronicwere and (Augsburg, Germany). Commercial products
investigated
tetramic acidsthrough
and theyyield ofinhibitors
act as hydroxyl ofradicals
acetyl- (Envidor, Oberon and Movento) were supplied
and
CoA PC degradation
carboxylase, of MB under
interfering visible
in lipids light
synthesis. from Fitodolores S.L. (Murcia, Spain). Zinc oxide
irradiation.
They haveIt awasdifferent found that mode GF/TiO2 NTA
of action, (ZnO, 99.99%) and zinc titanium oxide (Zn2TiO4,
photoelectrode
spirotetramat isexhibited
a systemic intense light absorption
compound (it moves 99.9%) were obtained from Alfa Aesar (Karlsruhe,
through the leaf cuticle and is translocated in Germany). Titanium dioxide P25 Degussa (TiO2,
phloem and xylem throughout treated plants),
unlike spiromesifen and spirodiclofen which act as
99.5%) and zinc titanate (ZnTiO3, 99.5%) were
purchased from Nippon Aerosil Co Ltd (Osaka,
1
149
contact pesticides. They are used to control mites, Japon) and Sigma-Aldrich (St. Louis, US),
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

PHOTOCATALYTIC ACTIVITY OF g-C3N4-TiO2 NANOCOMPOSITES FOR NOx REMOVAL

Photocatalytic Activity of g-C3N4/TiO2 Nanocomposites for NOx PP1-9
Removal
I. Papailias1,2, T. Giannakopoulou1, N. Todorova1, D. Demotikali2, C. Trapalis1. (1) NCSR Demokritos - Institute of
Nanoscience and Nanotechnology, Patriarchou Grigoriou & Neapoleos, 15310, Ag. Paraskevi, Greece,
c.trapalis@inn.demokritos.gr. (2) National Technical University of Athens, Department of Chemical Engineering,
15780, Athens, Greece.

g-C3N4/TiO2 nanocomposites were prepared by simple mixing

of melamine and TiO2 in different ratios and pyrolysis at 550
o
C. The g-C3N4/TiO2 samples were characterized and tested for
photocatalytic NOx removal. The results showed that the band
gap of the nanocomposites was tuned between 2.68 - 3.14 eV
depending on the component ratios. The g-C3N4/TiO2 with ratio
1/3 exhibited the best photocatalytic activity especially under
visible light irradiation, which was attributed to the favourable
combination of the two semiconductors.

Introduction. Traditionally, TiO2 is considered photocatalysts, but also a significant decrease of

as one of the most promising photocatalysts NO2 emissions (Figure 1).
because of its good physicochemical properties
[1]. However, because of its large band gap energy
(~3.2 eV) TiO2 mainly exerts photocatalysis under
UV light [2]. Recently, graphitic carbon nitride (g-
C3N4) has emerged as a novel photocatalyst owing
to its easy preparation and visible light compatible
SiO
band2-TiO NANOCOMPOSITE
gap (~2.7 ANDg-C
eV) [3]. Particularly, ITS3NUTILIZATION
4 can IN ECOLOGICAL PHOTOCATALYSIS
SiO 2TiO2 nanocomposite and its utilization in ecological will be filled
PP1-10
form 2 heterojunction with TiO2 resulting in in by
photocatalysis.
decrease of the electron-hole recombination and EAAOP4
enhancement of the photocatalytic
J. Subrt1, T. Szavsk 2
, L. Kiklavov2,activity under 2, J. Jirkovsk3, F. Peterka2, J. Kupk1. (1) Institute of
M. Jakubikov
visible light
Inorganic irradiation
Chemistry AS [4].
CR, 25068 e, Czech Republic, subrt@iic.cas.cz, (2)Technical University of Liberec,
Objectives.
Studentsk 1402/2
This461 17 Liberec
work 1, (3) the
deals with J. Heyrovsky
synthesisInstitute of Physical Chemistry of the ASCR, Dolejkova
2155/3,
and 182 23 Pragueperformance
photocatalytic 8, Czech Republic.
of g-C3N4/TiO2 Figure 1. Photocatalytic efficiency of TiO2 and g-
composites for NOx removal, in connection C3N4/TiO2-1/3 nanocomposite under visible light.
to 2 based
SiO2 TiO nanocomposite paint was developed and its
their electrochemical and optical properties. use for air cleaning as well as for design of self-cleaning
Methods. Different weight ratios Conclusions. Nanocomposite g-C3N4/TiO2
surfaces ofwas successfully tested. The material exhibits also
melamine/TiO2 (3/1, 1/1, 1/3) were dry-mixed visible light active photocatalysts were prepared
strong and
antibacterial effect. The coating is formed by isolated
o
annealed at 550 C in a tube furnace, for 3 hours by a simple one step pyrolysis method. This work
islands of titania photocatalyst surrounded with the SiO2 matrix
under Ar flow, giving the g-C demonstrated the enhanced photocatalytic activity
3N4/TiO
while the 2 SiO2 matrix is keeping units of aggregated TiO2
nanocomposites. The materials were characterized of the prepared nanocomposite materials in
photocatalyst separated and can isolate the photocatalyst from
by XRD, SEM, FT-IR, Raman and UV-vis. comparison to the pure components. The g-
direct The
contact with the substrate on which the material is
NOx removal performance of the materials C N4/TiO2-1/3 nanocomposite was the most
applied.was
The dried3 composite is highly porous, thus allowing to
examined using an ISO standard procedure. successful at NOx removal, while keeping the NO2
gases to penetrate easily to the photocatalyst particles and back.
Results. The XRD analysis revealed The paintthe can emissions very low.
be used in various aspects of environmental
formation of g-C3N4 and the bi-phasial structure of
photocatalysis and, owing to its self-cleaning efficiency, also
Acknowledgements
TiO2. The presence of g-C3N4 in the composites for improvement This of appearance
research of by
is supported various objects2015
the IKYDA andand
was confirmed by the measured FT-IR and Raman without
monuments changing its colour
12chn205 PhotoTiGRA projects. and overall appearance.
spectra. The SEM results depicted layered g-C3N4
and small TiO2 particles, while the morphology of References
the composites was in accordance to the ratios [1] H. Tada, M. Fujishima, H. Kobayashi, Chem. Soc.
of its very efficient photocatalytic function. The
used. Under UV irradiation, pure TiO2 showed Rev., 40 (2011) 4232.
integration
[2] H. Yan, H.of further
Yang, nanostructured
J. Alloys materials
Compd., 509 (2011) L26.
better activity in NO oxidation than the other
Background: In recent years, with
[3] Y.titanium dioxide
Wang,may enhance Angew.
its features
Chem.or
samples. When visible light was there has beenthea
used though, Wang, X.C. M. Antonietti,
tremendous amount of research and development add newEngl.,
Int. Ed. properties to these
51 (2012) 68. products [11].
g-C 3N4/TiO2-1/3 nanocomposite demonstrated by
in the [4] Q. Xiang, J. Yu, M. Jaroniec, J. Phys. Chem. C, 115
far thearea
bestofDe-NOx
photocatalysis,
activity.aThis
process included in
nanocomposite Objectives:
a specialnotclass (2011) 7355. The main objective of the study was
showed onlyofbetter
oxidation techniques
NO removal thandefined as
the other to develop a new type of purely inorganic
Advanced Oxidation Processes (AOPs), all photocatalytic coating, transparent and highly
characterized by the same chemical feature,
production of OH radicals [1]. 150photoactive. The material should be based on
commercially available components. The material
 P H O T O C A TA L Y T I C OX I D A T I O N

DEGRADATION OF EMERGING POLLUTANTS UNDER SOLAR IRRADIATION USING

Degradation of Emerging Pollutants under Solar Irradiation using will be filled
NOVEL TiO2-ZnO/CLAY NANOARCHITECTURES in by PP1-11
novel TiO2-ZnO/Clay nanoarchitectures
EAAOP4
M. Tobajas, C. Belver, J.J. Rodriguez.
Universidad Autnoma de Madrid, Facultad de Ciencias, Seccin de Ingeniera Qumica, C/Francisco Toms y
Valiente 7, 28049 Madrid, Spain, montserrat.tobajas@uam.es

Emerging contaminants, such as pharmaceuticals, are currently

ZnO
under study due to the increasing concern on the risks they pose
TiO2
e- Heterojunction
with an
on humans and the environment. Herein, the solar photocatalytic
technology is used for degradation of a drug model using novel
e- CB
exfoliated
CB

TiO2-ZnO/clay nanoarchitectures. These photocatalysts are

layered clay
VB
VB

h+
h+
prepared by heterojunctions between TiO2-ZnO semiconductors
and an exfoliated layered clay. The main aim is combining the
Photocatalytic
photoefficiency of both semiconductors while assembling on the
degradation of
acetaminophen
surface of an exfoliated clay. Fairly photodegradation rates were
under solar light reached after 600 min upon solar light. The reaction conditions
were optimized to achieve high photoefficiencies.

reaches 70% of conversion after 1 h with the TiO2-

Contamination of water is one of the major 0.5%ZnO/clay, which shows higher photocatalitic
challenges for the preservation and sustainability of activity as compared to TiO2/clay and TiO2-
the environment. The focus for water pollution 0.2%ZnO/clay. The effect of the amount of catalyst
research is extended to a group of unregulated and pollutant on the photocatalytic degradation
pollutants so-called emerging contaminants, such were also tested. When the amount of TiO2-
as pharmaceuticals, AND
SPECTROSCOPIC personal care products and CHARACTERIZATION
PHOTOCATALYTIC 0.5%ZnO/clay is 500 OF mg/l,MODIFIED
the degradation rate
Spectroscopic
surfactants
TITANIUM [1]. and Photocatalytic
Many
DIOXIDE-BASED researches are Characterization
MATERIALS currently FOR WATER of Modified
reaches DECONTAMINATION
90%, which is higher than those PP1-12
Titanium
focusses on theDioxide-based
removal of these Materials
compounds forusing
Water Decontamination
corresponding to 50, 100 and 250 mg/l, with values
different technologies, among them photocatalysis
P. Bro, M. Surwka, M. Buchalska, M. Kobielusz, S. Og, M. near to 60%. W.
Trochowski, Hence,
Macyk,anJagiellonian
amount of University
500 mg/Lin was
appears
Krakw,asFaculty
an optimum alternative.
of Chemistry, This3,technology
Ingardena 30-060 Krakw,considered
Poland, bros@chemia.uj.edu.pl
optimum. Regarding the acetaminophen
usually uses zinc oxide (ZnO) and titanium dioxide concentration, it was found conversion values about
(TiOO2) as photocatalysts.
OH O
However, they show
OH Usinga alow sol-gel90%
technique
using aconcentrations
series of titanium lowerdioxide-based
than 20 mg/l.
photocatalitic activity in treating materials very lowmodified with ions
Increasing and oxides of concentration
the acetaminophen other metals was seems
concentration contaminants and show lower Thetomaterials
synthesized. decrease were
the characterised
electrostatic spectroscopically
interaction of the site
photoefficiency
O under solar
O light. and the photocatalytic
with lower testsaffinity
were forconducted. Two herbicides
aceta molecules, which is
Cl Cl
The objective of this work is to obtain were activechosenfavor for as the adsorption
model water
of contaminants:
aceta molecules onto the
phtocatalysts for the degradation of the widely used 2,4-dichlorophenoxyacetic
surface of the catalyst. The andphotocatalitic
acid (2,4-D) 2,4,5-
pharmaceutical, Clacetaminophen, astrichlorophenoxyacetic
model degradation acidof(2,4,5-T). The dependence
acetaminophen of theby
can be described
emerging Cl pollutant by usingCl photoactivity
solar light. Among the of the materials onreaction.
a pseud-first-order synthesisThe parameters
excellent
alternative (temperature
novel ofphotocatalitic
calcination, typeactivity and concentration
shown ofbydopant) TiO2-
2,4-D pathways 2,4,5-T to prepare
nanoarchitectures, the colloidal route is used was found
in thisand discussed.
0.5%ZnO/clay can be attributed to the higher
work [2]. Thus, novel TiO2/clay, TiO2- content of ZnO. The heterojunction between TiO2-
Titanium dioxide and
0.2%ZnO/clay has beenTiOconsidered
2 -0.5%ZnO/clay as a are only slightly
0.5%ZnO favour active,
the whereas,
separation thoseofcalcined
charges,at
valuable
photocatalystsmaterial
haveforbeendecades
prepared[1]. andThetested research
for the 600C
avoiding (both anatase and rutile
the recombination in most
process cases) are
and enhancing
done in this
degradation period confirms
of acetaminophen its suitability
in aqueous solutions.in usually the most active
the photoefficiency ones.
of these Materials modified
nanoarchitectures.
tinctorial and cosmetic industry, but also in with metal oxides are rather more active than those
The structuraland
photovoltaics characterization
heterogeneous of these materials
photocatalysis Acknowledgements
modified with the corresponding metal salts. These
show the creation of anatase phase with crystal size This work was supported by Spanish MCINN through the
[2] to either synthetize or degrade chemical observations provide useful insights into the
Projects CTM2013-43803-P and CTQ2013-41963-R.
values around
compounds 20 nm in all cases. There is no
[3,4]. designing
C.B. of new
is indebted to semiconductor
the MINECO for photocatalysts.
a Ramon y Cajal
formation of other titania or zinc oxide phases. The postdoctoral contract.
Our studies focus on developing
anatase phase is anchored on the surface of a new titanium
dioxide-based
exfoliated clay.photocatalysts for characterize
degradation by of
o
450 C
These materials References 2,4-D o
600 C
two
BET model
surfaceherbicides:
area values2,4-dichlorophenoxyacetic [1] I. Muoz, M.J. Gmez, A. Molina-Daz, M.A.J.
ogress in herbicide's

close to 180 m2g-1, with

o
900 C
acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid Huijbregts, A.R. Fernndez-Alba, E. Garca-Calvo.
degradation / %

contribution of both micropores and mesopores. 40

(2,4,5-T) (see graphical Chemosfere 74 (2008) 37. [2] C. Belver, J. Bedia, J.J.
The photocatalytic degradation abstract).
of acetaminophen These
Rodriguez, Appl. Catal. B 176 (2015) 278.
compounds are used to destroy weeds in cereal
crops plantations [5]. Good solubility in water
makes them easy in use, but this feature also 151 20 1
generates a risk to aquatic organisms. The problem
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

PRODUCTION AND VISIBLE LIGHT PHOTOCATALYTIC ACTIVITY OF Mn-DOPED ZnO

Production and visible light photocatalytic activity of Mn-doped ZnO will be filled
MICROPARTICLES in by PP1-13
Microparticles
EAAOP4
B.Haspulat1, H. Kam1, H.Memi1 (1) Seluk Universty, Department of Chemical Engineering, Konya, Turkey,
bircanhaspulat@selcuk.edu.tr.

Chemically synthesized in different ratios ZnO and MnO metal

oxides composites were used as photocatalyst for decolorization
of malachite green organic dyes under both UV light and
natural sun light irradations. The chemically synthesized metal
oxide composite photocatalyst were characterized by using
scanning electron microscopy, FT-IR spectra, UV-Vis
spectroscopy measurements. The photocatalytic property of
composite was evaluated by decolorization of malachite green
dyes under both UV light and natural sun light irradations. With
addition of MnO to ZnO, the photodegradation of malachite
green dye increased under natural sun light irradation.

The Graphical Illustration (Figure,

Scheme, etc.) should not exceed
Organic the size
dyesofused
this area.
in the textile industry are oxidant and catalyst. Also, the photocatalytic
one of the worst sources of the environmental properties of MnO metal oxides have great
contaminations due to their non- attention due its semiconductive electronic
biodegradability and high toxicity to aquatic properties [2].
creatures and carcinogenic effects on humans. Different kinds of metal oxide mixtures can be
PHOTOCATALYTIC
InPhotocatalytic
order to decrease DEGRADATION
the damage OF EMERGING
caused used CONTAMINANTS
byContaminants for higher VIA ADVANCED
photocatalytic efficiency under
Degradation of Emerging via Advanced will be filled
TITANIUM
organic dye DIOXIDE
pollution NANOSTRUCTURES
to the environment and daylight [3]. For example, TiO2, ZnO, MnO in have
by PP1-14
Titanium Dioxide Nanostructures
humans, the use of photocatalysts to degrade been used due to their excellent photochemical EAAOP4
1
organic
P. Falaras , M. Arfanis1,in
compounds 1
contaminated
P. Adamou air or 1, M. stability,
, N. G. Moustakas Antoniadou1low
, A.G. cost
Kontosand1
non-toxicity.
. (1) Institute of In the
Nanoscience and Nanotechnology,
water, or to convert them into harmless National Center for Scientific
literature, there are not 153
Research Demokritos, 10 Aghia
a lot workParaskevi,
about the
Attiki, Greece,
chemicals has p.falaras@inn.demokritos.gr
been extensively studied. For this photocatalytic activities of ZnO and MnO.
purpose, metal oxide nanoparticles such as Generally the other authors focus on the
ZnO[1], MnO[2], TiO 2[3], etc were While conventional
studied. wastewater treatment
photodegradation of pollutants methods seem toeither
as catalyst be
ZnO and MnO are both promising materials unable to infully combination
degrade emergingof TiO2contaminants
and ZnO or TiO contributing
2 and MnO.
to
their applications as photocatalyst waterin pollution,
the heterogeneous
In this work, wephotocatalysis can be a suitable
synthesized ZnO/MnO by using
decolorization of organic dyes[1,2]. add-on process chemical for recalcitrant
methods. waterIn treatment.
synthesis This work
procedure,
ZnO is an important IIVI semiconductor, examines the photo-degradation
H2C2O4.2H2O aqueous of two frequently
solution was added detected
to the
which is a promising material for theemerging fabrication contaminants
solution(caffeine and salicylic
containing acid)
Zn(NO using 10m
3)2.6H2O and
of high technology applications such anodized
as light-titanium
MnSO dioxide nanotubes. These nanostructured
4.H2O under stirring. After adjusting the pH
emitting diodes, sensors, photoluminescent materialsandwere characterized using SEM,
value with ammonia to 7,micro-Raman and UVis
the mixture solution
photo-catalysts materials due to its Vis widetechniques.
band Photocatalytic
laying at the experiments
room temperature under UV for irradiation
1 h. The
gap (3.37eV), and excellent electro illustrated and opticalthe significant
precipitatephotocatalytic
is separated efficiency
from theofsolutionthe tested by
properties [1]. ZnO has great research TiO2 nanotubes
and samples and
filtration, highseveral
washed decomposition
times withrates for water
distilled both
application prospects for examined emerging
photocatalytic pollutants.
and absulate Thin then
ethanol, filmsdried
of commercial
in air at 80 C TiOfor
2
degradation of pollutants In addition, ZnO nanoparticles (Evonic P25) were used for comparison.
4 h. The result powders were obtained by thermal
nanomaterials which is known as the decomposition of the precursors at 450 C for 2 h
environment-friendly material also have the in air.
advantages of non-toxic, low cost and chemical The morphology
emerging and spectral
contaminants, analysis were
a combination of
1.Background
stability, becoming the most promising and the MWWTPs with highly efficient microscopy
characterizated by scanning electron advanced
most
Waterwidely
qualitystudied
is underphotocatalytic
threat due to material
organic (SEM), processes
oxidation FTIR spectra (AOPs) can (FT-IR), UVvis
be a promising
after following TiO .
pollutants released into water sources. Such
2 spectroscopy (UVvis) analysis. In
treatment technology. AOPs are able to degrade addition, the
In the enviroment applications,
organic compounds enter the aquatic medium in MnO metal photocatalytical
organic pollutants activities
by forming of the
highly ZnO/MnO
reactive and
oxides different
several are usedways,
widely. Because
with the MnO
two most metal
common composite catalysts
non-selective were Amongst
radical species. characterized
the AOPs, by
oxides posses unique
being them dumped directly in the water orphsysiochemical monitoring
heterogeneous the degradation
photocatalytic of malachite
processes green
use
properties,
indirectly fromthey have been studied
municipal wastewateras adsorbent,
treatment various semi-conductive metal oxides that can
absorb light of appropriate wavelength dictated by
plants (MWWTPs). Whilst household and
industrial wastewater treatment has been 152
the semiconductors band gap (Eg), thus creating 1
implemented progressively across Europe hole/electron charge carriers that can efficiently
 P H O T O C A TA L Y T I C OX I D A T I O N

A SOLAR ANNULAR PHOTOREACTOR PACKED WITH A MONOLITH COVERED WITH AN

A Solar Annular Photoreactor Packed with a Monolith Covered with will be filled
ACTIVE SOL-GEL TiO2 TO PURIFY A GAS STREAM in by PP1-15
an Active Sol-Gel TiO2 to Purify a Gas Stream.
EAAOP4
C. Rodrigues-Silva1,3, R.A.R. Monteiro1, M. Dezotti2, A.M.T. Silva1, V.J.P. Vilar1 (1) Associate Laboratory LSRE-
LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. (2)
Chemical Engineering Program - COPPE, Federal University of Rio de Janeiro, P.O. Box 68 502, 21941-972, Rio
de Janeiro, RJ, Brazil. (3) Institute of Chemistry, University of Campinas, PO Box 6154, 13084-971 Campinas, SP,
Brazil. E-mail: caio.rodrigues@iqm.unicamp.br.

Cellulose acetate monoliths (CAM) were used as support for the

deposition of TiO2 films to fill an annular photoreactor
equipped with a compound parabolic collector. Cellulose
acetate monoliths were coated by dip-coating method using the
prepared TiO2 sol-gel. Using such setup, an efficient single-pass
gas-phase conversion was achieved in the mineralization of n-
decane, a model volatile organic compound. The efficiency of
the photocatalytic oxidation process on n-decane degradation
was evaluated under different operating conditions, such as
fixed bed size packed with CAM, number of TiO2 thin layers on
CAM, feeding concentration, feed flow rate, feed relative
humidity and oxygen, and incident irradiance.

INTRODUCTION
another important feature in gas-phase PCO as it
The concentration of volatile organic directly affects the catalyst activity, homogeneity
compounds (VOCs) indoors has been reported to and adhesion to its surface. The support should be
be up to tenCHARACTERIZATION
SYNTHESIS, times higher than in AND outdoor
PHOTOCATALYTIC ACTIVITY
transparent to UV radiation OF NIOBIUM
allowing willthe photo-
Synthesis, characterization
environments.
OXIDE MATERIALS
High concentrations and photocatalytic
of VOCs activity of Niobium
activation of the whole coating, resistant to in
be filled
photo- PP1-16
-3 by
Oxide materials.
(reaching up to 1720 g m ) are emitted into the oxidation and finally should act as a EAAOP4 pollutant
environment1 during the1,2 process ,1 of wastewater
J. Marugn , L.A. Morais , C. Adn , A.S. Arajo,2, A.P.M.Acatalyst Guedescontact
,2
. promoter.
treatment in sewage treatment plants (STPs),
(1) Department of Chemical and Environmental Technology, ESCET, Universidad Rey Juan Carlos, C/ Tulipn s/n,
mainly as a result of the aeration process and
28933 Mstoles Madrid, Spain, javier.marugan@urjc.es.
In this context, TiO2 thin-films supported on
mechanical
(2) Institut ofagitation,
Chemistry, as Universidade
well as different steps
Federal do in cellulose
Rio Grande do Norte,acetate
Av.monoliths (CAM)Filho,
Senador Salgado werenprepared
3000,
the sludge
Natal, treatment [1], n-decane being detected
RN-Brazil. for n-decane PCO. A lab-scale continuous-flow
-3
up to 400 g m . Its toxicological information is annular photoreactor was employed in photo-
still limited, but it can have adverse effects A on series
oxidation experiments
of mesoporous Nb2in
O5 order to evaluate
photocatalysts wasthe
0.25 a)
human health, such as irritation of the mucous practicable
synthesized using use and procedures
different efficiency and of TiO 2-based
niobium
NaNbO -P123
membranes,Nbmalaise 2 5
and fatigue [1].
3
O -commertial sources.monolithic
All materials catalysts. Aiming a catalyst
were characterized by XRD, efficiency
UV
0.20 NaNbO
vis DRS,enhancement
TEM, SEM, for
FTIRthisand
particular
BET application,
techniques. Thethe
Advanced Nb oxidation processes (AOPs) have
3
O 2 5
effect oxidation
photocatalytic of different of multi-layered
methanol under TiO
UV cellulose
2 and the
HCHO production (mM)

been0.15widelyPhotolysis
studied and applied in the treatment
N-Nb O 2 5

acetate monoliths
of water and air, due to their efficacy to oxidize photochemical propertieson of the the
photocatalytic
samples activitywas
persistent organic compounds up to their total
was assessed.
investigated for increasing For the most efficient
concentration catalysts. n-
of samples,
0.10 decane PCO was evaluated as
Photocatalytic activity of the oxides is not directly a function of feed
mineralization to CO2 and H2O. Among the AOPs, flow rate, n-decane concentration, feed relative
photocatalytic oxidation (PCO) has been reported related to their absorption capacity and may be closely
0.05
in the literature as a promising method for the related humidity
to other and incidentsurface
structural, irradiance.
and morphological
treatment of gas phase organic pollutants. Among parameters.
METHODSThis work studies the methodology to
the 0.00
semiconductors, titanium dioxide synthesized mesoporous Nb2O5 and tries to correlates
(TiO2) has
0 20
been widely used due
40 60
to time
80
its (min)
100 120
superior photocatalytic TiO2 photocatalyst
the physico-chemical propertieswas withprepared by solgel
the photocatalytic
Irradiation
activity, chemical stability, low environmental activity method
and the using
light tetra-n-butyl
absorption titanium
of as
different precursor.
Nb2O5
impact and low cost [1-4]. The
materials. detailed procedure was adapted from Sun et
al. (2012) as follows: 20 mL Ti(OC4H9)4 (97%,
The application of PCO for VOCs Aldrich) was dissolved in 80 mL absolute ethanol
mineralization is challenging and depends on and the obtained solution was added drop-wise
various factors such as reactor design, flow rate, Thethe
into chemical
mixturesynthesis
solutionofcontaining
the photocatalysts
80 mL
Many works have reported the use of advanced
humidity, pollutantforconcentration
oxidation processes the treatment and catalyst
of hazardous ethanol, 6 mL distilled water and 8 mLparticles
based upon nanosized niobium oxide has
acetic acid
used. The selection of the support material is been carried
under vigorous out by means
stirring. The of fourtransparent
resulting different
organic and inorganic compounds present in methodologies. Figure 1 shows the steps followed
aqueous media. Between them the heterogeneous to obtain the four niobium oxides materials.
photocatalysis couples low-energy ultraviolet light
with semiconductors to form high oxidant species
153 1
as hydroxyl radical (OH). TiO2 has been
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

MODIFIED GYPSUM PLASTERS FOR PHOTOCATALYTIC DEGRADATION OF will be filled

Modified Gypsum Plasters for Photocatalytic Degradation of
ACETALDEHYDE in by PP1-17
Acetaldehyde
EAAOP4
M. Janus1,2, K. Zajc1, J. Zatorska1 , E. Kusiak-Nejman1, A. Czyewski1, A.W. Morawski1. (1) Institute of Inorganic
Technology and Environment Engineering, West Pomeranian University of Technology, Szczecin, Puaskiego 10,
70-322 Szczecin, Poland, (2) Department of Sanitary Engineering, West Pomeranian University of Technology,
Szczecin, Al. Piastw 50, 70-310 Szczecin, Poland, mjanus@zut.edu.pl
100
Dark Light
Amount of contaminant [%]

90 irradiation
80 The self-cleaning properties of gypsum plasters, containing co
70 modified TiO2/N, C photocatalysts were determined through the
60
degradation of gaseous acetaldehyde under UV-vis irradiation. The
50
40
impact of treatment temperature, structural properties as well as
30 non-metals presence in the TiO2/N,C additives on the self-cleaning
20 abilities of gypsum plasters was discussed.
10
0
0 30 60 90 120 150
time [min]
The photodecomposition of acetaldehyde
for gyp+TiO2/N,C-100 sample

Preparation of TiO2/N,C photocatalysts

Introduction
15 grams of starting TiO2 (dried slurry at 90
A development of photooxidation processes C, rinsed with aqueous solution and washed with
based on titanium dioxide (TiO2) has been applied distilled water to 6.80 pH) was placed in a central
in paints, textiles and others [1, 2] as
THERMAL AND PHOTOCATALYTIC part
OFof tubular furnance and heated up to 100, 300
photocatalytic
Thermal andactive Photocatalytic LatelyREACTION
materials. Reaction great
of NO with
NO
Ethanol
or 600
WITH ETHANOL
C, maintaining constant flowwill of be filled
inert gas.
attention has been given to the studies of building Ultimately, when the temperature reached desired in by PP1-18
products revealing self-cleaning properties and point, the inert gas was replaced with EAAOP4
gaseous
capability to 1improve
F. Solymosi indoor
, Gy. Halalsi1
or outdoor
, T. Bnsgi 1
. (1) air quality Reaction
MTA-SZTE ammonia, bubbled trough DreschelGroup,
Kinetics and Surface Chemistry Research bottle,
[3]. Especially
Rerrich Bla tr acetaldehyde
1, 6720 Szeged,is one offsolym@chem.u-szeged.hu
Hungary, the main containing 50 mL of n-hexane. The final step of
indoor air pollutants releasing by synthetic the photocatalyst preparation process was
materials or domestic chemistry [4]. maintained for 1.5 hours.
Little attention is given to the Au/TiO 2 catalyses effectively the thermal and photo-induced (see
popular
building materials such as gypsum,figure) whichreduction
is
Preparation
of NO with 2H5OH. By2 plasters
of theCgypsum/TiO means of IR
spectroscopy
environmentally friendly and fireproof material. two absorption
Raw gypsum bands due to isocyanate
(supplied by Dolina Nidy (NCO)
Sp. z
-1
species at 2210 and 2180 cm have been detected. Incorporation
o.o.) and the respective TiO2 photocatalyst were of
The objective of the present research N into TiOto
was 2 enhanced the reduction of NO, which occurred
mechanically mixed at weight ratio - 10 wt %. The even in
investigate the photocatalytic activityvisible of gypsum
light. As the work function of TiO is 4.6 eV
homogenous powders were blended with water
2 is less that that
plasters loaded with nitrogen and of carbon
Au (5.31co- eV),(water
an electron transfer from
to gypsum ratio TiO 2 to Au 0.80).
equalled particlesThe
is
modified TiO2 in the presence of UV-vis light. which isobtained
assumed, enhanced by illumination.
pastes were poured into silicone moulds
Materials (20 x 20 x 6 mm) and dried at 40 C for 72 hours.
The commercial titanium dioxide (Grupa Determination of the gypsum plasters
Azoty Zakady Chemiczne Police S.A., Poland) photocatalytic activity
used as a crude material, was modified with The photocatalytic activity of the obtained
nitrogen and carbon. The source of nitrogen and gypsum plasters were evaluated by the degradation
carbon in the photocatalysts was ammonia gas and of gaseous acetaldehyde (concentration 850 ppm).
n-hexane, respectively. Additionally, commercial consisting
Figure of a quartz
1 shows tube of
scheme (8 the
mm id) connected
photocatalytic
titania P25 (Evonik, Germany) and unmodified
1. Introduction to a capillary tube. The flow rate was
reactor. Two gypsum plasters were situated 40 ml/min.
in the
TiO2 (denoted as starting TiO2) were used as The carrier
central gasreactor
part of was Ar. The volume
(reactor reaction250 products
mL).
reference materials. The additive of the selected were analyzed with bya 4 UV-vis
HP 4890 gas
The increased use ofmatrix
oxygenated Reactor was surrounded lamps (22
photocatalysts to gypsum amountedorganic
to 10 chromatograph
W, equipped
Philips) and placedwith PORAPAQ
inside Q+S
thermostatic
compounds,
wt %. particularly ethanol, as fuel or Al 2 Odegradation
and 30-m
chamber. Thelong
processHP-PLOT
of acetaldehyde 3 column.
additives for automotive vehicles initiated a great Photocatalytic
deal of study of the reaction between NO and was carried outreaction
at 20 was
C. Afollowed
certain inamount
the same
of
way as described in our previous paper [3]. We
ethanol. It was found that ethanol is very effective used a 15 W germicide lamp (type GCL
for the catalytic destruction of NOx over Ag
catalysts) [1]. The primary subject of the present
154
307T5L/CELL, Lighttech Ltd., Hungary), which 1
emits predominantly in the wavelength range of
work is to study the thermal and photocatalytic
 P H O T O C A TA L Y T I C OX I D A T I O N

EFFECT OF LEDS DISTRIBUTION IN THE PHOTOCATALYTIC REACTOR DURING willTHE

Effect of LEDs distribution in the photocatalytic reactor during the be filled
TEREPHTHALIC ACID OZONATION WITH VxOy/ZnO in by PP1-19
terephthalic acid ozonation with VxOy/ZnO
EAAOP4
I. Fuentes1, J.L. Rodrguez1, H. Tiznado2, J.M. Romo-Herrera 2, T. Poznyak1, J.I. Chairez3. (1)
IPN (SEPI-ESIQIE), U.P.A.L.M., Mexico city, Mexico, ilianafuentes_84@yahoo.com.mx.(2) UNAM-CNyN, Km. 107 Carretera
Tijuana a Ensenada, Baja California, Mexico (3) IPN (UPIBI), Av. Acueducto S/N., Mexico city, Mexico

Photocatalytic ozonation process has the advantage to treat toxic

and recalcitrant pollutants. Furthermore, the irradiation sources
with uniform
(2) Instituto Politcnico Nacional (UPIBI-IPN), intensity
Av. Acueducto S/N.,and narrow
Mexico, emission
Mexico city spectrum are
required in photocatalytic processes. Therefore, two LEDs
distribution in presence of ZnO impregnated with vanadium was
investigated to eliminate a model compound (terephthalic acid).
The results exhibit that vanadium increased the absorption of
visible-light. Meanwhile, XPS spectra indicate that VxOy/ZnO
has good chemical stability. Also, TEM confirms the presence of
VxOy/ZnO as thin flakes mixed with ZnO crystals.

1. Introduction LEDs irradiation was performed by two ways: one

was using a glass body located at the centre of
Photocatalytic ozonation is part of the advanced reactor to provide central emission (LEDsc), and the
oxidation processes that have gained greater other was placing the LEDs in the outer walls of
attention in recent years [1]. The combination of reactor (LEDsp). Initial ozone concentration was 10
ozone and photocatalysis offer the advantage to mg L-1 and the gas flow was 0.5 L min-1. The
treat recalcitrant and toxic pollutants [2]. Two of the catalyst concentration was 0.1 g L-1. All the
most attractive semiconductors to BISPHENOL
use in experiments were carried out at the initial pH
PHOTOCATALYTIC REMOVAL OF A WITH A MAGNETICALLY SEPARABLE
Photocatalytic
photocatalytic Removal
processes are TiOof Bisphenol
2 and A with solution
ZnO [3] and, a Magnetically
(pH 4.0). Separable will be filled
TiO NANOCOMPOSITE
2.3 Ozone generation and ozone consumption in by PP1-20
TiO2 its
2
although Nanocomposite.
main activity is seen in the UV region,
Ozone was generated using dry oxygenEAAOP4
and a
its application to visible-light is feasible. Several
S. Dominguez1, M.J. Rivero1, I. Ortiz1 (1) Department of corona
Chemical discharge
and Biomoleculartype Engineering,
generator University
(HTU500G, of
modification methods have been studied to achieve
Cantabria, ETSIIT, Av. Los Castros, s/n, 39005 Santander, Spain. dominguezs@unican.es
a wider band gap [4]. Moreover, the photocatalytic AZCO INDUSTRIES LIMITED Canada). The
processes require irradiation sources of more ozone concentration in gas phase was control with
In order anto ozone
facilitateanalyser
the catalystBMT recovery
964 BT after(BMTthe
uniform intensity and narrow emission spectrum bisphenol A (BPA) photocatalytic degradation, a magnetic
[5]. In this respect, LEDs have demonstrated Messtechnik, Berlin). The dissolved ozone in water
layer by layer
wascomposite
determined of by magnetite (Fe3OOzone
a Dissolved 4), silica (SiO2)
Analyser
comparable results to those obtained with
and titanium dioxide
(DOA, (TiO2Russia).
LEPSE, ) was successfully synthetized. It
fluorescent lamps [6], yet with greater operational
was characterized by Fourier
2.4 Analytic methods transform infrared (FT-IR),
advantages. For these reasons, the aim of thisdynamic work light
is to study the modification of ZnO with vanadium TA decompositionUV-vis
scattering and diffuse reflectance
was followed by HPLC
spectroscopy (UV-vis using
technique DRS).a The photocatalytic
Perkin-Elmer Flexaractivity
coupledof
to make it active in the visible region and also,
the synthetized catalyst was tested under light
with PDA detector. A Prevail Organic Acid 5m irradiation.
investigate the LEDs distribution effect (central and
After 240 column Fe3O4@SiO
min the(150mm x 4.6mm) 2@TiO2 achieved a BPA
was used with a mobile
external) over the removal of a model compound
removal andphase
mineralization
of 25mM KH2PO4and
of 62 % and25acetonitrile
% respectively.(80:20)
(terephthalic acid) in photocatalytic ozonation
process. adjusted atmethod
attractive 2.3 pH for H3PO
withthe 4.The flow was
photocatalysts set[6,
reuse to
Introduction 0.6 ml min-1 and the TA degradation was followed
7].
2. Materials and methods at 190 nm while the final products were detected at
Nowadays
2.1 Catalystthe presence and persistence in the
preparation this work a Fe3O4@SiO2@TiO2 photocatalyst
In nm.
environment of some contaminants of emerging 210
ZnO powder and ammonium metavanadate were was
2.5 synthesized
Catalyst and characterized.
characterization Its
concern (CECs),
purchased such as pharmaceuticals
from Sigma-Aldrich and used without and photocatalytic activity in BPA mineralization
pesticides, is a subject The UVVIS diffuse reflectance spectra were
further treatment. The of public was
catalyst interest. Due by
prepared to under
recordedlight
on an wasUV-VISevaluated
PerkinandElmer compared
Lambda to9
the low removal efficiency of conventional
impregnation method as previously reported [7]. commercial TiO .
treatments, these compounds are commonly found with an integration sphere. Specic surface area
2
The resulting material was designed VxOy/ZnO. was determined from the nitrogen adsorption
in2.2
thePhotocatalytic
effluents of municipal wastewater
ozonation procedure treatment
plants (WWTPs) isotherms at -196 measured in a Micromeritics.
The TA solutionor(30mg
in lakes and ozonated
L-1) was rivers, which
in a Materials
XPS andwere
spectra methods acquired with an X-ray
presents a risk for human health and environment
double-vessel Pyrex semi-batch reactor (2.0 L) at
[1]. InThe particular, photoelectron spectroscopy sysem (Riber LDM-
25C. mixture those suspectedwas
ozone/oxygen of altering the
introduced Photocatalyst synthesis
32), which has an analysis chamber equipped with
endocrine system of living organisms,
into the reactor by four ceramic porous filters. the
endocrine disrupting compounds (EDCs), have 50 mL of an 0.7 M ammonium hydroxide
solution (NH4OH, Panreac) were introduced in a 1
drawn increasing attention over the last decades
[1, 2]. Bisphenol A (BPA) is a representative
155
L round bottom flask reactor. A solution of 0.8 M 1
EDC widely used in the plastic industry. ferric chloride hexahydrate (FeCl 3 .6H 2 O, Sigma-
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

SONOPHOTOCATALYTIC DEGRADATION OF PARACETAMOL USING Pt-TiO2 NANO-

Sonophotocatalytic degradation of paracetamol using Pt-TiO2
COMPOSITE
will be filled
PP1-21
in by
nanocomposite
EAAOP4
A. Ziylan-Yavas1,Basak Savun Hekimoglu1, N.H. Ince1*
1
Bogazici University, Institute of Environmental Sciences, 34342, Istanbul, Turkey, asu.ziylan@boun.edu.tr

ultrasound UV The presence of pharmaceutical residues in fresh water bodies is

an emerging issue due to their undesirable effects on aquatic
organisms. This study aimed to investigate elimination and
overall degradation of a common anti-inflammatory
Pt-TiO2 pharmaceutical-paracetamol in water by catalytic oxidation
using both high-frequency ultrasound and UV-irradiation in the
presence of Pt-TiO2. It was found that a significant
improvement on the catalytic activity of Pt-TiO2 nanocomposite
was achieved by hybrid process (sono-photocatalysis) rather
PCT
than photolysis and sonolysis which could be attributed to the
60 min
enchancement of the rate of surface excitation, reduction of
no PCT
30 % mineralization
surface corrosion and increase in the rate of mass mass transfer
to the solid surfaces.

In recent years, pharmaceuticals have emerged as This study aims to investigate the degradation of
significant pollutants of aquatic environments. PCT by sonocatalysis and sono-photocatalysis
Sewage treatment plants (STPs) play an important using lab-made nanocomposites of TiO2 supported
role in removing pharmaceuticals from influent by platinum. The performance of applied
waters, however conventional technologies seem processes was evaluated by monitoring parent
to be inefficient in complete removal of these compound elimination, carbon mineralization and
EFFECT
compounds OF Ag[1,2]. ON THEParacetamol
PHOTOCATALYTIC (PCT) ACTIVITYhydrogenOF ZnO SEMICONDUCTORS
peroxide formation. PCT sorption on
Effect of Ag
ASSESSED
[acetaminophen, BYon the
PHENOL Photocatalytic
CONVERSION
para-acetylaminophenol] Activity is of ZnO
IN AQUEOUS Semiconductors
catalystSOLUTIONS
and potential metal leaching into aqueous PP1-22
Assessed
widely used by as Phenol
an analgesicConversion in Aqueous
and antipyretic drug Solutions
solution during sonication were also tested.
allJ.L.over
Fariathe
1
world.
, M.J. SampaioTo1, M.J.Lima
avoid accumulation
1
, D.L. Baptista2of , A.M.T. Silva1, C.G. Silva1. (1) LCM Laboratory of
paracetamol
Catalysis andin the aquatic
Materials environment,
Associate Laboratoryseveral
LSRE LCM, Materials
Faculdadeand Methods Universidade do Porto,
de Engenharia,
Rua Dr. Roberto
research groups Frias s/n, 4200-465
are utilizing Porto, Portugal,
advanced oxidationjlfaria@fe.up.pt. (2) Instituto de Fsica, Universidade
Federal do Rio Grande where
do Sul, Porto Alegre, 91501-970, Paracetamol sulfate potassium salt was purchased
processes (AOPs), a highly reactive Brazil.
from Sigma and a 500 mg/L of PCT stock solution
intermediate like HO is generated, to achieve the
was prepared. Pt-TiO2 nanocomposite was
destruction of this compound in water [36]. Metal supportedsynthesized
semiconductor photocatalysts were synthesized
sonolytically using H2PtCl2 and
by depositing silver powdered TiO2 (Degusa P-25) in aat.%)
particles at different loads (0.25-1 over
multi-wave
One of the important AOPs is photocatalytic ZnO materials by a liquid bath
impregnation
ultrasonic emitting method.
at 200 kHz The(Kaijo,
efficiency
4021,
oxidation of organic pollutants by the of use
the of a
materials is assessed
Japan). by the kinetics
The procedure comprisedfor heterogeneous
of the following
semiconductor catalyst. Upon photolysis with UV of phenol and some derivatives using simulated
photocatalysis steps: i) mixing of 1 mM of metal salt with 0.4
light, catalyst undergoes a surface solar reactionlightin irradiation. The best activity was obtained with
mM PEG-MS (polyethylene-glycol monostearate)
which electrons move from the valence0.25 bandat.%
to theAg loaded on ZnO prepared by thermal decomposition
+ in 60 mL of ultrapure water followed by purging
conduction band (e ) leaving positiveofholes zinc (h )
acetate achieving a mineralization
of the solutions with Ar forof1058min, % ii)
in 60 min.
sonication
behind [7]. Photocatalytic activity of TiO 2 can also
Selective trapping of photogenerated
of noble metal/PEG-MScharge solutioncarriers
for 60 minon under
the
be enhanced by irradiating a solution surface withof the Ar photocatalyst,
atmosphere; iii) willaddition
demonstrate that phenol
of 15 mmoL TiO2 to
ultrasound which generates i) very-short oxidationlived
proceedseachbysolution
direct electron
followed transfer to the valence
by sonication againband
for 30
local hot spots generated by collapseof ofthe
acoustic
excited semiconductor photocatalyst.
min during air bubbling; iv) separation of the
cavity bubbles, ii) continuous mixing and iii) a nanocomposites via filtration through 0.2 m
light emission of a wide wavelength range [8]. Milipore when
membrane-a drawback (OmniPore) followed
Water the
Besides, quality
use ofand availability
noble metals such hasas become
Pt, Pd anda represents considering the use byof
collective society concern, leading to a growing washing
direct withirradiation.
solar pure water and drying
Several studies at report
constant
an
Au has lately emerged as a promising option for o
temperature (60inC) for
conscientiousness
immobilizing on TiO on owing
the issues related
to the high with
Schottky improvement the12 performance
h. of these
2
treatment
barriers of and
thesereuse
metalsofthatthisinhibit
natural resource of
combination of semiconductors by loading them with noble metals
finite quantity After silver,
each sampling,
gold and samplesplatinum),were that filtered
e-/h+ pairs by and
actingincreasing limited
as e- traps or byaccess.
promoting (e.g.,
through a 0.45 m membrane filter
act as
followed by
The intensification
interfacial charge transferof industrial
processesand agricultural
[6,9,10]. electron sinks, trapping the photoexcited electrons,
activities has led to the contamination of PCTextend
and contenttheandabsorption
carbon mineralization
spectrum over analysis by
the low
groundwater by fertilizers and other chemicals. using HPLC
energy (visible)andregionTOCof analyzer. Hydrogen
the electromagnetic
Phenol and its derivatives can be found in wide spectrum due to the occurrence of surface
industrial effluents (e.g., olive oil mills,
petrochemical, pulp and paper industries) and are
156 plasmons, which contribute to increase the yield
and lifetime of the charge separation state [2, 3].
1
known as toxic and highly stable organic
 P H O T O C A TA L Y T I C OX I D A T I O N

NOVEL PHOTO-EFFICIENT ANISOTROPICALLY FUNCTIONALIZED PHOTOCATALYSTS

Novel Photo-efficient Anisotropically Functionalized Photocatalysts
will be filled
PP1-23
in by
EAAOP4
Sofia Karapati1, Tatiana Giannakopoulou1, Nadia Todorova1, Nikos Boukos1, Dimitra Dimotikali2, Christos
Trapalis1*. (1) Institute of Nanoscience & Nanotechnology, NCSR Demokritos, 153 43, Agia Paraskevi Attikis,
Greece, *c.trapalis@inn.demokritos.gr. (2) National Technical University of Athens, Department of Chemical
Engineering, 157 80, Athens, Greece .

Novel anisotropically functionalized TiO2 photocatalysts were

prepared by a simple chemical route. Pickering emulsions
were used. TiO2 nanoparticles were functionalized with
hydrophobic as well as hydrophilic modifiers. The synergistic
effect of the surfactants was examined through amphiphilic
TiO2 treatment with combination of a hydrophilic polymer
(polyethylene glycol)/hydrophobic (oleylamine) surfactant.
The modified photocatalysts were characterized and their
photocatalytic activity was determined. The anisotropically
functionalized photocatalysts applied in photoactive cements
shown superior activity in NO oxidation and NOx removal.

recorded up to 500 C. TEM micrographs revealed

Janus nanoparticles with anisotropic properties the formation of an amorphous Angstrom ()
has attracted the attention of scientific community scaled monolayer and a thick layer 1-2 nm,
since they enable the synthesis of advanced surrounding the majority of hydrophobic and
engineering materials. They consist of particles the amphiphilic TiO2 nanocrystals correspondingly.
two sides of which
MODIFICATION chemically
OF GAS SENSING differ as for
PROPERTIES OF TiO2 NANOMATERIALS BY
Modification
polarity, charge,AND
ALIOVALENT
of Gas
etc. and Sensing Properties
are appliedCATIONS
ISOVALENT
of
in scientific TiO 2 Nanomaterials
Excellent resultsby
will be filled
concerning photonic efficiency PP1-24
in by
Aliovalent and Isovalent Cations
fields such as catalysis, tissue engineering, were recorded also for the cementitious materials
EAAOP4
emulsions stabilization
B. Lyson - Sypien 1 and2,photonic
, A. Kusior M. Radecka crystals.
2 with hydrophobically
, M. Rekas2, J. ukrowski 3
, M. Gajewska3, K. modified
MichalowTiO 2 nanoparticles
Mauke 4,5
,
T. The
Graule 4
, K. Zakrzewska 1
. (1) AGH University of Science andcompared
Technology, toFaculty
unmodified
of photocatalyst.
Computer Science, The best
aim of this study is the synthesis of novel photocatalytic behavior was ofobserved in case of
Electronics and Telecommunications, Krakow, Poland, lyson@agh.edu.pl. (2) AGH University Science and
photoactive cementitious materials containing low
Technology Faculty of Materials Science and Ceramics, Krakow, Poland.containing
cements (3) AGH University of Science
amphiphilic TiOand
2. This was
concentrations
Technology, Academic of modified
Center forTiO 2 (2.5%,
Materials and1% and
Nanotechnology, Krakow,toPoland.
attributed (4) EMPA,effect
the synergistic Swiss of
Federal
hydrophobic /
0.5%) in order to be used as catalysts for oxidation
Laboratories for Materials Testing and Research, Laboratory for High Performance
hydrophilic Ceramics, Duebendorf,
functionalization of nanoparticles: the
of toxic air(5)pollutants.
Switzerland. Paul Scherrer This would
Institut, 5232beVilligen
achieved PSI, Switzerland.
attached hydrophobic groups facilitate the
through the synthesis of scalable anisotropic accumulation of TiO2 at the cement surface and its
nanoparticles. Modified nanoparticles should not
perform neither superhydrophilicTheproperties aim of this research wastotoirradiation
exposure and air pollutants,
examine modification while the
of hydrogen
sensing properties attached
of TiO 2
hydrophilic
based OH
nanomaterialsgroups
by of
twopolyethylene
kinds of
because they will sediment in cement matrix glycol enhance the De-NOx ability.
leading to inhibition of air pollutants oxidation cations: aliovalent Cr (+3) and isovalent Sn (+4). Nanopowders of
nor superhydrophobic since they will pure escape TiO to2,the
TiO2: 5 at.% Cr and TiO2 + 10% Sn were obtained
environment. Thus, in this study a balance using of Flame
theseSprayAcknowledgements
Synthesis, FSS. The influence of anatase and
properties was investigated. rutile predominating Thepolymorphic
financial support formbyon thegas
GSRTsensing behaviour
projects GE1813 -
of modified TiO2PolyGRAPH nanopowders and was observed.
12CHN205 TiO2: 5 at.%
- PhotoTiGRA Cr
is highly
For the synthesis, Pickering emulsions exhibits p type
were used. conductivity. The gas sensor response to
appreciated.
Hydrophobic and hydrophilic TiO2 hydrogen modification is improved for nanosensors that exhibit rutile
with various concentrations of polymorphic oleylamineform.
References
(C18H37N) and polyethylene glycol
Figure 1. TEM
(H(CH2CH2)nOH) 2were image of TiO 2 investigated. The [1] N. Zahn and G. Kickelbrick, Colloids Surf. A:
(SSA
synergistic = 62.7ofmthe
effect /g) surfactants was examined Physicochem. Eng. Aspects 461 (2014) 142-144.
through amphiphilic TiO2 treatment. [2] A. Perro, N.P. Pardhy, B.M. Budhlall, Langmuir 26
(2010) 13130.
The modified TiO2 nanoparticles showed [3] Y. Wang, C. Zhang, C. Tang, J. Li, K. Shen, J. Liu,
improved In Qu,
X. ourJ.previous
Li, Q. Wangwork
and we focused
Z. Yang, on modelling
Macromolecules 44
Nowadays, dispersion
driven by in chloroformlevel
an increasing solvent
of hydrogen
(2011) 3787sensing
3794. behaviour of pure TiO2
compared
pollution to the
created by non-treated. Weight
our civilization peopleloss and
search
combustion nanopowders
[4] A. Bachinger,[3].S.The aim and
Ivanovici of this research J.is to
G. Kickelbick,
for new energyofsources
both and
organic
try tocompounds were
prevent further describe
Nanosci.the mechanism
Nanotechnol. 11 of the interaction
(2011) 8599. between
degradation of the environment. The approach to hydrogen and TiO2 based nanopowders modified
this problem reveals in developing modern
environmental sensors especially for toxic,
157
by aliovalent Cr and isovalent Sn cations. Having1
in mind that TiO exhibits two main polymorphic
2
explosive and harmful gases that inform us about
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

Photocatalytic oxidation
PHOTOCATALYTIC of As(III)
OXIDATION in aqueous
OF AS(III) solution with
IN AQUEOUS TiO2 WITH TiO2will
SOLUTION be filled
OBTAINED
in by
obtained
BY by a modified
A MODIFIED SOLGEL solgel
METHODmethod PP1-25
EAAOP4
M.J. Lpez-Muoz, L. Cerro, J.M. Raez, R. Snchez, N. Milln, Environmental and Chemical Engineering Group,
Universidad Rey Juan Carlos, C/ Tulipn s/n, Mstoles, Madrid, Spain, mariajose.lopez@urjc.es.

High active TiO2 photocatalysts were synthesized through

a solgel method in which the hydrolysis of Ti(IV) n-
butoxide was carried out by water released in the
esterification reaction between a carboxylic acid and
ethanol in the presence of an inorganic acid.
The influence of several parameters of synthesis (nature of
inorganic acid, temperature of synthesis, calcination and
hydrothermal processing) on crystalline and
morphological properties of materials obtained were
investigated. The synthesis procedure allowed the control
of hydrolysis and condensation of the precursor leading to
well-crystallized materials. The photocatalytic activity of
the samples was evaluated by their performance for the
oxidation of As(III) to As(V) in aqueous solution.

homogeneous titanium dioxide network. This can

Arsenic pollution of water has become in the last have a detrimental influence on the morphological
years a major environmental
PHOTOCATALYTIC concern in OF
DEGRADATION manyORGANIC and crystalline properties of the resulting
DYE (METHYLENEBLUE) OVER materials
countries
SULFUR worldwide.
Photocatalytic The occurrence
DOPEDdegradation
TiO PREPARED ofoforganic
As
BYinSOL-GEL
water
dye (methyleneblue)
and
PROCESS over sulfur
as a consequence, on their photocatalytic PP1-26
is due
doped to both
TiO2natural
prepared processes
2
that mobilize
by sol-gel processAs performance.
from soils and1 sediments and 2 to anthropogenic
Jung-Hoon Y , Sang-Hun Nam , Ki-Hwan Hwang1, Hyeon Jin Seo1, Jin-Hyo Boo1. (1) Department of Chemistry,
activities. In aqueous systems As exists
Sungkyunkwan University, Suwon
primarily as To avoid this inconvenience different approaches
IIIO440-746, South Korea, thank42@hanmail.net. (2) Institute of Basic Science,
oxyanions of As(III) (H 3x As 3
x; arsenite)
Sungkyunkwan University, Suwon, 440-746, South Korea. and have been investigated, among them carrying out
As(V) (H3xAsVO4x; arsenate). Compared with the synthesis in mixed organic solvents composed
As(V), As(III) is more toxic and has higher In mobility of acetic
this study, sulfur dopedacidTiOand isa prepared
low molecular weight sol-gel
by a simple alcohol
in the environment. In addition, the removal of titanium
in the presence ofoxide
sulfuric acid asO)catalyst [4-6]. In
2
process with hydroxide (Ti(OH) with different
arsenite species is more difficult thanthiourea arsenates
2
as 1, 2these
and conditions,
3 wt%. Theitphotocatalytic
has been reported the control
activity of TiOof
therefore a previous oxidation of As(III)powders to As(V)was evaluated
the hydrolysis rate which is ascribed to the gradual
2
using UV-vis absorption spectroscopy
is usually required to achieve the removalthrough of arsenic releaseof ofmethyleneblue
degradation water molecules solution.in Photocatalytic
situ by the
from polluted water. esterification reaction between
activity of sample for degradation of methylene blue showed acetic acid andthatthe
2 wt% sulfur alcohol.
doped TiOFollowing
under this procedure,
visible light has in theactivity
higher present
With this objective, heterogeneous photocatalysis workpowders.
several TiO 2 samples have been prepared. The
2
with titanium dioxide has been successfully thanapplied
undoped TiO However, in the 3 wt% doped TiO2,
efficiency was rapidly reducedtobelow
objective has been evaluatethethe influence
of the of some
2
for oxidation of As(III) to As(V) intheaqueous synthesis parameters such as
value
nature
1 wt%
of extensive
chemicals
systems [1,3]. Most work reported until now deal doped TiO , which was attributed to either the
involved, of temperature
sulfur elementsofon the synthesis or
2
with commercial titania samples so it interstitial can be of incorporation
hydrothermal processing,
the TiO
on leading
2 lattice or
the crystalline
great interest the development of new materials that the existence of inactive sulfur elements, to the
predominant propertiesofand
trapthe photocatalytic performance
level. for
show a high photocatalytic activity for the process. generation states around the fermi
aqueous As(III) oxidation of the titania materials
One of the methods most widely used for synthesis obtained.
of titanium
TiO2 hasdioxide is the used
been widely solgel
as aprocessing
pigment since basedas This powder was calcined in the furnace at 600 oC
on the hydrolysis and polycondensation
early as 1916 [1] and considered as the most reactions of For60preparation
for min. of TiO2 samples Ti(IV) n-
Ti(IV)
promising alkoxides or halides.
photocatalyst This procedure,
in environmental cleanup, butoxide (TNB, Ti(OC
Synthesized S-doped 4H9)4)TiO was2 used as titanium
powders were
however, has as main
mainly stimulated bydrawback
the discoverythe difficulty for
of its water source. After dissolving
characterized by SEM, EDS, the alcoxide in absolute
XRD, UVvis, FT-
controlling the under
splitting activity hydrolysis
ultravioletrate(UV) of light in the ethanol,
titanium acetic acid
IR and Raman was added
spectroscopy under stirring. The
tests.
precursors
early 1970s due[2].to However,
their highits reactivity towards
limited UV-driven reactions were catalyzedactivity
The photocatalytic by eitherofsulfuric
S-doped or nitric
TiO2
water. Aslargely
activity a result, uncontrolled
inhibits local
its overall under acid.
precipitation
efficiency For awas
powders first evaluated
series of samples,
using UVvisthe ageing of the
absorption
may
naturaloccur preventing
sunlight, the formation
which consists of 5% UVof(300 a mixture was performed
spectroscopy by keeping the
through degradation synthesis
of methylene
400 nm), 43% visible (400700 nm), and 52% blue (MB) solution with 1 ppm concentration.
infrared (7002500 nm) [3]. One of the potential
solutions for improving its efficiency is to shift its 158 1
absorption from the UV region into the visible-
 P H O T O C A TA L Y T I C OX I D A T I O N

EFFECT OF OXIDATION SILVER STATE ON TiO2-CeO2 PHOTOCATALYSTS FORwill THE

Effect of oxidation silver state on TiO2-CeOSOLAR
PHOTODEGRADATION OF PHENOL USING 2 photocatalysts for the
be filled
AND SIMULATED SOLAR SUNLIGHT PP1-27
in by
photodegradation of phenol using solar and simulated solar sunlight
EAAOP4
J.C. Arevalo1, J. G. Torres1,A. A. Silahua1. (1) Universidad Jurez Autnoma de Tabasco,Carretera Cunduacan-
Jalpa Km 1 colonia la Esmeralda C.P. 86690,Cunduacan, Tabasco ,Mxico.carlos.arevalo@ujat.mx

The aim of this work was study the effect of the silver
state as dopant on the TiO2-CeO2 for the phenol
photodegradation in an aqueous medium using solar and
solar irradiation simulated. The materials were prepared
by the sol-gel method using mild conditions, treated at
500 C with two different gas streams (O2 and H2).
Materials were characterized by DRX, SEM, N2
Physisorption, and UV-Vis DRS. Materials treated in H2
flow have the characteristic absortion of Surface Plasmon
Resonance, also their values bandgap energy are greater
than pure TiO2. Meanwhile solid treated with O2 showed
higher photocatalytic activity.

able to perform this task but in the presence of UV

TiO2 is the most widely used semiconductor in light [10].
photocatalytic processes due to their high
photoactivity, no toxicity, chemical stability and According to the above, the aim of this work
low cost [1]. Unfortunately, the photocatalytic was to join the use of composite materials
degradation efficiency on the surface of TiO2 (photoactive in the visible) and silver impurities
particles is still low, which is due to the fast (doping) in order to increase the photocatalytic
recombination rate of photogenerated electro-hole activity of materials under simulated solar
PHOTODEGRADATION
Photodegradation of 17 17 -METHYLTESTOSTERONE
OF -Methyltestosterone with Simulated WITH SIMULATED
Solar SOLAR
will be filled
pairs [2]. Another drawback is that the band gap of irradiation, on behalf of application in the
RADIATION USING SUNTEST CPS + WITH TiO2-Gd 3+AND TiO2-Sm 3+
+ 3+ 3+
in by in PP1-28
Radiation
TiO Using SUNTEST
2 semiconductor lies in the UV CPSregion with TiO2 -Gd
which and TiO
treatment -Sm contaminants present
of 2organic
EAAOP4
makes it inactive
1
under visible
1
light,1
irradiation, 1
water, using a renewable energy source like
D. de la Cruz
requiring , J.C. Arevlo
external UV light , J.G.
to Torres
carry out, H. Prez-Vidal
for the , L.G. de la Cruz2. (1) Universidad Jurez Autnoma de
sunlight and minimize costs in the process of
Tabasco, Mxico, (2) Universitat Rovira i Virgili, Tarragona, Spain. durvel.delacruz@ujat.mx
generation of electron-hole pairs efficiently advanced oxidation.
increasing the cost of the process [3]. Recently
The photocatalytic
Photocatalysts were oxidationprepared of using17 the -methyl
sol-gel
there has been increased interest in extending the
testosterone
method (MT)
using was
mild carried
conditions, out the
using SUNTEST
content of CeO2
spectral response of this material in the visible 3+ 3+
CPS+ wasand TiOfixed2 doped
at 0.1,with
0.25Sm and and0.5 Gd
wt% synthesized
respectively
region in different ways: doping with metallic [4]
by sol-gel.
and These
silver materials
doped atwere
0.5 characterized
wt%. In a by SEM-a
beaker
and non-metallic [5] impurities, mixing with
EDS, stoichiometric
UV-Vis-DRS. Results amount showed,
of at 500water,
deionized C, thein
others semiconductors [6] and generating
formation
which of the
an anatase
precursorssemi of phase
Ce and with
Ag asalts
surface area
(nitrates)
deficiencies of oxygen in the surface [7]. of 80 m 2
/g. The solar photodegradation wasafollowed
were dissolved and mixed with portion up of
The titania mixed with other semiconductors for by UV-Vis,
butanol. AfterLC-MSD-TOF
under constant and stirring,
TOC. slowlyThe best drip
example CeO2 improves his spectral response conversion
Titanium was Butoxide
obtained with with 0.5% wt Sm/P-25
a second portionand of
towards the visible region, generating a special 0.3% wt and Sm/TiO
Butanol 2 sol-gel
as solvent to avoidwithwaste
[MT]o=5in themg/mL for
container.
electron transfer process that increases the each case.
At roomIt wastemperature
found that the increased
a gel, which photocatalytic
was broken to
production of electron-hole pairs [8]. Also activity
theis complete
directly related with the
the addition increasing
of the alcoxide, of was
the
increases the specific area, stabilizes the anatase dopantformed.
percentage;Finallyit is attributedhydroxide
ammonium to the inhibition
was added of
phase and reduces the crystal size. It is therefore anataseasphase contrary
hydrolysis to the The
catalyst. DegussasystemP-25.was kept under
possible to find report describing the coupling of close conditions
formation. The gelfor was24dried in a Then
hours. rotary the excess
evaporator
In this work, the photocatalytic oxidation of MT
CeO 2 with other semiconductors or insulators to solvent
at 80 Cwas removed
using vacuum, by then
evaporation
the powderin anobtained
stove at
in the presence
augment of TiO2 Degussa
their photoactivity [9]. P25 and TiO2 70 left
was C until
in ancrystals
oven toamber,
dry at which
120 Cwere for 24 screened
hours.
doped with Sm3+ and Gd3+ is studied. In order to for calcination
The samples were at 500 C with
calcined at a800
heating
C for rate4 of 2
hours
Furthermore,
decrease noble metal
the speed impurities as dopants
of recombination in the C / heating
min forramp 4 hours in a furnace, under two
with of 2 C/minute.
act as electron
Degussa P25, it traps
has been in the triedsurface
to improveof TiO the2, different flow conditions
The Degussa P25, were to 60 with
fitted ml/min the insamean
capturing electrons
efficiency of charge in the conduction
separation with the band purposeto oxidizing (atmospheric oxygen)
percentages of rare earths by theand reduction
impregnation
reduce
that thespecies
these recombination of electron-hole
may be available pairs,
in the reaction (hydrogen)
method. Foratmosphere.
both casesThis sameused
it was procedure
rare earthwas
which increase
medium for a longer thetime.photocatalytic
The reductionactivity.
of this performed
nitrates to synthesize
to obtain 0.3% and a pure0.5%TiO 2 sample
weight to the
in all get
Specifically, thesome
recombination; silverresearchers
nanoparticles haveare capable
succeeded a grip. The rare earths were diluted in water and
samples.
in several ways: through periodic controlled mixed with commercial TiO2 for three hours in a
lighting and through the degradation of organic
compounds electrochemically assisted [1,2].
159
rotary evaporator, the final samples were calcined
at 500 C
1
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

PHOTOCATALYTIC DEGRADATION OF PHENOL BY char/N-TiO AND char/N-F-TiO

Photocatalytic degradation of phenol by char/N-TiO2 and char/N-F-
2 will be2 filled
COMPOSITE PHOTOCATALYSTS in by PP1-29
TiO2 composite photocatalysts
EAAOP4
P. Karagianni1, M. Antonopoulou1, A. Giannakas1,V. Makrigianni1, Y. Deligiannakis1, I.K. Konstantinou1
(1)Department of Environmental and Natural Resources Management, University of Patras, 30100, Agrinio,
Greece. E-mail: mantonop@upatras.gr; iokonst@upatras.gr
n the present work, the preparation of tire-char/-TiO2
(CTN) and tire-char/-F-TiO2(CTNF) composite catalysts by
a solgel method was investigated. XRD analysis showed
formation of TiO2 anatase phase, as well as a small fraction of
brookite phase. UVvis DRS spectroscopy showed that
both NF and N-doping resulted in a decrease in the band gap
energy. The photocatalytic activity of PC/doped-TiO2
composite catalysts were investigated for the degradation of
phenol in aqueous suspensions. The photocatalytic
degradation followed pseudo-first order kinetics. According to
our results the pyrolytic char acts as a very efficient electron-
acceptor from doped-TiO2 particles resulting in decreased e-
h+ pair recombination and subsequently in enhanced
production of HO that oxidized phenol.
1. Introduction In the present work, the preparation of pyrolytic
char/N-TiO2 and pyrolytic char/N-F-TiO2
In recent years, photocatalysis mediated by composite materials by a solgel method, was
semiconducting materials represents a well- investigated. The photocatalytic performance of
established Advanced Oxidation Process (AOP) the catalysts has been assessed for the
attracting considerable interest for the removal of photodegradation as well as the total
various non-biodegradable and/or toxic organic mineralization of phenol aqueous solutions.
PHOTOCATALYTIC
Photocatalytic
pollutants from reduction REDUCTION
aquatic OF Cr(VI)
of Cr(VI)
environments BY char/TiO
by
[1-3]. char/TiO COMPOSITE
2 2 compositePHOTOCATALYSTS: will be filled
OPTIMIZATION
photocatalysts:
Although TiO2 is AND MODELING
Optimization
the most USING THE
and modeling
widely investigated RESPONSE
using 2.the SURFACE
response
Experimental surface
Section METHODOLOGY in by
PP1-30
(RSM) EAAOP4
methodology
semiconducting (RSM) material, its UV-driven
M.photocatalytic
Antonopoulou1activity caused by1, its
, I. Chondrodimou wide
I.K. bandgap1
Konstantinou The char was derived from the pyrolysis of used
(3.2 eV for anatase
(1)Department and 3.0 eV
of Environmental andfor rutileResources
Natural crystalline rubberUniversity
Management, tires at 450 C in30100,
of Patras, oxygen-free
Agrinio, atmosphere
phase)E-mail:
Greece. and the high recombinationiokonst@upatras.gr
mantonop@upatras.gr; probability of under vacuum for 4 h and purified with HNO3 2 N
photo-induced electron (e-)hole (h+) Inpairs are
the present solution
study, theunder vigorous stirring
photocatalytic [4]. of Cr(VI)
reduction
limiting factors for solar applications [1,4]. N-doped and NF co-doped
using char/TiO2 composite catalyst under simulated TiO 2 catalysts were
solar
Various approaches have been adopted irradiation to improve wasprepared
studied via a solgel
in detail. method using
Chemometric NH4Cl and
optimization
the photocatalytic efficiency of TiO2 and toolsinclude
such as NH 4F
response as surface
N and methodology
NF dopant(RSM) precursors,
and
morphological modifications, such as experimental increasing design respectively,
were used havingto Ti:N modeland/or
and Foptimize
molar ratio the of
surface area and porosity, as well asoperational chemical parameters
1:1. Then, the photocatalytic
of the appropriate amount of char
reduction (0.2, 0.5
of Cr(VI)
modifications e.g. by incorporation of inadditional the presence ofg) MeOH.
was added RSM andwas thedeveloped
black solby was left for 12a h
considering
components, usually metals and non- metals, centralin composite
the under stirring.
design withThefourresulted suspension
input variables i.e.was spread
catalyst
TiO2 structure [1]. Moreover, it concentration, has been into Petri dish, dried for 24 h
initial concentration of Cr (VI), pH and % MeOH at 110 C under
demonstrated that the rate of photodegradation of
concentration. ambient
It air andthat
was found calcined for 1 h atvariables
the selected 500 C. For havethe
pollutants by TiO2 is enhanced by loading TiO2 effect
significant preparation
on Cr (VI) of removal
blank TiO 2 sample,
efficiency. Thethe same
results
onto adsorbents with high adsorption demonstrated capability. procedure
the was role
important repeated without
of the the addition
selection of the of
This capability can facilitate the conditions
appropriate char. The in crystal
order tophasesachieve of the
all highest
preparedremoval
catalysts
proximity/reaction of pollutant with efficiency. the TiO2 were characterized by recording their X-ray
surface, where the photocatalytic degradation of
1. Introduction diffraction (XRD) ofpatterns
The main objectives this studyusing
were a)a toBrker
assess
pollutant takes place and enhance the overall Advance
the removalD8of the instrument.
toxic heavyCrystal size b)was
metal Cr(VI) to
process
The water performance
pollution [4-5].
caused by heavy metal ions calculated bythe
investigate the well-known
effect of Sheerers equation.
four parameters
Apart fromanactivated
represent important carbon (AC), pyrolytic
ecological char
and health The ultravioletvisible
(catalysts concentration, diffuse
initialreflectance
concentrationspectraof
(PC) from tire-rubber, a newest type
hazard and had gradually become a major concern of adsorbent Cr (VI), pH and % MeOH concentration) onbythea
(UVvis DRS) of the catalysts were measured
similar
worldwide to carbon black (CB),
[1]. Chromium (VI) has
is onebeen recently
of the most PerkinElmer
total process (Lamda 35) spectrophotometer.
efficiency and c) to model and
used as another support in order to
frequent and toxic heavy metals in wastewaters improve the Photocatalytic experiments
optimize the photocatalytic procedure were carried out inofa
by means
photo-efficiency
arising from various of TiO 2 with processes
industrial promisingsuch results
as asolar simulator
central composite Atlas Suntest
design and XLS+
response (Heraeus,
surface
[4,5].
electroplating, pigment production, leather Germany). Illumination was provided with a
methodology.
tanning, textile dying, wood preservation, as well xenon lamp (2.2 kW) which was jacketed with
as finishing of metals and plastics. In contrast with 2. Experimental Section
the relatively low toxic and insoluble at pHs over 5
in aqueous systems trivalent chromium (Cr(III)),
160
Char/TiO2, named as CT 0.5/2 was prepared based
1
 P H O T O C A TA L Y T I C OX I D A T I O N

FUNCTIONALIZED TiO2 CONTAINING PAINTS FOR LONG-TERM NO POLLUTANT will be filled

Functionalized-TiO2 Containing Paints for Long-term NO Pollutant
OXIDATION
Oxidation in by PP1-31
EAAOP4
Sofia Karapati1, Tatiana Giannakopoulou1, Nadia Todorova1, Nikos Boukos1, Dimitra Dimotikali2, Christos
Trapalis1*. (1) Institute of Nanoscience & Nanotechnology, NCSR Demokritos, 153 43, Agia Paraskevi Attikis,
Greece, *c.trapalis@inn.demokritos.gr. (2) National Technical University of Athens, Department of Chemical
Engineering, 157 80, Athens, Greece .

In this study, photo-efficient functionalized TiO2 nanoparticles

2.5
Materials
with hydrophilic and hydrophobic organosilane compounds
NO
NO2 were prepared. The modified photocatalysts were grafted by an
Photonic efficiency (moles/einstein)

2.0 NOx
amorphous organic layer as TEM depicted which is a
1.5 combination of both modifiers as FT-IR and Thermal Analysis
showed.
1.0
The modified photocatatalysts were applied in water based
0.5 paints (20%, 10% w/w). The composite products showed
0.0
increased De-NOx ability accompanied by low concentrations
P25 APOD1 APOD2 APOD3 of toxic NO2 pollutant.
Samples

increased photonic efficiency as for NO removal

The development of photoactive paints has in comparison with TiO2 photocatalyst.
attracted the attention of scientific community
since it is an effective way to reduce NOx air Concerning the photocatalytic paint samples
TiO
TiO 2 2/ Graphene Oxide photocatalysts: comparative investigation of
/GRAPHENE
pollutants OXIDE
accumulated in PHOTOCATALYSTS:
street canyons and COMPARATIVE with commercial INVESTIGATION
photocatalyst, the NO OFoxidation
underground
composites car
COMPOSITES parks.
WITH
with ex-EX- ForAND
and these large SYNTHESIZED
IN-SITU
in-situ scale TiO
synthesized and2 NOxTiO removal
2
was continuously reduced while PP1-32
applications, those materials should present photo- NO2 production was gradually enhanced.
efficiency and inhibition
Nadia Todorova 1 of their
*, Aristotelis own1, Tatiana
Trapalis degradation. Contrariwise,
Giannakopoulou 1 the coatings
, Ilias Papailias 1
, Jiaguo Yuwith
2
. modified P25
The incorporation
(1) NCSR Demokritosof -widely
Instituteused photocatalysts
of Nanoscience show restricted
and Nanotechnology, production
Patriarchou Grigoriou of&NO 2 and higher
Neapoleos, 153
such TiO2 nanoparticles
as Paraskevi,
43, Ag. in paints results in the
Greece, *n.todorova@inn.demokritos.gr. values of NOx removal till the end of UV-
formation of Laboratory
(2) State Key toxic photoxidants (O3, PAN)
of Advanced Technology irradiation.
for Materials Synthesis The andphotonic
Proceeding, efficiency of composite
Wuhan University of
.
because of the
Technology, Wuhan radicals
OH430070, derived from NO2
China. photocatalytic products was further improved as
pollutant. Thus, the development of photoactive the hydrophobic
TiO2/rGO composite surfactant concentration
photocatalysts were prepared raises
bytill
paints contributing to efficient NO oxidation to
hydrothermal theres
treatmentan equilibrium
of graphene of both organic
oxide withcompounds.
ex-situ
restrictive production of toxic NO2 and enhanced crystallized This
TiO2 was as wellattributed
as withtotitania
the synergistic
precursor. effect
Better of
environmentally-friendly NOx is very challenging. hydrophilic
interfacial contact between/ the hydrophobic
TiO2 and theproperties treated
rGO is perused
This study focused on the synthesis ofbynovel nanoparticles
in-situ synthesis of the show.
TiO2 on Thethehydrophilic
rGO sheets preparation
utilizing
photoactive paints including functionalizedthe - TiO shape
2 2 improved
of TiOfeatures
control its latter.
of the compatibility to paint
Higher BET while
values
nanoparticles (20%, 10% w/w) with controlled the hydrophobic
and Eg narrowing one inhibited
was achieved when the production
TiO2 was of
.
hydrophilic / hydrophobic properties for oxidation synthesized OH in radicals
presence and ofthusgraphene.
NO2 increase. This type of
of toxic air pollutants. composites exhibited better De-NOx under visible light
activity attributed to more efficient light absorption and
The surfactants used for the modification Acknowledgements
charge separation.
The financial support by the GSRT projects GE1813 -
process were the hydrophilic 3-(2-
aminoethylamino)propyltrimethoxysilane and the PolyGRAPH and 12CHN205 - PhotoTiGRA is highly
appreciated.
hydrophobic
Graphene-coupled n-octadecyltriethoxysilane.
TiO2 is regarded as highly The peaks originating from the GtO were not recorded
water-based paint was because
promising photocatalyst cordiallyof provided
favourable by e -
indicating formation of well mixed TiO2/graphene
VITEX.
transfer from The TiO treated nanoparticles showed
2 to the graphene layers. References
nanocomposites. The Raman spectra revealed
improvedgraphene
Reduced dispersion
oxidein(rGO) ethanol solvent
is mainly used for in presence of J.rGO in L.the composites
[1] C. Aguia, Angelo, M. Madeira and A.with the
Mendes,
comparison with
modification of TiOnon2 treated
owing TiO 2. Weight
to its hydrophilicloss highest
Catal. Today loading. The morphology of the
46, 3843 (2010).
and exothermic
properties peaks were recorded
and semiconductor behaviourup [1].
to 500 C
It has composites
[2] J. Kolarikwith and in-situ
J. Toftum, synthesized
Build. Environ. exhibited
TiO2 57 (2012).
for established
been functionalizedthat the 2.
TiOactivityTEM micrographs
of the TiO2/rGO more layered orientation and higher BET SSA in
396
revealed an organic
photocatalysts layer surrounding
is dependent the contact
on the efficient treated [3]
comparison
S. Laufs, G. to the W.
Burgeth, composites
Duttlinger, R.with ex-situ
Kurtenbach,
TiO 2.
between The modified
the two components nanoparticles depicted
[2]. Homogeneous M. Maban,TiO
prepared C. Thomas, P. Wiesen and J. Kleffmann,
2. All rGO-containing photocatalysts
distribution and improved interface contact Atmos. Environ.
showed small but 44 (2010)
gradual2341. decrease of Eg from 3.2
between TiO2 and rGO is pursued.
In the present work, the influence of the 161
eV to 3.08 eV with the increase of GtO loading.
The photocatalytic activity of the two groups of 1
coupling method of TiO2 with graphene sheets on composites was evaluated in NOx removal from
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

PHOTODEGRADATION OF BTX UNDER UV-A LIGHT WITH N-DOPED CATALYSTS

Photodegradation of BTX under UV-A light with N-doped catalysts
will be filled
in by PP1-33
EAAOP4
M. L. Gimenes1, A. M. Ferrari-Lima1; R. G. Marques1, N. R. C. Fernandes-Machado1. (1) Universidade Estadual
de Maring, Av. Colombo 5790, 87020-900, Maring, Brasil, marcelino.gimenes@gmail.com.

N-doped TiO2 and TiO2/ZnO catalysts were prepared by sol gel

method and calcined at 380 and 500 C. Its photocatalytic activity
was tested in the photodegradation of BTX under UV-A light.
Photocatalysts were characterised by textural analysis, XRD,
XPS and photoacoustic spectroscopy. BTX samples were
analyzed by gas chromatography applying the headspace
technique. The photocatalytic reactions followed the first order
kinetics for BTX reduction and the kinetics constants were found
to be about 24x10-3 min-1 for N-TiO2 and N-TiO2/ZnO calcined
at 500C.

Introduction degradation kinetic constant of each compound and

TiO2 is the most used photocatalyst due to its low are summarized in Table 2.
cost, easy availability, and chemical stability.
Table 2. . Kinetics parameters of benzene, toluene and
However, the pratical application of TiO2 is still xylenes degradation under UV-A radiation (120 min)
limited. In this sence, many efforts have been Catalyst
(120)min. kma 103 (min1)
applied in order to enhance TiO2 photocatalytic
activity [1]. In the present investigation, N-doped Ti 380 9.690.43
TiO2/ZnO and undoped TiO2/ZnO catalysts were Ti 500 11.540.48
prepared and its photocatalytic activity was tested TiZn 380 7.880.94
in the photodegradation of BTX under UV-A light. TiZn 500 25.100.60
PREPARATION OF B-DOPED TiO2 WITH ENHANCED PHOTOCATALYTIC N-TiZn 380 9.911.12
ACTIVITY
Methods
Preparation of B-doped TiO2 with enhanced photocatalytic activity will be filled
UNDER VISIBLE-LIGHT IRRADIATION N-TiZn 500 24.240.40 in by PP1-34
under
TiO2/ZnOvisible-light
and N-TiOirradiation
2/ZnO (TiZn and N-TiZn)
EAAOP4
were synthesised by sol gel technique, calcined at
C.Drosou1 , F.Panagiotou1, K. Tyrovola1, N.P.Xekoukoulotakis1The best result of
. (1) Department was obtained when
Environmental mixed TiZn
Engineering,
380 and 500C
Technical and then
University characterised.
of Crete, A mixture
Polytechneioupolis, of
GR-73100 catalyst
Chania, was applied. Doping with nitrogen did not
Greece
BTX (100 mg L -1
edrosou@isc.tuc.gr each) was prepared and used in enhanced the photocatalytic activity as much as
the photodegradation tests under UV-A rediation mixing TiO2 and ZnO oxides. The TiO2-ZnO
with 1 g L-1 of catalyst.
100 An efficient interface effect is associated
hydrothermal-assisted to the reduction
synthesis of TiOof 2
Results e Discussion recombination
nanoparticles doped with boronrate (B)[1].
wasMeanwhile,
developed. doping
Tetrabutylthe
Doped
80 catalysts showed higher specific surface
titanate was usedcatalysts
as titaniumwithprecursor
nitrogencompound
reduces andthe boric
band acidgap
area than undoped
max =435nm source.energy, which isphotocatalysts
associated to were
the enhancement
characterizedof
% EE2 degradation

ones due to the presence

as boron of The prepared
nitrogen the catalystinfrared
activity under visible light.
60 [1-2] (Table 1). Anatase (A) and byrutile (R) transform
Fourier spectroscopy (FTIR). The
phases of titania were found when the Conclusion
catalysts activity of prepared nanoparticles was evaluated in
photocatalytic
were 40annealed at 500C. The presence of rutile
terms of the degradation
Undoped andofN-doped the synthetic
TiO2/ZnO hormone
catalysts 17a-
have
phase can be beneficial since itethinylestradiol reduces (EE2)synthesized
been under artificialby solar irradiation
a simple (>280nm)
method and the
recombination
20 rate [3]. The level of nitrogen in N- light
and visible (=435nm).
nitrogen dopingTheir
causedphotocatalytic activity
a red shift in the was
absorption
doped catalysts was found to be 0.64 at%. compared with band.
the commercially
The oxides TiZnavailable
500 andP25N-TiZn
Aeroxide. It was
500 showed
0 found that the synthesized B-TiO2activity
efficient catalytic exhibited a good photoactivity
in degrading the BTX in
Table 1. Catalysts
P25 Characterization.
TiO2 B-TiO2 at =435nm (almostaqueous80% EE2under
solution degradation) in 120 minutes
visible light.
Catalyst BET area Band Gapcompare with P25
energy which was almost inactivated.
Acknowledgements
(m2.g-1) (eV)
The authors would like to thank CAPES and CNPQ for
Ti 380 97.8 3.20 the financial support
Ti 500 34.6 3.18 states of oxygen. In contrast, it was reported in
Titanium
TiZn 380 dioxide-with
161.0 anatase structure-
3.34 is one References
other studies that the boron incorporation into
of the
TiZnmost
500promising71.7 photocatalyst. Its3.36properties [1]
TiOA.M. Ferrari-Lima, R.P. de Souza, S.S. Mendes R.G.
2 can induce a blue shift due to the decrease of
such high380
N-TiZn efficiency, low cost, nontoxicity
175.7 2.94 and Marques,
crystal size
M.L. Gimenes, N.R.C. Fernandes-Machado,
[1-3].
chemical stability, make TiO be suitable Catalysis Today, 241 (2015) 40.
N-TiZn 500 102.1 2 2.88 [2] K.M. Parida, J. Brundabana Naik, Journal of Colloid
photocatalyst in various fields, such as energy In present study, an efficient hydrothermal
and Interface Science, 333 (2009) 269.
storage, photocatalytic splitting of
The first order kinetic constants, km, were water for assisted synthesis of TiO 2 nanoparticles doped
[3] J.G. Yu, Y.R. Su, B. Cheng, Advanced Funcional
hydrogen
calculated production,
by obtainingairthe purification, removal
average value of
for the with boron was
Materials, 17 (2007) 1984 developed. Tetrabutyl titanate
organic and inorganic pollutants and disinfection. (Ti(OCH2CH2CH2CH3)4, TBOT) was used as
However, the major TiO2 drawback is that because
of its bang gap (3.2eV), ultraviolet irradiation is
162
titanium precursor compound, boric acid (H3BO31)
as boron source and ethanol as solvent. In a typical
required to facilitate the electron-hole separation synthesis procedure, tetrabutyl titanate (3.4g of
 P H O T O C A TA L Y T I C OX I D A T I O N

GREYWATER AS A SUSTAINABLE WATER SOURCE: A PHOTOCATALYTIC TREATMENT

Greywater as a sustainable water source: A photocatalytic treatment will be filled
TECHNOLOGY UNDER ARTIFICIAL AND SOLAR ILLUMINATION in by PP1-35
technology under artificial and solar illumination
EAAOP4
S. Tsoumachidou1, T. Velegraki1, I. Poulios1.(1) Laboratory of Physical Chemistry, Department of Chemistry,
Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece, stsoum@gmail.com

Given the worldwide water scarcity and future demands, the

utilization of recycled wastewater as an alternative water source
is gaining increasing attention. Greywater, the wastewater
generated from washing activities in households (excluding
blackwater) which is around the 75% of the total domestic
wastewater flow, has a high potential for recycle and reuse
options. Greywater treatment can provide reclaimed water in
sufficient amounts for reuse options, inducing a reduction of
potable water requirement within a household.
In this paper, the photocatalytic degradation of simulated
greywater (SGW) is investigated. The mineralization of SGW
by heterogeneous and homogeneous processes was investigated
under artificial and solar irradiation and the effect of various
operating variables has been assessed.

Water is an essential resource for survival of all living standards, social and cultural habits, type
living creatures. Safe and sufficient quantity of (i.e. soaps, toothpastes, shampoos, detergents, etc.)
water is necessary for a healthy growth. A third of and quantity of household chemicals used, and
the world's population is facing some form of length of time for which greywater is stored before
water scarcity. [1] Water scarcity is a worldwide being used. Bathroom greywater contains soaps,
PHOTOCATALYTIC
problem, even in places DEGRADATION
that were traditionallyOF ACETONE USINGtoothpaste,
shampoos, TITANIAbody PREPARED BY shaving
care products,
Photocatalytic
ELECTROSPINNING
conceived as water ample Degradation
TECHNIQUE of Acetone
regions (Europe, Japan,Using Titania
waste, skin,Prepared by lint, and traces of urine
hair, body fats, PP1-36
etc.), which needs to be Electrospinning
prevented with several Technique and faeces. Laundry greywater contains high
actions to guarantee
G. Skouras 1
, G. Tatsi1,the water supply
N. Todorova 2
for all
, C. Trapalis 2
the
, T. concentrations
Vaimakis 1
. of chemicals from soap powders
people. Wasteofwater
(1) University recycling
Ioannina, is emerging
Department as an
of Chemistry, 45110, (such
Ioannina, as Greece,
sodium, phosphorous, surfactants and
gskouras@cc.uoi.gr.
(2) Institute
integral partof Material
of water Science, NCSR, Demokritos,
demand management. 15310, Ag. Paraskevi,
nitrogen), Athens,
bleaches, Greece.
oils, paints, solvents, and non-
Domestic water recycling is an attractive option biodegradable fibres from clothing. Greywater
due to relatively high domestic water consumption originating from kitchen sink contains food
coupled with an intensive population. [2] This study presents residues, a high
combination
amounts of of oilsol-gel
and fat,method and
dishwashing
In order to reduce the water stress, especially electrospinningin technique
detergents.for the fabrication
Greywater of TiO
originating fibers of
from2 automatic
developing countries, greywater mixed (GW)anatase and rutile phase
dishwasher for bacteria,
contains acetone decomposition. The
foam, food particles,
management is becoming really important. fibersDespite
characterized highusingpH, hotthe water,
adsorption-desorption isotherms
odour, oil and grease, of
organic
the described inadequate greywater management nitrogen (BET model), UV-DRS spectroscopy,
matter, salinity, soaps, suspended solids andXRD and SEM
risks, greywater has an increasing international techniques. The turbidity.
photocatalytic[1] activity of the titania fibers was
recognition as an alternative water source investigated
for reuse by the Amongdecomposition of acetone Advanced
the so-called under ultraviolet and
Oxidation
such as garden irrigation, toilet flushing, washing visible irradiation. Processes (AOPs), photocatalytic oxidation has
vehicles and others. Greywater should, therefore, shown great promise in the treatment of
Introduction
be regarded as a valuable resource and not as a Results and Discussion
wastewater, since it could be suitable to remove
waste.
Titanium Greywater
dioxide reuse is an effective
is known as the most measure
suitablefor recalcitrant
The BET analysis organicshowed
compounds
that the[3] and able
specific surfaceto
saving water onto the
semiconductor domestic
be used due tolevel and reducing
its biological and achieve
area of the theprepared
disinfection
samplesof were
wastewater [4]. The
equal (T10) and
load on wastewater
chemical inertness, treatment plant. Where
strong oxidizing power,water low photocatalytic
lower (T20) than decomposition
P25. The calculated of band organic
gaps
is
costscarce
and and
longexpensive, greywater
time stability against reuse may lead
photo- and compounds
(Table 1) from of environmental concern (e.g.
UV-DRS spectroscopy of UV
the
to considerable
chemical corrosion.economic
Acetonebenefits.
(C3H6[1] O) is one of the filters,
samples detergents,
are lower than fragrances,
Degussa etc.) has means
P25 that been
Greywater
most common is defined
indoor air as wastewater
pollutants that that comes studied
that are extensively
active in theduring
visiblethe last 25XRD
region. yearspatterns
and it
from kitchen
several sinks, baths,
industries andwashing
household machines
purposes.and has
show been
thatdemonstrated that in
the rutile phase it can
our be an alternative
samples is in a
hand basins excluding
Electrospinning wastewater
is a broadly used from toilets and
technology for to
higher conventional
proportion thanmethods
Degussa for P25.
the SEM
removal
images of
urinals (blackwater).
electrostatic fiber formation which utilizes organic
show small pollutants from from
bars ranging water.0.8 Additionally,
to 3.5m. The an
The characteristics
electrical forces to produceof greywater
polymer depend
fibersonwith the advantage of the photocatalytic
acetone decomposition (Table process
2) showedis itslower
mild
number
diametersof occupants,
ranging from the age 2nm distribution of the
to several operating
photocatalytic conditions
activityand thesamples
in our fact that it can be
in contrast to
occupants,
micrometerstheir using lifestyle
polymer andsolutions.
water usage patterns, powered
the reference by sunlight,
Degussa thusP25reducing
undersignificantly
ultraviolet
irradiation but under visible light irradiation the
163 prepared samples showed better photocatalytic
behavior and exceeded the Degussa P25 activity.
1
Materials and Methods
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

AN ECOTOXICITY BASED LAB-SCALE OPTIMIZATION FOR REMOVAL OF0 THREE

An ecotoxicity
ANTIBIOTICS IN Abased lab-scale
SUSPENDED optimizationREACTOR
PHOTOCATALYTIC for removal of will be filled
in by PP1-37
three antibiotics in a suspended photocatalytic reactor EAAOP4
Can Burak ZKAL2, Mattia MAROTTA 2, Luigi RIZZO 2, Sreyya MER 1*
(1) orlu Engineering,Faculty, Envrionmental Engineering Department, Namk Kemal University, orlu 59860,
Tekirdag, Turkey
(2) Department of Civil Engineering, University of Salerno, 84084, Fisciano (SA), Italy,
* smeric@nku.edu.tr
Since most of antibiotics have been demonstrated to be
low degradable in biological treatment systems,
advanced oxidation processes have gained an essential
attraction to oxidize them. This study attempts to
optimize the removal of 10 mg.L-1 of three antibiotics
(ampicillin, amoxicillin and clarithromycin) in
suspended photocatalytic oxidation process at varying
catalyst doses and pH conditions following a matrix
approach. The process efficiency was evaluated in terms
of degradation, mineralization and eco-toxicity. A
different rate of mineralization and degradation was
observed for each antibiotic. pH and TiO2/antibiotic ratio
were found to be important factors for process
optimization. TiO2 doses were also sufficient for
degradation and mineralization of transformation by-
products being possible promoters of toxicity formation.
Keywords: Antibiotics, Ampicilline, Amoxicillin,
Clarithromycin, Daphnia magna, Photocatalysis, TiO2
ongoing process mechanism and TOC values
Background representive of the mineralization rate [8].

THEAntibiotics
INFLUENCE are highlyOF consumed
POLYCHROMATIC for human and LIGHT ON Mineralization
CARBOFURAN rates and DEGRADATION
UV absorbane findings were
The Influence
veterinary treatment.ofAs Polychromatic
used a portion Light (1-10%)onisCarbofuran Degradation
correlated with in to Daphniawill
pH and toxicity beIN
magna.
ZnO
filled
AQUEOUS
remained
SUSPENSION
unchanged and reach urban wastewater in by PP1-38
ZnO Aqueous Suspension
treatment plants (UWWTP) where they are not Materials and Methods EAAOP4
1 2 2
Anelka Tomaevi
biodegraded effectively, Duan
and canMijin
reach , Aleksandar Marinkovi
surface waters in , Antonije Onjia3.
effluents, of
the(1)Institute Pesticides
thus andsevere
they pose Environmental Protection,
risk to the Chemicals
aquatic Banatska 31b,11080 Belgrade-Zemun, Serbia,
Andjelka.Tomasevic@pesting.org.rs.
environment [1,2]. (2) University of Belgrade, Faculty of Technology
Ampicillin (AMP), and Metallurgy,(AMX) and
amoxicillin
Karnegijeva 4, 11000 Belgrade, Serbia. (3)Vina Institute ofClarithromycin
Nuclear Sciences,(CLRT)
Universitywere
of Belgrade, P.O. Box
provided from a
The high polarity and
522, 11001 Belgrade, Serbia.non-volatile nature of most
antibiotics contribute to their stability in water matrices pharmaceutical company at ingredients purity and used
rather. Antibiotics have potential to promote as obtained. Titanium dioxide (TiO2) (CAS# 546-68-9)
development of antibiotics CHresistant
3 (AR) Osram
bacteria and waspurchased
ultra-vitalux by Sigma-Aldrich.
lamp (315-400 nm, 300 NuveW) and ND12ZnOdistilled
was
AR genes causing non-easily mediated diseases [1].used to study water
the system was used for
photocatalytic the freshly prepared
degradation solutions
of insecticide
-1
CHin the UWWTP with aThe
finaleffect
concentration of 10 mgL of each antibiotic.
O
Thus, removal of antibiotics 3 carbofuran
effluentsin water. of the operational parameters such
urged the application H of new and improvedaswastewater
initial carbofuran concentration, pH and initial salt concentration
Experimental
O
treatment technologiesN such as advanced oxidation
(NaCl, NaNO3, Na2CO3, and Na2SO4) was studied. The
CH
processes (AOPs). 3 photodegradation TiO nanoparticles were subjected to adsorption
rate2 was higher in acidic than in alkaline
O experiments under dark conditions with (5 min) and
conditions.
Photocatalysis has been demonstrated to degrade When salt effect was studied,
without ultrasound it was found
irradiation (40000thatHz).
sodiumAll
carbonate
effectively most of the antibiotics, but mostly far fromwas the
experiments were performed in a batch reactorsodium
most powerful inhibitor used, while system
dealing process efficiency
ZnO of the same reactor treating
chloride was theunder
weakest one. photon
an incidient Under fluxthe ofemployed
36,6 w/m2 conditions,
measured by
them at the same process conditions andalmost considering
complete disappearance
Universal of
photometer. 88.48
A mg/L
300 mL of rectangular
insecticide,Pyrex
and
UV-vis
effluent toxicity [1,3,4]. -1
57% TOC occurred within
reactor 2 h. with
was filled The 10 ionmgL
chromatography results.
antibiotic solutions
In this study, showed
three antibiotics were treated lab- the Three
in a that doses of TiO
mineralization led2, to
(0.5-1-2 gL-1acetate
oxalate, ) and four pHformate
and (3, 5, 8,
degradation 11) values were investigated considering pKa values of
ions induring
scale suspended photocatalytic media irradiated a newthe process.
light flux adjustable photo-reactor at the same treatment the studied antibiotics and zero point charge of TiO2
conditions. Concentration of antibiotics was set to 10 (6.2) during matrix approach based experiments for each
mgL-1, to enable (i) assessment of PC process efficiency antibiotic. pH was measured at the end of each treatment
Carbofuran
within is atimebroad-spectrum
a measurable carbamate
scale, and (ii) the accurate cycle.
duringTiO was added
the2 process justpresence
in the after pHofadjustments and
2 g/L of ZnO,
insecticide, acaricide
determination of organic andcarbon
nematocide
with thewhich was
analytical before
also inthethe
UV presence
irradiation ofwas0.2
turned
g/Lon.of ZnO. It is a
introducedemployed
techniques in 1965in[1].
this According
work to EPA, WHO confirmation
Analysis that, in the present photoreaction, the
and EC classification carbofuran is highly toxic
PC process efficiency was evaluated in terms of
originating of ions are independent from
compound [2]. Also, carbofuran presents a high The treated samples
concentration were pesticide
of both, filtered through
and 0,45 um
catalyst.
variations/reductions in UV absorbance as assign of (Cellulaseacetate) to remove TiO2 particles. TOC
persistence in water due to its chemical stability, Obtained results implied that formation of ions
consequently, it is detected in both, surface and depend of type of applied light and type of
wastewater. As carbofuran exhibits a special
refractory character to biodegradation methods [3],
164catalyst. Therefore, as TOC was not completely
removed in our experiments, the identification of
1
 P H O T O C A TA L Y T I C OX I D A T I O N

PREPARATION OF OCTAHEDRAL ANATASE TITANIA PARTICLES FOR DECOMPOSITION

Preparation
OF CHEMICALofAND
octahedral anatase titaniaPOLLUTANTS
MICROBIOLOGICAL particles for decomposition PP1-39
of chemical and microbiological pollutants
Z. Wei, M. Endo, B. Ohtani, E. Kowalska
Institute for Catalysis (Catalysis Research Center), Hokkaido University, Sapporo 001-0021, Japan,
wei@cat.hokudai.ac.jp.
Octahedral anatase particles (OAPs) were prepared by an
ultrasonication (US)hydrothermal (HT) reaction of partially
proton-exchanged potassium titanate nanowires (TNWs). The
photocatalytic activities were examined for oxidative
decomposition of acetic acid, dehydrogenation of methanol,
decomposition of bacteria cells and growth inhibition of mould
fungi. The optimized conditions of USHT process resulted in
preparation of titania powders containing higher content of
OAPs, and thus possessing enhanced photocatalytic activities. It
was found that morphology of the OAP products had obvious
influence on degradation efficiency of both chemical and
biological pollutants.

In order to design photocatalysts with enhanced measurement of amount of carbon dioxide (CO2)
photocatalytic activity, it is necessary to study the and hydrogen (H2) liberated from an aerated
correlations between physical/structural properties solution of aqueous acetic acid (CO2 system) and a
and photocatalytic activity. The morphology of deaerated solution of aqueous methanol in the
photocatalyst particles is one of the possible presence of in-situ deposited platinum (H2 system),
candidates among the properties influencing respectively. A 400-W high-pressure mercury
photocatalytic activities. Therefore, morphology lamp was used for the photoirradiation (>290 nm).
POLYMER MODIFICATION OF TIO2 NANOPARTICLES VIA THE GRAFTING TO
ofPolymer
anatase titania photocatalysts
modification of TiO nanoparticles
possessing eight via the graftingproperties
Antimicrobial to were examined
will be filledfor
APPROACH,
thermodynamicallyFOR ENHANCEMENT 2
most stable of{101} OF facets
THEIR PHOTOCATALYTIC
bacteria (EscherichiaPERFORMANCE
coli) and mould infungi by PP1-40
approach, for enhancement their photocatalytic performance.
(octahedral 1,2anatase particles, OAPs) has been (Penicillium chrysogenum and EAAOP4
Aspergillus niger)
2,3 2,4
E. Vasilaki
studied , M. Kaliv
in detail. , N. Katsarakis
It was found that OAPs , M. Vamvakaki2,3under
prepared . (1) Department
vis and/orof Chemistry, University
UV irradiation andofinCrete,
the dark.
by an ultrasonication (US)hydrothermal Electronic
71003, Heraklion, Crete, Greece. (2) Institute of (HT) Structure & Laser, FORTH,
For antibacterial 71110, Heraklion,
properties, Crete, was
photocatalysts
Greece, chemp802@edu.chemistry.uoc.gr. (3) Department of Materials Science and Technology, University of
reaction exhibited relatively higher activities for added to bacteria suspensions, continuously stirred
Crete, 71003, Heraklion, Crete, Greece. (4) Center of Materials Technology & Photonics, School of Applied
oxidative decomposition
Technology, of organicInstitute
Technological Educational compounds and irradiated
of Crete, 71004, [4]. The
Heraklion, Crete, antifungal properties were
Greece.
under aerated conditions, but poor activities for the tested by agar plate method, where basal medium
photocatalytic reaction under deaerated conditions was supplemented with titania samples [5].
[1,2]. In the present study, optimization In this work,of the enhancement of the photocatalytic performance of
preparation conditions, such as TiO amount of The products contained higher content of OAP
2 nanoparticles was achieved by a facile route, via their in situ
precursor, volume of water and HT temperature, were prepared successfully. The correlation
surface modification with polymer chains. Random copolymers
have been investigated. between the morphology and photocatalytic
were synthesized by RAFT and/or free radical copolymerization
acitivity shows that the products with higher
and their attachment onto the surface of anatase titania
Partially proton-exchanged potassium titanate content of OAP resulted in higher level of
nanoparticles was performed via the grafting to method. The
nanowires (60600 mg) were ultrasonically photocatalytic activity. It was found that OAPs
hybrid catalysts were tested for their photocatalytic performance in
dispersed in Milli-Q water (2080 mL) for 1 h. showed high antimicrobial properties, probably
the removal of methylene blue dye. The enhanced photoactivity of
The suspension was placed in a sealed Teflon due to their sharp edges and small sizes (large
the modified photocatalysts compared to that of bare TiO2,can be
bottle (100 mL) and then heated for 24 h (423463 interface between titania and microorganism). The
attributed to their superior features, such as their increased
K). After cooling, white precipitate was collected comparison between antimicrobial properties of
dispersion stability and the higher dye adsorption capacity.
by centrifugation and dried at 393 K for 12 h. OAPs and commercial titania photocatalysts of
Photocatalytic activities of prepared samples were similar physical properties will be discussed in
measured by two reaction systems with detail.

References
synthesized by RAFT or free radical
[1] Z. Wei, E. Kowalska and B. Ohtani, Chem. Lett., 2014, 3, 346-348.
[2]InZ. Wei,
the E.search for and
Kowalska more effectual
B. Ohtani, treatment
Molecules, polymerization. In the case of RAFT
2014, 19, 19573-19587.
methods
[3] Z. Wei,for the elimination
E. Kowalska, J. Verrett,ofC.water pollutants,
Colbeau-Justin, H. Remita and B. Ohtani, Nanoscale,
polymerization, 2015, 7, 12392-12404
(2-(dodecylthiocarbonothioylthio)
advanced
[4] oxidation
E. Kowalska, Z. Wei, B.processes
Karabiyik, A. (AOPs)
Herissan,have
M. Janczarek, 2015,was
et al., Catal. Today.,acid)
-2-methylpropanoic 252, 136-142.
prepared using a
emerged as promising alternatives,
[5] A. Markowska-Szczupak, and among
K. Wang, P. Rokicka, M. Endo, et al., J. Photochem.
synthetic Photobiol.
route proposed byB,,
Lai2015, 151,
et al [1]54-62.
and was
them, heterogeneous photocatalysis has attracted used as the chain transfer agent (CTA). The
significant attention. TiO2 is a semiconductor
material that has been most extensively used for 165
(co)monomers used were poly(ethylene glycol)
1
methyl ether acrylate (PEGA), methacrylic acid
the photocatalytic degradation of numerous (MAA) and dopamine methacrylamide (DMA)
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

MONOLITHIC CATALYTIC BED COATED WITH TiO2 P25 TOWARDS THE

Monolithic Catalytic Bed Coated With TiO P25 Towards the will be filled
PHOTOCATALYTIC REDUCTION OF Cr(VI) IN2 A SIMULATED SOLAR SYSTEM in by PP1-41
Photocatalytic Reduction of Cr(VI) in a Simulated Solar System
EAAOP4
B. A. Marinho, R. O. Cristvo, J. C. Lopes, R. A. R. Boaventura, V. J. P. Vilar, LSRE - Laboratory of Separation
and Reaction Engineering - Associate Laboratory LSRE/LCM, Faculdade de Engenharia, Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. belisamarinho@fe.up.pt
Hexavalent chromium reduction to the trivalent state was
evaluated in a solar driven photocatalytic system, using cellulose
acetate monolithic structures coated with TiO2-P25 thin films, in
the presence of citric acid. Heterogeneous photocatalytic
processes are more attractive for water treatment, since the need
for a post-filtration step is avoided. Firstly, the effect of the
number of TiO2 coating layers on the Cr(VI) photoreduction was
analysed. The catalytic activity increased substantially from 3 to
6 layers, and afterwards remained unchanged. The influence of
citric acid concentration was also studied. Its gradual addition
along the reaction improved the reaction rate. Using two doses
of citric acid (0.072 mM), the reduction of 0.0192 mM Cr(VI)
was achieved in 45 min (2.17 kJ L-1).

Introduction deposition, sputtering or dip coating methods.

Materials as ceramic tiles, stainless steel, paper,
Recently, the photocatalytic reduction of Cr(VI) fiberglass and glass were already tested as
to Cr(III) using different semiconductors has supports. However, thin-walled monolith
received considerable attention [1]. Due to its high structures of cellulose acetate is a promising
stability and relatively low cost, TiO2 is the most alternative since it is UV-transparent, lightweight,
frequently
FABRICATION usedON PDMSphotocatalyst.
FILMS OFIn the
TEXTURED PYRAMIDAL
inexpensive and STRUCTURE
easily VIA PS BEADS
Fabrication
photocatalytic
WITH DIFFERENT on PDMS
process, films
FOR(eof
electron
SIZE

) textured
and hole (hpyramidal
SELF-CLEANING
+
) structure
APPLICATION via PSshaped polymeric material PP1-42
[2].
beads
pairs arewith different
generated due tosize
thefor self-cleaning
photons absorptionapplication
with higherY1, energy
Jung-Hoon Sang-HunthanNam2, the
Ki-Hwansemiconductor In 1this
Hwang1, Hyeon Jin Seo work,Boo
, Jin-Hyo the
1 photoreduction of hexavalent
. (1) Department of Chemistry,
bandgap. The generated
Sungkyunkwan photoelectrons
University, Suwon can Korea,
440-746, South react thank42@hanmail.net.
chromium present in aqueous
(2) Institute of Basic solutions
Science, was
with Cr(VI) originating
Sungkyunkwan University,Cr(III)
Suwon,[1].440-746, South Korea. investigated using TiO2-coated cellulose acetate
monolith structures in the presence of citric acid
As the anodic reaction is sluggish, an arrest of irradiated
In this study, we have by simulatedPDMS
fabricated solar light.
film of textured
Cr(VI) reduction is observed because of the
pyramidal structure via polystyrene (PS) spheres with various
Cr(V)/(IV)/(III) species reoxidation by holes or Methods
sizes. PS spheres were synthesized by emulsifier free emulsion
OH radicals. On the contrary, Cr(VI) removal in
polymerization method.
Cr(VI)Pyramidal
solutionssilicon
were structure
prepared wasfrommade
K2CrbyO
the presence of sacrificial organic agents is 2 7
wet chemical etching
(Merck, process
purity using TMAH1,5-diphenylcarbazide
99.9%). solution. Textured
complete in less time, as the short-circuiting
pyramidal structure was fabricated
(Merck, purity 98%) usingwasPSused
monolayer having
as colorimetric
process is hindered (Graphical abstract). In many
various sizes on reagent
the Si (100)
to substrate Cr(VI)
determine with pyramidal structure.
concentration. TiO2
cases, organic compounds (as citric acid) are
These structuresP25 had powder
high contact angle ofbyabout
was supplied Evonik150 degree.
(formerly
present simultaneously with Cr(VI) in the
Also, these structures
Degussa) haveand a higher
used as reflectance
delivered,of without
about 100%
further
wastewater as a result of different industrial
than flat structure. These structures
modification will be applied
or purification. Someto characteristics
the catalyst
processes, being important to take into account
industry becauseofitP25 haspowder
a high provided
reflectance withmanufacturer
by the self-cleaningare
their contribution.
effect. given in Table 1. Cellulose acetate monolithic
Most of the information on water treatment by (CAM) structures (TIMax CA50-9/S - LC = 80
photocatalytic processes is concerned to the mm, d2ch = 9 mm 9 mm, ew,ch = 0.1 mm) were
evaluation
Nature hasof represented
compoundsa wide removal varietyusing
of Figure
evenly 2(a)coatedshows
usingthat image suspensions
aqueous of a PDMSofbased P25
semiconductors surfaces
superhydrophobic in suspension.
with low or high However,
water pyramidal structure method
by the dip-coating have a (Dip-Coater
size of 221.4RDC m.15,
heterogeneous
adhesion. processes
The lotus are more
leaf, with attractive
an ultrahigh for
water Pyramidal structures GmbH
Bungard Elektronik have been& Co.aligned
KG). with an
Several
real applications,
contact angle (CA)eliminating
but ultralow thewater
needadhesion,
for a post-is interval
P25 powder of 2 m.layers (3 12) were deposited by
filtration step as
demonstrated andthe
allowing, at therepellent
ideal water same time, the
super- immersing the monolithic structures into an
semiconductorsurface
hydrophobic reuse. and shows excellent self- aqueous suspension at a withdrawal rate of 0.8 mm
cleaning
Supportsproperty
can be [1].
coatedThese
with superhydrophobic
catalyst films by s1, assuring a thin and uniform film on each
surfaces with a CA higher than 150 have
several methods, such as chemical/physical vapour received substrate surface (samples were dried at 50C for
considerable attention due to their importance in 30 min between each layer deposition). Before
fundamental research and practical applications [2]
and many efforts have been made in developing an
artificial superhydrophobic surface by mimicking
166 1
 P H O T O C A TA L Y T I C OX I D A T I O N

NEW COMPOSITES OBTAINED BY FRIENDLY CONDITIONS FOR ADVANCED

WASTEWATERS PROCESS PP1-43
New Composites Obtained by Friendly conditions for Advanced Wastewaters Process
Maria Visa1, Andreea Chelaru1 1R&D Center Renewable Energy Systems and Recycling, Transilvania University of
Brasov, Eroilor 29, 500036, Romania

The goal of this paper was to develop a new composite at low-temperature using TiO2modifed fly ash (TiO2-
MFA), composites based on interaction in alkaline solution using hydrothermal methods, to obtained
crystalline nanocomposite at room temperature without heat treatment stage.These composites are
interesting to be applied in visible photocatalysis/adsorption simultaneous advanced wastewater processes.
Combining fly ash with titanium dioxide has the following advantages: (1) the titanium oxide crystallites
grow on the support fly ash), (2) pollutant molecules migrate to the surface of TiO 2 can be degraded by
photocatalysis and (3) fly ash substrates are regenerated in situ. The nancomposites were synthesized from
Degussa P25 and fly ash activated in sodium hydroxide solutions (NaOH) at hydrothermal conditions,
resulting anatase and rutile crystalline phases by controlling the content of water/solvent. The composites
were characterized by the scanning electron microscopy (SEM) and atomic force microscopy (AFM) for
morphological characterization of the surface, X-ray diffraction (XRD) for phase and crystallinity analysis,
UV-VIS spectroscopy to calculate the energy band gap, surface analysis by determining the contact angle,
porosity analysis (BET) and isoelectric point (pHzpc).The photocatalytic property of the composites was
evaluated by dye (methyl orange), surfactant (sodium dodecyl sulphate) degradation under UV and Visible
irradiation. The adsorption tests were made on heavy metal (Cu 2+) cation. Properties of composites were
correlated with the adsorption/photocatalytic activity of the samples.

GREEN TECHNOLOGIES BASED ON ADVANCED OXIDATION PROCESSES (AOPs): WATER

Green Technologies based on Advanced Oxidation Processes (AOPs): will be filled
DECONTAMINATION BY PHOTOCATALYSIS USING SOLAR LIGHT in by PP1-44
Water Decontamination by Photocatalysis using Solar Light
EAAOP4
M.E. Borges1, P. Esparza2, M. Sierra1, J.C. Ruiz-Morales 2, P. Martn-Zarza2, J. Mndez-Ramos 3, P. Mora3.
1
Chemical Engineering Department, 2 Chemistry Department, 3 Physic Department. University of La Laguna.
eborges@ull.es/ Facultad de Qumica., Av. Astrofsico Fco. Snchez s/n, La Laguna, Tenerife, 38200, Spain.

Solar energy, along with other renewable

resources, could potentially solve environmental
problems, as demonstrated by recent
(1) Institution, Address, Town, Country, first_author_email@address. (2) Institution, Address, Town, Country.
developments in the use of solar energy, such as
solar photocatalysis. The solar photocatalytic
technology has been demonstrated to be effective
for treating groundwater, drinking water,
wastewater and air and soil pollution. In this
work, a solar photocatalytic application for
wastewater decontamination is presented studying
several materials as phototcatalyst. Luminiscent
material has been evaluated as up-conversion
materials for enhancing photocatalytic activity.
1

Photocatalysis using solar light is an
environmental application of Advanced Oxidation
Processes (AOPs). The increase in greenhouse gas
emissions and air/water contamination within
decades have led to the development and
integration of green technologies mainly based on
renewable sources, photocatalytic processes for
air/water decontamination using solar light is a
sustainable and environmental friendly
technology.
In this study, some natural volcanic materials
photocatalyst was carried out in a 100 ml quartz-
Erlenmeyer mounted over a parabolic radiation
colector. The reaction mixture inside the
Erlenmeyer was maintained in suspension by
magnetic stirring. As light source, natural sun
radiation was used.
167
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

Substituent
SUBSTITUENT Effects on theON
EFFECTS Photocatalytic Degradation of
THE PHOTOCATALYTIC Arylazo
DEGRADATION will
OF be filled in by
ARYLAZO
EAAOP4
Pyridone
PYRIDONE Dye: AnAN
DYE: Experimental and Theoretical
EXPERIMENTAL study
AND THEORETICAL STUDY PP1-45
J. Dostani1, D. Lonarevi1, M. Zlatar1, F. Vlahovi2, D. Jovanovi1, (1) Institute of Chemistry, Technology and
Metallurgy, University of Belgrade, Belgrade, Serbia, jasmina@nanosys.ihtm.bg.ac.rs (2) Innovation center of the
Faculty of Chemistry, University of Belgrade, Belgrade, Serbia

A series of arylazo pyridone dyes with substituents ranging

from strong electron-donating to strong electron-
withdrawing groups were subjected to photocatalytic
degradation. The effects of the substituents on the structure
and reactivity of investigated dyes via photocatalysis was
quantified using Hammett equation. The most vulnerable
position to be attacked by hydroxyl radical was predicted
according to calculated electronic charges and Fukui
functions. The results showed that the reactive site shifts
from nitrogen atom linked to benzene ring to nitrogen atom
linked to pyridone ring going from dyes with el.-donating
group to dyes with el.-accepting group.

investigated dyes, 5-(4-substituted arylazo)-6-

Background hydroxy-4-methyl-3-cyano-2-pyridones and their
Over the past decades, photocatalysis using structural characterization were given elsewhere
irradiated titanium dioxide particles has been [5]. The photocatalytic degradation of synthesized
extensively used as an attractive way for waste dyes was investigated using commercial catalyst
TiO 2, Aeroxide TiO2 P25. of TheEVALUATION
photocatalytic tests
SOLAR
water LIGHT-ZnO
purification DEGRADATION
[1].degradation
The main advantage OF
of ETHYLPARABEN:
the STATISTICAL OF
Solar light-ZnO of ethylparaben: Statistical evaluation will be filled
OPERATING is
photocatalysis FACTORS
its ability AND
to ESTROGENIC
generate highly were performed in an open cylindrical
ACTIVITY in by PP1-46
operating factors and estrogenic activity
active hydroxyl radicals, which are capable to thermostated Pyrex cell of a 1 L capacity EAAOP4 using
degrade a great
Z. Frontistis 1
, A.variety
Liangouof1
organic
, O. Zervakicompounds.
1
, S. Arapitsa1,A Osram
M.I. Karga 1
Vitalux
, D. Venieri ,2
, D.lamp (300 1. W).
Mantzavinos The initial
(1) Department of
numerous studies University
Chemical Engineering, have of Patras,
shownGR-26504 suspension
that Patras, pH was adjusted(2)
Greece, zaxoys@gmail.com. toSchool
12 using
of sodium
Environmental Engineering,
photodegradation Technical
rate is strongly Univeritybyof the
governed hydroxide
Crete, GR-73100 solution.
Chania, GreeceThe mass of the used TiO2
pollutant structure and the electronic nature Parabens
of the in the during
aquaticexperiments
environment wasare0.5typically
g; the concentration
found at theof
-5
substituent group [2]. Hammett substituent ng/L to g/L dye
levelssolution
and was
are 10
suspected mol/L;
to while
behave the
as volume of
endocrine
constants, which quantify the disruptors. the dye solution
electron Although was 500photocatalysis
semiconductor mL. based on
withdrawing or donating capabilities ofTiO 2 has been widely investigated for environmental
a given Thematerials
structural andas electronic properties of orthe
substituent, have been successfully applied to remediation, other such ZnO may exhibit equal
greater studied dyes were calculated at M062X/6-
photoactivity.
obtain quantitative description of many chemical 31+G(d,p) level wasof theory. Atomictocharges
equilibriums and reactions [3]. A factorial design approach implemented assess using
the
importance ofnatural population
ethylparaben analysisg/L),
(500-1500 (NPA) and reactivity
treatment time
Objectives (3-9 min), ZnO indices,
(100-500 i.e. mg/L),
condensed photonFukuifluxfunctions
(1.1 10-6were
-7.3 10 used
-7
to predict reactive site of hydroxyl
E/(L.s)), initial pH (3-9) on the amount of paraben degraded radical attack,
In this study, the applicability of the Hammett andsolar
to explain the reactivity
under simulated irradiation; paraben differences
concentration between
and
relationship to the description of the electronic substituted dyes. resulted in the most important,
time, as well as their interaction
properties and photoreactivity of arylazo pyridone
positive effects. Results
dyes was performed. DFT based reactivity
Furthermore, changes in estrogenicity upon oxidation were
descriptors, e.g. condensed Fukui function were The molecular structures of Screen
the investigated
monitored employing the Yeast Estrogen (YES)
used to predict the preferred site of hydroxyl arylazo pyridone dyes with atom numbering are
bioassay.
radical attack [4]. To the best of our knowledge, presented
thisParabens,
is the first
estersattempt to apply DFT
of 4-hydroxybenzoic acidbased
with (i.e. typicalinforScheme
natural1waters).
(D1-D8). At applied pH,
an alkyl ordescriptors
benzyl group, dye Figure 1 shows the form,
exists in anionic Paretowhich chartrepresent
reactivity to have been employed
the study of reaction for
"resonance
of the
about a century
mechanism as preservatives in
of photodegradation of foodstuff,
arylazo statistically important variables and(A) their
hybrid" between azo anion and
hydrazone anion (Hy) canonical forms with
pyridone dyes through hydroxyl radical attack.
cosmetics and pharmaceuticals and personal care interactions according to the Lenths
negative charge being delocalozed over pyridone
method.
products. Parabens in the aquatic environment are
Methods
typically present at the ng/L level and are oxygen and1.azo
Table nitrogen
Variables atoms.
of the Tabledesign.
26 factorial 1 presents
suspected to behave as endocrine disruptors [2]. of the computed atomic charges for O1
Humic pyridone
Photon
A detailed procedure for the synthesis oxygen
Parabenand Time N3 and N4
ZnO azo nitrogen
acidatoms.flux The
Semiconductor photocatalysis may offer an pH
g/L min mg/L mg/L
appealing methodology to treat such contaminants; E/(L.s)
in this respect, the degradation of ethyl paraben 168 500 3 100 3 0 7.3 10-7
1
employing simulated solar radiation and ZnO as 1500 9 500 9 10 1.1 10-6
 P H O T O C A TA L Y T I C OX I D A T I O N

PREPARATION AND APPLICATION OF HYBRID PHOTOCATALYSTS BASED ONwill be filled

Preparation and Application of Hybrid Photocatalysts Based on
BRAZILIAN CLAYS AND TiO2 FOR NOx DEGRADATION
Brazilian Clays and TiO2 for NOx degradation in by PP1-47
EAAO P4
R. F. Tessinari1 , I. Jansson 2, M.Canela 1, R. Portela3 , S. Surez2, P. vila 3, B. Snchez2
(1) UENF - Universidade Estadual do Norte Fluminense Darcy Ribeiro, Av. Alberto Lamego, 2000, Campos dos
Goytacazes, Brazil, e-mail: mccanela@gmail.br (2) CIEMAT- Renewable Energy Division, FOTOAIR: Analysis and
Photocatalytic Treatment of Pollutants in Air Unit. Avda. Complutense 40, 28040 Madrid, Spain. (3) CSIC-Institute
of Catalysis and Petrolchemistry (ICP), SpeICat: Spectroscopy and Industrial Catalysis group. 28049 Cantoblanco,
Madrid, Spain

Hybrid materials composed by natural clays and

titanium dioxide (TiO 2/clay=50/50) were prepared
and tested for NOx photocatalytic degradation. 29%
NOx conversion was achieved with the hybrid
containing Spanish sepiolite. Among Brazilian
clays, a montmorillonite presented the highest
conversion of NOx (18%).
.

adsorbent of possible by-products generated by

Introduction
photocatalytic process. In this work, we combined
NO x are produced from the reaction of nitrogen two types of Brazilian natural clays and a Spanish
and oxygen gases in the air during combustion, one with TiO 2 in order to verify the efficiency of
mainly at high temperatures. The main natural elimination of NOx by photocatalysis/adsorption.
source is lightning and the main anthropogenic Materials and Methods
source is the use of internal combustion engines ,
which has drastically increased the presence of The hybrid photocatalysts were prepared by
nitric
DEGRADATION OF ENDOCRINE DISRUPTORSmechanical
oxide in the environment. USING SIMULATEDmixing in a proportion of 1:1 of TiO 2
SOLAR IRRADIATION
Degradation of Endocrine Disruptors using simulated (G5 Cristal)solar
will be filled
AND Cu2O/BiVO4
Heterogeneous photocatalysis has4been employed
and a clay, extrusion and treatment in byat PP1-48
irradiation and Cu2O/BiVO 500 C for 4 h. Three types of clays were used:
for degradation of1 compounds containing sulfur and EAAOP4
1 1 1montmorillonite1 (BR), sepiolite (ES) and kaolinite
Y. Kanigaridou , A. Petala , Z. Frontistis ,
nitrogen in gaseous phase, through formation of by-D.I. Kondarides , D. Mantzavinos . (1) Department of Chemical
Engineering, University of Patras, GR-26504 Patras, Greece, (BR). The materials were termed as TiO 2/M ont
zfrontistis@chemeng.upatras.gr
products which can deactivate the catalyst or (50/50), TiO 2/Sep (50/50) and TiO 2/Kaol (50/50).
produce other atmospheric pollutants. Hybrid NOx ofphotodegradation
photocatalysts can be an alternative to remove Thethese
efficiency Cu2O/BiVO4 as tests were conducted
a catalyst for the
photocatalytic according
degradationto ISO
of 22197-1 Aon
Bisphenol the simulated
under following
compounds by photocatalysis and adsorption experimental conditions: total gas flow=3 L min -1
(Portela et. al 2012). Natural clay minerals with solar irradiation in environmentally relevant matrices was ,
-2
large specific surface, and therefore high adsoption investigated.[NO]=1000
It was found v, RH
ppbthat 25=50%,
solar I = 10 is
photocatalysis Wm an ,
efficient irradiation time =300 min.
capacity, can be used as catalyst supports and have method for the degradation of BPA in aqueous
a synergistic effect in the reaction acting solutions.
as Process performance was affected by several
factors, such as irradiation time and type, catalyst
concentration, BPA concentration, pH and water matrix. The
optimumResults
loading of Cu2O was found to be 0.75%. BPA
removal efficiency was higher at a high pH. Interestingly
Table 1. S ome photocatalyst characterization results
unlikely other photocatalytic materials,, the presence of
Anatasebicarbonates resulted in increased process efficiency. The
MIP S areawas BET S area
to 50% Pore
after volume
Composite crystallite catalytic
size activity reduced five consecutive
runs. m g-1 m g-1 cm3 g-1
nm
TiO 2/Sep (50/50) 13 95 136 0.62
TiO2/M ont (50/50) 20 67reaction kinetics
125 in model solutions,
0.42 as well as in
The endocrine system consists of glands and environmentally relevant samples.
hormonesTiO 2/Kaol
that are (50/50)
responsible for 20
the growth, 60 73 0.54
development, maturation and reproduction of Photocatalytic experiments were conducted in a
human and animals. Endocrine disruptors (EDCs) cylindrical pyrex glass reactor (V=120 ml). Solar
are natural or synthetic compounds that can have irradiation was emitted by an Oriel LCS - 100 W
consequences on the function of human's and solar simulator system. Changes in BPA
animals' endocrine system. EDCs affect the concentration were followed by high performance
activity, the synthesis, the metabolism and the liquid chromatography (HPLC).
secretion of hormones, even in small
concentrations (ng/L - g/L). They are the cause of 169 1
The optimum Cu O loading after testing a range
2
of 0.5-3 % was found to be 0.75%. BPA removal
growth and reproduction disorders. Also, EDCs
 P O S T E R P R E S E N TA T I O N S - 1 st D A Y

SOLAR LIGHT INDUCED DEGRADATION OF ETHYL PARABENS WITH Cu2O/BiVO - filled

Solar light induced degradation of ethyl parabens with Cu2O/BiVO4- will 4be
STATISTICAL EVALUATION OF OPERATING FACTORS in by PP1-49
Statistical evaluation of operating factors
EAAOP4
A. Petala1, R. Bontemps2, A. Spartatouille2, Z. Frontistis1, D.I. Kondarides1, D. Mantzavinos1. (1) Department of
Chemical Engineering, University of Patras, GR-26504 Patras, Greece, zfrontistis@chemeng.upatras.gr (2)
Universit Claude Bernard Lyon 1 69100 Villeurbanne, France
Ethyl paraben (EP), an emerging micro-pollutant
representative of the parabens family, has been subject to
photocatalytic degradation under simulated solar radiation
using Cu2O/BiVO4 as the photocatalyst.
A factorial design approach was implemented to assess
the importance of ethyl paraben concentration (500-1500
g/L), treatment time (10-60 min), catalyst concentration
(100-500 mg/L), bicarbonates concentration (0-500 mg/L)
and initial pH (3-9) on the amount of ethyl paraben
removed; initial ethyl paraben and time, as well as their
interaction resulted in the most important effects. In
addition, the presence of bicarbonates resulted in
increased process efficiency.
.

Parabens, esters of 4-hydroxybenzoic acid with concentration were followed by high performance
an alkyl or benzyl group, have been employed for liquid chromatography (HPLC). Table 1 shows the
about a century as preservatives in foodstuff, tested variables of the 25 factorial design, where
cosmetics and pharmaceuticals and personal care each variable takes a low and a high value.
products [1]. Although they can be degraded
PHOTOCATALYTIC
relatively easily in TRANSFORMATION
conventional wastewater OF THETable ANTIPSYCHOTIC
1. Levels of variablesDRUG
of theRISPERIDONE
25 factorial design.
IN AQUEOUS
Photocatalytic MEDIA
treatment plantstransformation ON REDUCED GRAPHENE
of the antipsychotic
[2], they are continuously released drug OXIDE-TiO
risperidone COMPOSITES:
in aqueous media SYNTHESIS,
on reduced PP1-50
Ethyl- 2
CHARACTERIZATION AND DEGRADATION KINETICS Time Catalyst Bicarbonates
graphene
due to their high usage
oxide TiO2 and,
composites:
therefore, Synthesis,
frequentlycharacterization
paraben and degradation kinetics pH
(min) (mg/L) (mg/L)
met in
Vasilios theChristos
Sakkas, aquatic environment
Hadjicostas, Paola Calza,(including
Claudio Minero, Maria(g/L)
Kalaboka and Triantafyllos Albanis
freshwater, marine water and sediments). Parabens 500 10 100 3 0
In
arethetypically
present study reduced
present graphene
at the level and
ng/L oxide TiO2 are
composites were synthesized at two different ratios (1:10 and
1:5) through a hydrothermal method
suspected to behave as endocrine disruptors.using graphite and commercial1500 P25 as
60 starting materials.
500 Scanning
9 Electron
500
Microscopy (SEM), Transmission Electron Microscopy (TEM), (mg/L) X-ray diffraction (XRD), Fourier transform infrared
Semiconductor photocatalysis using solar
spectroscopy (FTIR), BET surface area and ultravioletvisible (UVVis) absorption spectroscopy were employed
irradiation as the source of photons for the Figure 1 shows the Pareto chart of the
to investigate the morphology and properties of the produced composites.
activation of the catalyst
The photocatalytic has received
performance of TiOconsiderable
2-P25 catalysts, was statistically
evaluated under important variables
artificial solar and light
light and visible their
attention
in over asthe
distilled water, well past few surface
as, different years. waters
Bismuth interactions
(at natural according
pH) with respect to the Lenths
to risperidone method.
(antipsychotic drug)As
vanadate (BiVO4)
degradation. is a chemically
TiO2photocatalyst (P25) was usedstableas reference
and catalyst
seen, allfor comparison
variables havestudies.Irrespectively
a positive effect of onthe the
nontoxic aqueous
irradiated photocatalyst
matrix,that can absorb visible
the photocatalytic lightof the concetration
efficiency tested composite of materials
EP removed under simulated
with thesolar light
treatment
to degrade
was contaminants
higher compared to baredue
TiOto suitable
2-P25. This band-gap
observation wastime, moreinitial
pronounced
EP and fortheir
the degradation
interactionofimposing
risperidone the
energy
in aqueous (ca. 2.4undereV).
solutions visibleBiVO composite
light irradiation.
4 greater effects.
photocatalysts exhibited enhanced visible-light
photocatalytic activities probably due to the
extending of absorption towards visible light and
enhancement of charge separation efficiency by
forming heterojunction structure at the contact
interface of metal oxides and BiVO4 [3].
In this work, the photocatalytic degradation of
ethyl paraben under simulated solar irradiation on
Cu2O/BiVO4 was investigated with emphasis on
the effect of operating variables.
Photocatalytic experiments were conducted in a
cylindrical pyrex glass reactor (V=120 mL). Solar
irradiation was emitted by an Oriel LCS - 100 W
solar simulator system Changes in EP Figure 1. Pareto chart of the standardized effects.

170 1
 P H O T O C A TA L Y T I C OX I D A T I O N
Heterogeneous Photocatalysis and Ozone Oxidation for the Removal
HETEROGENEOUS PHOTOCATALYSIS
of Nonylphenol and AND OZONE
Short-Chain Nonylphenol OXIDATION
Ethoxylates FOR THE REMOVAL OF
from
NONYLPHENOL AND SHORT-CHAIN NONYLPHENOL ETHOXYLATES FROM AQUEOUS
Aqueous Matrices PP1-51
MATRICES
E.E. Klontza1, N.P. Xekoukoulotakis2, E. Diamadopoulos,2. (1) University of the Aegean, Analysis and Simulation of
Environmental Systems Research Unit, Department of Mathematics, 83200 Samos, Greece, rklontza@gmail.com (2)
School of Environmental Engineering, Technical University of Crete, University Campus, GR-73100 Chania, Greece
The aim of this work was the application of heterogeneous
photocatalysis mediated with TiO2 suspension and oxidation with
ozone for the removal of nonylphenol (NP) and short-chain
nonylphenol ethoxylates (NP1EO and NP2EO) from aqueous
solution and from the final effluents of a municipal wastewater
treatment plant. Both techniques were found to be very effective
and the percentage of removal was greater than 90%. The degree
of mineralization was assessed through the reduction of (DOC)
during ozonation. The photocatalytic oxidation of the compounds
followed first-order kinetics, while pseudo-first order and second
order kinetic models were applied in the case of oxidation with
ozone. The experimental data derived from ozonation were fitted
in second order models. The reaction rates were higher during the
oxidation of aqueous solution in all cases.

1. Introduction (Crete, Greece). The samples were collected in

Catalytic processes taking place in semiconductor
suspensions (TiO2, ZnO, WO3, CdS) in the
presence of natural or artificial light are utilized by
heterogeneous photocatalysis and are able to
oxidize completely organic and inorganic
pollutants without further environmental impacts
[1]. At the end of the 1970s, trihalomethanes and
other organohalogenated compounds were
identified in the drinking water as chlorination by-
products, so the use of ozone as chlorine alternative
in the disinfection of water has increased
significantly [2].
Nonylphenol polyethoxylates are recognized as
endocrine disrupting compounds and their toxicity
and estrogenicity is increasing with the shortening
of the ethoxylate chain [3, 4]. They are detected in
the final efuents of sewage treatment plants [4, 5,
6]. In Greece, they have been detected in different
stages of the wastewater treatment process [7, 8, 9]
as well as in industrial wastewater [10].
In the present work, both methods were tested for
their ability in removing nonylphenol (NP) and
short-chain nonylphenol ethoxylates (NP1EO and
NP2EO) from aqueous matrices (aqueous solution
and final effluent of a municipal wastewater
treatment plant). For each method, the reduction of
DOC, the decrease in the pollutants concentration
and the kinetic parameters were determined.
2. Materials and methods
2.1. Sampling and quantitation of the compounds
Grab samples were collected from the effluent of
Municipal wastewater treatment plant of Chania
amber glass bottles and were analyzed
immediately. In each sample pH, chemical oxygen
demand (COD) and total suspended solids (TSS)
were determined. Chemical oxygen demand and
total suspended solids were measured according to
standard methods 5220D and 2540D, respectively
[11]. In cases where preservation of the samples
was necessary, formaldehyde solution was added (1
ml/100 ml of sample) [12, 13].
The separation and quantitation of NP, NP1EO
and NP2EO was achieved using reversed-phase
high performance liquid chromatography with
fluorescence detector. A Hewlett Packard 1100
series HPLC with SUPELCOSILTM LC 18 (15cm
length X 4.6mm ID X 5m film thickness)
equipped with a fluorescence detector operating at
305 nm and 227nm (emission and excitation
wavelength respectively). The mobile phase
consisted of A: acetonitrile and B: H2O. The elution
program was gradient with a flow rate of 0.5 ml
min-1 from 90% to 100% A [14].
2.2. Photocatalytic oxidation of short-chain
nonylphenol ethoxylates
The laboratory experiments for the photocalytic
oxidation were executed using a cylindrical glass
reactor placed on a magnetic stirrer. TiO2 was
selected as a catalyst, due to its advantages [15] in
comparison with others. It was used as a suspension
in aqueous solution or in spiked wastewater
chlorinated effluent sample. The final concentration
of NPnEOs in the aqueous solution prepared with
Milli-Q water was 750 g l-1. The wastewater
sample which was used in the test was a filtered

1
171
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

PHOTO-FENTON DEGRADATION OF PHARMACEUTICAL DIPHENHYDRAMINE willIN WATER

Photo-Fenton degradation of pharmaceutical diphenhydramine in be filled
AT CIRCUMNEUTRAL pH in by PP2-1
water at circumneutral pH
EAAOP4
S. Esplugas1, S. Plaza1, A. De Luca 1, P. Marco1, J. Gimenez1. (1) Department of Chemical Engineering, Faculty of
Chemistry, Universitat de Barcelona, C/Mart i Franqus, 08028, Barcelona, Spain. email: santi.esplugas@ub.edu.

The need for acidification in photo-Fenton process (Fe2+/3+,

H2O2, h) is often outlined as one of its major drawbacks.
Nevertheless, recent studies have shown that this process also
occurs at circumneutral pH in the presence of natural organic
matter in water matrixes. In this work, resorcinol was
selected as organic precursor. The results showed that the
total transformation of diphenhydramine was reached after 60
minutes with the highest concentrations (150 mg/L of H2O2
and 5 mg/L Fe2+). However a low mineralization was
achieved. Moreover the Fe2+ concentration was kept constant
during all the experiments. The complex formation of Fe2+
with dihydroxybenzene isomer seems to improve the
extension of the iron solubility.

lack of efficiency of photo-Fenton at neutral pH

Diphenhydramine hydrochloride (DPH) is the could be solved by the presence of dissolved
classic H1 receptor antagonist used in pregnancy organic matter (DOM), due to the ability to form
for the treatment of allergics, nausea and vomiting stable complexes with iron [4, 8] at any pH.
as well as an analgesic adjuvant in cancer pain.
DPH has relatively low molecular weight (291.81 In this context, the aim of this work was the
g/mol) with high solubility in lipids, making it removal of DPH in aqueous solution by photo-
readily bioaccumulative. Low concentrations of Fenton at circumneutral pH. The acidification of
STUDY OF AMICARBAZONE PHOTODEGRADATION BY DIFFERENT ADVANCED
these compounds
Study [1] have been
of Amicarbazone found in the bythe
Photodegradation solutionAdvanced
Different is avoided by the will addition
be filledof
OXIDATION PROCESSES
environment [2]. Despite these low concentrations, resorcinol (RES, di-hydroxy benzene isomer)inused by PP2-2
Oxidation Processes
concern for 1 these pollutants 1comes from their to simulate organic matrix in water and toEAAOP4 generate
bioaccumulation and
M. P. Silva , A. C. persistence
S. C. as University
Teixeira . (1), well as their ferricarboxylates
of So Paulo, complexes.
Chemical Engineering Department, Avenida Prof.
Luciano Gualberto, tr. 3, 380, So Paulo, Brazil, marpradosilva@usp.br.
resistance to conventional wastewater treatments
[3]. Their degradation is necessary to prevent Samples of 2 L of 50 mg/L of DPH mixed with
accumulation in the aquatic environment and 50 mg/L of RES were treated by photo-Fenton, at
injuries to living organisms and human neutral pH, by using an UV-A photochemical
Thehealth.
UV/H2O2 and photo-Fenton processes are compared for the
Advanced Oxidation Processes (AOPs) may reactor
be a of the herbicide at different concentrations of H2O2 (15, 75
oxidation amicarbazone (AMZ), used
solution in the treatment of this contaminants [4]. and 150 mg/L) and Fe2+ (1.25, 2.5 and 5 mg/L),
extensively for weed control and developed to replace atrazine
As known, AOPs comprise a range of techniques added as Fe(SO4).7H2O. The photonic flow was
in large-scale cultivation. This investigation configures an
which can generate highly oxidant species measured
able tocontribution since with o-Nitrobenzaldehyde actinometry
original studies devoted to exploring AMZ
oxidize these substances to CO2, Hdegradation [9] and it was 3.59 J/s at 365 nm. During the
2O and by these advanced oxidation processes (AOP) are
inorganic salts [5]. Among these processes, photo- unknown.experimentation, the temperature of the solution
presently The photo-Fenton reaction shows the
Fenton can be an efficient route higher for the was kept at 25 C by controlling the temperature of
pseudo first-order rate constant at pH 3, with lower rate
degradation of a wide assortment ofconstants organic thanthe jacket of the reservoir tank by an ultra-
UV/ H2O2 process at pH 5 and 7. Addition of
refractoryChemical structure
compounds in of
water [6]. The main thermostat bath The information of the
organic matter decreased the degradation rates of pesticide in all
amicarbazone.
reaction involved in the production studied of free experimental device may be found elsewhere [10].
systems, via scavenging
Concentration of DPof hydroxyl radicalusing
was monitored and screen
a High
hydroxyl radicals is spontaneous dueeffect to produced
the by these materials.
presence of H2O2. In the presence of light and at Performance Liquid Chromatograph (HPLC) from
pH 3, the reaction system is autocatalytic, Agilent (Agilent 1260 Infinity). Total Organic
because Fe (III) reacts with H2O2 giving Fe2+ [7]. Carbon (TOC) was measured with a Shimadzu
The optimal pH for this process is 2.8, because the TOC-VCSN analyzer. Hydrogen peroxide
Background
solubility of Fe 3+ hydroxy complexes decreases for consumption was monitored by a
pH Pesticides
values higher thandetected
3 [8]. inThe need for
shortwaters
abstract spectrophotometric method during
indicating the novelty and main findings of the of-
AMZ belongs to the chemical photo-
group
have been surface degradation
triazolinones, reactions
has high (Hach LangeinDR
solubility 3900).
water (4.6ThegL
acidification
and ground inwater
the photo-Fenton
around the world process is often
work
[1,2]. should be
They 1 included here (Times New Roman 9 pt,
outlined as one of its major drawbacks. Therefore,
justified) and changes
shouldat notinexceed
pH concentration
4.9), the
is size of
of iron
considered
this in recalcitrant
area.the form of Fe and
reach surface waters through discharge of (II) was
therefore monitored
presents a by
risk a
to colorimetric
humans healthmethod
as well
there is strong
industrial interest processes
synthesis in workingand at neutral pH to
A Graphical
agro-industry Illustration at the left side should be readable in
avoid pH adjustment. The equipment
problems related toColor
the according
for the to
asBlack the 1,10-phenantroline
environment [7]. standardized
wastewaters, from spray andboth
pesticide and
procedure
&
(ISO
White
6332).
formats.
containers, spills due to improper handling Authorsand and the Silva
emailet address
al. (2015) ofshowed
the corresponding
that AMZ canauthorremain
should be typedinas surface indicatedwaters
above inmoreTimesthan New three
Romanmonths,
8 pt
disposal, agricultural runoff etc.
The persistence of pesticides in aquatic systems
172
italic. First author depending of environmental conditions [8]. This1is
MUST be the presenting author and MUST
register for the enough
SPEA8 Meeting.
time for it travels significant distances
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

COMBINED NANO ZERO-VALENT IRON IMMOBILIZATION AND HETEROGENEOUS

CombinedPROCESSES
FENTON Nano Zero-
ero-valent Iron Immobilization
FOR REMOVAL and Heterogeneous
OF METRONIDAZOLE PP2-3
Fenton Processes for Removal of Metronidazole
Xiangyu Wang
Wang*,Peng Liu. Faculty of Environmental Science and Engineering, Kunming University of Science
and Technology, Kunming 650500, P.R. China, famdct@sohu.com.
For the first time, the removal of metronidazole (MNZ) with
combined nano zero-valent iron (NZVI) immobilization and
Fenton processes (PPN-Fenton) was reported. PPN-Fenton
demonstrated excellent capability for removal of MNZ. Such
performance might be attributed to high reactivity of PPN and
heterogeneous Fenton oxidation of MNZ. Results show that
complete degradation of MNZ was achieved within 40 min with
PPN dosage of 15mg, H2O2 concentration of 6.60 mmol/L,
initial MNZ concentration of 100 mg/L, under temperature of
25C and pH of 5.0. In addition, the possible MNZ
degradation mechanism by PPN-Fenton was proposed. This
study suggests that the PPN-Fenton reaction may be a
promising technology for treatment of antibiotic wastewaters.

1. Introduction evaluate its efficacy for removal of MNZ. The

For more than a decade, a great deal of interest third objective is to propose the possible
has developed in degradation of pollutant by nano degradation mechanism of MNZ with two
zero-valent iron (NZVI) remediation technology, different treatment processes: reductive
which is environmentally friendly[1-3]. However, degradation and heterogeneous Fenton oxidation.
in practical, the applicability of NZVI is hindered 2. Methods
by aggregation of NZVI. In addition, degradation For the fabrication of PPN hybrids, three
of some persistent pollutants with NZVI is hard to processes occurred successively: the
INTERMEDIATES
obtain OF DEGRADATION GENERATED
an idealof efficiency. DURING THE ofFIRST OXIDATION
Intermediates degradation Therefore, the
generated during functionalization
the first oxidation states ofhydrophobic
PVDF

STATES OF
combined PHENOL
processes IN A PHOTO-FENTON
of NZVI and Fenton have SYSTEM membranes by in situ polymerization of AA, the
PP2-4
phenol in a photoFenton system
been investigated for in situ remediation. By incorporation of ferric ions within hybrids via ion

adding H2O2 into the reaction system, Fe2+ exchange process, and the reduction of NZVI

produced with Fe0 corrosion is capable of precursor, whether in Fe2+ or Fe3+ forms, by KBH4.


promoting decomposition of H2O2 into OH. Batch reaction took place in a serum bottle
Compared to homogeneous Fenton process,
OH
OH the containing 15 mg PPN and 50mL MNZ with OH

advantages of heterogeneous Fenton The process

study hasconcentration
considered the of formation
100mg/L. The bottles derived
of isomers were placedfrom
OH

include wider pH range and less sludge formation the on a rotary

dihydric rings shaker (50 rpm, 251C).
(pyrogallol, Certain
phloroglucinol,
CATECHOL PHENOL HYDROQUINONE
C6H6O2 C6H6O C6H6O2
OH

[4-6]. OH amount of and

hydroxyhydroquinone)
OH
H2Oquinones.
OH

2 was added
OH
The into the bottles
oxidation after the
through 20
To prevent aggregation of NZVI, a wideparasubstituted
variety min viaof reaction to initiate
with the theFenton process.
OH

is favored, formation of
OH

PYROGALLOL

of supporters have been proposed to hydroquinone, stabilize Liquid sample wasand

pbenzoquinone taken offcorresponding
their from the supernatant,
isomers.
C6H6O3 OH
OH
RESORCINOL HYDROXYHYDROQUINONE

NZVI[7,8]. In this study, NZVI was immobilized and then filtered through species
a pieceinofthemembrane
C6H6O2 C6H6O3
O
O Besides, catechol
OH
is the predominant
O
OH
O
reaction,
in PAA functionalized poly(vinylidene fluoride)
OH filterwould
which eventually
OH OHwith be a pore size toofpyrogallol
degraded 0.45m. and Meanwhile,
muconic
(PVDF) membrane to reduce their aggregation acid. However, 10L1M tert-butanol
the oxidation was added into via
by metasubstituted the also
filtrate to
takes
O
o-BENZOQUINONE PHLOROGLUCINOL O
C6H4O2 C6H6O3
DIHYDROXYBENZOQUINONE p-BENZOQUINONE

extent. The as-prepared composite is donated place, as prevent

although in a the oxidation
minority way.ofBased
radical.onFor thecomparison,
results, the
C6H4O4 C6H4O2

COOH

PPN. In previous literatures, Fenton process could

stoichiometry MNZof thewas proposed
removed with 15mg system
reactions non-immobilized
has been
H COOH OH O O
O
OH

be conducted together with NZVI technology for NZVI. The concentration of MNZ and
H H OH

estimated.
OH
O
H
Z,Z-MUCONIC ACID Z,E-MUCONIC ACID E,E-MUCONIC ACID

wastewater treatment.pathway However, few intermediates were analyzed with HPLC/MS

C6H6O4 C6H6O4 C6H6O4

Chemical
investigations have been reported in using (Agilent 1100) equipped with a UVVis detector.
PAA/PVDF immobilized NZVI (PPN) and H2O2 3 Results and discussion
as combined processes (PPN-Fenton) for removal 3.1 Characterization of PPN composite
of antibiotics (such as metronidazole). The presenceand
2. Materials of methods
elemental Fe signal in EDS
1. Introduction
Metronidazole (MNZ) is a widely used antibiotic spectrum of as-prepared PPN (Fig1(a)) indicated
thatStudies
has potential carcinogenicity The experimental assays of this work of have been
reported in literature and mutagenicity
concerning to the successful
carried
synthesis and
out with aqueous
immobilization
phenol solutions
NZVI
of the
500
ifevolution
its level is of
increased. Thus, the removal of
toxicity in artificial wastewatersMNZ in PVDF membranes. NZVI were formed on
iscontaining
of great concern. In this regard, the objective of mL. The
surface andspecific
inside catalyst
the pore dose
withforless
each experiment
aggregation
phenol, present a significant increase was added as ferrous ions (FeSO4 2H2O, Panreac
current
during study
the earlyis stages
to investigate the degradation
of the oxidation treatment. (Fig1(b)).
performance of MNZ by PPN-Fenton. The second 80%).
3.2 RemovalThese reagents
of MNZ are mixed
by different in a photo
materials
This fact could be directly related to the formation catalytic reactor equipped with a cooled quartz
objective is to characterize
of intermediate compounds synthesized PPN by
characterized andhigh
to Removal of MNZ with different materials is
sheath where the UV lamp is inserted (Heraeus
chemical stability and difficult to be mineralized
[12]. In this way, although phenol can be
TQ150, Hg medium pressure, 87.4V, 167.3W,
2.20A), with 95% transmission between 300570
173 1
effectively removed, it does not mean that the nm. The reaction mixture is homogenized by a
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

DETERMINATION OF THE DEGRADATION PATHWAYS INVOLVED DURING THE

Determination
TREATMENT OFof the degradation pathways
CIPROFLOXACIN involved during
BY PHOTO-ELECTRO the PROCESS
FENTON PP2-5
treatment of Ciprofloxacin by Photo-Electro Fenton process
P. Villegas-Guzman 1, F. Hofer1,2, C. Pulgarin2, R. Torres-Palma1. (1) Universidad de Antioquia, Calle 70 No. 52-
21, Medellin, Colombia, ricardo.torres@udea.edu.co (2) Ecole Polytechnique Fdrale de Lausanne, EPFL-SB-
ISIC-GPAO, Station 6, CH-1015, Lausanne, Switzerland.

The degradation of ciprofloxacin (CIP), a common

antibiotic, was studied using Photo-Electro Fenton (PEF).
The contribution of different processes implied in PEF were
investigated: Photolysis (UV), Electrochemical Oxidation
(EO) and Electro-Fenton (EF). Higher degradation rates
were observed during the Fenton based treatments. However,
an enhancement of the mineralization was achieved with the
PEF process. The antibiotic activity (AA) showed to be
closely related to CIP structure variations. Therefore, the
identification of the main degradation by-products was
carried out as well as their AA. Finally, the possible
degradation pathways of PEF process were proposed.

Introduction [4]; however, under the authors knowledge, there

The presence of antibiotics in residual waters is is no publications about the treatment of CIP by
one of the major health issues of the 21st century. PEF. Moreover, previous investigations have
Prolonged exposure time of antibiotics with shown the environmental risks associated to
microorganisms induces bacterial resistance antibiotics degradation by-products [5] and so it
leading to ineffectiveness of their treatment. becomes necessary to identify CIP by-products
ELECTRO-FENTON
Inefficiency TECHNOLOGY
of conventional water FOR THE TREATMENT OF DYE AND
Electro-Fenton
PHARMACEUTICAL
technology
EFFLUENTS
for thetreatments
treatment ofand dyetheir
and biological activity. Thiswillinformation be filled
PP2-6
regarding the degradation
pharmaceutical effluents of some antibiotics contributes to a better understanding of in bythe
causes them to accumulate in the environment, degradation pathways involved during EAAOP4 CIP
consequently
M.A. Sanroman a 1world
, E. Bocos 1
, E. Alfaya1, O.and
environmental human
Iglesias 1
, E. Rosales 1
treatment with
, M. Pazos 1
this
. (1) complexofprocess.
Department Chemical Therefore,
Engineering,
health concern. University of Vigo, Isaac
Ciprofloxacin (CIP),Newton Building, Campus
an antibiotic As Lagoas,
the main Marcosende
objective of this 36310,
study Vigo,
was toSpain,
investigate
sanroman@uvigo.es.
used against Gram-positive and Gram-negative the relationship between the degradation by-
bacterial infections, is partDegradation of these degradation products and the antibiotic activity, which leads to
resistant pollutants, commonly products In this study, determine
known as emergent the applicability of sandwich
the degradation cathode when
pathways formedCIP by is
contaminants (EC), which are found in different the combination of carbon
submitted to PEFfiberprocess.
sheets and granular activated
types of waters: natural water and wastewaters carbon [1].in electrochemical treatment of two dyes (Reactive
A solution to this problem is the use of Advanced Black 5 and Rhodamine B) and an antibiotic such as
Oxidation Processes (AOPs), which by hydroxyl chloramphenicol was demonstrated. Initially, the effect of the
Methodology
radical formation are able to degrade cathode
EC, ason the The H2O2experiments
generation and weredecoloration
carried outofindyes a 250wasmL
Power supply
antibiotics, and eliminate OH most organicevaluated. matter After determining the
reactor equipped with an external lampoptimal operational
present in waters. Photo-electro Fenton (PEF)conditions,
is a the process was
(max=254 nm).carried out inthrough
The flow continuous mode in
the reactor was
H2O2
quite recent AOP based on the combination a column
of the cell of reactor
34 mL with
min-1 multiple
and cathodes
the airflow and anodes,the
through
processes Airphoto-Fenton
O2
and electro-oxidationobtaining
[2]. near completewas
cathode chloramphenicol
of 838 degradation
mL min-1.in the The
inlet
This process has shown to be highly efficient effluent.for Summing up, sandwich
electrochemical cell was made cathode seemsof to a 4be cm2 a
the degradation of several organic pollutants suitableincathode material forstable
dimensionally the electrochemical
anode (Ti/IrO2) oxidation
and a 4 of
cm2
Pollutants
which different degradation processes could recalcitrant
be compounds
gas diffusion in continuous
cathode (GDE) mode.that was electrically
involved: photolysis, direct and/or indirect supplied with a current of 20 mA. CIP solutions
electrochemical oxidation and hydroxyl radical (0.1 mM) were prepared using distilled water with
attack. PEF could be considered an environmental sodium chloride
reached an excellent (0.05stateM) ofthat was used [2].
development as
1. Introduction
friendly technique since no critical reagents are supporting
They employ electrolyte and ironcurrent
the electrical sulfate to(0.09 mM)
generate
needed.
Nowadays, One an of increasing
the majornumber advantages of this
of hazardous as

OH,the avoiding
Fenton catalyst.
the use Antibiotic
of chemicals Activity
and (AA)
thus,
technique is related to the electro-generation
organic compounds are being discharged into the of was measured
reducing by the inhibitor
the potential hazards ofhalothe methodology
process. The
hydrogen peroxide,
environment, so that whichthere makes
is a ofpublic
this a concern
feasible using Escherichia
degradation mechanism coliof (Gram-negative)
the organic pollutants and
system the
about to world
be handle and automatized.
environmental situation.Several
More Staphylococcus
follows the Eq. 1aureusand 2, (Gram-positive)
where M represents as the
studies have shown
specifically, that CIPindustry
textile can be degradedgenerates by tested material,
anode bacteria. M( The

OH)mineralization
are the adsorbed level was
radicals
photo-chemical and
approximately 10.000 electro-chemical
different syntheticprocessesdyes [3] obtained
on by measuring
the anode, the Total
R is the organic Organic
matter and X Carbon
are the
inorganic ions.
annually, discharging a high percentage of its
production into the environment, mostly into the 174 M + H2O M(OH) + H+ +e- (1)
1
wastewater. Similarly, pharmaceuticals, personal
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

ELECTROKINETIC-FENTON TECHNOLOGY: A SOLUTION IN THE IN SITU REMEDIATION

Electrokinetic-Fenton Technology: A Solution in the in situ
OF HYDROCARBONS POLLUTED SOILS
will be filled
PP2-7
in by
Remediation of Hydrocarbons Polluted Soils
EAAOP4
M.A. Sanromn1, C. Sandu1,2, M. Popescu, E. Rosales1, E. Bocos1, G. Lazar2 M. Pazos1. (1) University of Vigo,
Campus As Lagoas -Marcosende 36310, Vigo, Spain, sanroman@uvigo.es. (2) Vasile Alecsandri University of
Bacau, Calea Marasesti 157 600115, Bacau, Romania.
In this study, an Electrokinetic-Fenton (EK-Fenton)
process was designed and several techniques were coupled
to enhance the process.
The feasibility of the developed EK-Fenton for the removal
of dye, polycyclic aromatic hydrocarbons and pesticide
from clay and sandy soils was demonstrated. In all cases,
the natural iron in the soils acted as catalyst for the
Fentons reaction. Moreover, key operational parameters
such as H2O2 concentrations, facilitating agents (citric acid,
surfactants) or pH of electrolyte were optimised.
The results obtained indicate the suitability of EK-Fenton
in the treatments of real soils with high content in iron and
petroleum hydrocarbons open an alternative in the
technological challenge of the in situ treatments of soils.

a small area of soil close to the cathode chamber

1. Introduction and the need to treat the liquid collected in
The environmental effects of contamination in chambers. To overcome these problems several
soils and water have been increasing in the last technologies have been performed in combination
years. Most of the released pollutants come from to electrokinetic treatments.
anthropogenic sources and are persistent in the Advanced oxidation processes have shown a
APPLICATION
environment. OF ELECTRO-FENTON
The of TREATMENT
accumulationtreatment these FOR THE ELIMINATION OF
Application of
IMIDAZOLIUM
electro-Fenton
IONIC LIQUIDS FROM
for the
POLLUTED
elimination
high potential forofthe treatment of different
WATER
will be organic
filled
PP2-8
contaminants
Imidazolium in Ionic
low permeability
Liquids from soils poses awater
polluted compounds due to the generation of nonspecific in by
significant environmental problem difficult to EAAOP4
and highly reactive species. When this technology
M. Pazos
tackle. For1, this
E. Bocos 1
reason, several1,investigations
, E. Rosales 1
M.A. Sanromnhave (1) Department of Chemical Engineering University of Vigo,
is Vigo,
coupled to electrokinetic, a combined
Isaac Newton Building, Campus As Lagoas,
been focused to solve this technical challenge by Marcosende 36310, Spain, mcurras@uvigo.es.
technology named electrokinetic-Fenton (EK-
application of in situ remediation technologies. Fenton) is performed. This technique consists in
Total petroleum hydrocarbons (TPHs) are one of several
the most common pollutants present in the soils This study stages:
focusesi)on thethe
transport of Fentons
application reagent
of electro-
(hydrogen
Fenton process peroxide)
using iron into the polluted
alginate beads soil byasthe
(FeAB)
due to industrial activities, accidental spills, etc. electric field action, of ii)polluted
in situ water
generation of OH
These pollutants may be toxic for microorganisms,catalyst for the
radicals
treatment with Ionic
plants and a source of contamination inLiquids. FivefromIonichydrogen
Liquids were peroxide decomposition
selected in order toby
Fenton
evaluate the reaction
effect of with
the the iron
length of present
the alkyl in
chainsoil,
groundwater.
and the nature of the anion on the degradation.iii)
according to the equation 1[2], and
Conventional treatment technologies such asInitially, subsequently,
the optimum the FeAB
reaction of degradation
dosage and the kineticof the
bioremediation, vapour extraction or pump-and-degradation pollutants of bytheoxidation
pollutantsreaction with OH radicals.
were determined. After
treat usually require long operational periods andoptimisation, H2O2 + Fe the2+ effect
Fe3+ of+ OHthe+ current
OH- (Eq.intensity
1)
can be mainly used as containment technologiesapplied on the degradation and mineralisation of the
with high operation and maintenance costs [1].compounds Thus, were
to improve
studied. theThedegradation reactions,
results indicate it is
that
Therefore, the development of new in situthe electro-Fenton necessary to increase processthe is mobility of the hydrogen
a good option for the
treatments able to overcome these drawbacks iscomplete peroxide across theofsoil
elimination and the solubility
hazardous of iron
contaminants,
required. Among the different in situ treatments, it h andI organic i Li pollutants
id f from solid matrix. Recently,
is important to highlight the electrokinetic the addition of facilitating agents such as
remediation. This technique is based on the surfactants or complexing agents to the processing
application of a low intensity current to an complete
fluid has beenelimination
appliedoftothese pollutants.
enhance Although
the feasibility of
1. Introduction it is possible the regeneration of Fe 3+
to Fe2+
electrokinetic cell filled with a polluted soil, both the process.
ofOverits the past decades,
extremes connected the use
to oftwo
Ionicelectrode
Liquids during the electro-Fenton, the main drawback of
(ILs) has been extended to a broad
chambers. This current promotes the movement of number of Theprocess
this aim of is thethis impossibility
study is to toanalyse operate the in
industrial
the applications,
pollutants from the anode generally involving
chamber towardwater
the decontamination
continuous of TPH-polluted
process. On thissoilsway, using the
streams. ILs
cathode are usually
chamber. The composed of an inorganic
main problems of this enhanced EK-Fenton
immobilisation of process. For thisonpurpose,
the catalyst the
different
anion and are
treatment an the
organic cation [1].ofInitially
concentration regarded
the pollutants in EK-Fenton
supports, suchprocess was initially
as alginate, has beeninvestigated
studied [4]. for
as green solvents, during the last years the The aim of this work was to evaluate the
toxicity of ILs on different organisms has been
demonstrated [2]. Since they are continuously 175
feasibility of the electro-Fenton process for the
elimination of five ILs from water. The FeAB
1
released on the industrial streams, it can be dosage was initially optimised. Besides, the
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

HIGHLY ORDERED SPHERICAL SBA FOR CONTAMINANTS REMOVAL VIA FENTON

Highly Ordered Spherical SBA for Contaminants Removal via Fenton
PROCESS PP2-9
process
Marcelo G. Rosmaninho1, Flvia C. C. Moura1, Amanda R. Martins, Adriana B. Salviano, Aline A. S. Oliveira.
Universidade Federal de Minas Gerais, Avenida Presidente Antnio Carlos, 6627 - Pampulha, 31270-901, Belo
Horizonte,Minas Gerais,Brasil. (1) mgrosmaninho@gmail.com

Silica SBA-15 was synthesized for the first time with spherical
morphology via non-hydrothermal sol-gel method. Analysis by
TEM showed that the SBA-15 presents highly organized
structure with hexagonal pores. The synthesized SBA was
applied as support for Fe catalyst, giving the SIFe catalyst. The
iron nanoparticles supported were used for carbon deposition on
the surface of SBA from ethanol via Chemical vapor deposition -
CVD. The catalyst obtained by CVD was named SIFeC. SIFe
and SIFeC were employed in quinoline and methylene blue
oxidation reactions, showing promising results. It is observed
that the carbon coating stabilizes the SBA and favors oxidation
reaction.

Introdution
only by complex synthesis routes, mostly
Highly ordered mesoporous silica have been involving high pressure. In this work, we proposed
widely used recently as adsorbents, catalysts and a very simple and low cost method for the
catalyst supports [1]. A special family of highly preparation of highly ordered spherical SBA-15
ordered mesoporous silica called Santa Barbara and its application as catalyst support.
Amorfa (SBA)[2,3]
REMOVAL has acquired greatFROM
OF BETA-BLOCKERS importanceAQUEOUS The MEDIA
activity of
BYthe catalysts basedONTO
ADSORPTION on SBA-15 was
inRemoval
nanotechnology.
GRAPHENE ofOXIDE
Beta-Blockers from Aqueous Media by Adsorption
evaluated in quinoline ontooxidation reactions. One of PP2-10
Graphene
The SBAs can Oxide present cubic or hexagonal the main contaminants currently generated are the
structure. Among
D. A. Lambropoulou, these materials,
G. Kyzas, the SBA-15
A. Koltsakidou, has D.nitrogen
S. Nanaki, Bikiaris organic molecules originated from
been
Aristotle extensively studied due
University of Thessaloniki, to 24present
GR-541 Thessaloniki,petroleum-based fuels, the main energy source
Greece, dlambro@chem.auth.gr
mesoporous structure with one-way hexagonal today. The presence of these compounds in fuels is
ordering, connected by micropores withThe aim of this undesirable
diameters study is thebecause
adsorptiontheyevaluation
produce of graphene
environmental
ranging from 2 to 30 nm and with oxide (GhO) aspollutants
remarkable adsorbent(NOx)material for the
during removal of
combustion, beta-the
affect
thermal,
60
hydrothermal and mechanical
PRO
blockers existed stability
stability in wastewaters.
of fuels The
over two
timemodel
and aredrug molecules
suspected to be
[3,4]. were atenolol carcinogenic
(ATL) and agents propranolol
and acid (PRO). After the
rain precursors.
27
ATL
24
pseudo-1st order

The highly ordered silica can be prepared characterization

by a of GhO surface with SEM images, FTIR
50 pseudo-2nd order 21
Ce (mg/L)

18

variety of methods using surfactants asspectroscopy templates. was used in order to confirm some possible
Methods
15
40 12
Ce (mg/L)

most common method used is adsorption the sol-gel interaction between drugs and adsorbent. The
9

The30 zoom-in 6

PluronicdataP123
weresurfactant (2g) was Freundlich
dissolved in
3

[5,6].
20
adsorption equilibrium
20 30 40 50 60 70 80 90 100 110 120 130
t (min) fitted to Langmuir,
Pure mesoporous silica is an inert and
matrix, which 50mL of milli-Q
Langmuir-Freundlich model water and 10mL
calculating theHCl (conc) under
maximum
10
usually exhibits low adsorption capacity adsorption
and lowcapacity stirring at 40
(67 and Cmg/g
116 for 2h.
for Then
PRO and4.5mL
ATLof(25
tetraethyl
C),
catalytic
0
0 50activity
100 due
150 to200the 250
absence
1200 respectively). The
of heteroatoms orthosilicate
temperature (TEOS)
effect was added dropwise,
on adsorption under
was tested
that provide active sites. Several studiesand
t (min)
the the
report stirring forparameters
thermodynamic 4h at 40 C. Aftercalculated.
were 20h the temperature
Finally,
dispersion of different atoms on the surface desorption was then
of the of drugs fromincreased
GhO wasto evaluated
85 C andbymaintained
using bothfor
silicate materials in order to provide aqueous eluants 48h.
catalytic The obtained
(pH 210) solids
and organic were filtered and washed
solvents.
active sites on the surface and/or in the cavities of with deionized water until conductivity reached
the1.mesoporous silica. values lower than 10 S/cm. From there they were
Introduction their adsorption, because PRO possesses an extra
The synthesis of silica dried in an oven at 60 C for 12h and calcined at 1
Beta-blockers are ain class the shape of of spheres with
pharmaceutical benzene-1 ring, which is by far more inactive
well defined size and pore diameter has been the C min to 550 C for 6h to obtain pure SBA-15.
compounds, among others, that are not effectively compared to the second amino group of ATL.
object of several studies, because the control of the To produce the SBA-15 impregnated with iron
removed during wastewater treatment, while they Based on the above, their removal characteristics
particle morphology and pore size opens upwater new (SIFE), Fe(NO3)3.9H2O was dissolved in ethanol
are detected in various environmental were investigated and compared in detail based on
possibilities for the application of these materials and mixed with SBA-15 previously dispersed in
samples [1]. Since the traditional water and the differences in their physicochemical properties
in adsorption, chromatography, catalysis ethanol. The mixture was allowed to stir at 30 C
wastewater treatment technologies are not ableand to and chemical structures. The effects -1 of different
pharmaceuticals. To the best of our knowledge, for 24h before calcination at 1 C min to 300 C
remove compounds like beta-blockers from the adsorption conditions on ATL and PRO removal
SBA-15 with spherical morphology for 1h. SIFe was subjected to a CVD process
water, different treatment options isareobtained
under were also studied: solution pH, temperature, and
discussion to eliminate them. Recent studies have adsorption time. Finally, the adsorption isotherms
studied photocatalytic degradation for the removal
of beta-blockers, ozonation or adsorption with
176 1
and kinetics of the adsorbents were studied and
discussed in order to understand the adsorption
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

PHOTO-FENTON REACTIONS PROMOTED BY Fe/C COMPOSITES PRODUCED FROM IRON

Photo-Fenton
RICH MINERALreactions
WASTES promoted by Fe/C
AND BIO-OIL composites
AQUEOUS ACID produced from
FRACTION PP2-11
iron rich mineral wastes and bio-oil aqueous acid fraction.
M. G. Rosmaninho 1, F. G. Mendona1, J. D. Ardisson 2, R. M. Lago1, J. C. Tristo3. (1) Universidade Federal de
Minas Gerais (UFMG), Antnio Carlos 6627, Belo Horizonte, Brazil, mgrosmaninho@ufmg.br. (2) Centro de
Desenvolvimento da Tecnologia Nuclear (CDTN), Antnio Carlos 6627, Belo Horizonte, Brazil. (3) Universidade
Federal de Viosa (UFV), Campus Florestal, Florestal, Brazil

In this work, active photo-Fenton materials based on Fe/C

composites were produced from the bio-oil aqueous acid
fraction (AAF) and laterite, a Fe rich mining waste. The thermal
treatment of the obtained mixture with Fe3+extracted containing
organic compounds in different temperatures, i.e. 500, 650 and
800C, produced three Fe/C composites. At 500 and 650C it
was observed the presence of phases of Fe3+, characterized by
Mssbauer spectroscopy and DRX. At 800C phases of Fe0
were identified, besides Fe3+. The composites produced were
tested for the oxidation of methylene blue (MB) with H2O2 in
photo-Fenton reactions, showing promising results.

On second step, the materials produced on the

Introduction
first step (500 mg) were heat-up in a horizontal
Many industrial activities lead to high amount of tubular furnace under nitrogen flow (50 mL min-1)
iron-rich wastes, like the laterite in the iron mining at 500, 650 and 800 C for one hour (rate of 10 C
USE OF PHOTO-FENTON PROCESS TO REMOVE minORGANIC
-1
Three MATTER
).Matter composites FROM
were FULLER
thenwillproduced:
andUsered-mud
Of in the Bayer
Photo-Fenton ProcessProcess To toRemove
obtain Organic From Fuller be filled
CLAY CONTAMINATED
aluminium. These wastes With WITH INSULATING
shownInsulating
a relative Oilhigh OIL FAFe500, FAFe650 e FAFe800. in by
These materials PP2-12
Clay Contaminated
concentration of iron and could be used in many were characterized by Mssbauer Spectroscopy EAAOP4
Milady R. Apolinrio
environmental da SilvaIn
applications.
1
, Eduardo
the lastdeyears
O. Rodrigues
the
2
,(MS),
Flvio S.X-Ray
Silva1, Mrcia M. Kondo
Diffraction
1
, Rossano
(XRD), Elementary
Gimenes 1
. (1) Itajub Federal University
application of such waste-based materials on (UNIFEI)- Av. BPS, 1303,
Analysis Itajub, Minas
(CHN), Gerais State,
simultaneous Brazil thermos-
miladyapolinario@hotmail.com. (2)Federal Institute of Inconfidentes- Praa Tiradentes, 416, Inconfidentes, Brazil
Advanced Oxidative Processes (AOP), especially gravimetry and differential thermal-analysis (TG-
Fenton-like reactions, has been of high interest.[1] In this DTA),
work, the Scanning
use of Electronic
photo-Fenton Microscopy
process to(SEM),treat
Energy Dispersive
contaminated Fuller ClaySpectroscopy
with insulating(EDS),degraded
Infra-red
In this work an innovative method to extract the
mineralspectroscopy
oil from power (FTIR) and Ramanwas
transformers spectroscopy.
investigated.
residual iron from the laterite (a mining waste)
The results indicated a 20 and 21% oil and grease and
using the aqueous acid fraction (AAF), by-poduct Each photo-Fenton reaction was conducted
total carbon removal, respectively. Chemical oxygen
from the fast pyrolysis of biomass to produce bio- using 10 mg of composite and 20 mL of
demand (COD) and polychlorinated biphenyl reached 60
oil, was proposed. Using this method, the iron Methylene Blue dye solution (50 ppm). Initially
and 90 % (Figure 1) removal, respectively. No changes
from laterite is extracted by the AAF and, after the composites and the MB were kept under
in crystalline structure of the Fuller clay were evidenced.
termal treatment at different temperatures, an Fe/C magnetic agitation and dark condition for 24 hour
These results indicated that the photo-Fenton process
composites are obtained. These composites were to observe any adsorption effect. After this time,
was effective to treat the contaminated Fuller clay.
then tested in photo-Fenton reactions to methylene 0.3 mL of an 35 vol.% hydrogen peroxide were
Figure 1. Chemical Oxygen Demand (COD), oil and Grease,
blue (MB) dye removal. added and
Total Carbon and polychlorinated
the mixture was biphenylplaced
(PCB) in removal
an UV
percentagereactor
from equipped
contaminated with a 15
Fuller clay W afterHg-lamp.
photo-Fenton The
(max =photo-Fenton
254nm). Initialreactions
COD: 297,0gwereL -1made
of O2under
. magnetic
Experimental stirring and room temperature, and the
concentration of MB was monitored using a UV-
The Fe/C composites were obtained by a series Vis spectrometer (Shimadzu model UV-2550) at
of thermal treatments. On the first step, iron-rich (GC-MS 7890-Agilent).
fixed wavelength of 610 nm. In order to verify
The mineral oil is the mainly electric
laterite waste (50 mg) was mix to aqueous acid insulator in possible changes in the Fuller clay structure due
the electric
fraction (20 energy
mL), and transformer.
heat at 100This C foroil 24
canhour
be to For comparison,
chemical treatmentpureby photolytic
photo-Fenton reaction
process,(in
used
underfor a longstirring
magnetic period inofatime
closed until it loses
flask. After the
the absence Spectroscopy
Infrared of hydrogen peroxide) and pure (FT-IR;
Fourier Transform Fenton
insulating capacity
iron extraction due to
process, thethe degradation
resulted mixture of was
the reaction (under 100, dark condition) were Nalso realized
Spectrum Perkin Elmer), 2 sorption
oil, generating
heat-up at 100 C many oxidized
in an open flask organic
until products.
complete to the composite FAFe650.
isotherms and surface analysis by BET, X-ray
Depending on the aorigin
drying, producing blackof the mineral insulation
solid. Diffraction (XRD- X'Pert Pro- Panalytical) and
oil it can be contamined with polychlorinated Scanning Electron Microscopy (SEM SS-550-
biphenyl (PCB), which are carcinogenic
compounds. The reclamation process used to
retain the undesirable compounds from degraded
177
Shimadzu) were employed.
Contaminated Fuller clay sample showed 297.0
1
-1
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

STUDY OF REDUCTIVE REACTIONS INVOLVED IN THE PHOTO-FENTON PROCESS USING

Study of reductive reactions involved in the photo-Fenton process
ZERO VALENT IRON (ZVI)
will be filled
PP2-13
in by
using zero valent iron (ZVI)
EAAOP4
A.M. Amat,1, L. Santos-Juanes1, R.F.Vercher, A. Arques.
(1) Grupo de Procesos de Oxidacin Avanzada. Departamento de Ineniera Textil y Papelera.
Universitat Politcnica de Valencia, Plaza Ferrndiz y Carbonell s/n, Alcoy Spain. aamat@txp.upv.es

The use of zero valent iron (ZVI) as iron source in photo-Fenton

process has deserved an increasing interest by researchers in the
last years. Since iron is oxidized in aqueous media a reduction
reaction must be coupled. Although the attention is normally not
focused in these reactions, they could be important in the
treatment of some kind of pollutants. The main goal of this work
is the study of the reductive reactions involved in photo-Fenton
process when ZVI is employed. A combined process with
reductive an oxidative reactions have been carried out. The
reduction of 4-nitrobenoic acid has been observed while other
pollutants did not suffer any change in reductive conditions.
Some factors like pH, conductivity, H2O2 concentration have
been also studied.

Introduction acid, caffeine and paracetamol in a concentration of

5mg/L each one. Different process conditions were
In last the years, use of Photo-Fenton process as
applied to enhance oxidative or reductive reactions:
tertiary treatment has focused a great proportion of
tap or deionized water, 3 different values of pH,
the published papers. For this reason, the possibility
hydrogen peroxide presence or absence. Finally a
of run thePHOTO
SOLAR process atFENTON
neutral orTREATMENT
circum-neutral pH OFisPHENOLIC COMPOUNDS
Solar Photo-Fenton Treatment Of Phenolic combined
Compounds process
Commonlywas COMMONLY
evaluated with FOUND
will bea filled
first
probably
IN FOODthe mail goal toINDUSTRY
PROCESSING achieve. The use of PP2-14
reductive step followed by a conventional photo- in by
Found In Food
heterogeneous Processing
catalyst, in this Industry
case inorganic
Fenton process. EAAOP4
supports like zeolites, or activated carbon can be
Rosa F.Vercher Sara Garca-Ballesteros1, Margarita Mora1, Consuelo Sabater 1, M. Angeles Castillo1, Antonio
1,
usedArques
while1 yinAna
other applications iron oxides or zero
Mara Amat1. (1) Grupo de Procesos de OxidacinResultsAvanzada.
and Conclusions
Dpto de Ing. Textil y Papelera. Univ.
valent iron (ZVI) are applied.
Politc. de Valncia, Pza Ferrndiz y Carbonell 1, 03801-Alcoy ,rverche@txp.upv.es
Only 4-nitrobenzoic . (2)acidDpto Biotecnologa.
suffered chemical
Univ. Politc. de Valncia, Camino de Vera s/n, 46022-Valencia
Zero valent iron photo-Fenton produces the reduction while it had the lowest kinetic constant
oxidation of the pollutants in homogeneous and in when the oxidative reaction was applied. 4-
heterogeneous phase. Dissolved iron acts A representative
in of Food processing
aminobenzoic acid was waste water
detected as mixture
the mainofby 8
homeogeneous phase like iron oxide surfaces pollutants
can (tannic
productacid,
formedelagic acid,
in the 2,4-dinitrophenol,
reduction gallic
of 4-nitrobenzoic
produce heterogeneous reactions. In one way acid, orprotecatechuic acid, vanillic acid, syringic
acid. 4-hydroxyaminobenzoic acid wasacid and also
another, an oxidation reaction of the ZVIsinapic must acid)detected
was treated
whenby solar photo-Fenton
reductive reaction timeporcess.
was high. The4-
involve the corresponding reduction reaction. aimThis
of thesenitrobenzoic
study is toacid
determine the effect
degradation of operational
by reductive way was
reaction can produce hydrogen peroxide variables or can (pH, H2O2 at
enhanced andhigher
Fe2+ amount)
pH values. for this porpouse
In any case,
directly react with one of the pollutants present. experimental design methodology
reductive reactions caused based on Doehlert
TOC decrease. matrixes
Reactivity of the pollutants in a reductive reaction has been used. Different bioassys were carried out to prove the
will depend on the presence or not- of deactivating In contrast,
treatment efficiency this compound
for wastewater showed the worst
detoxification.
groups. This first step can enhance the later photo- degradation rate when a conventional photo-Fenton
Fenton conventional oxidation. was applied. For these reasons a reductive and
oxidative processes must not be carried out
In this research the reductive reactions involved simultaneously. It is recommended a first reductive
in ZVI photo-Fenton treatment of 5 pollutants have step (in hydrogen peroxide absence) followed by a
been studied. Some of the possible affecting factors conventional photo-Fenton process using dissolved
have been also tested. iron of first step.
(Table 1). Dohelert desing matrix. Illumination time
Introduction
Methods required to degrade the 80% of the mixture of the 6
Acknowledgements
Wastewaterssteel
Commercial fromwool
food has
processing industry
been used as ZVI (wine
and pollutants (t80%) was used as response.
Authors want to acknowledge Financial support
and stream
the coffe production,
containingoil, cork
five boiling...)have
pollutants represent
been from the Spanish Government (Project CTQ2012-
an important
passed through environmental concern.selected
it. The pollutants They showwere:a 38754-C03-02) is gratefully acknowledged.
complexacid,
benzoic composition and in particular,
4-nitrobenzoic phenols and
acid, p-toluensulfonic Table 1. Dohelert desing matrix
related compounds are difficult to degrade by
classical means. Advanced oxidation Porcesses
(AOPs have been demonstrated as potential 178 N
Experiment
[Fe2+]
(mg/L)
[H2O2]
(mg/L)
pH1

tratment for this type of compounds [2]. The 1 3 55.25 3.9

F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

PHOTO-FENTON MEDIATED DEGRADATION, MINERALIZATION AND DETOXIFICATION

Photo-Fenton
OF mediated
THE INSECTICIDE degradation, IN
THIACLOPRID mineralization
AQUEOUS MEDIAand PP2-15
detoxification of the insecticide thiacloprid in aqueous media
C. Berberidou1, V. Kitsiou1, D. Michailidou1, D. Lambropoulou1, A. Kouras1, C. I. Kosma2, T. A. Albanis2, I.
Poulios1 (1) Laboratory of Physical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki,
Thessaloniki, Greece, cberber@chem.auth.gr. (2) Department of Chemistry, University of Ioannina, 45110,
Ioannina, Greece.
Degradation and mineralization of thiacloprid, a neonicotinoid
80
insecticide often present in drinking water, by homogenous
photocatalytic oxidation in the presence of UV-A and visible
% Biolluminascence inhibition

60 light has been studied. The effect of various operating conditions

such as Fe3+ and H2O2 concentrations in the photodegradation
kinetics was investigated. Mineralization via the organic content
40

20 reduction (DOC) and inorganic sulphur and nitrogen evolution of

the insecticide was examined. The use of UV-A irradiation
0
0 50 100 150 200 250 300
resulted in all cases in higher initial degradation and
time (min)
mineralization rates, while ecotoxicity in the presence of 7 mg L-
Variation of ecotoxicity of 20 mg L-1 1
Fe3+, 100 mg L-1 H2O2 and UV-A was completely removed
thiacloprid solution using the photo-Fenton
reagent (7 mg L-1 Fe3+, 100 mg L-1 H2O2, within 300 min of illumination.
UV-A.

Pesticides are widely used as a result of intensive nm. Changes in the concentration of thiacloprid
agricultural practices [1]. As these contaminants were monitored via its characteristic absorption
are in many cases toxic and non-biodegradable, band at 280 nm using a UV-Visible
they tend to accumulate in the environment and to spectrophotometer (UV-1700, Shimadzu).
magnify through the global trophic network with Determination of dissolved organic carbon (DOC)
unpredictable consequences [2]. Thiacloprid was conducted according to standard methods by a
HOMOGENOUS PHOTOCATALYTIC
({(2Z)-3-[(6-Chloropyridin-3-yl) DEGRADATION
methyl]-1,3- TOC OF THE HERBICIDE
analyzer (Shimandzu VCSH CLOPYRALID5000). IN
Ions
Homogenous
AQUEOUS MEDIA:
thiazolidin-2-ylidene}
Photocatalytic
KINETICS, Degradation
cyanamide) isMINERALIZATION
an insecticide
Of Thewere
Herbicide
AND TOXICITY
determined by a Shimadzu system
will be filled
equiped PP2-16
in by SPEA8
ofClopyralid In Aqueous
the neonicotinoid class,Media:
with Kinetics,
high water mineralization
with a CDD-6A and toxicity conductometric detector.
solubility,
C. Berberidouused, V.
1
onKitsiou
agricultural
1
crops to control
, F. Kondyli-Sarika 1
a Ecotoxicity
, D. Lambropoulou 1
was ,determined
, A. Kouras 1 1
byLaboratory
I. Poulios . (1) a Microtox of M500
Physical
variety ofChemistry, Department
insects, primarily of Chemistry,
aphids Aristotle University
and whiteflies analyzerof Thessaloniki,
using marine Thessaloniki, Greece,
bacteria Vibrio fischeri.
cberber@chem.auth.gr.
[3]. Studies of the environmental behavior of TCL In the case of UV-A irradiation, photo-Fenton
have shown that the molecule is resistant for 6 and degradation of aqueous thiacloprid solutions of 20
more months to the degradation inDegradation
80 water by and mg mineralization of clopyralid,
L-1 initial concentration, using 7a mg systemic
L-1 Fe3+
hydrolysis in acidic or neutral media Alternative herbicide often reported to occur in drinking water,
and increasing H2O2 concentrations up to about by the photo-
% Bioluminescence inhibition

treatment methods currently employed60 Fentonfor andthe Ferrioxalate

100 mgreagents L-1 ledin the to presence
increase ofofUV-A the andinitial
degradation of agrochemicals in visible water light and hasdegradation
been studied.rates;
3+
The effect of various
nonetheless, operatingthe
increasing
40

wastewater include Advanced Oxidation conditions as Fe , oxalatefrom

Processessuch concentration and 100
H2O2toconcentrations
200 mg L-1 in hadtheno
(AOPs). Among them, homogenous photocatalytic
20
photodegradationfurther kinetics was investigated.
beneficial effect sinceMineralization
greater peroxidevia
oxidation mediated by the photo-Fenton the organic
reagent content dosages reduction
may be(DOC) and inorganic
responsible for hydroxyl nitrogen
radical
(Fe3+/H2O2/UV-A or Visible) has been 0
0 50
evolution
effectiveof thescavenging.
100
insecticide Similar
150 200
was examined. The use
results were of UV-A
obtained in the
for the degradation of various contaminants
time (min) irradiation
foundresulted
casein of all photo-Fenton
cases in higherdegradation
initial degradation and
of thiacloprid -
in industrial
Variation or domestic
of ecotoxicity of 40 wastewaters,
mg L -1 mineralization
including rates,
under while
visible light. Moreover, mineralizationL of
ecotoxicity in the presence of 7 mg
1 3+ -1
clopyralid agrochemical
toxic solution using the photo-Fenton
substances, such Fe , 100 as mg carbon
L H2Owas 2 and UV-A
faster wasUV-A
under completely removed to
in comparison
reagent (7 mg L-1 Fe3+, 100 mg L-1 H2O2, withinstudy240 min of illumination.
insecticides
UV-A. and herbicides [4]. Our current visible light. Evolution of inorganic sulphur and
investigates the potential of the photo-Fenton nitrogen during photocatalysis, reached almost
reagent to degrade thiacloprid under various 90% in both cases, within 180 min of UV-A
operating
Among the conditions,
various as well assubstances
organic mineralization
that andare illumination
wastewaters. A under variety optimum conditions.
of toxic agrochemical
reduction
known as of ecotoxicity
water pollutants, under optimal conditions.
pesticides are a major Ecotoxicity
substances, such was as completely removed
insecticides within 300
and pesticides has
Bench scale
pollution sourcephotocatalytic
for both ground experiments
and surface were min
been of UV-Ain illumination,
studied regard to their under the same
photocatalytic
performed
waters. [1]. in In ahighly
closed Pyrex cell countries
industrialized of 600 the ml conditions.
degradation,This factpresence
in the highlightsofthe potential
artificial or ofsolar
the
capacity,
problem of fitted with awastes
pesticide centralis 9mainly
W lamp, relatedunder
to photo-Fenton
illumination, with reagent to purifyresults,
very encouraging waterwhile or
constant
wastewater, magnetic
recycling,stirring. The spectral
elimination response
of packaging wastewater
studies dealing containing
with real or pesticides,
simulated whichwastewater are
of
andthetheUV-A irradiation
remediation source, rangedsoils.
of contaminated betweenFor characterized
have revealedfor that their their
high toxicity
complete and or resistance
partial
350-400
developing nmcountries,
(max: 366 thenm),mainwhile that of
problem is the to biodegradation.
degradation is possibleDetermination
via the above of major
mentioned
visible irradiation
elimination of unused source(forbidden),
ranged between 400-520
obsolete and intermediate
method [6].by-products
Our current is currently
study in progress,
investigates
unusable pesticide stocks. As these xenobiotics are heterogenous photocatalytic decomposition and
in many cases toxic and non-biodegradable, they
have the ability to accumulate in the environment
179
mineralization of clopyralid mediated either by the
photo-Fenton or the Ferrioxalate reagent, in order
1
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

Homogeneous photocatalysis
HOMOGENEOUS PHOTOCATALYSISfor the removal
FOR of UV filter
THE REMOVAL OFpara-
UV FILTER PARA- will be filled
in by
aminobenzoic acid
AMINOBENZOIC ACIDin IN
aqueous solutions
AQUEOUS by means
SOLUTIONS BY of artificial
MEANS OF ARTIFICIAL ILLUMINATION PP2-17
EAAOP4
illumination
S. Tsoumachidou1, I. Poulios1.(1) Laboratory of Physical Chemistry, Department of Chemistry, Aristotle
University of Thessaloniki, 54124 Thessaloniki, Greece, stsoum@gmail.com

The presence of personal care residues in the environment is an

emerging issue due to their uncontrolled release to the
environment. Several effects have been shown to occur from
continuous exposure, which slowly accumulate to manifest
100 Fe3+/uv-a themselves into an irreversible condition affecting living
organisms, ecosystems and public health. In this paper, the
90
Fe2+/uv-a
80

homogeneous photocatalytic degradation of para-aminobenzoic

% elimination of PABA

70

acid (PABA), a UV filter, which is present in many types of

60

50

40

30
Fe3+/visible personal care products, is investigated, in order to identify the
20
Fe2+/visible
optimum homogeneous photocatalytic system that should be
applied to the further investigation of the treatment of grey
10

0
photo-fenton reagent
water. The oxidation of PABA by photo-Fenton process was
Elimination of PABA within 30 minutes, in the investigated under artificial UV-A and visible irradiation and
presence of photo-Fenton reagents (Fe3+/H2O2 and the effect of various operating variables, the catalyst and
Fe2+/H2O2) under artificial UV-A and visible
irradiation (initial conditions: 0.02 g L-1 PABA) oxidant concentration, as well as the temperature has been
assessed. The PABA degradation in acidic medium was
evaluated by the decrease in PABA absorbance on the
spectrophotometer.

Pharmaceutical and personal care products dermological problems and undesirable estrogenic
(PPCPs) are emerging contaminants that have and antithyroid effects. Therefore, many countries
HSO
drawn5 /M
- n+
/UV-A
extensive LED AND PHOTO-FENTON PROCESSES
n+ attention due to their potential have limited FOR its WINERY
presence inWASTEWATER
cosmetic products and
HSO
TREATMENT 5
-
/M /UV-A LED and Photo-Fenton Processes for Winery PP2-18
hazardous effect on ecological system and the surface waters by setting maximum safety
human Wastewater
beings. Since Treatment
PPCPs had been designed to measures.
M. S. Lucas
be lipophilic and
1
, J.biologically
Rodrguez-Chueca persistent,
2
quite
, T. Silva 2
, C.a Amor
lot 2, G. Li Puma1, J.A. Peresacid
p-Aminobenzoic 2
. (1)(PABA)
Chemicalis Engineering
a compound of
Department, Loughborough
of them resist to biodegradation [1]. Consequently,University, Loughborough, LE11 3TU, United Kingdom,
particular concerns. Since M.P.Lucas@lboro.ac.uk.
patented in 1943, PABA
a wide(2) Centro range de Qumica
of PPCPs de Vilahave Real, Departamento
been detected de Qumica,
was oneUniversidade
of the first de active
Trs-os-Montes
ingredients e Alto
to Douro,
be used in
5000-801 Vila Real, Portugal.
throughout the world in surface water (e.g. lakes sunscreen and most widely used in sunscreen and
and rivers), soil, sludge, fish and even the humanwastewater
Winery pharmaceutical
treatment products
through in concentrations
the applicationup of to
body [2].100
Advanced Oxidation
UV-A LEDs 23 W/m
2 5% [4]. The continuous
Processes
UV-A LEDs 70 W/m
2
(AOPs) based inputon ofthe
PABA into the
generation of
As one of the important PPCPs, sunscreens areradicals
environment
[HSO5-/Mthrough
n+] and personal
hydroxyl care applications
UV mercury lamp No radiation
sulphate radicals (photo-
attracting increased public concern and Fenton) scientificwith has caused
LEDs particular concerns since the previous
75
UV-A was evaluated. At 323K, best
COD removal (%)

interest, 50
because the consumption of sunscreens
efficienciesis studies
were demonstrated
obtained when was that
used asPABA
catalyst can
Co 2+ increase
(79 and
increasing due to the growing awareness 64%ofofthe COD andphotosensitivity
TOC removal,and lead to DNA
respectively), damage
while at 293K [5].theIn
need of 25
prevention from skin cancer. best Cosmetic
results werethe obtained
early 1980s,with Fe researchers
2+ (65 and demonstrated
52%). The HSO that
5
-

sunscreens have been used over 75 /Fe years

2+/UV-Aas PABA increases the formation
LED process present important advantages of a particular
protection 0 from skin photodamage. UV comparatively filters are DNA
to thedefect in human process
photo-Fenton cells [6].(Fe Contamination
2+/UV-A LED) of
vital ingredients ofTime sunscreens and othersince personal the require
aquaticpH environment
adjustment andwith doesPABA from
0 20 40 60 80 100 120
(min) it does not not generate
care products
Influence of UV as they
source in thearePMS/Co(II)/UV
treatment process. () UV-A LED 70 W/m2; ()
capable of absorbing,
ferric hydroxide sunscreen
sludge. Fromand this
otherwork,personal
it can care products may
be highlighted that
reflecting
UV-A LED 23 and/or
W/m2; () scattering
UV mercury lamp; UV()radiation,
No HSOUV-B5 /M /UV-A
- n+ haveLEDoccurred [7]. Nevertheless,
oxidation process can presently
be considered there is a
(290-320 nm) 2.5and
radiation. Conditions:
6.5; T = 323 K.
mM PMS; UV-A
1 mM Co; (320-400
pH nm) technology
promising little information on the in
for application environmental behavior
real scale agri-food
wavelengths, and therefore they are wastewater added to treatment and fateplants.
of this compound in natural water [2]. As
creams, shampoos, hair sprays, hair dyes, lipsticks, a consequence, is of great importance to find out
skin lotions, and many more products, to protect ways of inactivation
important or eliminating
the possibility of using PABA HSOand - the
5 /Co
2+
1. Introduction
us Winery
from itsindustries harmful effects on human
produce large amounts of skin and others UV filters in
without pH adjustment [5]. surface or wastewaters.
health.
wastewater One[1]. hundred
A high thirty
organicone load, ingredients
acidic pH and are Among
Bearing the theprevious
so-called in mind advanced
the main oxidation
objective
listed as UV filters in the
seasonal variability caracterize these effluents International Cosmetic processes, homogeneous
of this study is evaluating the performanceand heterogeneous of
Ingredient
which areDictionary occasionally and Handbook
released into [3]. municipal
Although photocatalytic
SR-AOPs as anoxidation alternative have shown,process
treatment recently,for
their beneficialsystems.
wastewater effects areHowever, known, use conventional
of UV filter great
winerypromise in theand
wastewater, treatment of wastewater,
their comparison with
containing products has been
treatments do not provide an effective treatment of correlated with groundwater and contaminated
photo-Fenton treatments under the air. same The
winery wastewaters mostly due to there seasonality operational conditions.
and presence of refractory compounds such as
phenolic acids. 180
2. Material and Methods
1
Advanced Oxidation Processes (AOPs) have the Different winery wastewater were studied with a
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

HIGHLY STABLE IRON CATALYSTS OBTAINED BY CHEMICAL ACTIVATION OFwill SEWAGE

Highly stable iron catalysts obtained by chemical activation of sewage
SLUDGE WITH FeCl3 FOR CWPO
be filled
PP2-19
in by
sludge with FeCl3 for CWPO
EAAOP4
J. Bedia, V.M. Monsalvo, A.F. Mohedano, J.J. Rodrguez
Seccin de Ingeniera Qumica, Facultad de Ciencias, Universidad Autnoma de Madrid, C/ Francisco Tomas y
Valiente 7, 28924 Madrid, Spain. jorge.bedia@uam.es

Iron-on-activated carbon catalysts for CWPO have been

prepared through FeCl3-activation of sewage sludge. The
purpose of the chemical activation with FeCl3 is twofold; (i)
produce carbon catalysts with a well-developed porous
structure and (ii) introduce stable iron in the carbon matrix that
acts as active phase in CWPO processes avoiding, or
substantially decreasing, the iron leaching. The effect of the
impregnation ratio was analysed. The carbons obtained show a
fairly good catalytic activity but a high stability, with almost
no iron leaching at the reaction conditions studied.

reaction takes place. So far, mesostructured

Introduction materials, zeolites , pillared clays, alumina and
Industrial wastewaters frequently contain activated carbon have been used as supports to
toxicants or hardly biodegradable compounds prepare these catalysts [3,4]. Unfortunately, most of
which remain unaltered upon conventional them, specially Fe supported on activated carbon
HYBRID MAGNETIC GRAPHITIC NANOCOMPOSITES FOR CATALYTIC WET PEROXIDE
Hybrid Magnetic
wastewater Graphitic
treatment systems. Nanocomposites
Advanced oxidation for Catalytic
catalysts, showed Wet relatively high iron will be filled
leaching due
OXIDATION APPLICATIONS inofbythe PP2-20
Peroxide Oxidation Applications
processes have the potential to remove this type of to the acidic pH or the low chemical stability
pollutants operating at or near ambient temperature supports. For these reasons, the stability EAAOP4
of these
R.S. Ribeiro 1
, A.M.T. Silva 2
, J.L. Figueiredo
and pressure based on the action of hydroxyl
2
, J.L. Faria 2
, H.T. Gomes
catalysts 1
.
is still a challenge because of iron leaching
(1) Laboratrio Associado LSRE-LCM, Departamento de Tecnologia and stableQumica e Biolgica,
catalysts must be Escola
developedSuperior de
to extend the
radicals [1]. Among them, Fenton process emerges
Tecnologia e Gesto, Instituto Politcnico de Bragana, Campus de Santaof
application Apolnia,
this 5300-857 Bragana,
process.
asPortugal,
a suitable way of treating
rui.ribeiro@ipb.pt. a wide variety of
industrial effluents
(2) Laboratrio [2]. This
Associado processDepartamento
LSRE-LCM, implies thede Engenharia SewageQumica,
sludge is Faculdade
generated de at
Engenharia,
increasing amounts
radicals from catalytic H O
generation of doHO
Universidade Porto, Rua Dr. Roberto Frias, 4200-465 2 2 Porto, Portugal.
derived from wastewater treatment demands.
decomposition by means of Fe2+ at acidic pH. Nowadays, management of sewage sludge includes
Fenton oxidation shows some Hybrid significant magneticcomposting
graphitic nanocomposites (MGNC) prepared
for farmland utilization, by
incineration
advantages, such as the fact that iron isinclusion a widely of and magnetite
landfillingnanoparticles
[5]. However, (obtained
this lastbywill co-be
available and non-toxic element and H2Oprecipitation)
2 is easy to into an organic-organic
severely limited in a self-assembly
short-term duesystem, to the
handle and the excess decomposes followedtoby calcination,
increasingrevealed
competitionhigh for
activity forspace,
landfill the catalytic
growing
environmentally safe products. Besides, wet it requires
peroxide oxidation
costs and more (CWPO) of environmental
stringent 4-nitrophenol regulations.
solutions
relatively mild operating conditions and (5 gsimple
L-1), with Incineration
pollutant removals
of sewage up sludge
to 1245 mg g-1strict
requires h-1 being
control
equipment. However its application to theobtained treatment when considering
of the pollutants the and mass
generated in manyratio cases
of real wastewaters has been so far limited mainly
[pollutant]/[catalyst] suffers= of
10.social
The and
stability of the
political MGNC catalyst
opposition. Different
due to the high requirements of H2O2against and ironmetal leaching
ways ofwas ascribed toarethebeing
valorization confinement
investigatedeffectinofthe
which results in high operational cost, and finally based
the carbon material.
last two decadesTheseincluding
observations,
the usetogether
of sewagewithsludge
the
leads to the generation of high volumes of Fe(OH)3 recoverable
magnetically as precursor characteristics of MGNC,
for adsorbent open new
materials with
in the neutralization step. prospects for the wide use of applications.
environmental this catalyst Recent
in highly efficient
studies have
To overcome the aforementioned drawback, CWPOiron applications.
reported that a wellstructured material with a high
can be immobilized in a stable form on a convenient C content can be obtained from pyrolysis of
support giving rise to a solid catalyst that can be biosolids [6,7]. In the literature, the preparation of
used in the so-called heterogeneous Fenton or carbonaceous materials with iron for CWPO has
Introduction Materials and methods
catalytic wet peroxide oxidation (CWPO). been scarcely investigated.
Catalytic wet
Important peroxide
efforts have beenoxidation
focused(CWPO)
on finding is Magnetite (Fe3O4) was synthesised by co-
The aim of this work is to prepare iron-on
widely recognized
catalysts as a low-cost
with adequate activity technology
and stability,fortaking
the precipitation of Fe2+ and Fe3+ (with a molar ratio of
activated biosolids catalysts for CWPO prepared by
degradation of persistent and bio-recalcitrant
into account the acidic conditions at which the 1:2) in basic solution (NH4OH), under inert
with FeCl and dried sewage sludge. The catalysts
pollutants in aqueous phase [1], typically operating atmosphere3(N2) at 30 oC, adapting the procedure
at low temperatures and atmospheric pressure [2].
CWPO relies on the ability of a given catalyst to
181
described elsewhere [7]. For that purpose, 13.44
mmol of FeCl2.4H2O and 26.88 mmol of
1
promote the formation of highly oxidizing hydroxyl FeCl3.6H2O were dissolved in 250 mL of distilled
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

SYNTHESIS OF Fe ON CARBON CATALYSTS OBTAINED FROM GRAPE SEEDS FOR will beCWPO
Synthesis of Fe on carbon catalysts obtained from grape seeds for
OF BISPHENOL A
filled
PP2-21
in by
CWPO of Bisphenol A
EAAOP4
E. Diaz, I.F. Mena, A.F. Mohedano, J.J. Rodrguez
Seccin de Ingeniera Qumica, Facultad de Ciencias, Universidad Autnoma de Madrid, C/ Francisco Tomas y
Valiente 7, 28924 Madrid, Spain. angelf.mohedano@uam.es

FRESH CATALYST
Grape seeds were used as precursor to develop a catalytic
support for the synthesis of Fe catalysts to be used in
catalytic wet peroxide oxidation reactions. Grape seeds were
subjected to pyrolysis and activation with air and HNO3
oxidation before the Fe incorporation by incipient wetness
impregnation. The characterization results indicated that the
GRAPE SEED
catalysis presented a significant narrow porosity and a
heterogeneous distribution of the Fe, mainly located on the
external surface of the catalyst. The catalysts showed a total
oxidation of BPA and a relatively high TOC conversion. In
spite of the leaching of Fe during the first stages of the
USED CATALYST
reaction, the most active catalyst showed a remarkable
stability in a long term run.

1. Background manufacture of flame retardants such as

tetrabromobisphenol A. Because of its slow self-
Advanced oxidation processes have the power to degradation or biodegradation in nature, BPA is
remove refractory or non-biodegradable pollutants found in influent and effluent of wastewater
operating at mild conditions (ambient temperature treatment plants, even in groundwater resources.
CARBON NANOTUBES AS CATALYSTS FOR WET PEROXIDEWWTPsOXIDATION:
andCarbon
pressure)Nanotubes
based onasthe Catalysts
action offorhydroxyl
Wet Peroxide SeveralOxidation: worldwide were studied will befor
filled
BPA
STRUCTURE-REACTIVITY RELATIONSHIPS in by PP2-22
Structure-Reactivity Relationships
radicals. Specifically, the potential of catalytic wet levels and reported BPA concentrations in influent
peroxide oxidation (CWPO), which implies the and effluent wastewater from 100 to 100,000 EAAOP4 ng/L
R.S. Ribeiroof1, M.
generation HOMartin-Martinez
radicals from 1
, B.F. Machado
catalytic H22,OP.2 Serp2and
, S. Morales-Torres
from 1 to 100 3
, A.M.T.
ng/L,Silva 3
, J.L. Figueiredo
respectively [4]. Up 3
, to
J.L. Faria , H.T.byGomes
decomposition
3
means
1
. (1)
ofLaboratrio
iron catalyst Associado
at acidic LSRE-LCM,
date, Instituto
most ofPolitcnico
studies on de the
Bragana, Bragana,issues
environmental
pH,Portugal.
has beenrui.ribeiro@ipb.pt.
widely demonstrated (2) Laboratoire de Chimie de Coordination
in the treatment caused by UPR BPACNRS have8241,beencomposant ENSIACET,
contributed to the
Universit de Toulouse UPS-INP-LCC, Toulouse, France. (3) Laboratrio Associado LSRE-LCM, Faculdade de
ofEngenharia,
industrial wastewaters [1,2].
Universidade do Porto, Porto, Portugal.
occurrence ecological risk, estrogenic activity and
On the other hand, agricultural wastes are the effects on the health of human and animals.
considered to be a very important feedstock Magneticsinceneat In andthisN-doped
work, we carbon
analyzenanotubes with application
the potential different
they are renewable sources and low costproperties materials.have of been synthesized
iron catalysts by chemical on
supported vapour deposition
modified grape
Thus, grape seeds represent up to 15% of and tested inseeds
the solid the for catalytic
CWPO using wet peroxide
BPA as target oxidation
compound. of
wastes from the wine industry. The use4-nitrophenol of grape solutions
The results g L-1) athave
(5 obtained relatively mild operating
been analyzed in terms
seeds for the preparation of catalyticconditions supports (atmospheric
of hydrogen pressure, T = 50 decomposition,
peroxide C, pH = 3) using a
target
seems to be very interesting owing to its catalyst
granular 2.5 g L-1 and
load =compound [H2O2]0 intermediates
conversion, = 17.8 g L-1. evolution
The results and
morphology and its ready availability from demonstrate
winery thatTOC the catalyst hydrophobicity/
reduction. The stability hydrophilicity
of the ismost a
works [3]. It could be prepared by physical determinant
and property in thecatalyst
interesting CWPOisreaction, since itby
also assessed affects
long the term
chemical activation methods, being a critic H2O2 decomposition.
rate ofpoint The controlled formation of reactive
continuous experiments.
the way of immobilized the iron along the radicals
process(HO and HOO) at hydrophobic surfaces avoids the
of catalyst synthesis. formation of non-reactive speciesand
2. Materials 2 and H2O), increasing
(Omethods
Bisphenol A (BPA) has been chosensignificantly as target the activity of the catalysts for pollutant removal.
compound due to the high world rate of The seeds used in this study were collected from
production, which reached about 5 million tons in grapes of the red variety Tinta de Toro harvested
2010. It is an anthropogenic compound extensively for red wine manufacture in Toro (Zamora, Spain).
consumed for manufacturing polycarbonates to (CNTs) The sizes are of the raw seeds
characterized are between
by high 2 and 3
external surface
Introduction
produce electrical and electronic equipment, area, mm. In the pretreatment,
significant the seedsand
mesoporosity are washed
easy
bottles,
Water isand beverage
a scarce containers.
resource subjectedThis compound
to high levels with distilled
modification of water and dried
the surface at 105making
chemistry, C forthem 24 h.
is also used in the production
of consumption and contamination. Advanced of epoxy resins to Then, the
particularly grape seeds
adequate forwere pyrolized
liquid-phase in a
reactionsrotatory
like
make protective
oxidation coatings,based
processes (AOPs), electrical
primarily laminates,
on the quartz [4].
CWPO furnace (CARBOLITE CB HTR 11/150P8)
liners, ofandhydroxyl
action coating radicals
in metal(HO cans ), for
are food
known and at 600 C for 2 h. The working temperature was
beverages. Other applications include the In a previous
reached at a 10 work [5], commercial
C/min heating rate CNTs and Nwere 2 was
solutions for the treatment of aqueous effluents successfully tested as catalysts for CWPO of phenol
containing recalcitrant, toxic and non-
biodegradable compounds. Among them, catalytic 182
solutions. In the current study, the effect of the1
CNTs structure on the catalytic activity is
wet peroxide oxidation (CWPO) is a water investigated using magnetic N-doped and undoped
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

EFFECT OF THE GOLD ADDITION TO Ag/ZrO2-CeO2 CATALYSTS BY RECHARGE willMETHOD

Effect of the gold addition to Ag/ZrO -CeO2 catalysts
IN THE CATALYTIC WET AIR OXIDATION2 (CWAO)
by recharge
OF PHENOL
be filled
PP2-23
in by
method in the Catalytic Wet Air Oxidation (CWAO) of phenol
EAAOP4
A. Silahua1, G. Torres1, J.C. Arvalo1, M. A. Lunagmez1, H. Prez1, J. Beltramini2. (1) Universidad Jurez
Autnoma de Tabasco, Km 1 Carretera Cunduacn-Jalpa, Cunduacn Tabasco, Mexico,
torremensajes@gmail.com. (2) ARC Centre of Excellence for Functional Nanomaterials. The University of
Queensland, St. Lucia, QLD 4072, Australia.
The Ag-Au bimetallic catalysts were prepared by Recharge
Method on different supports: ZrO2 and ZrO2-CeO2 (10 and 20
wt% of CeO2). Catalytic wet air oxidation of phenol with Ag-
Au was performed in a Bach reactor at 160C and 8 bar of
oxygen pressure. It shows that introduction of gold in the
catalyst modified material properties and this improved catalytic
activity for the phenol degradation. Results showed the best
performance using Ag-Au/ZrO2-CeO2 20wt%, removing all
phenol and 82% of abatement TOC because the concentration
of the intermediates as acetic acid decrease with gold addition
by recharge method .

Then the powder obtained was left in an oven to

Catalytic wet air oxidation (CWAO) it is dry at 120 C for 12 hours. The samples were
regarded one of the most important industrial calcined at 500 C for 12 hours with heating ramp
processes to destroy hazardous, toxic and non- of 4 C/minute.
biodegradable organic compounds present in
wastewaterOF
EFFECT streams.
CRYSTAL The process
SIZE AND involves
METAL the use
DISPERSIONThe ZrO OVER2-CeO 2 supports
Ag/ZrO -CeOwereFOR obtained
THE by using
of Effect
CATALYTIC
of Crystal
a tickle-bed WET or AIR Size
slurry and
reactors
OXIDATION
Metal Dispersion
operating
OF METHYL at over
cerium Ag/ZrO
TERT-BUTYL nitrate2-CeO 2 for salt (from
precursor
ETHER
2
(MTBE)
2 willAldrich).
be filled
PP2-24
the Catalytic
temperatures in theWet range Airof Oxidation
100-325 C of at Methyl
5-200 Tert-Butyl
Cerium aqueous (MTBE)were obtained byin the
Ethersolutions by
EAAOP4
bar pressures, with oxygen as oxidant agent [1]. stoichiometric addition of precursor to obtain 10
G. Torres1, Z. Guerra1, H. Prez-Vidal1, I. Cuauhtmoc1, A. Espinosa1,J.N. Beltramini2. (1) UJAT-DACB, Km-
and 20 wt% CeO2. For ZrO2-CeO2 the same
1Carr. Cunduacn-Jalpa,
For long catalytic oxidation reactions haveTabasco, Mxico, torremensajes@gmail.com (2) ARC Centre of Excellence for
Functional Nanomaterials, The AIBN anddecreasing methodology used toof Queensland,
School of Engineering, The University obtain the St. ZrO 2 without
Lucia, QLD
shown a positive effect controlling and cerium was followed and the precursor salt was
4072, Australia.
the pollutant concentration+ found in air and water
sources. On this regard, silver supported In this workadded
catalysts
to the n-butanol-water
Ag nanoparticles supported on mixture
ZrO2-CeO before
2
Oxidative Medium
adding it to the solution of zirconia n-butoxide-
have shown an excellent O2 behavior for thispromoted different amounts of CeO2 were studied. Results
reaction. withwater.
Silver as a metal Ag +
noble has special features reveals tothat the tetragonal ZrO2 phase (t-ZrO2) present in the
Vacancy (V )
improve catalytic oxidation reactions. It is0
catalysts
known is stabilized
The Ag by the presence
supported catalysts CeO2,prepared
of were preventing by
silver can chemisorb
Ce 4+
OCe2; silver can alsotransformation
3+
catalyze to the monoclinic phasemethod
deposition-precipitation (m-ZrO(DP) 2). CeO 2 can2 also
of ZrO and
CO oxidation, although at higher temperatures improve the reduction
ZrO2-CeOof2 Ag 2O as increase
supports adding also thetheappropriated
d-electron
than gold [2].After Reaction density of theamounts
surface of silver atoms. Furthermore
an aqueous solution containing CeO2 has a
silver
promoting effectnitrateon(AgNO
Ag/ZrO 3 ) to
2 because
obtain a of the
nominal strong metal-
concentration
The criticalTreatment
step inbythe H2 effective development of
support interaction
of 1.4% andofitsAg.relationship
Subsequently,of oxygen NaOH vacancies
was added of
CWAO is the preparation of an efficient
Vacancy (V0)
Ag
ZrO2-CeOand 2 support.
dropwise Thetoextent of reduction
the resulting solution of silver
under controls
constant
durable catalyst. Ce 3+ Therefore
4+Ce this paper deals with
the quantity of oxygen
stirring to getto abepHadsorbed
of 10. The during
samplesthe were
oxidation
dried
the study of the catalytic properties ofreaction. Ag-Au In general
at 120Ca for small crystalandsize
12 hours thenand high under
calcined metallic air
supported on BeforeZrO 2-CeO2 for the catalytic
Reaction wet canflow
dispersion enhance the activity
(60ml/min) of MTBE
at 300C for 4h,Catalytic
with a Wetheat Air
rate
oxidation degradation of Phenol using oxidation a batch of 2C/min. Finally, the catalysts were reduced
reactor unit. under H2 (60ml/min) at 400C for 4h, withpresent
a heat
For long catalytic oxidation reactions have shown Unfortunately this additive has been found
The ZrO2 support
a positive was prepared
effect controlling andusing zirconiathe
decreasing n- rate of 2C/min.
in groundwater andBimetallic
surface water Ag-Au due (1/1 molar
to leakages
butoxide
pollutant (Aldrich)
concentration as precursor.
found inA air mixture of n-
and water ratio)
from car supported
or underground catalysts fuel were tanks prepared
creating bya
butanol-water
sources. On this was stirred
regard, andsupported
silver kept in reflux
catalystsat recharge
serious method,
environmental which consist
problemin to duedeposit
to itsan
80C. Zirconia
have shown an n-butoxide
excellent behavior was added dropreaction.
for this by drop amount
refractory ofproperties
2 grams to of degrade
the monometallic
when releases catalyst
into
for 3 hours
Silver as a tometal this solution
noble has untilspecial
a gel was formed.
features to into the reactor, [6].
the environment once the reactor was purged with
The mixture
improve was constantly
catalytic stirred for It24ishours
oxidation reactions. known at nitrogen
This work fordeals
10 min at room
with temperature,
the study then the
of the catalytic
80C. Afterward
silver can chemisorb the water
O2 [1];and canalcohol remaining
also catalyze CO catalyst
properties was of reduced
Ag supported with hydrogen
on ZrO2-CeO for one
2 forhour
the
were eliminated
oxidation, although by the use of temperatures
at higher a rotavapor unit.than at a temperature
catalytic of 400 degradation
wet oxidation C, after theofreduction,
Methyl Tert the
gold [2-4]. Oxygen chemisorption on silver Butyl Ether (MTBE) using a batch reactor unit.
surface as a pretreatment generates various oxygen 183
The synergistic effect of metal and support on the 1
species such as bulk-oxygen (O) and subsurface reaction is also reported. The ZrO2 support was
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

CATALYTIC WET AIR OXIDATION OF METHYL TERT-BUTYL ETHER (MTBE) USING

Catalytic Wet Air Oxidation of Methyl Tert-Butyl Ether (MTBE)
Rh/TiO2-CeO2 AND RhAu/TiO2-CeO2 CATALYSTS
will be filled
PP2-25
in by
using Rh/TiO2-CeO2 and RhAu/TiO2-CeO2 catalysts
EAAOP4
G. Torres1, A. Cervantes1,2,Ma. A. Lunagmez1,2, G. Del Angel2. (1) UJAT-DACB, Km-1Carr. Cunduacn-Jalpa,
Tabasco, Mxico, torremensajes@gmail.com (2) Universidad Autnoma Metropolitana-Iztapalapa Laboratorio de
Catlisis, CBI, Departamento de Qumica, Av. San Rafael Atlixco 186 C.P. 09340 Mxico DF, Mxico

In this work, Rh/TiO2-CeO2 and RhAu/TiO2-CeO2 catalysts

were studied. Characterization of materials was done by BET
surface area, FTIR-pyridine, X-ray diffraction, H2-TPR, FTIR-
CO, ICP-OES, H2-TPD, TEM, HRTEM, TPO. Monometallic
catalysts were prepared by incipient impregnation loading
Rh 0 0 0
Ce02
Au

Rh
1w/w% of Rh. Bimetallic catalysts, the recharge method was
Support Support used and the amount of gold was equivalent to a monolayer of
chemisorbed hydrogen by catalyst. MTBE CWAO was carried
Polyols + Acetone
out in a batch reactor using a solution (150 mL) of 300 ppm of
CO2 MTBE and 1 g/L of catalyst. Bimetallic catalysts in the
presence of gold increase the catalytic activity and stability,
promoting a more efficient reaction path and a lower deposit of
organic material in the Catalytic Wet Air Oxidation of MTBE.

MTBE in the air and water has been source of Bimetallic catalysts are more stable than
serious pollution problems in the past, in several monometallic. The presence of gold improve
big cities of America and Europe [1]. This stability to the catalysts.
pollutant cause serious problems for human health; Based on the results, in the oxidation reaction of
for this reason the EPA banned its use in 2007 [2]. MTBE acid sites play a key role; these capture the
In this work, Rh/TiO2-CeO2 and RhAu/TiO2-CeO2 pollutant and cause the oxidation of this to meet a
OZONE ENHANCED
catalysts were studied. OXIDATION OF CYANOTOXIN rhodiumCYLINDROSPERMOPSIN
metal particle. Quickly reference WITH catalyst
TiO2
Ozone enhanced
CATALYST
Supports oxidation
were synthesized fromof sol-gel
cyanotoxin cylindrospermopsin
method, (RhTi) loses activitywith dueTiO2 catalyst
to the deposit of organic PP2-26
using n-butoxide titanium (Aldrich 97%) and material. The presence of cerium and gold helps to
cerium
Winn-Jung nitrate
Huang (Strem
1*
99.9 %)
, Chih-Chao Wuas
2
precursors.
, Ben-Ren The correspondence
Lu3, Address prevent the todeposit.
Winn-JungWith Huang, theDepartment
additionofof the
Safety, Health
rhodium and Environmental
precursor was RhCl3.3H Engineering,
2O. The Hungkuang
amount University. Taichung,
second metal, it Taiwan; Phone:in+886-4-26318652
is deposited preferential sites
ofext. salt
4000;wasFax: +886-4-26525245;
needed to obtain E-mail:1 huangwj@sunrise.hk.edu.tw
wt% and helping to prevent particle deposition covering
impregnated to the support by incipient material, in addition the presence of cerium
The stable tricyclic
impregnation method.structure
In the caseof the of cylindrospermopsin
bimetallic improve(CYN) thea oxide-reduction
cyanotoxin, has presented
properties,several
which
challenges to water treatment facilities,
catalysts, the recharge method was used and the as conventional treatment methods are limited
provoke a better conversion of MTBE in their. ability to
removeofit gold
amount fromwas water. This study
equivalent to ainvestigates
monolayer the of effectiveness of titanium
In the oxidation reaction dioxide
of MTBE 2) in found
(TiO was catalytic
that
ozonation for degrading
chemisorbed hydrogenCYN. byThe catalyst
chemical kinetics
[3]. ofthethe most
reactions of ozone
active (O 3)were
catalysts and hydroxyl
those who radicals
had a
(OH) with CYNofwere
Characterization determined.
materials The results
was done by BETthus obtained
higher that TiO 2ofsignificantly
amount acid sites. Theincreases the rate ofof
incorporation
surface
degradationarea, FTIR-pyridine,
of CYN by increasing X-ray diffraction, 2-
the rate ofHproductioncerium of promoted the formation
hydroxyl radicals (OH) by of these sites.
initiating theIt
TPR, FTIR-CO,
decomposition of OICP-OES,
3 on the catalyst H2-TPD,
surface.TEM,At a pH was
of 7 observed
with 1.0 Othat
3 -mg/Lthe and
reaction
500 mg/L routeTiOis 2;more
the
HRTEM, TPO. The
pseudofirst-order MTBE
ozone concentration
decomposition ratewas 300 (kDefficient
constant ) increasedin from
the presence
3.04 10of cerium
3 to 16.5310 monometallic
3 s1 and

ppm, of of
the ratio which
OH to 150 O3 mL were placed
concentrations (Rctin a batch fromcatalysts.
) increased 1.87 108Furthermore
to 126.4 10CeO 2 avoid
8. The accumulation
calculated second-
reactor
order rate with constant
a catalyst(kconcentration of 1 g/L. The
overall) of CYN with O3 and OH was 3.22 M
of organic material. Bimetallic
1 s1 without TiOcatalysts in the
2. The greatest
oxygen partial pressure was 8 bar and temperature presence of gold increase
improvement in koverall was observed at 500 mg TiO2/L, which increased koverall by a factor of five TiO the catalytic activity and
2
ofcatalyzed
80 . Pollutant degradation was monitored by stability, promoting a more
ozonation is an efficient method of oxidation reduces the toxic activitity of CYN. According to efficient reaction path
gas chromatography
Microtox (Varian starthe3400Cx
test results concerning andduring
) andof CYN
toxic activity a loweroxidation
deposit of organic material.
processes, catalytic ozonation
TOC ( TOC- VCSN SHIMADZU) .
may either increase or reduce the toxicity of CYN toward test samples of chemical properties. The toxic
effects on the samples are greatly affected by the TiO2 dosages and reaction time, possibly yielding by-
Acknowledgements Pharmacology, 70 (2014) S13-S17.
products
We that may alter
thank CONACYT by the
Ph.Dmutagenic
Scholarshipproperties of CYN.
to Adrin
Cervantes Uribe. [3] J. Barbier, J. C. Menezo, C. Montassier, G. Del
Angel , and J. M. Dominguez, Catalysis Letters, 14
References (1992) 37-43.
[1] J. A. Connor, R. Kamath, K. L. Walker and T. E.
McHung, Groundwater, 53 (2015) 195-206.
[2] M. Henley et al., Regulatory Toxicology and

184 1
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

NANOSTRUCTURED CeO2 AS CATALYSTS FOR DIFFERENT AOPs BASED IN THE

Nanostructured
APPLICATION OFCeO2 as catalysts
OZONE AND SOLAR for different
RADIATION AOPs based in the PP2-27
application of ozone and solar radiation
A. Rey, E. Mena, E.M. Rodrguez, F.J. Beltrn. Departamento de Ingeniera Qumica y Qumica Fsica,
Universidad de Extremadura, Avda. Elvas s/n 06006, Badajoz, Spain, anarey@unex.es.

Two CeO2 catalysts with different morphology (nanocubes and

nanorods) were synthetized by hydrothermal treatment,
characterized and examined for different AOPs (photocatalytic
oxidation, catalytic and photocatalytic ozonation) using DEET
as target compound. Neither significant DEET removal nor
mineralization was achieved by solar photocatalysis and the
catalysts did not show any beneficial effect during catalytic
ozonation. The best results were obtained in photocatalytic
ozonation process being nanorods more active under visible
radiation according to its lower band gap energy whereas
nanocubes presented the highest catalytic activity under total
solar radiation. The combination of CeO2 nanorods with TiO2
both supported in Raschig rings led to promising results for
continuous photocatalytic ozonation treatment.

Introduction Experimental
Water pollution due to specific organic Two CeO2 catalysts were synthetized by
contaminants (phenolic compounds, aromatic hydrothermal treatment according to a previous
hydrocarbons, pesticides, pharmaceuticals, etc.) is work [6]. Briefly, Ce(NO3)36H2O used as cerium
a growing problem that requires the precursor was dissolved in NaOH 6 M solution
implementation of advanced technologies capable and then transferred to a 125 mL autoclave (filled
PHOTOCATALYTIC
of removing not only OZONATION OF EMERGING
the initial compounds but CONTAMINANTS
at 75%) and heated during IN MUNICIPAL
24 h at 100 orWASTE- 180 C
Photocatalytic
WATER
also WITH
their A ozonation
MAGNETIC
metabolites. Amongof TiO
emerging
the-ACTIVATED contaminants
available CARBON
for nanorodsin municipal
CATALYST (NR) and nanocubes (NC), PP2-28
2
wastewater with
technologies, a magnetic
advanced TiO2-activated
oxidation processes carbon catalyst Finally, the precipitates were
respectively.
(AOPs)
A. Rey, have demonstrated
A.M. Chvez, to efficiently
P.M. Alvarez, remove
F.J. Beltrn. a
Departamento separated
de Ingenieraby centrifugation,
Qumica y Qumica washed
Fsica,sequentially
wide varietydeof
Universidad organic pollutants
Extremadura, Avda. Elvas due to the
s/n 06006, Badajoz, with
Spain, water and ethanol and dried at 100C
anarey@unex.es.
generation of oxidizing species, mainly hydroxyl overnight.
radicals, which non-selectively attack the Theorganic
degradation of metoprolol, DEET, ibuprofen and clofibric
matter [1]. Photocatalytic treatments areacid in a synthetic
promising Immobilization
municipal wastewater of TiO2effluent
and TiO was2-CeO 2 onto
studied.
Different
alternatives due to the possibility of using natural Raschig
ozone/solar rings
radiation (6 mm diameter)
processes were was carried
tested usingoutaby
solar light as a radiation source to TiO the dip-coating procedure. The coating suspension
2 supported magnetic activated carbon catalyst which was
minimize
treatment costs. Besides, the combination easily separable
of wasandprepared
reusable. with ultrapureoperating
Different water at pH=1.5
conditions with
photocatalysis with ozone increases the (catalystgeneration loading,HNO 3 andgas
ozone gL-1 of
150phase TiO2 P25 (Evonik)
concentration and gas or TiO2
flow
of oxidizing species leading to higher rate and of
degrees P25 and
the presence NR CeO2 (50:50) with the same
of carbonate/bicarbonate/phosphate total
ions)
mineralization than individual treatments were[2].studied.
For amount.
The Each coating
most efficient treatment cyclewas consists
photocatalyticin the
these processes, much of the researchozonation effort isleading immersion
to complete of emerging
the rings into theremoval
contaminants catalyst
-1
focused on the development of photocatalysts (99.9%) in less than 45 min with 65% TOC removal in 120 min.s ,
suspension, withdrawal at a speed of 0.65 mm
capable of effectively absorbing visible An light in of the catalyst loading did not improve the at
increase oven drying at 110C for 24 h, and calcination
order to increase the fraction of usable treatmentsolarwhereas 500Cgasfor 2 h.concentration
ozone A total of 3 and consecutive
gas flowcoatingrate
radiation compared to the commonly showed used TiO cycles
a 2positive effect. were A carried
negativeout withwas
effect 2 and TiO
TiOobserved in2-CeO
the 2
[3]. In this sense, CeO2 is a widepresence band-gap suspensions. The and
of carbonate/bicarbonate physicochemical
phosphate ions.properties of
semiconducting material which absorbs light in the as-prepared supported catalysts were determined
Photocatalytic
near UV and slightly ozonation is region
in the visible an Advanced
being its by a N
in 2 adsorption-desorption
synthetic aqueous effluent were isotherms,
carried XRD,
out in
Oxidation Process (AOP) based
unique properties as catalyst and catalytic supporton the TEM,
a solar SEM
simulator and diffuse
provided withreflectance
an air cooled UV-Vis
1500
combination of photocatalytic
highly shape-dependent [4]. The aim oxidation
of this work with spectroscopy.
W Xe lamp. Main operating conditions were:
ozone
focusedthatonhasthebeen demonstrated
application of two to efficiently
different V=750
Photocatalytic =2 mgL-1 ofwere
mL, CECs,0experiments eachcarried
EC (TOC out0=24
in a
-1 -1
remove a wide variety of persistent
nanostructured CeO2 catalysts in ozone and organic mgL
solar , pH
simulator 0 =7, C
(Suntest
CAT =0.19-0.75
CPS, Atlas) gL ,
providedQ=10-30
with
-1
pollutants [1]. Most
photocatalysis basedofAOPs
the studies
for theindegradation
photocatalytic of aLh1500, W CO3g =10-30
Xe mgL-1, atT=25-35C.
lamp operated 550 Wm2. Light ECs
ozonation have been conducted
DEET, a common insect repellent found inusing nanosized concentration was determined
transmission was restricted to >390 by HPLC,
nm by means short-
TiO 2 as catalyst
different which involves
aquatic environments [5].several problems chain
of a modified organic polyester
acids cut-off
by means of Ion
filter (Edmund
of separation and reutilization. Thus, the aim of Chromatography,
Optics) for visible total organic whereas
experiments carbon by a TOC
a window-
this work is focused on the application of a TiO2- analyzer, dissolved ozone and hydrogen peroxide
anatase supported magnetic activated carbon
catalyst (TiFeC) in the photocatalytic ozonation of 185
concentrations
spectrophotometry.
by means
Besides
of UV-Vis
photocatalytic 1
a mixture of emerging contaminants (ECs) in ozonation (O3-PhC), experiments of adsorption
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

KINETIC STUDY OF ETHILENETHIOUREA REMOVAL IN WATER BY OZONATION

Kinetic Study of Etilenethiourea Removal in Water by Ozonation
PROCESS
will be filled
PP2-29
in by
Process
EAAOP4
S. Bottrel1,2, E. Costa1, G. Cipriano3, M. Leo1, C. Amorim1 F. (1) Universidade Federal de Minas Gerais, Belo
Horizonte, Brazil..(2) Universidade Federal de Juiz de Fora, Juiz de Fora, Brazil. (3)Centro Federal de
Tecnologia de Minas Gerais, Belo Horizonte, Brazil. E-mail:camila@desa.ufmg.br

Etilenethiourea is a metabolites of widely consumed pesticide in

coffee crops. This work aims the kinetic study of ETU
degradation and mineralization in water by ozonization process
at different pHs (free, and fixed at 7 and 9). Experiments were
made to determinate the second order rate constant of the ETU
mineralization and degradation, through absolute rate constant
method. Preliminary results, that involve the global pseudo fist
order rate constant determination for the ETU mineralization,
showed that reaction at pH=7 were more efficient in the
mineralization of ETU aqueous solution followed by
ozonization conducted at pH=9 and finally, at free pH. The
pseudo first order constant for both, direct and radical reaction
of ozonization are been investigated for conclusion of the study.

sedimentation and filtration processes, found very

Due to an expressive growth in its agriculture low removal efficiency (~13-18%), indicated that
production, Brazil has become the biggest other treatments are necessary to remove these
consumer of agrochemicals in the world, with
pesticides from water [5].
sales increasing from $2 billion in 2001 up to $8.5
billion in 2011, accordingly
DEGRADATION to Brazils National
OF 8 POLLUTANTS COMMONLYOzonation FOUND INprocess can be advantageous to
FOOD PROCESSING
Degradation
Cancer
EFFLUENTS Institute Of(INCA)
8 Pollutants
BY ADVANCED
Commonly
communication
OXIDATION on
Found
PROCESS:
InOFood
remove ETU
AND
Processing
from
O
will be filled
aqueous matrix. The process is
/UVA-VIS PP2-30
in by
Effluents
pesticides fromBy Advanced
April 6, 2015. Oxidation
Therefore, inProceses:
Brazil O 3 and
based onOa3/UVA-VIS
3 3
variety of oxidation reactionsEAAOP4 that take
there
RosaisF.Vercher
a special
1 concern
, Sara about the1Diego
Garca-Ballesteros impacts place
Lpez1 Sofa in water
Rebagliato 1 once the decomposition
, Antonio Arques1, Ana M.Amatof 1 ozone,
y (1)
caused
Grupobydeagrochemicals on the Avanzada.
Procesos de Oxidacin environmentDptoand which
de Ing. Textil is highlyUniv.
y Papelera. unstable.
Politc.Ozonization of organic
de Valncia, Pza
on Ferrndiz
human y Carbonell
health and about methods
1, 03801-Alcoy for
, rverche@txp.upv.es compounds occurs through two main different
prevention and remediation of contamination. pathways, one of direct reaction with ozone and a
A second
representative one involving
of Food processing hydroxyl radicals
waste water (OH)ofand
mixture 8
Mancozeb is one of the most commonly used consists in a kind of Advanced Oxidative Process
agrochemicals on coffee crops production, pollutants (tannic acid, elagic acid, 2,4-dinitrophenol, gallic acid,
(AOP) [8]. One ozone basedacidAOP is sinapic
the peroxone
especially in Brazil [1] and consists of aprotecatechuic
mixture acid, vanillic
oxidation process,
acid, syringic
in which hydrogen
and
peroxide
acid)
can
of ethanediylbis (carbamodithioato) manganese was treated by ozone and ozone combined with visible light. The
aim of these be added
study is to
to increase
determine thethe
rateeffect
of ozone
of degradation
operational
and 1,2- ethanediylbis (carbamodithioate) zinc and (OH) radical formation [9]. Ozonation and
and it belongs to the pesticidesvariables group (pollutant concentration, O3 concentration and pH). For
this porpouse peroxone oxidation
experimental designwere methodology
efficient to remove
based ETU,
on
dithiocarbamates, which also includes but hasonlybeen ozonation at initial pH=11 achieved
ethylenebisdithiocarbamates (EBDC) metiram and Doehlert matrixes used. Results show that Ozone is a
very effective higher
treatment mineralization
to degradate efficiency
theese [7].
contaminants and the
maneb [1]. Ethylenethiourea (ETU) is Mancozebs
h + O3
and other EBDCs main metabolite combined
and some use In of this and UVA/VIS
O3 study the aim is to didproceed
not provewith to be
kinetic
studies have reported it to have carcinogenic, advantageous, except for case with worst operational
constants values determination for mineralization conditions.
teratogenic, and goitrogenic effects [2,3]. These and degradation of ETU with ozonation processes
characteristics together with high water solubility at different pH values by absolute rate constant
and moderate mobility make of ETU very probably method.
to affect both surface and groundwater the water
sources [1]. Therefore, for water purification 2 Metodology
tubular reactor with 1 L capacity, thermostatised by
Introduction
purposes, studies for remove this metabolite are of water.
OzoneSolar simulated
experiments werelight irradiations
carried out usingwerea
great importance.
Food processing industry (e.g. wine, oil mill or performed
cylindrical by means
bubble of a Xenon
column reactor,lamp
80 cmwhich
high was
and
cork boiling) produces eventually
4.5 cm in located
diameter,axially
with inside the volume
a useful tubular reactor.
of 1 L.
Conventional drinkinghighly
water polluted
treatmenteffluents,
systems
are usually ineffective to removephenolic
containing sugar, tannins or and
recalcitrant The O3 was bubbled through the ETU solution in
polyphenolic compounds.
contaminants [4]. A study Some studies [1]have
investigated ETU the reactor through a ceramic porous diffuser. The
reported that wastewater originated inflocculation,
the baking schematic
Table 1.diagram of the matrix
experimental set-up used
removal including coagulation, Dohelert desing
process of cork has low biodegradability and a
N [Pollutan O3
polyphenols concentration of 1300 mg/L. Recently,
advanced oxidation processes have been shown as 186
Experime
nt
t] (mg/L) production
n (mg/min)
pH
1
potential treatments for this type waste water [2] 1 3.5 0.6 7.5
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

REVERSE OSMOSIS FOLLOWED BY SOLAR PHOTO-FENTON OXIDATION FOR THE

Reverse Osmosis
INTEGRATED FollowedOF
TREATMENT ByWINERY
Solar Photo-Fenton
WASTEWATER Oxidation For The will be filled in
PP2-31
by EAAOP4
Integrated Treatment Of Winery Wastewater
L.A. Ioannou1, C. Michael1, N. Vakondios2, C. Drosou2, E. Diamadopoulos2, N.P. Xekoukoulotakis2, D. Fatta-
Kassinos1 (1) Nireas-International Water Research Center, University of Cyprus, P.O. Box 20537, CY-1678 Nicosia,
Cyprus, ioannou.lida@ucy.ac.cy. (2) Technical University of Crete, GR-73100, Chania, Greece.
The application of membrane processes for wastewater treatment
is rapidly expanding, due to their high organic/inorganic removal
efficiency, but the appropriate management of the concentrate
produced is a growing concern. This work investigated the
efficiency of reverse osmosis (RO) on the treatment of winery
wastewater followed by solar photo-Fenton oxidation for the
treatment of the concentrate. RO process reached 97% COD, 67%
total nitrogen, 76% total phosphorus, 94% total suspended solids
and 94% conductivity removal; demonstrating thus an excellent
solid and soluble salts separation. Moreover, toxicity and
phytotoxicity of the RO permeate were significantly reduced or
even eliminated at the optimum experimental conditions. Further
treatment of the RO concentrate by solar photo-Fenton oxidation
achieved an efficient COD reduction up to 75%.
the membrane concentrate effluent of a variety of
Background wastewater streams.
There are numerous treatment options available The main objectives of this study were the
for the management of winery wastewater (i.e. investigation of the efficiency of (i) a pilot-scale
physicochemical, biological and advanced RO process to remove both the organic/inorganic
oxidation processes (AOPs)), which vary with compounds and the ecotoxicity from real winery
respect to their efficacy, cost and reliability [1]. wastewater and
SOLAR
Membrane PHOTO-FENTON
technology asWith a WITH
means SIMULTANEOUS
of separation, ADDITION OF(ii)
OZONEsolar photo-Fenton
FOR will beoxidation
Solar Photo-Fenton
WASTEWATER TREATMENT
Simultaneous Addition for Of
the Ozone
treatmentFor of the RO concentrate. filled
PP2-32
concentration, and purication of various in by
Wastewater Treatment
compounds is wide spread in industrial processes, Material and methods EAAOP4
including
S. Sanchis1among other
, L. Meschede 1
, A.various
Serra1, G.agro-industrial
Sixto2, J. Garcia-Montao1. (1) Leitat Technological Center, C/Innovaci
effluents (i.e. olive mill; winery; molasses-based (2) DEISA,
2, 08225 Terrassa, Barcelona, Spain, ssanchis@leitat.org Pre-filtered winery Goytisolo
C/ Jos Agustn effluents30-32 (glass microfilter
08908 Hospitalet
distillery; de Llobregat,
dairy wastewater, Barcelona,
etc.) [2]. Spain Whatman, 1 m) were used for the RO experiments
with the following qualitative characteristics:
More specifically, reverse osmosisAn(RO) is
innovative pH: 6, COD:
technology 5353 )mg
(FentO L-1, BOD5:aiming 424 mgatLthe -1, TS:
3 is developed
currently considered to be the state-of-the-art efficient, inversatile
5040andmgsustainable
L , TSS: 66treatment
-1 mg L , TP:
-1 2.1 mg Lreal
of diverse
-1 , TN:
industrial wastewater treatment applications [3]. FentO
wastewaters. 10 mg L-1, EC: 3.34 mS cm-1, and TPh: 20 mg L-1.
3 consist in the simultaneous combination of
The advantages offered by RO have the been wellphoto-Fenton process with ozonation at laboratory
solar
documented in the literature, such as the excellent The RO pilot unit (volume: 30 L) was
scale, leading tomanufactured
a positive social by2+and economical impact
GE-Osmonics, and isatequipped
mid
effluent quality, the easy operation,term. the The
low combination of Fe /H O /O /UV led to higher
footprint and the availability to operateefficiencies
in a wide than with a2+ AG2521TF spiral-wounded
2 2 3 polyamide
Fe /H2(Desal)
membrane O2/UV, with O3 and a nominal Fe2+/H2membrane
O2/O3
range of temperatures and pH [2]. However, RO
separately whensurfacetreating area
highlyofpolluted wastewaters like an
process suffers from various drawbacks, effluent such as the 1.2 m . The photocatalytic
2
comingexperiments
from the pharmaceutical
were conducted industry.
in a For that
batch reactor
concentrate generated, the membrane fouling, the
reason, FentO 3 could be a promising technology for reducing
pre-treatment needs, the energy cost,theand the load(volume:
organic of highly
300 mL) made
polluted
of borosilicate
industrial effluents
glass and
beforecontrol
a
membrane replacement [4]. More specifically, equipped with
the refining treatment double wall for temperature
subsequent (T= 250.1 (theA performance
oC). Newport of a(Lamp
91193 biological
Xe-OP,
resultant RO concentrate, which comprises 15-20%
treatment will be1kW)
assessed later on though respirometry).
of the volume of the feed stream, contains almost solar simulator was used for these
all the contaminants present in the original experiments.
The development
wastewater of levels.
at elevated efficient and versatile
Consequently, it is and pressure for improving the degradation
COD measurements were performed using
processes aimed at the removal
vital to explore appropriate treatment processes for of efficiency and iv) the electricity consumption due
MerckSpectroquant kits, and BOD was
emerging/priority/specific
the effective abatement substances in water as
of RO concentrates to the use of UV lamps.
determined using the 444406 OxiDirect meter.
well as the treatment of highly polluted
organic contaminants under an acceptable level. industrial
Total suspended solids (TSS), total solids (TS),
wastewaters is of great interest in order to avoid Until today, there is almost no information in the
AOPs areand known for theirto ability total nitrogen (TN) and total phosphorous (TP)
pollution damages publicto mineralize
health anda literature about the combination of both
wide range of organic compounds [5], and have were measured according to Standard Method
environment. Among the technologies more technologies in the same process, and the works
been successfully applied 2540B, 2540D, 4500 N and 4500-PE, respectively
widely used for this kind both for the treatment
of treatments, advanced of related are focused on the removal of certain
winery wastewater, [6]. Toxicity and phytotoxicity measurements were
oxidation processesas(AOPs)
well as for are the treatment
based on the of compounds in synthetic aqueous solutions
generation of highly oxidizing agents like including pesticides [1-2] and aromatic acids like
hydroxyl radicals (OH). The Fenton process, 187
p-coumaric acid [3], terephthalic acid [4] and p-1
which consists in the catalytic decomposition of hydroxybenzoic acid [5] and using UV lamps
2+
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

FENTON AND ELECTROCHEMICAL OXIDATION FOR THE TREATMENT OF ACTUAL

Fenton and Electrochemical Oxidation for the treatment of actual
WASTEWATER COMING FROM AN ORGANIC-SYNTHESIS CHEMICAL PLANT
will be filled
PP2-33
in by
wastewater coming from an organic-synthesis chemical plant.
EAAOP4
C. Sez, J.F. Prez, J. Llanos, C. Lpez, M.A. Rodrigo, P. Caizares.
Department of Chemical Engineering. Faculty of Chemical Science and Technology. University of Castilla-La
Mancha. Campus Universitario s/n 13071 Ciudad Real. Spain, cristina.saez@uclm.es
Wastewater produced in pharmaceutical manufacturing plants
are complex and highly toxic, as a consequence of the numerous
processes and reagents involved. In general, Advanced oxidation
processes are adequate technologies to treat those wastewater due
to the high oxidizing power of the hydroxyl radical. In this work,
a comparative study between Fenton Oxidation and Conductive-
diamond Electro-oxidation to treat a great variety of actual
organic-synthesis wastewater is conducted. Results show that
electrooxidation is generally more efficient than fenton oxidation
and also can treat every aqueous effluent regardless the pollutant
contained in the water, achieving high mineralization
percentages if necessary. Because of this versatility, CDEO is a
promising alternative to Fenton Oxidation to treat organic-
synthesis wastewater.

Introduction stronger oxidizing processes. A plausible approach

is the use of Advanced Oxidation Processes
Typical manufacturing wastewater generated in the (AOPs). During the recent years, different AOPs,
pharmaceutical industry include fermentation including Fenton Oxidation, Ozonation and
broths, process liquors, solvents, equipment Electrochemical Oxidation, have been widely
EFFECT
washwater, OF FEED
spilled COMPOSITION
materials, off-spec ON THE
products andPERFORMANCE
studied to treat OF synthetic
A POLYETHERSULFONE
industrial will wastes
be filled in
UF
Effect
MEMBRANE
of Feed Composition
IN These
A PHOTOCATALYTIC
on the Performance
MEMBRANE
of a Polyethersulfone
REACTOR PP2-34
used processing aids. aqueous
UF Membrane in a Photocatalytic Membrane Reactor effluents can laboratory and bench-scale plants,in bybut
be classified into two groups according to the unfortunately, only few papers have focused EAAOP4on the
S. Mozia,process
synthesis D. Darowna, they A.W.
comeMorawski. West Pomeranian
from: fermentation or University
treatment of Technology,
of actual aqueous Szczecin,wastes
Institute[1].
of Likewise,
Chemical Technology
organic-synthesis. Theand Environment
former produces Engineering,
wastewater Puaskiego
they10,are70-322
mainly Szczecin,
based Poland;
on the treatment of the
sylwia.mozia@zut.edu.pl
containing high concentrations of sugars, proteins, average effluent, but not on the study of each
nitrogenous Thetogether
investigations on the effluent.
influenceAtofthis feed composition on theto
membrane and phosporic compounds particular point, it is important
The changes of the 2 TiO
100

withaftersome
separation other nutrients.
properties 80
fouling
These effluents are and stability of a polyethersulfone ultrafiltration
point out that due to the diversity of characteristics
economically
35h of the
photocatalysis-UF process and 60 efficiently
membrane
treated using in aofphotocatalytic membrane
the effluents generated reactor (PMR)
in bath-operated are
organic- 2-
biological processes.
with TiO alone,
2 40 The latter make use presented.
of one It wasmanufacturing
or found that amongst plants,various inorganic
there is not salts:
a SO
single
4
%R

TiO + high concentration 2- -

in a series ,ofHPO 4 , HCO3 technology
, the latter one contributed
meets alltothe therequirements
permeate fluxin
2

more batchsalts
of inorganic reactor vessels
20
reaction, which
or TiO with salts and
separation
humic acidsand purification steps to make the
2
0 decline to the highest
every extent what was
industrial assignedBecause
facility. to the alkaline pH
of this,
- -
desired dextran 40 000 g/mol
before after 35h
product. Numerous types of chemical of feed containing HCO . The presence of
wastewater management from pharmaceutical
3 HCO 3 had also a
dextran 70 000 g/mol
reactions, TiOrecovery process, and negative are
chemicals influence on the requires
facilities effectivenessa of the
deep removal of ofhumic
understanding each
+ salts
acidsoffrom
drugwater.particular
Based oncase the monitoring
in order toofdevelop
dextransan rejection it
2 2 TiO + HA + salts

employed in order to produce a wide variety adequate

100 100

80
products. Therefore,
80
wastewater generated iswas found that the membrane lost its separation properties
wastewater management system. In this contect, the after
and highly 40toxic, containing a35h wideofrange
operationaim in the PMR, dueis to
to the abrasive action of TiOof
60 60
complex of this work evaluate the effectiveness 2
particles. In the presence
Conductive Diamond Electrohcemical the
of the salts and/or humic acids extent
%R

%R

40
of 20pollutants: organics (remaining reagents, Oxidation
reaction products and
20
by-products, solvents) of the deterioration
and andofFenton
the rejection characteristics
oxidation to treat awas setlessof severe
actual
than when TiO suspension in pure water was used.
0 0

ionic compounds (reagents, acids/bases) resulting

before after 35h before after 35h 2 wastewater generated in an organic-synthesis
in both high chemical oxygen demand (COD) and pharmaceutical plant.
salinity levels. They also present toxicity and high
Introduction Experimental
values of chemical oxygen demand and low Materials and Methods
In recentoxygen
biological years demand
the photocatalytic
(BOD), posing membrane
a threat A flat sheet polyethersulfone (PES) UE10
reactors (PMRs) have gained significant
to regular wastewater treatment plants (WWTP) attention membrane (Trisep Corp., USA) with the molecular
Actual wastewater
due to their
because some ofattractiveness
the compounds as may
an alternative for
greatly inhibit weight cut off (MWCO) of 10 000 g/mol
conventional methods
the activities of microorganisms.of water/wastewater (according
All to the manufacturer)
the samples used in this was
work used.
are The
real
treatment. These hybrid systems take advantages effective
wastewater(working) membrane area was 0.0025
effluents coming from an organic-
2
of bothmost
When photocatalysis and membrane
of the pollutants separation.
are not amenable to m . A commercially
synthesis available
pharmaceutical TiO2 Aeroxide
manufacturing plant. The
Photocatalysis is used for the decomposition
biological treatments, it is necessary to adopt of P25 (Evonik, Germany) at a concentration of 0.5
3
organic pollutants, while a membrane allows to g/dm was used as a photocatalyst. Various
separate the photocatalyst and, potentially, the
contaminants and by-products of their degradation
188aqueous solutions were applied as a feed: (1)
ultrapure water (F1); (2) solutions of hydrogen
1
from the treated solution [1]. carbonate, sulphate and hydrogen phosphate
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

TREATMENT OF LAUNDRY WASTEWATER USING A HYBRID SYSTEM COUPLING

Treatment of laundry wastewater using a hybrid system coupling will be filled
BIOLOGICAL METHOD WITH UV/O3 OXIDATION AND MEMBRANE SEPARATION in by PP2-35
biological method with UV/O3 oxidation and membrane separation
EAAOP4
S. Mozia1, M. Janus2, P. Broek1,2, S. Bering2, K. Tarnowski2, J. Mazur2, A. W. Morawski1. (1) West Pomeranian
University of Technology, Szczecin, Institute of Chemical Technology and Environment Engineering, ul. Puaskiego
10, 70-322 Szczecin, Poland, (2) West Pomeranian University of Technology, Szczecin, Faculty of Civil
Engineering and Architecture, al. Piastw 50, 70-311 Szczecin, Poland, e-mail: sylwia.mozia@zut.edu.pl
water Possibilities of application of a 3-step hybrid system
combining biological treatment followed by advanced
permeate
LAUNDRY
UV/O3 oxidation and membrane separation(ultrafiltration
(UF) and nanofiltration (NF)) to treat and reuse the
wastewater from an industrial laundry are presented.
laundry Application of a MBBR bioreactor allowed to reduce the
wastewater total organic carbon concentration for ca. 90%. The UV/O3
pretreatment prior to UF was found to be an efficient
sludge
method of the membrane fouling alleviation. During UF
MBBR O3/UV the turbidity of wastewater was reduced below 1 NTU. The
UF permeate was further treated during NF. The NF
UF permeate exhibited very low conductivity (25 - 75 S/cm)
NF
and contained only small amounts of Ca2+ and Mg2+
discharge/ (below 0.7 and 0.2 mg/dm3, respectively) thus it could be
post-treatment retentate recycled to any stage of the laundry process.

Introduction technological water. The latter wastewater stream

contained mainly chlorides.
The average water consumption in the industrial
laundry
PERFORMANCEAlbatros located in Nowe Czarnowo inMEMBRANE
OF A PHOTOCATALYTIC REACTOR WITH
Table 1. Composition of laundry A TiO UFbe filled
wastewater used
Performance
Poland
MEMBRANE (washing of70a Photocatalytic
DURING tons of laundryOF
REMOVAL
Membrane
per day) ACIDS
HUMIC
Reactor with WATER
a TiO2 UF will
2
PP2-36
3 in theFROM
experiments in by
Membrane
amounts to During
500 m Removal /day. Thisof Humic quantity Acidsis from Water
Parameter Unit Value
EAAOP4
comparable to the consumption of water in a little
A. W. Morawski, K. Szymaski, S. Mozia. West Pomeranian UniversitypH -
of Technology, Szczecin, Institute of 7.5
town. Therefore, it is important to analyse the
Chemical Technology and Environment Engineering, ul. Puaskiego 10,anionic
70-322 Szczecin, Poland, 3
SPC mg/dm 28.2
possibilities and perspectives
amor@zut.edu.pl, of water reuse in the
sylwia.mozia@zut.edu.pl SPC non-ionic mg/dm3 27.6
laundry. The investigations on the influence of
90
COD mgfeed
O2/dm composition
3
717on the
In this work removal a hybrid system permeate
combining flux and humic acids (HA) removal in
3 a photocatalytic
80 in feed BOD 5 mg O 2 /dm 264
biological treatment with advanced
membraneUV/Oreactor equipped
total removal (F0 vs. P5) 3
Cl- with a TiOmg/dm2 ultrafiltration membrane
3
562
oxidation
70 and membrane separation are to treat and
presented. TiO2 P25Ptotal was used as mg/dm a photocatalyst.
3 Alkaline
4.22
reuse60 the wastewater generated in an industrial
conditions (pH 9, F3) had PO4a3-negative influence
mg/dm3 on both 12.9 permeate
TOC removal [%]

laundry is presented. The influence flux ofand UVthe efficiency of total organic mg/dm
carbon3 (TOC) removal in
50 Ntotal 14
irradiation time on the efficiency of decomposition the PMR whereas at pH 3 (F2) and pH 6.5 3(F1) no membrane
TOC mg/dm 172
of organic
40
pollutants present in the effluents fouling from
occurred. In the presence of HCO3-, SO42- and HPO42- at
a pilot scale bioreactor was investigated. both lowThe (F4) and highThe (F5) concentrations
were the membrane in afouling
30

effluent after various time of exposition to the experiments realized hybrid

20 was more severe system
than in the absence of of
consisting these(1) species (F1, F2, F3)
bioreactor, (2)
action of UV/O3 was further what treated in
was attributed to a lowerand efficiency of HA mineralization in
ultrafiltration (UF) followed by nanofiltration
10 photoreactor (3) UF/NF membrane unit.
the feed. Addition of TheCa2+ and Mg2+treatment
biological to the F5 was feed (F6) allowedintoa
performed
(NF).0 improve the efficiency of TOC removaloperated
and reduce the severity of
F1 F2 F3 F4 F5 F6 pilot scale bioreactor in MBBR (Moving
experiments membrane fouling. Bed Biofilm Reactor) technology. The wastewater
Experimental
was treated in a two - stage aerobic reactor, where
Introduction
The wastewater was obtained from Albatros Sp. efficiency
the biofilm in grew
PMRs on withsmall,
ceramic freelymembranes.
floating
zA o. photocatalytic
o. Sp. K. (branch: Nowe Czarnowo, Poland). Syafei
polymeric et al. [3] described
elements with a removal
large of NOM
contact area. and
The
membrane reactor (PMR) is a performance of a surface
PMR with
The laundry
hybrid system wastewater was taken from
in which a photocatalytic the
process specific biofilm area photocatalytic
was 600 m2/m flat3.
retention tank and then mechanically pretreated. sheet
During ceramic
the membranes.
treatment process Yuthe et enrichment
al. [4] evaluated
of the
and a membrane separation occur simultaneously. the
wastewater used
The photocatalysis in the the
enables research was a mixture
decomposition and raw influence
wastewater of HAwithconcentration
nitrogen compounds on membrane and
of (i) wastewater stemming fromwhereas
washing fouling
adjustmentand of treatment
pH wereefficiency
necessary.in a system with a
mineralization of organic pollutants, a tubular alumina ultrafiltration
processes (industrial laundry
membrane retains the photocatalyst in the reaction wastewater) and The advanced oxidation of membrane
the wastewater and TiO was2
(ii) wastewater from the regeneration of ion photocatalyst-coated polypropylene
conducted in a pilot scale photoreactor presented beads.
medium and allows its recovery and reuse [1].
exchangers
Humic acids that
(HA),are being used a for softening
fraction of natural of inInFig.
the1. present work the investigations on the
removal of humic acids in a photocatalytic
organic matter (NOM), are formed as a result of
biochemical decomposition of the organic 189
membrane reactor equipped with a tubular TiO2
ultrafiltration (UF) membrane are discussed. The 1
remains. They affect taste and colour of potable effect of feed water composition and pH on the
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

ANTIBIOTICS CONTAMINATED WASTEWATER TREATMENT BY OZONATION AND

Antibiotics Contaminated
OZONATION COMBINED WITHWastewater Treatment
BIOLOGICAL by Ozonation and
PROCESS PP2-37
Ozonation Combined with Biological Process
R. B. P. Marcelino1, C. C. Amorim1, A. L. Emrich1, M.M.D. Leo1, Federal University of Minas Gerais, Av.
Antnio Carlos, 6627, Belo Horizonte MG, Brazil,camila@desa.ufmg.br.

The degradation of a real antibiotic wastewater by ozonation

and by its combination with aerobic biological degradation
have been studied. Although ozonation for complete
mineralization is expensive and hard to be achieved, its
combination with a biological treatment can be used to
Real Up to 99% of improve cost efficiency.
Wastewater color and Even though ozonation alone was able to reduce more than
Ozonation amoxicillin 99% of the amount of antibiotics and color present in the real
or removals (O3)
Aerobic pharmaceutical wastewater, the combined treatment system
and 98,5% of
Biodegradation COD removal
also achieved more than 98.5% of COD and 90% of toxicity
+ Ozonation (Bio + O3). removals, preventing dangerous and biorecalcitrant
compounds from reaching water resources.

TOC removal with .1.44 g O3L-1h-1.

Advanced Oxidation Processes (AOP),
particularly ozonation, have been studied and have Biodegradation alone removed more than 70%
proven effective for the degradation of antibiotics. of the initial wastewater TOC. The combination of
Few works, however, have studied the destruction biodegradation and ozonation was able to improve
of antibiotics in real pharmaceuticals wastewaters the organic matter degradation. More than 98.5%
[1]. Ozonation for complete
MINERALIZATION OF ANILINE AND REACTIVE DYE organic matter of the original
BLUE 5 wastewater
SOLUTIONSCOD was removed
BY will
Mineralization
mineralization mayofbeaniline
expensiveandandreactive
thereforedyeitsBlue(more
5 solutions
than 99% byof color and amoxicillin beremovals
filled
PHOTOCATALYTIC OZONATION PP2-38
photocatalytic
combination with ozonation
a biological treatment is widely were achieved similarly to ozonation in by
process
EAAOP4
reported to reduce operating costs. In this context, alone). Moreover, final wastewater ecotoxicity has
C. A. Orge, M. F. R. Pereira, J. L. Faria. Laboratrio Associado LSRE-LCM, Departamento de Engenharia
the aim of this study is to apply ozonation and its also decreased in comparison of ozonation alone.
Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal,
combination with aerobic biological process for
carlaorge@fe.up.pt Ozonation process reduced around 62% of original
the treatment of a real wastewater from industrial toxicity while the treatments combined removed
amoxicillin production. This work targets at theThe
90%. degradation
observed ofsynergy
aniline (ANL)
achievedandwith
C. I.the
Reactive Dye Blue 5 (RDB) favors
combination by photocatalytic ozonation as
the AOP acceptance in athe
final
Ozonation experiments were performed presencein ofa P25.polish
In ordertreatment,
to verify thepreventing
presence of synergetic
toxic and
bubble column borosilicate glass reactor with 500
effects, photocatalysis (Light/P25)
biorecalcitrant compoundsand catalytic ozonation
from reaching water
ml of wastewater in a semi-batch mode for 180
(O3/P25) were also carried out, as well as, photo-ozonation.
resources.
min. The reactor was connected to OWith 3 generator
the exception of photocatalysis alone, all tested oxidation
that concentrates oxygen from air. processes Combinedeasily degraded both model compounds. This result
Acknowledgements
TiO2
experiments were performed by 12 dayswas of aerobic
expected since O3 by itself attacks selectively aromatic
biodegradation followed by 180 minutes moieties andof unsaturated bonds, like
Authors would suchto as thank
ANL and RDB. On
FAPEMIG andtheIara
ozonation with 1 LO2min-1 and pH=10. The
other hand, in terms of TOC removal,
Project/BNDES for thephotocatalytic ozonation
financial support and the
biological process was performed accordingly was the to most efficiency processindustry
pharmaceutical achieving fora mineralization
the trustworthy
UV/Vis light
the Zahn Wellens inherent biodegradability
higher than 80%.collaboration.
methodology [2].
Introduction References
All the experiments were able to remove the
Photocatalysis
wastewater has proved
original color, as adequate
shown for in the
the The
[1] removal
I. Oller, of pollutants
S. Malato,J. was carried out in a
A. Snchez-Prez,
degradation of a wideand
Graphical Abstract, range
HPLCof pollutants,
tests showed butthat
in glass immersion
Science ofphotochemical reactor loaded
The Total Environment, 409
some
up to cases
99% of thethecomplete mineralization
initial amoxicillin is only
was removed with 250 mL (2011) 4141.(C0 = 1 mM) or RDB (C0 =
of ANL
slowly
and up toattained. Because ofremoval
80% of aromaticity that, its intrinsic
(absorbance 200 ppm)
[2] Test No.and
302B:125 mg ofBiodegradability:
Inherent photocatalyst. The
economic
at 254 nm)advantage
was achieved.is mostly perceptible for reactor was equipped with
Zahn-Wellens/ EVPA a Heraeus TQ 150
Test, Oecd,
diluted streams [1]. medium-pressure mercury vapour
OECD Publishing, 1992. lamp located
The ozone consumption ranged from 0.84 to
axially and a DURAN 50 glass cooling jacket
In addition
1.92 gO3L-1tohphotocatalysis,
-1
ozonation
. Statistical analysis is ablethat
suggests to was placed around the lamp (main resulting
selectively
the optimalconvert recalcitrant
experimental organic (pH
conditions compounds
= 9.6 ;
emission lines at exc = 365, 405, 436, 546 and 578
and can flow
oxygen be usedrate with
= 1.0) superior
would performances
achieve 46% in of
nm). The experiments were performed at 150 cm3
some high strength waste waters [1]. Molecular
ozone can oxidise water impurities via direct
selective reactions between ozone (O3) and other
190
min-1 and with an inlet ozone concentration of 50 g
m-3. The catalyst selected was commercial TiO1 2
from Evonik Degussa Corporation, sample P25.
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

COMBINED BIOLOGICAL-CHEMICAL TREATMENT OF LANDFILL LEACHATE APPLYING

Combined Biological
CONTINUOUS SLUDGEREUSE
Chemical Treatment
IN FENTON of Landfill Leachate
PROCESS PP2-39
Applying Continuous Sludge Reuse in Fenton Process
K. Klein1,A. Kivi1,M. Trapido2, T Tenno1. (1) University of Tartu, Institute of Chemistry, Ravila St. 14A, 50411
Tartu, Estonia, kati.klein@ut.ee. (2) Tallinn University of Technology, Department of Chemical Engineering,
Ehitajate Rd. 5, 19086 Tallinn, Estonia.

Landfill leachate containing significant concentration of

A: Conventional Fenton process. B: Sludge
reuse, WER=50%, CAC, H2O2/Fe2+= 40/1
(w/w). C: Sludge reuse, WER=50%, CAC,
H2O2/Fe2+=20/1 (w/w). D: Sludge reuse,
WER=50%, IAC, H2O2/Fe2+=10/1 (w/w); E:
Sludge reuse, WER=100%, IAC;
H2O2/Fe2+=10/1 (w/w).
recalcitrant organic substances was treated in a three-stage pilot
plant: biological pre-treatment, Fenton-like process applying
continuous sludge reuse and biological post-treatment. It
revealed that intermittent addition of catalyst (IAC) with
H2O2/Fe2+ w/w of 10/1 (series D) resulted in a higher increase
of BOD7/COD ratio and cyclic addition of catalyst (CAC, series
C) with same dose ratio caused higher COD removal efficiency.
Lower process efficacy due to sludge reuse was compensated by
reducing water exchange ratio (WER) to 50%. During the ferric
sludge reuse of 12 times, process efficacy did not decrease and
waste sludge production decreased 13.7 fold.

Landfilling involves formation of heavily February, 2015), mean values of BOD7, COD,
polluted leachate which must be considered and NH4-N, phenols were 6380 mg/L, 11 720 mg/L,
dealt in accordance with environmental permits. 1170 mg/L, 72 mg/l, respectively. Furthermore,
Leachate may contain large amounts of parameters of the leachate varied substantially:
biodegradable organic matter as well as values of BOD7, COD and NH4-N varied up to
biorefractory
A: Conventional Fentoncompoundsprocess, B: [1,2].
SR, Although 5.9, 5.8 and 3.2 times, respectively. Additionally,
2+
EVALUATION
biological
Evaluation
WER=50%, SAC, OF
2/Fe AN
treatment
H2Oof ALTERNATIVE
methods
an= 40/1 are
alternative
(w/w); the
C: METHOD
cheapest
method and forFOR
raw WASTEWATER
leachate
wastewater had treatment
a strong TREATMENT
distinctive odour.
SR, WER = 50%, CC, H2O2/Fe2+=20/1 (w/w);
CONTAINING
most
containing PESTICIDES
environmentally
pesticides 2+ USING
friendly
using PHOTOCATALYTIC
solutions
photocatalytic for oxidationFirstly,OXIDATION
and landfill AND
raw constructed leachate CONSTRUCTED
was subjected to PP2-40
D: SR, WER=50%, IAC, H2O2/Fe =10/1
wastewater
WETLANDS
wetlands
(w/w); treatment, they
E: SR, WER= 100% IAC, H2O2/Fe =may 2+not be sufficient biological pre-treatment reactor. Applying
treating
10/1 landfill
(w/w). 1 leachate1 [2]. Therefore, different 1 biological
1 pre-treatment
2 BOD
2 7 , COD3 removal
V.Kitsiou , C. Berberidou , D. A. Lambropoulou , . Antoniadis , C. I. Kosma , T. A. Albanis , E. Ntonou ,
physico-chemical
G.Zalidis3, I. Poulios treatment
1 methods
. (1) Department have been
of Chemistry, Aristotleefficiencies
University of of 99% and
Thessaloniki, 86% were achieved,
vasso_k3@hotmail.com.
applied for main-,
(2) Department pre- orUniversity
of Chemistry, post-treatment. One
of Ioannina, leaving
(3) School of Agriculture, BOD7, University
effluent Aristotle COD concentrations
of 60
widely investigated process is the Fenton process,
Thessaloniki. mgO2/L, 1485 mgO2/L, respectively. Biological
which reduces the organic load, decreases Aim of the pre-treatment
the present work is removed
the study additionally >99% of NH4-
and the experimental
toxicity and increases biodegradability of theof anN,
evaluation 83% of phenols,
alternative wastewater 86%treatment
of lignin and tannins.
system, which
wastewater [1,2]. Fenton process has also severalthe action
combines Second step of the treatment
of photocatalytic oxidationwas withFenton-like
surface
important drawbacks, e.g. high flow constructedprocess
chemical withThis
wetlands. SBRlow modification and ferric sludge
cost and environmentally
consumption and formation of hazardous friendly waste
system is reuse.
basedAs on Fenton processof includes
the utilization formation
solar irradiation and of
sludge [3]. Thus, different Fenton-likenatural processes hazardous ferric sludge
processes for wastewater treatment purposes. (secondary pollution),
have been developed continuously. Experiments were which needsin pilot
conducted further scaletreatment and as
using artificial increases
well
Main objectives of the work are to study landfill operational costs, it is essential
as solar irradiation, for the treatment of the pesticide clopyralid. to study iron
leachate treatment process combiningThe biological
data evaluationsludgerevealed
reuse thatopportunities.
the combined In current
system may study,
pre-treatment with Fenton-like process effectivelyandreduce Fenton-like
the organicprocess
load, aswas well applied to remove
as the toxicity of
biological post-treatment; and to evaluate, clopyralidhow and recalcitrant
may provide organic
a compounds
promising solution and increase
for the
Graph of the wastewater treatment biodegradability of biologically
operation of Fenton-like
system using the combined action of
process influences
treatmentthe of wastewater containing pesticides in the nearpre-treated
future.
combined process efficiency. wastewater. Increase of biodegradability is
photocatalytic oxidation and
Treatment
constructed of landfill leachate was studied in
wetlands required to apply final purification with activated
three-stage continuous pilot plant including sludge treatment.
activated sludge pre-treatment tank (BIO1), To reduce secondary pollution caused by the
Agrochemical
chemical treatmentwastewater
tank (CHEM) fromandwidespread
activated pyridine-carboxylic
treatment process, ferric acid),sludge
a systemic herbicide
reuse during 12
intensive
sludge agriculture in
post-treatment the(BIO
tank Mediterranean Region from
cyclesthe waschemical
applied.class Sinceofapplying
pyridine ferriccompounds,
2) with volumes of sludge
is polluting
16L, 1.6L and water
4L, with pesticides.
respectively. Although
Influent they
for pilot often
reuse, detected
hydrogen in drinking
peroxide waterdegradation
[6]. Clopyralid is
play an
plant wasimportant
obtainedrole fromin aagriculture,
municipal pesticide
landfill may be persistent
additionally catalysed in soil under
by ferric compounds anaerobic
from
compounds
located nearcould cause (Estonia),
Tallinn significant which
environmental
started conditions,
sludge, low itiron(II)sulphate
presents high solubility
dose was in water
used. At and
the
problems in
operating upon their release to the environment
2003. is particularly
beginning of the stable against ofhydrolysis
first treatment a series, thereand
[1]. Their the
During widespread
period ofapplication
that studyis(July,
an important
2014 photolysis. Its chemical
was a fast decrease in the stability
of the mixturealong pH withto its
3.
concern due to their high toxicity, their ability to mobility enables this herbicide to penetrate
accumulate, as well as their tendency for mobility
and the long-term effects on living organisms. 191
through soil, causing a long term contamination of
ground water and surface water supplies [7, 8]. 1
Advanced oxidation processes (AOPs) have been Experiments were conducted at pilot scale using
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

TREATMENT OF TABLE OLIVE WASHING WATERS USING CONSTRUCTED WETLANDS

Treatment of
FOLLOWED BYTable Olive Washing Waters Using Constructed
ELECTROOXIDATION PP2-41
Wetlands Followed by Electrooxidation
T. Tatoulis1,A. Stefanakis1, S. Zapantiotis2, Z. Frontistis2, A.G. Tekerlekopoulou1, C.S. Akratos1 , D. Mantzavinos,2
D.V. Vayenas2,3. (1) Department of Environmental and Natural Resources Management, University of Patras,
Agrinio, Greece. cakratos@upatras.gr (2) Department of Chemical Engineering, University of Patras,
Caratheodory 1, University Campus, GR-26504 Patras, Greece .(3) . Institute of Chemical Engineering Sciences,
Foundation of Research and Technology (FORTH), Patras, Greece
The production of table olives is a significant economic activity
in Mediterranean countries which produce the majority of the
global production. The production process generates large
volumes of washing waters (TOWW) that are characterized by
high organic matter and phenol contents and extremely high
salinity values. Two pilot-scale constructed wetlands units were
set-up and operated. TOWW was introduced into both units,
which were operated under 4 and 2 days of hydraulic residence
time. After a four-month operation period, COD removal rates
for the planted unit reached 99% (mean removal rate of 87%),
while the unplanted unit had a removal rate of around 70%. The
effluent of CWs was post treated with electrooxidation. The
color and COD removal at 166 mA/cm2 were >99% and 45-90%
at 240 min, respectively.

World table olive annual production is estimated photo-Fenton (Benitez et al. 2001), and combined
at approximately 1.5 million tons (Kyriakou et al., biological and chemical treatments (Rivas et al.,
2005; International Olive Council, 2002), while 2001, Beltran-Heredia et al., 2000; Benitez et al.,
the majority of this production takes place in 1997; 2001; Kotsou et al., 2004).
DESIGN
Design OF
Mediterranean HETEROGENEOUS
countries (mostly
of heterogeneous Fenton FENTON
Spain, FILM-BASED
Italy and
film-based PHOTO-REACTOR
Constructed
photo-reactor forwetlands (CWs)
the treatment FOR THEpresently
ofare
TREATMENT
Greece) (Beltran-HerediaOF PHARMACEUTICAL et al., 2000). COMPOUNDS
Table IN WASTEWATER
considered the most promising STREAMS
technology to treat PP2-42
pharmaceutical compounds in wastewater streams
olives can be classified into three types based on wastewater, due to their low cost, simple operation
R. Molina
their colour:
1
, M.M. Benacherine
green, black, , and
2
Y. Segura 1
, J.A.
black Melero1, F. and
through Martnez 1
. (1) Department
maintenance, andof Chemical
favourableand appearance
Environmental Technology, Universidad
oxidation (Beltran-Heredia et al., 2000). In Rey Juan Carlos, 28933, Mstoles,
(Shutes, 2001). Spain, raul.molina@urjc.es
Although CWs have been (2) used to
Laboratoire
Greece, table des olive
Sciences et Technologie
production is de lEnvironnement.University
estimated at Mentouri
treat a variety Constantine1 Algeria
of wastewaters, until now only five
45,000 t/year of black olives and 20,000 t/year of attempts to treat olive mill wastewater (OMW)
green olives by approximately Cooler out
75In factories
this work, thehavedesign
beenandpublished
optimization (Bubba et al., 2004;
of a photo-Fenton
(Kyriakou et al., 2005; Kopsidas, 1992). Table
Cooler in
reactor Kappelakis
is proposed. et al., 2009;
The UV-Vis lamp is Grafias
immersedet al.,
in 2010;
the
olive processing wastewater Fenton --like (TOPW) is a serious solution,
wastewater whereas
Herouvim the2011;
et al., Fenton-catalyst
Gikas et al.,is2013).
covering Thethe
aim
environmental threat due to its seasonal inner
catalyst
production
wall of theofreactor,
this studyobtaining a direct
is to present theirradiation
preliminaryfrom the of
results
and to its high organic and phenolic load lamp. The layerpilot-scale
(Kotsou was prepared following
horizontal a dip-coating
subsurface method.
flow (HSF) CWs
et al., 2004). Typical characteristics Different of TOPWsolutions for the
treating dip-coating
pre-treated TOPW technology have been
in a Mediterranean
include a wide range of UV pH values (from
UV--Visible lamp
studied,
3.6 from
to goethite
climate..dispersions in water to different solgel
13.2), high loads of suspended solidstechniques (0.030.4 for theThe preparation of iron oxides.
electrochemical Other parameters
mineralisation (EM) of
g/L)FEED
andTANKhigh organic matter content (BOD5: such as0.1
the velocity
organicandpollutants
number ofiscoatings were new
a relatively evaluated for
technology
6.6 g/L and COD: 0.316.2 g/L) (Kotsou the et elimination
al., for ofthecomplex
treatmentmixtures of pharmaceutical
of wastewaters of moderate
2004; Kopsidas, 1992). compounds in concentration,
urban wastewaters i.e. and effluentsoxygen
chemical generated by
demand
hospitals. (COD) < 5 g L1. The main advantage of this
In previous years, TOPWs were usually retained technology is that no chemicals are used. In fact,
in evaporation ponds, causing bad odours and in only electrical energy is consumed for the
some cases surface and groundwater pollution mineralisation of organic pollutants on high
(Beltran-Heredia et al., 2000). In recent years, a oxidation power anodes. An ideal anode for this
great variety of treatment methods have been type of treatment is the boron-doped diamond
tested for TOPW treatment including: aerobic (BDD) electrode characterised by high reactivity
degradation systems (Benitez et al., 1997) or towards organics oxidation and efficient use of
anaerobic digestion (Borja et al., 1993; Wheatley, electrical energy.
1990), ozone oxidation (Rivas et al., 2000), Fenton
oxidation (Rivas et al., 2003), a combination of Two identical pilot-scale HSF CWs were
UV radiation and hydrogen peroxide as well as constructed at the Department of Environmental

192 1
F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S
W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON

MODIFIED FENTON CHEMISTRY TO REMEDIATE GROUNDWATER CONTAMINATED BY

Modified Fenton Chemistry to Remediate Groundwater Contaminated by
COMMERCIAL GASOLINE/ETHANOL BLEND: APPROACHES TO APPLY H2O2
will be filled
PP2-43
in by
Commercial Gasoline/Ethanol Blend:approaches to applyH2O2
EAAOP4
Luiza N. Andrade1, Camila C. Amorim1, Fernanda G. Morais1, Alexandre B. Almeida2, Sandrine F. Arajo1,
Mnica M. D. Leo (1)Department of Sanitary and Environmental Engineering (2) Department of Chemistry
Engineering, Universidade Federal de Minas Gerais, Belo Horizonte, Brazil Email:camila@desa.ufmg.br
Modified Fenton chemistry was investigated for In Situ
Modified Fenton Chemistry Chemical Oxidation for remediation of groundwater
Oxisoil contaminated by gasoline/ethanol blend. Experiments used
Fe3+ + H2O2 Fe2+ + H+ + HO2 natural groundwater, and oxisoil with high iron concentration.
Gasoline used on this study contained high ethanol fraction,
CaO2 Liquid H2O2 which generated a plume with elevated organic carbon
20000
concentration and increased the solubility of the BTEX. Were
16000 Readily tested two different approaches to apply H2O2: using liquid
H2O2 (mg/L)

Scavenged
12000 H2O2, and using CaO2 that slowly releases H2O2 on
8000 groundwater. Results showed that CaO2 is more effective for
Slowly released DOC degradation, achieving 48% removal in 7 days of
4000
and consumed experiment. For BTEX, both approaches, and even the soil
0
0 2 4 6 12 14 16 control presented results below detection limits in an hour of
Time (days) reaction.

Introduction releases H2O2 in contact with water as presented

by the Equation 1.
The increased fraction of the population depend
ent on groundwater as the main source of supply CaO2 + 2 H2O Ca(OH)2(s) + H2O2 Eq.[1]
created a fragile scenery where groundwater
contamination has become an environmental This work presents two different approaches for
concern. TOXICITY
In Europe groundwater contamination Modified
byTEXTILE WASTEWATER Fenton Chemistry in soils rich in iron
ACUTE EVALUATION OF REAL oxide, to Treated
clarify the TREATED will
BY beoxidant:
Acute
fuels is Toxicity
the causeEvaluation
SOLAR-PHOTO-FENTON
of 15% soil of Real Textile
contamination Wastewater by more applicable filled
PP2-44
Solar-Photo-Fenton
registers [1]. Brazilian gasoline/ethanol blend has liquid H 2 O2 or CaO 2 , to promote ISCO reaction
in byfor
groundwater remediation contaminated EAAOP4by
an important characteristic due the constant
Starling. Maria Clara,1, Reis, Beatriz G1, Amorim, Camila C. 1
gasoline/ethanol
, Leo, Mnica, D 1
blend.
. camila@desa.ufmg.br(1)
increase of ethanol fraction, that nowadays is 28-
Universidade Federal de Minas Gerais,Antnio Carlos, 6627 - Bloco 2 - sala 4626 CEP 31270-901 - Belo
30%.
Horizonte MG, Brazil. Methodology
The addition of ethanol to gasoline/ethanol blend The experiments were carried out using an
has important impacts on their behaviour Textile wastewaters
on contain
oxisoil dyes,and
samples salts and other
natural chemicals
groundwater which
both from
groundwater. Compounds (e.g., benzene, contribute
toluene, to wastewaters
the regionacute of toxicity. Biological
Minas Gerais, treatment
Brazil. This only
is a
ethylbenzene and xylene) increase its solubility is usuallyonnot effective
mining regionto remove organic,
which soil color
presentscontent and
abundant
water in presence of ethanol [3, 4], ecotoxicity.
and they Therefore,
hematiteAdvanced Oxidation
and low organic Processes (AOPs),
matter.
become less biodegradable [3, 5]particularly once all photo-Fenton systems, have been widely tested as
dissolved oxygen is used for ethanol, singlethat The contaminated
or complimentary
is treatment systems,plumealthough,
was prepared by the
the potential
preferentially degraded. to reduce toxicity dissolution
of AOPs ofis 10% (v/v) Brazillian
controversial. commercial
The present work
monitors toxicitygasoline/ethanol
during the reaction blend inof natural
textile groundwater
wastewater
Oxidation is currently been used for treatment remediation throughsamples. This mixture was
solar-photo-Fenton. The agitated
treatment forwas
10 minutes,
able to
o
of contaminated groundwater and the In Situ reduce dissolved 150 rpm
organic at 252
carbon C, and
(DOC) the
andfraction
achievedsoluble on the
complete
Chemical Oxidation (ISCO) technique involves color removal. groundwater
Toxicity has was
also collected
been and
removed, named
but it as
hasgasoline
shown
the use of oxidants on the soil. ISCO great variation groundwater.
is an during reaction due to the formation of different
.effective technology to remediate groundwater organic compounds.
For the oxidation tests, 250 mL reactors were
contaminated by gasoline, and it is important to filled with 200 mL gasoline groundwater, and 20
test different oxidants. Modified Fenton chemistry g.L-1 of the oxisoil. The oxidants H2O2 (Fmaia)
can be used such as ISCO since the reaction of and CaO2radicals
selective (Sigma-Aldrich) were added
[8]. Although, (20 g.L-1to
their potential ),
H21.O2 can
BACKGROUND
occur by the natural iron oxides present and
reducethe toxicity
reactors were kept on a shaker
is controversial [1] andat 150 rpm
require
onTextile
the soil.industry
Recent studies suggest that
is traditionally known the process
for its at 252oC during
attentive 14 days. Aanalysis,
case-by-case soil control especially
(oxisoil +
can be effective, however
pollution intensive production H O can be readily
2 2processes which gasoline
regardinggroundwater)
time of reaction and as
a control
detected(just gasoline
by Trov et
scavenged.
require A different
a large amount of approach
chemicals,instead
waterusing
and groundwater)
al. (2012)[9].In werefact,
also analysed.
the number of studies
liquid H
energy 2O2 is to
[1].Most of use compounds
the dyes applied that
in thereleases
textile regarding AOPs and toxicity has greatly increased
H O (e.g., Na CO , MgO , CaO ) [6]. of
In their
this Redox
over the pastPotential
years [10].(Sanxin SX630) and pH
processes are non-biodegradable as a result
2 2 2 3 2 2
(Digimed DM-22) were analysed directly on the
systems
high the use
molecular of CaO
weight and2,complex
for example,
structuresslowly
[2],
One of the most applied AOP processes is
andsome of them are proved to be toxic, such as
the azo dyes[3]. It is estimated that up to 50% of 193
photo-Fenton, which has been pointed out as 1a
cost-effective option for degradation of textile
dyes may be present in the final wastewater[4], wastewaters [11]. In this system, iron oxides
 P O S T E R P R E S E N TA T I O N S - 2 nd D A Y

Photo-Fenton treatment
PHOTO-FENTON of the antineoplasmatic
TREATMENT drug 5-fluorouracil:
OF THE ANTINEOPLASMATIC DRUG 5-FLUOROURACIL:
KINETICS AND
Kinetics and TRANSFORMATION
Transformation PRODUCTS
Products PP2-45

A. Koltsakidou, M. Sykiotou, E. Evgenidou and D. Lambropoulou,

Aristotle University of Thessaloniki, Panepistimioupolis, Thessaloniki, Greece, dlambro@chem.auth.gr

In this study the investigation of the homogeneous

photocatalytic treatment of the antineoplasmatic
drug 5-fluorouracil by photo-Fenton reaction has
been carried out. The effect of various parameters
like the initial concentration of 5-fluorouracil, the
concentration of Fe3+ or H2O2 was studied. The
rate of degradation was also compared to the rate
achieved by using heterogeneous photocatalysis,
and it appeared to be slightly higher. The
degradation kinetics appear to follow the first-
order kinetic law. The transformation products that
are produced during the photocatalytic treatment of
the studied drug were also identified by means of
liquid chromatography coupled with mass
spectrometry (LC-MS).
Figure 1. Degradation of 5-fluorouracil by photo-
Fenton, TiO2 and photolysis treatment ,at 20min of
irradiation.

In the last years, cytostatic drugs demand in used without any further purification. Hydrogen
developed
Multistage countries has
Treatment grown considerably,
System
MULTISTAGE TREATMENT SYSTEM FOR BIODIESEL for due
Biodiesel peroxide
Wastewater (30%)by
WASTEWATER wasMoving
obtained from will
BY MOVING Panreac
BED and
be filled
toBed
the Biofilm
high incidence of cancer [1-3]. Given the ferric sulfate Fe (SO ) .7H O were in byby
supplied
BIOFILM REACTOR ReactorAND andADVANCED
Advanced Oxidation
OXIDATION Processes
PROCESSES 2 4 3 2
EAAOP4 PP2-46
concern over the risk posed by the presence of Riedel-de-Haen and were used as received. LC-
these compounds in water 1
bodies, and hence
1*
the MS grade
1
solvents (methanol/water)
2
were supplied
Luciano O.
possible Gonalves
impacts Camila health
on ;public C. Amorimand ; aquatic
Monica M. D. byLeo
Merck.; Daniel
HClV.andM. NaOH
Oliveirawere Rodrigo Prado1the
usedG.toP.adjust .
1
Universidade Federal de Minas Gerais, Av. Antnio Carlos, 6627, Belo Horizonte, Brazil. 2Escola Politcnica da
ecosystems a greatProgram
USP, Post-Graduate deal in of Civil
research
Engineering - Sanitary pH
is being when Engineering.
Hydraulic necessary. Ultra-pure water was used for
e-mailcamila@desa.ufmg.br.
carried out on technologies for their removal[4]. the preparation of all solutions throughout the
Among them, photo-Fenton process has been experimental work.
intensively studied and seems to be a This work aimedIrradiation
promising to evaluateexperiments
the biodieselwere carried treatment
wastewater out in a
technique for treating waters contaminated with Suntest CPS+ apparatus
by multistage systems combining moving bed biofilm reactor (Heraeus Germany)
highly recalcitrant organic contaminants, (MBBR) like withsimulating
photo-Fenton naturalprocess.
sunlightBiodiesel
irradiation.wastewater
The light
cytostatic drugs, because of its high efficiencycontains source was
andhigh organic matteran (TOC>
air-cooled 1,000 xenon
mg Llamp
-1
, and(2.2
COD>kW)
cost effectiveness compared with other3,500 advanced -1 jacked with special glass filters restricting the
mg.L ). MBBR process achieved 69% of COD removal
oxidation processes (AOPs)[5]. and 70% of TOC. transmission of wavelengths
The photo-Fenton 90%belowand 29056%nm. of A tap
TOC
Under this light, the application of photo-Fenton water
removal. The multistage coolingtreatment system showed an overallat
circuit maintained the temperature
reaction (Fe3+/H2O2/solar radiation) efficiency for theof 97% 251 o
for CODa removal
C. In typical photocatalytic
and 89% for TOC run 100 ml of
removal.
degradation of 5-fluorouracil (one of Optimized the most conditions
5-fluorouracil
by factorial planning showed the use of at
solution with initial concentration a
commonly used cytostatic drugs worldwide) in 10
MBBR reactor with (sludge mg/L wereold putof 30indays theand reactor
250 mg.Lwith-1 Fethe
aqueous matrices has been explored. The and 800scopemg.L appropriate amount of iron.It The
H2O2 for photo-Fenton. pH wasanadjusted
performed acute
was to evaluate and to optimize the effects ecotoxicity test with the luminescent marine bacteriumprocedure.
of most at the beginning of the experimental Fischeri
influenced parameters, such as initialAliivibrio substratein raw The reactionin the
wastewater wassample initiated by adding
post MBBR the
biological
concentration, iron concentration andprocesses peroxideand aappropriate amount of hydrogen peroxide
test sample of the best results of the processes of followed
concentration. Moreover, in order to elucidate the
photo-Fenton, by switching
peroxidation / UV onand thephotolysis.
lamp. At specific time
mechanistic details of the photo-Fenton assisted intervals, samples were withdrawn from the
photodegradation of 5-fluorouracil under reactor, were filtered through a 0.22 mm cellulose
simulated solar irradiation, the intermediates that and finalized
membrane by ozonation
filter (MF-Millipore assisted Membrane
hydrogen
INTRODUCTION peroxide13 treatment for USA)
the and effluent with fora
are formed during treatment were identified using Filters, mm, Bedford, then used
-1
Biofuels
LC/MS offer some benefits compared to fossil
techniques. further analysis. initial COD 6,800 mg.L . The
pharmaceutical
fuels, such as reducing
5-fluorouracil analyticalthegrade
emission
(99%ofpurity)
gases was
that entire system reached
5-fluorouracil 99%, and 98%
and transformation efficiency
products for
(TPs)
cause the greenhouse
purchased effect, highindustry
by Tokyo Chemical availability
and from
was the removal of COD
concentration and color, respectively.
was determined by a Shimadzu
common sources, features non-polluting, Optimization of the conditions in AOP systems
biodegradable and contribute to sustainability [1].
Biodiesel may be generated by converting biomass 194
can lead the cost reduction of these processes.
Since the iron dosage should be evaluated for each
1
(oil vegetable or animal fat) in a reaction in the system as the geometry of the reactor used [10]
 1

F E NTON AN D FEN TON LIK E P ROC E SSE S C A TA LY TI C R E D OX P ROC E S S E S C OU P L I N G A OP S

W I TH OTHER PROCESSE S P ILOT- SC A LE STUD IE S A N D F I E L D A P P L I C A TI ON OZONA TI ON
Oxidation of Water Soluble Biosolids by Free Radicals Mechanism.
OXIDATION OF WATER SOLUBLE BIOSOLIDS BY FREE RADICALS MECHANISM. A
A UV/Vis Spectroscopy Study
UV/VIS SPECTROSCOPY STUDY PP2-47

E. Giannakopoulos1,2, G. Psarras2, G. Oron3 and I. Kalavrouziotis1*

1
School of Science and Technology, Hellenic Open University, Tsamadou 13-15 & Saint Andrea, 262
22 Patras, Greece
2
Hellenic Agricultural Organization-"DIMITRA"-Institute for Olive Tree, Subtropical Crops and
Viticulture, (Lab. of Plant Mineral Nutrition & Physiology of Chania), Heraklion, Greece
3
Ben-Gurion University of the Negev, J. Blaustein Institutes for Desert Research, Zuckerberg Water
Research Center, Kiryat Sde Boker, Israel 84990

*Corresponding author E-mail: ikalabro@eap.gr,

ABSTRACT
The oxidation of water soluble biosolids by complexation with natural polyphenolics with
activity free radicals such as gallic acid (GA) in alkaline pH under ambient O2 and
temperature is investigated. UV/Vis spectrum between 600 and 800nm wavelengths for
complex shows formation of new species which contain stable phenol-based p-type radicals,
with pH-dependent concentration.

Keywords: Water Soluble Biosolids, Oxidation, Polyphenols, Free Radicals.

INTRODUCTION
COST ESTIMATION OF SOLAR PHOTO-FENTON PROCESS IN RACEWAY PONDwill be filled
Management of water
Cost estimation of soluble biosolids (SL) process
solar photo-Fenton accountsinforraceway
a major portion
pond of the cost of the PP2-48
REACTORS AS TERTIARY TREATMENT in by
wastewater
reactors astreatment process and represents significant technical challenges [1]. In many
tertiary treatment
EAAOP4
wastewater treatment 1 facilities, the bottleneck of the sludge handling system is the dewatering
I.M. Romn Snchez , M. Segura1, A.M. Freitas2, G. Rivas Ibez1, M.C. Campos-Maas1, S. Arzate1, J.A.
operation [2].
Snchez Prez 1 Advanced sludge treatment processes such as thermal and thermochemical
processes
(1) Research[3],
Centreor onchemical oxidation
Solar Energy (CIESOL),using hydrogen
University peroxide Almera,
of Almera-CIEMAT, [4] have been
Spain, developed in
iroman@ual.es
(2) Department
order to improve of Chemistry
sludgeand Biology, Federal
dewatering andUniversity of Technology-Paran,
to facilitate handling and Curitiba,
ultimateBrazil.
disposal. These
methods degrade water soluble biosolids (SL) such as proteins and polysaccharides reducing
the (SL) water retention properties.The Theuseuse
of of sludge,
raceway as reactors
pond a raw material
for solarfor processinghas
photo-Fenton and
recycling for new products is becoming a real challenge.
been recently proposed. As tertiary treatment, two goals should
be achieved, bacterial inactivation and persistent
microcontaminant removal. This is the first cost estimation for
photo-Fenton process in a raceway pond reactor. Conversely to
THEORETICAL BACKGROUBD CPC, the main contribution to total cost is operation- cost
The Polyphenolics/Polyphenolics anion/Polyphenolics
(90%) giving rise to free a lowradical triad (PhOH/PhO
dependency /PhO )
of costs on liquid
represents compounds that have greatdepth.importance in ais wide
This estimation only a range
startingofpoint
physicochemical
encouraging moreand
biological processes in humification [5]. The
research on UV/Vis
process spectrum
optimization, of and
theseadditional
couples in aqueous
economic
solutions, is strongly depending on studies basedpotential
pH, redox on pilot scale experiments.
Eo, Pb effect, numbers and position of
substituents on the phenolic ring. Substituents such as carboxyl (-COOH) and hydroxyl (-OH)
groups on the phenol ring can significantly influence the electron density on the ring and
thus modify UV/Vis spectrum dramatically. The UV/Vis spectrum of the PhOH governs the
reaction of PhOH with O2 to form free radical PhO- [5]. At alkaline pH the pKa's of the
maintenance costs were considered as 2% of
PhOH are outstanding
An economic assessment indicators of the electron amortization
of microcontaminant density in thecosts.
aromatic ring of the members
Reactant costs, Creactant,
of these and
removal triads (electrophilicity)
disinfection of a realand thus are excellent
secondary tools to predict
consider the mass of hydrogen half-cell
peroxidereduction
and iron
WWTP
potentialseffluent using
for both thesolar photo-Fenton
one-electron in a
and two-electron couples, which in turn allow estimation
needed to achieve the necessary inactivation. The
raceway
of rate pond reactorfor
constants (RPR)
the isreactions
presented.of these triads. A molecular
unitary reactant costsmodel
were:which represents
0.5 /kg the
H2O2, and
above is the Gallic
Photo-Fenton process acid (GA, 3,4,5-trihydroxylbenzoic
was performed in a PVC acid).
0.25 /kg iron salt.GA
Theisenergy
a natural polyphenol
cost was estimated
which exhibits
raceway the most
pond reactor, withconsiderable
18 L capacityantioxidant
and 5 by calculating
capacity the power
in plants required to model
and a successful move for
the
cm liquid
the radicaldepth with a volume/surface ratio of 50 paddlewheel; the considered
properties of natural humic acid with pKa's 4.3 (carboxyl group) 8.8, 11.4, 11.7power cost was 0.1
L m-2. Water
(hydroxyl was mixed
groups). The and
(SWS)set inand
motion by a
GA mixed,
paddlewheel. Before the treatment, pH was set at
195
/kW h. Working time (tw) of the treatment plant
under ambient O2 and temperature at alkaline
was the average solar hours per year, 3055 h. Staff
pH. The redox mechanism degradation of watercost
6.5 to partially remove bicarbonates. To achieve was not included since it is not directlyUN-Vis
soluble biosolids is controlled by related
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

ECO-EFFICIENT TREATMENT OF EFFLUENTS OF THE MANUFACTURING INDUSTRY:

Eco-Efficient Treatment Of Effluents Of The Manufacturing
ELECTROCOAGULATION PROCESS WITHIN ECOWAMA PROJECT
will be filled
PP3-1
in by
Industry: Electrocoagulation Process Within ECOWAMA Project
EAAOP4
S. Sanchis1, D.Gali1, M. Aliaguilla1, D. Anguera1, A. Serra1, F.X. Simon1, J. Garcia-Montao1.
(1) Leitat Technological Center, C/Innovaci 2, 08225 Terrassa, Barcelona, Spain, ssanchis@leitat.org

The ECOWAMA project proposes a new eco-efficient closed

cycle management model for the treatment of effluents of the
metal and plastic surface processing industry. The process is
based on electrochemical technologies, which provide chemical
free performance, including electrocoalescence (pulsed electric
field, PEF), electrocoagulation (ECo), electrooxidation (EO)
and electrowinning (EW). The hydrogen produced during
ECo/EO processes is recovered, as well as valuable substances
(Ni, Cu, Ag and Zn) with a high purity (>99%) from the ECo
sludge -by means of EW. The water is finally treated through
desalination (DS) in order to obtain high purity water for
recycle, while the acid for dissolving is totally recycled using
electrodialysis (ED).

high purity. The outcome of this is a valuable raw

Annually, European metal finishing and coating material that can be easily sold or reused for
operations produce over three hundred thousand
STM/STP operations.
tonnes of hazardous waste and consume over one
hundred million cubic meters of water for cleaning The technical objectives of the project are:
of surfaces and as basis for galvanic solutions.
The wastewater of the metal and plastic surface To remove 99.9% w/v oils/greases
ELECTROIRRADIATED TECHNOLOGIES FOR THEthrough
REMOVAL OF OXYFLUORFEN
PEF (pre-treatment) FROM
Electroirradiated
processing
SOIL WASHING industry technologies for
(STM/STP) is extensively
WASTES
the removal of oxyfluorfen from soil and will desalination
be filled
PP3-2
(Multistage humidification/dehumidification, in by
washing wastes
contaminated with oils and greases, organic
MHD) as post treatment to achieve EAAOP4
a rest-
loading, a salt fraction and especially with heavy
M.A. Rodrigo1, E. Vieira dos Santos2, C. Sez1, C.A. Martnez-Huitle 2
, P. Caizares
conductivity of
1
,
maximum 18 S/cm.
metals
1 (e.g. Ni, Cu, Zn and others). Though EU
Department of Chemical Engineering. Universidad de Castilla La Mancha. Campus Universitario s/n.
legislation related to sewer1Institute
manuel.rodirgo@uclm.es chargesofand increasing
Chemistry, ofECo
Federal University and EW
Rio Grande process
do Norte, Lagoato Nova
recoverCEPover
cost of water, energy and raw materials, STM/STP Soil washing80% usingofsurfactant solutions
at least three is ametals
different very effective
(Ni, Cu,
enterprises have high interest on efficient, cost- and widely used
Zn ettechnique
al.) out offor the remediation
STM/STP effluent.ofThe polluted
purity
effective and sustainable treatment of their soil. However,of it
theismetals
not a finalistic
will be >technology
99%. and once the
effluents and recovery of valuable substances. pollutant is transferred to the washing-solution, the
H2O OH + H+ + e Low concentration of SDS

waste To develop
has to bean EO In unit
this to remove
ECOWAMAs (ECO-efficient management resulting
OH
of aqueous
organic loading
treated.
to a residual
work,
value of less than
it is
studied the feasibility of electrolysis, sono-electrolysis and
Oxyfluorfen

WAter in the MAnufacturing industry) approach

Oxyfluorfen
CO2

OH O + H+ + e-
1% rest-loading.
photo-electrolysis with boron doped diamond anode to treat
combines wastewater treatment with recovery of
2 O O2
BDD 2 OH H2O2

ultrapure water, highly valuable metals the andeffluent of a surfactant-aided soil washing
and process
reuse ofand
OH + H2O2 HO2 + H2O High concentration of SDS
H2O2 O2 + 2H+ + 2e-
O2 + O O3 To enable the recovery the
energy. Therefore an environment friendly, it is pointedhydrogen from ECo/EO processes inaspects.
out some important
CO2
mechanistic a fuel
Atrazine

effective and innovative system is developed

2SO42- S2O82- + 2e- E= 2.01 V
Results confirm
cell that
stackcombined
as a power processes
source are
for efficient
the process.for
including ECo, EO and EW technologies. the removal 80%
Scheme of the electrochemical reactions and size particle
and total mineralization
of hydrogen of oxyfluorfen.
generated is converted TOCto
Additionally, hydrogen produced during ECo and and COD areenergy
removed from
in the fuelthe
cell.start of the treatment but
EO processes are used to deal as feed for fuel cells the key of the treatment is the reduction in size of the
to generate electricity which reduces the energy micelles. To integrate the single units to a pilot
demand of the overall process. Pre- and post- scale system running at a ~500 l/h flow-rate.
treatment
Introduction are carried out to remove oils/greases To develop and to adapt a global control
(electrocoalescence) and conductivity in system
the soil washing
including energyefficiency
management.and in the
Pesticides are very useful compounds
(desalination). The heavy metals are separated in characteristics of the washing waste, focusing on
agriculture
from which help stream
the wastewater to increase productivity
through but
an electro- To
the effect of make a verification
the size particle andof the economic
oxidation
at the same process.
precipitation time theyAfter
are metal
hazardous for human
dissolution from and environmental
mechanisms sustainability ofmicelles.
of oxyfluorfen/surfactant the process
health and the environment
precipitation sludge a and novelso, their occurrence
electrowinning enabling a more resource efficient and
in wastewater
process usingshould
novelbe prevented.
electrodes,Amongst the
optimised recycling economy
various pesticides
geometry that have
and process been studied
management reduces withthea
view to develop alternative Materials
Two strategiesand methods
were carried out in order to
dissolved metal ions to a solidand environmentally
aggregate state with
acceptable treatment systems, oxyfluorfen has Oxyfluorfen(2-chloro-1-(3-ethoxy-
received considerable attention. For this reason
technologies is Surfactante-Aided Soil Washing
4nitrophenony ) -4- (trifluoromethyl), 99.8% 196
purity, HPLC-grade acetonitrile, ethyl acetate and
1
(SASW), successfully studied for the remediation hexane were obtained from Sigma-Aldrich (Spain).
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

REMOVAL OF ORGANIC MATTER OF OIL FIELD EFFLUENT WATER BY

Removal of organic matter of oil field effluent water by
ELECTROCHEMICAL OXIDATION AND ELECTROFLOTATION TREATMENT
will be filled
PP3-3
in by
electrochemical oxidation and electroflotation treatment
EAAOP4
E.M. Saggioro1, G.S. Cunha2, A.J.B. Dutra2
(1) Fundao Oswasldo Cruz, Departamento de Saneamneto e Sade Ambiental, Av. Brasil, 1480, Rio de Janeiro,
Brazil Country, enrico.saggioro@ensp.fiocruz.br.
(2) Universidade Federal do Rio de Janeiro, Laboratrio de Eletroqumica Aplicada/COPPE, Ilha do Fundo, Rio
de Janeiro, Brazil

The aim of the study was evaluated the electrochemical

process for remove organic matter of oil field effluent under
electrooxidation and electroflotation aspects. The cathode
was always stainless steel sheet and anode was titanium
coated with ruthenium oxide. Differents voltages were
evaluated (3.5, 4.5 and 5.5 V). Each 10 minutes the sample
was withdrawn for chemical oxygen demand (COD)
analysis. The global electrochemical process removed
almost 90% of COD at 5.5 V. In addition, in this study was
possible to quantify separetely both the fraction of organic
matter removed by electroflotation and that removed by
electrooxidation. Hence, electroflotation removed more
organic matter than electrooxidation.

bubbles promoted a considerable collision between

Background bubbles and particles due increment on the surface
The production of oil field extraction, transport area of contact [3].
and purify generate bulk effluents that are The electrooxidation of organic pollutants occur
separated
NEW by process
INSIGHTS platform.
INTO Oilfield water can
THE ELECTRO-OXIDATION OF AorMODEL
directly PHENOLIC
indirectly. COMPOUND,
When oxidationwill is
be directly
New Insights into
be various hazardous
p-CRESOL: EFFECT
the Electro-Oxidation
compounds
OF ELECTRODE which include: of
a a
MATERIAL
Model Phenolic
AND ELECTROLYTE
filled
PP3-4
performed, the pollutants destruction in by
handle
Compound, p-Cresol: Effect of Electrode
large amount of oil, salinity, sand, suspend solid, Material and Electrolyte
anodic oxidation. In this method, the EAAOP4
reaction
ammonium,
M.J. Rivero1, heavy metals,
C.J. Escudero 1
, O.and microorganisms
Iglesias 1
, S. Domnguez1, I. Ortiz
occurs
1
. (1) Department
with adsorbedof Chemical
hydroxyland Biomolecular
radicals generated
[1].
Engineering, University of Cantabria, Av, de los Castros s/n, at 39005,
the Santander,
surface ofSpain,
anode from oxidation of water
The electro-oxidation
(acid performance of p-cresol
and neutral media) [4]. was investigated with
The Electrochemical treatment of wastewater is a
different commercial anodic materials currently available (Nb/BDD,
powerful advanced oxidation process for
Ti/Pt and Ti/RuO In2) the
usingliterature,
Na2SO4 and it isNaCl
possible to foundThe
as electrolytes. the
environmental safe control of water pollution. This
reduction of p-cresol concentrationand
electroflotation and TOC was monitoredon
electrooxidation under the
method is offering high removal efficiencies in operational
the different conditions
remediation to evaluate However,
of wastewater. the efficiency
the ofworks
the
lower temperature, with simple andtreatment.
compactThe concentration
have not shown , Cl-dates
of SO42-the , ClO3- of
andthefree individual
chlorine
equipment and natural control handling.was
Moreover,
determined contribution
to analyse theofeffect of the supportingprocess
each electrochemical electrolytes
in the
there is no need for additional chemicals
and gainthat
information
sameabout
cell. the indirect
Nahui oxidation
et al. (2008), mechanisms
Bande et al.of(2007)
PC.
prevent other generation products [2]. Under the experimental
e Hosny conditions
(2006) studiedNb/BDD the was the compounds
organic electrode
material that reached the using
highestelectrochemical
degradation and column
mineralization,
When the electrochemical treatment is using outSO remove
carried Na system.
2 4 as electrolyte. The use of NaCl hindered
in a column, two phenomena in the same time for They did not take into account the percentage of
mineralization and the electrodes showed different capacities to
pollutants remotion can occur: electroflotation electrochemical oxidation. The remediation
generateand
reactive chlorine species.
electrooxidation. efficiency was attributed only particles removed
Figure electrochemical
through 1 shows the normalized
flotation [1,PC and TOC
3, 5].
Electro-oxidation is a highly effective remediation
Electroflotation is a process that promote adhesion concentrations obtained for the three anodic
technology to degradeparticles
and floats pollutants organic compounds present
to the surface of ain materials
The aim and of the
thetwostudy was toAfter
electrolytes. evaluate
5 min the
of
wastewaters.
water body by Thetiny
main drawbacks
bubbles include[1].
electrolysis the The
costs treatment
electrochemical
PC process
removalforwas
remove organic matter
complete using
associated
principal with the electrode
advantages material and electrical
of electroflotation and of oil field
Nb/BDD andeffluent
Ti/RuOunder electrooxidation and
2 anodes with NaCl as
supply.
traditional flotation concern (PC)
In this study, p-cresol the was
fast selected
rate ofas electrolyte.
electroflotation aspects.
Using the same electrolyte and Ti/Pt
model
particles phenolic
remove, itsubstance
can achieveto simultaneous
analyze the anode the full removal was attained after 180 min.
performance of different anodic materials
flotation and coagulation producing less sludge. and When Na SO was used, the complete removal
2 4
electrolyte
Finally, thecompounds.
equipment and instruments are easy was only obtained with the Nb/BDD anode after
handling1 and compact. Furthermore, 120 minutes, whereas with Ti/Pt and Ti/RuO2 PC
electroflotation
0,8 is an improvement through small reductions of 89% and 46% were attained
uniforms bubbles (diameter 20 m). These micro respectively
Methodology after 5 hours.
0,6
PC/PC0

In these working conditions the maximum

0,4

0,2
197
mineralization after 5 hours was 30% with1
Nb/BDD and Na SO . The use of Ti/Pt showed
2 4
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

PHOTOELECTROCHEMICAL STUDY OF TiO2 NANOTUBES GROWN BY ANODIZATION ON

Photoelectrochemical study of TiO2 nanotubes grown by anodization
SPUTTERED VS. EVAPORATED Ti LAYER
will be filled
PP3-5
in by
on sputtered vs. evaporated Ti layer
EAAOP4
J. Krysa1, S. Kment2, Z. Hubicka3 , K. Lee4, and P. Schmuki4
(1) University of Chemistry and Technology Prague, Technicka 5, 16628 Prague, Czech Republic
(2) Palack University, RCPTM, Joint Laboratory of Optics, 17. listopadu 12, 771 46, Olomouc, Czech Republic
(3) Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 14800 Prague, Czech Republic
(4)Department of Material Science WW-4, LKO, University of Erlangen-Nuremberg, Martensstrasse 7, 91058
Erlangen, Germany, Josef.Krysa@vscht.cz
This paper describes the formation of transparent TiO2
nanotube layers formed by complete anodization of deposited
metallic Ti thin films on an FTO glass substrate. The quality of
the deposited metal (adherence and layer density) governs the
anodization process. Ti films were deposited using electron
beam evaporation or a magnetron sputtering. Sputtered metal
layer is denser than the evaporated layer where some pinholes
can be observed. The electrolyte may therefore be able to
penetrate the evaporated layer, which leads to current leakage
during anodization. Both of the layers are well crystallized by
annealing. However, comparing the photoresponses of the
layers, the TiO2 nanotubes formed on a sputtered layer show
about a 19 times higher photoresponse than those formed on the
evaporated layer.

anodization for TiO2 nanotubes on an FTO

For the development of optical, electronic and substrate. If there is low adherence and a loose
display devices, interest in transparent electrodes metal layer, the layer is easily lifted off during
has increased greatly. In particular, transparent
PREPARATION ANDsubstrate
PHOTOELECTROCHEMICAL anodization.
PROPERTIES This OF means
WO3that LAYERS the deposition
TiO2 on a conductive is considered to be
Preparation
PREPARED BY and photo-electrochemical
SEDIMENTATION AND
one of the most promising electrodes for DSSCs SPRAY-PYROLYSISproperties
method can also of WO
affect TiO2 3 nanotubeswill be filledon
grown
in by PP3-6
layers prepared FTO glass.
and also display devices.byTo sedimentation
produce a transparentand spray-pyrolysis EAAOP4
oxide
Josefelectrode, the materials
Krsa, Martin are usually
Zlmal. University deposited
of Chemistry Thick titanium
and Technology, films, as5, starting
Prague, Technick substrates
166 28 Prague 6, for
onCzech Republic, krysaj@vscht.cz
a conductive glass electrode using a doctor TiO2 nanotube growth, were deposited by means
blade, silk screening, dip coating and layer-by- of magnetron sputtering. It is generally known that
layer methods. So far, most transparentTwo TiO2 different
the methods were used
thick sputtered metalforcoatings
the preparation
suffer from of a
nanostructures have consisted of nanoparticle tungsten oxide layers on fluorine doped tin
low adhesion. For such films the anodization to oxide layered
layers. To use transparent TiO2 nanotube support glass. First method
produce nanotubesis based on simple
or even sedimentation
the contact with water
structure, a nanotubular layer grown on of a commercially
bulk available
solutions often WOmeans3 particles formingpeel-off.
their complete particular The
layers with considerable
metal substrate had to be transferred to transparent photocurrents.
insufficient adhesion is mainly Theduesecond method
to the organic
substrate by a lift-off and attachment process consists
with of contaminants
spray-pyrolysis on of the synthetized
surface of the precursors
substrate.as In
TiO2 nanoparticles [1]. acetylated peroxotungstic
order to improve acid andthe ammonium
adhesion paratungstate.
of titanium
Influence ofadvanced
several crucial parameters
treatments thesuch as wavelength
Fluorine-Tin-Oxide
This paper describes the formation of transparent
of light, layer thickness
(FTO) glass and calcination
substrate temperature Activated
were performed. on the
TiO2 nanostructures such as nanotube layers that photocurrent
produced substrates was werestudied.
depositedAll WO via3 layers
the havepulsed
are formed by complete anodization of deposited monoclinic crystalline
magnetron structure.
sputteringLayers usingprepared
the pureby titanium
spray
metallic Ti thin films on an FTO glass substrate.
pyrolysis produce comparable
target. The operatingorpressure
higher of photocurrents
0.2 Pa was as kept
This results in highly transparent particulate TiO2 layers
constantbutduring
the issue the isdeposition.
their mechanical
The dutystability
cycle of
nanostructure-coated electrodes that which providedependstheon the was
pulse conditions
90 % and of spray pyrolysis.was 50 kHz.
the frequency
significantly enhanced transparency compared
with the classical nanoparticle layers. In order to Self-organized TiO2 nanotubes were grown by
form directly grown anodic TiO2 nanotube electrochemical anodizing the sputtered Ti films at
structures precursor
50 V in asolution is delivered downwards
of 0.5towt% the
Tungstenontrioxide
an FTOtogether
glass substrate,
with other Ti metal
metal
heated support
most typical
FTO glass.
electrolyte
Spraying was repeated
could be deposited on the substrate using
oxides such as titanium oxide and zinc oxide is electron NH4F + 2 wt% H2O in ethylene glycol. The
beam evaporation or a sputtering method. ItThe up to several
produced hundred
titania times towere
nanotubes obtainthoroughly
sufficient
widely used for photocatalytic experiments. is amount of WO in the layer.
quality band
indirect of the deposited metal
gap semiconductor (Eg ~governs the
2.52.8 eV) characterized by XRD, Raman spectroscopy, SEM
3

anodization
that process
can capture whether the12layers
approximately are solar
% of the well and photothermal deflection spectroscopy (PDS).
anodized orand
spectrum not.can
In particular, a properly
absorb light in the adhered
visible The photoinduced functionality of titania
metal layer
spectrum up toand500anmdense
[1]. Itmetal
is alsolayer allow
convenient nanotubes and single compact TiO2 layers was
material to be used for hydrogen production via
photoelectrochemical water splitting [2]. 198 1
Layers formed by particles of material have
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

DIFFERENT APPROACHES OF ADVANCED OXIDATION PROCESSES FOR THE

in PP3-7
will be filled
TREATMENT OF A PHARMACEUTICAL WASTEWATER
Different approaches of Advanced Oxidation Processes for the
by
treatment of a pharmaceutical wastewater
EAAOP4
Y. Segura(1), F. Martnez(1), A. Petre(2), J.A. Perdign(2), S. lvarez(3),J. Garca(3), G. Pliego(4), P. Garca-Muoz(4)
(1) Department of Chemical Engineering, Universidad Rey Juan Carlos, Mstoles (Spain)
(2) Department of Chemical Engineering, Universidad Alcal, Alcal de Henares (Spain)
(3) Department of Chemical Engineering, Universidad Complutense de Madrid, Madrid (Spain)
(4)Department of Chemical Engineering, Universidad Autnoma de Madrid, Madrid (Spain)

Two different treatments (electrochemical oxidation and Fenton

using zero-valent iron) have been proposed for the treatment of a
real pharmaceutical wastewater. Both treatments achieved
significant total organic carbon removal. Up to 99% in the case
of electrochemical oxidation using boron doped diamond
Toxic organic electrodes and a potential difference of 4 V. In the case of
pollutants ZVI/H2O2, TOC removal of ca. 65% was reached when using
the stoichiometric amount of H2O2 and a ZVI/TOC ratio of 6
being considered a low-cost technology. Both systems set legal
requirements in terms of the maximum industrial discharge
values.

oxidation processes which are often used in

It is only in the recent years that the pharmaceutical conjunction with the traditional methods for
manufacturing facilities were worldwide treatment of pharmaceutical wastewaters.
considered significant sources of pollution in the
environment [1-3]. Recently, the review of Gadipelly et al. [5]
proposed, as the most common and successful
Pharmaceutical pollution originated from
WO3 manufacturing
THIN FILMSfacilities PREPARED causesBY SEDIMENTATION AND PLASMA SPUTTERINGwill be filled
treatment technology to be applied to a
WO3 Thin Films Prepared by local
Sedimentation
drug pollution
and Plasma Sputtering
pharmaceutical wastewater, a pre-treatment stage
PP3-8
above and beyond the pollution caused by comprising advanced oxidation processes. in by
This was
household discharge. In the Patancheru industrial EAAOP4
mainly to2 remove2 the recalcitrant/refractory
area1,ofJ. India,
J. Krsa Olejnek 2 worldwide1,2production
, M. Brunclkov
a major , Z. Hubikasite2
Kment2compounds,
, . of , P. Krov , M. adaare
which Zlmal1non-biodegradable
, M.usually .
(1) Institute
genericofdrugs,
Chemical theTechnology, Technickdrugs
most abundant 5, 166 were
28 Prague, Czech Republic, Josef.Krysa@vscht.cz.
(2) Institute
detectedof[1]Physics, Academy
up to of Sciences of theabove
Czechthe Republic, Na Slovance 2, 182 21 Prague, Czech
followed by an effective biological treatment.
at levels 100 g/L, well
Republic.
highest concentration previously reported The present for any work deals with the comparison of
Although, the degree of removal of pharmaceutical
pharmaceutical in any wastewaterphotoelectrochemical properties of the layers prepared by
compounds in water or synthetic industrial effluents
type of effluent
sedimentation wereand reported
magnetron sputtering deposition under
by different alternative technologies has been
[4] and significantly high concentrations
found for different fluoroquinolonevarious modes (upof plasma excitation. The presence of crystalline
in numerous studies over the last ten
antibiotics
to 31 mg/L of ciprofloxacin). A fiveWO 3 is essential
in for the significant photocurrent response.
years, scarce literature exists on the
years survey
Whereas amorphous samples were not photo-electro-chemically
pharmaceuticals removal in real pharmaceutical
the USA found that the pharmaceutical formulation
containedactive, drugsannealed samples reveal significant photocurrent
wastewater. Different type of advanced oxidation
facilities effluents at processes such as O3/OH, H2O2/UV, Fe2+/H2O2,
concentrations up to 1000 times higher than density. It seems that3+/Hdifferent 2+surface configuration3+ and
different density of oxygen atoms at (002) and (200) facets can
Fe 2O2, Fe /H2O2/UV and Fe /H2O2/UV have
effluents from a WWTP treating regular domestic
result in different rate of photocatalytic water oxidation. Even
been successfully applied to increase the overall
and hospital wastewater [3].
layers prepared by sputtering achieved comparable
Chemical Oxygen Demand (COD) removal
It has been suggested that those photocurrents
type of effluents as layers prepared by sedimentation, combined
efficiency [6].
should be treated on-site (at thelayers achieved approximately
manufacturing This works two investigates
times higher the
photo-currents
efficiency of two
plant) in order to reduce the load of than total
drug sum of photocurrents
residues different of advanced
separate layers.
oxidation processes
in the environment [3]. In a recent study, Deegan et (electrochemical oxidation (EO) and zero-valent
al. [4] provided a review on the current knowledge
Tungsten
regardingtrioxide (WOof
the range 3) treatment
is promising
methodsmaterial
availablephotocurrent response. peroxide,
iron with hydrogen Whereas(ZVI/H amorphous
2O2)) for the

with forelectrical and optical properties

the pharmaceuticals removal from that industrial
are samples were not photo-electro-chemically active,
removal of mixed-complex organic compounds
exploited in a variety of applications
wastewaters in order to get an overview of the such as annealed samples
contained in reveal photocurrent
the wastewater density
produced by a
2
photolysis [1], electrochromic
effectiveness of the various devices [2] oroptions.
treatment gas than 400 mA/cm at voltage potential 1 V,
Ithigherdischarge
pharmaceutical business located in Spain, before
sensors.
wasTungsten
focused trioxide
on the iscomplementary
also indirect band- treatmentdepending on film thickness
to the andenvironment
receiving crystallographic
or sewer
gap methods
semiconductor (E g 2.52.8 eV)
such as membrane filtration, reverse with orientation.
system.
attractive electrical and optical properties [3].
osmosis and activated carbon
WO3 can capture approximately 12% of the solar
and advanced LayersThe prepared by sputtering
electrochemical oxidation achieved
runs were
spectrum and can absorb light in the visible comparable photocurrents like layers prepared by
spectrum up to 500 nm. Given its band gap, WO3 sedimentation. However combined layers achieved 1
is a more suitable material for photo- 199 approximately two times higher photo-currents
than total sum of photocurrents of separate layers
electrochemical water splitting than TiO2
prepared by particle deposition and by magnetron
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y
A comparative study of sol-gel and anodically grown TiO2 will be filled
Aphotoanodes
COMPARATIVE STUDY OF SOL-GEL ANDinANODICALLY GROWN TIO in by
and their application the photooxidation of2 PHOTOANODES
AND THEIR APPLICATION IN THE PHOTOOXIDATION OF CHLORAMPHENICOL EAAOP4 PP3-9
chloramphenicol

A. Chatzitakis1, . Papaderakis1, N. Karanasios2, J. Georgieva3, E. Pavlidou4, G. Litsardakis2, I. Poulios1,

S. Sotiropoulos1
(1) Department of Chemistry, Aristotle University of Thessaloniki, 54124, GREECE, a.e.chatzitakis@smn.uio.no
(2) Department of Electrical Engineering, Aristotle University of Thessaloniki, 54124, GREECE, (3) Rostislaw
Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia 1113, BULGARIA, (4)
Department of Physics Aristotle University of Thessaloniki, 54124, GREECE.

The aim of this work has been the development of

efficient TiO2-based photoanodes for the detoxification of
organics. Sol-gel particulate TiO2 (SGT) layers were
grown on Ti substrates (using an iso-propoxide precursor)
and TiO2 nanotubes (TNTs) were formed by appropriate
anodization of the same substrate in glycerin solutions.
EIS spectroscopy together with Mott-Schottky plots were
used to find the charge transfer resistance, surface area
and flat band potential of the photoanodes.
Photovoltammetry experiments showed that the incident
current-to-photon efficiency (ICPE) of the TNTs
electrodes was 3.5 times higher than that of the SGT ones
due to a higher surface area, lower recombination rates
and higher light absorption. For the same reasons the
TNTs showed a much higher chloramphenicol photo-
electrolytic degradation rate.

BORON-DOPED DIAMOND ANODIC OXIDATION OF AMOXICILLIN WASTEWATER:

Boron-dopedEVALUATION
STATISTICAL
diamond anodic oxidation of amoxicillin AND wastewater: will be filled
PP3-10
Photoelectrocatalysis (PEC [1])OF canOPERATING
enhance the FACTORS The experimental ANTIBIOTIC
conditions RESISTANCE
for the preparation
in by
Statistical evaluation of operating
photooxidation of organics at appropriate factors and antibiotic resistance
of both types of TiO2 are given in Table EAAOP4 1.
photoanodes
Z. Frontistis1(often coupled
, A. Ioannidi 1
, K. with the1,simultaneous
Kassara G. Voukelatos1, D. Venieri,2, D. Mantzavinos1. (1) Department of
production of hydrogen
Chemical Engineering, Universityat ofthe cathode-see
Patras, GR-26504 Patras, Table 1. zaxoys@gmail.com.
Greece, Methods and conditions
(2) School offor the
Environmental
Graphical Engineering,
Illustration above). Technical
TheUniverity
scope ofof theCrete, GR-73100 Chania,
fabrication Greece
of the TiO2 photoanodes
research presented in this paper has Antibiotics been the formulation
Sol-gel effluents contain Anodichighoxidation
concentrations of
development of efficient TiO2-based photoanodes biorecalcitrant compounds.
TiSP:EtOH:HNO In this
3
respect,
Anode: anodic
Ti oxidation
Distance on
for the detoxification of the boron-doped antibiotic diamond
:H2O:PEG (BDD) was tested to treat
Cathode: Pt amoxicillin
2cm in
chloramphenicol. To that directionwater. sol-gel 1: 36.5 : 0.35 :
A factorial
on Ti design Glycerin solution,
to assess 0.5
particulate TiO2 (SGT) layers were grown 1.35 approach
: 2 (molar was implemented the
substrates (using an iso-propoxide precursor) importance
and of ratio);dip-coating
initial COD (1000-2000 wt%mg/L),
NH4F, treatment
10 wt% Htime 2O;

(15-90 min),
by current (0.3-0.5 anodization voltage 60V;
TiO2 nanotubes (TNTs) were formed (extraction rateA),
of electrolyte concentration (2-4
appropriate anodization of the same substrate in g/L NaCl) and initial pH (3-9)
-1 on the anodization
amount of COD time 2removed;
h
2 cm min )
glycerin solutions. Fig.1 shows the initialSEM
COD andAll time, as wellwere
samples as their interaction
annealed at 500resulted
o
C forin 90the
micrographs of the two types of TiO most2 important,
films positive effects.
minutes with heating rate 5o C min-1. For
prepared. Furthermore, the evolution ofthermal
comparison, antibiotic activity, (T-TiO
electrodes assessed by the
2) were
microtiter broth alsodilution
prepared method
by directandannealing
the determination
of Ti foil atof
Minimum Inhibitory the same Concentration
conditions. (MIC) regarding specific
microbial growth, was also followed, alongside the kinetics of
COD removal. XRD proved that, following annealing at 500 0C,
both materials were in the form of anatase. EIS
Antibiotics formulation effluents are typically Figure 1 (Fig.
spectroscopy shows2) together
the Pareto chart of the
with Mott-Schottky
Figure 1 SEM by
characterized micrographs of sol-gel prepared
low biodegradability due to (i) statistically
plots were used important
to findvariables
the charge andtransfer
their
TiO (left) and ofanodically
the 2 presence grown TiO
pharmaceutically active
2 interactionssurface
resistance, according
area toand
theflat
Lenths method. As
band potential of
nanotubes
compounds(right).
at relatively high concentrations (mg/L seen,
the all variables but initial solution pH have a
photoanodes.
to g/L), and (ii) the fact that these compounds are positive effect on the response (i.e. amount of
designed to be biorecalcitrant [1]. COD removed) with the treatment time, initial
In recent years, electrochemical oxidation over COD and their interaction imposing the greater 1
boron-doped diamond (BDD) has gained particular
attention as a treatment technology for the
200effects.

mineralization of industrial effluents [2].

 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

OPTIMIZATION AND MODELING OF IOHEXOL TREATMENT BY ADVANCED OXIDATION

Optimization And Modeling Of Iohexol Treatment By Advanced
PROCESSES IN ENVIRONMENTALLY RELEVANT MATRICES
will be filled
PP3-11
in by
Oxidation Processes In Environmentally Relevant Matrices
EAAOP4

S. Giannakis1, M. Pastor Gelabert2, S. Schindelholz1, J.M. Furbringer3, C. Pulgarin1

1
SB, ISIC, Group of Advanced Oxidation Processes, cole Polytechnique Fdrale de Lausanne (EPFL), Station 6,
1015 Lausanne, Switzerland, stefanos.giannakis@epfl.ch
2
Escola Tcnica Superior d'Enginyeria Qumica (ETSEQ), Universitat Rovira i Virgili (URV), 43007 Tarragona,
Spain.
3
SB, Physics Section Management, cole Polytechnique Fdrale de Lausanne (EPFL), Station 3, 1015 Lausanne,
Switzerland

In this work, an Iodinated Contrast Medium (ICM),

Iohexol, was subjected to treatment by 4 Advanced
Oxidation Processes (AOPs) (UV254, UV254/H2O2, Fenton,
UV254/Fenton). The operational parameters effect was
systematically challenged and the following ranges were
tested: pH: 3-11, [Iohexol]: 10-1000ppm [Iron]: 0-50ppm,
[H2O2]: 0-1000ppm. The presence of Iohexol is equally
expected in urban and hospital wastewater, patients urine,
as well as drinking water, and the aforementioned matrices
were spiked with Iohexol to investigate the treatment
efficiency of AOPs. Finally, optimization of the treatment
conditions, as well as modeling of the degradation was
performed, by acquisition of linear and 2nd order models.

SONOPHOTOLYTIC MINERALIZATION OF CARBAMAZEPINE matrix to In eliminate IN AQUEOUS

this pollutant was SOLUTION:
investigated.
Sonophotocatalytic
During theMODELLING
last decades,Mineralization
the appearance of Carbamazepine
and Aqueous will be filled
KINETIC Finally, modeling of the degradation process in bywas PP3-12
Solution: kinetic
accumulation modelling
of anthropogenic pollutants has been performed and optimization of the EAAOP4 treatment
set as a high priority health-issue in Switzerland. conditions
A.J. Expsito, A.Durn, J.M. Monteagudo, V. Monsalve. Escuela Tcnicawas achieved.
Superior de Ingenieros Industriales,
The micropollutants
Instituto (MPs),
de Investigaciones are anthropogenic
Energticas y Aplicaciones Industriales (INEI. Universidad de Castilla-La Mancha,
substances
Avda. Camilo thatJos
appear in13071
Cela 3, ng-g/L level
Ciudad in (Spain),
Real UVC light was supplied by low-intensity, low-
natural AntonioJose.Exposito@uclm.es
waters. Pharmaceutically active compounds pressure Hg lamps, in a treatment with UV as
(PhACs) are special micropollutants due The to the single acting process
sono-photodegradation source, ofor the supporting
antiepileptic the Fenton
drug
complexity of their structure, the polymorphism reaction; Fenton in
carbamazepine is studied. The combined process of dark conditions waslow also
and the variation due to the precedent metabolism performed.
frequency ultrasound (US) Aandwide range irradiation
ultraviolet of values(UV) was
in the human body [1]. Iodinated Contrast Media investigated
assisted with H2O2 has been evaluated.to optimize the treatment, such as: pH
(ICM) are non-biodegradable and from
thus, model
A kinetic was3-11, Fe (II)and
applied 0-50found
ppm, to H2Oreproduce
2 0-1000 ppm, both in
invulnerable to treatment in conventional degradation andamineralization
variety of initial of Iohexol concentrations
carbamazepine (10-1000
satisfactorily.
wastewater treatment plants (WWTPs); The model for includes
ppm).a Blankscavengerexperiments were performed
term characterized by kscv in. Mili-
As
instance, Iohexol is an ICM with a low
reaction Q water,
progresses, intensification
the amount of available in synthetic
radicals decreases secondary
biodegradability and removal efficiencies andofthe11scavenger
to wastewater
effect is lessand important.
synthetic urine, and spiking of real
16% in a conventional WWTP [2]. It was the No1
Under optimal matrices
conditions, (hospital
CBZ WW, secondary
is degraded in WW and urine)
10 minutes,
pollutant in terms of concentration, in the hospital
whereas was assessed.
TOC decreases by 60%Dilution
in 35ofminutes
the urine(87% matrices
in one was
wastewater of the University Hospital (CHUV) hour). in also considered as a measure of enhancing the
Lausanne [3] and 2nd highest concentration in Lake AOPs action. Finally, the systematic assessment
Leman [4]. was analyzed by MINITAB for Windows,
providing with 1st order models with interactions,
Advanced Oxidation Processes (AOPs), based on through the full factorial designs of experiments
the action of the extremely oxidative hydroxyl The overall
assayed, CBZ as
as well degradation
2nd order(US/UV/H 2O2) is:
models deriving
Background
radical ( OH),and Objectives
have been long known to be through
d [CBZ ] the Response Surface methodology
kUS [CBZ ] kUV [CBZ ] (k3 k scv )[ H 2O2 0 0.0203 t [CBZ ]
efficient
The useinofdegrading recalcitrant
high-frequency compounds
ultrasound [5]. towards
has proved dt the optimization of the treatment.
In this work, the efficiency of AOPs
to be effective to remove organic contaminants against where C is the concentration of CBZ at time t
Iohexol
[1], degradation
but they is Low-frequency
are costly. studied; four methods
ultrasoundof Concerning
(mM); kUS y kwastewater-related matrices, the
UV are the pseudo-first order rate
treatmentarehave
systems been assessed
controversial, and may
since they the effect of
not yield most
constants suitable method
for each processto USdegrade
and UV Iohexol is the
respectively
various operational parameters was estimated.
enough OH radical species during the pyrolysis The direct UV-C
(0.001 and 0,028 min photolysis at neutral
1 pH. The
as calculated little
optimal treatment configuration and the
of water molecules and the positive effect can be preferred improvement
experimentally. obtained
k is also by UV-C/H
calculated in2Oprevious
2 dont
3
attributed to improvement in the mixing
conditions. There is a lack of information about 201
tests as 0.0276 mM1 min1). kscv was estimated to
be 0.0014 min-1. Figure 1 compares experimental 1
the reaction mechanism of US in homogeneous data for a typical run with the empirical model,
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

PHOTODEGRADATION OF 2,4-DICHLOROPHENOL IN AQUEOUS SYSTEMS UNDER

Photodegradation Of 2,4-dichlorophenol In Aqueous Systems
SIMULATED AND NATURAL SUNLIGHT
will be filled
PP3-13
in by
Under Simulated And Natural Sunlight
EAAOP4
S. Ledakowicz1, M. Foszpanczyk1, D. Gryglik2, M. Gmurek1.
(1) Lodz University of Technology, Faculty of Process and Environmental Engineering, ul. Wlczaska 213, 90-
924 d, Poland, stanleda@p.lodz.pl
(2) Lodz University of Technology, Faculty of Civil Engineering, Architecture and Environmental Engineering,
Al. Politechniki 6,90-924 Lodz, Poland

1.0
pH 10.8
The pollution of aquatic environment by trace amounts of
anthropogenic chemical substances has a hazardous impact on
0.8
regular development of plants and animals as well as on the
human health. The work presents results of studies on 2,4-
2,4DCP

Dichlorophenol degradation in aqueous solutions using

/C0

0.6 hv NaN3
photochemically initiated processes by simulated and natural
2,4DCP

t-BuOH SOD
hv+RB
sunlight. Rose Bengal and derivatives of porphine and
Ct

0.4
phthalocyanine were used as sensitizers. The influences of
various process parameters on the reaction rate were
0.2
investigated. The major role of singlet oxygen in 2,4-DCP
degradation was proved. On the basis of experimental data
0.0
0 1000 2000 3000 4000 5000
reaction rate constants of photosensitized oxidation reaction of
Time, s 2,4-DCP were determined.

currently popular, using photochemical processes

Background for the purification of wastewater or water
Dichlorophenols are derivatives of phenol. They treatment is very effective in removing pollutants
areNEW
A widely used in TO
APPROACH organic synthesis in theKINETIC OF PHOTOSENSITIZED OXIDATION
HETEROGENEOUS
A New Approach
production To Heterogeneous
of pharmaceuticals, Kinetic Ofpresent
disinfectants,
in the wastewater, howeverwill
Photosensitized only at low
be filled
PP3-14
concentrations. However, in many cases, advanced in by
Oxidation insecticides, fungicides, herbicides
preservatives, oxidation methods have limited application. EAAOP4An
[1]. 2,4-dichlorophenol (2,4-DCP) is a colorless, alternative process seems to be photosensitized
M. Gmurek1, S. Ledakowicz1.
crystalline solid [2]. It is an attractive the initial
(1) Lodz University of Technology, Faculty of Process and oxidation process,
Environmental particularly
Engineering, using molecular
ul. Wolczanska 213,
product, which is used
90-924 Lodz, Poland, in industry, for example for
marta.gmurek@p.lodz.pl oxygen. An interesting option appears to be the
the production of higher chlorophenols [3]. photooxidation of phenolic compounds by singlet
Industrial manufacturing of 2,4-DCP in the world oxygen due toofitsstudies
advantage of use oxygen from
The
is based on the chlorination of melted phenol with work presents results on the heterogeneous
degradation air and solar radiation.
gaseous chlorine. 2,4-DCP, like phenol, have a of butyl- and benzylparaben in aqueous solutions
using photochemically
high toxicity to living organisms [4,5]. 2,4-DCP is Objectives initiated processes. TPP was
a compound characterized by high toxicity, immobilizedso inHerein
polyurethane
we presetnanofabrics by electrospinning
results of photooxidation of 2,4-
even the small amount released method. into the The major role of the singlet
dichlorophenol under oxygen was proved.
simulated The
and natural
environment pose serious consequenceskinetic [2]. Itstudy
is showed
sunlightthatviathesinglet
heterogeneous photodegradation
oxygen generated by exited
of parabens could
well known that very low levels of chlorophenols, be modeled using
photosensitizers. The Langmuir
objective is Hinshelwood
to define the
including 2,4-DCP in water cause model. However,
significant this model
conditions does
that not fully reflect
maximize the character
the reaction rate of
of the photosensitized
deterioration of its taste and smell. Contamination oxidation degradation
photosensitized process. Theofaim2,4-DCP
of this study
in the
by 2,4-DCP in environment may occur was as a to developaquatic
result a kinetic model
solution, to in a heterogeneous
determine the kinetic system,
constants
of degradation herbicides which 2,4-
e.g. will be and
expandto the knowledge
compare the of the photosensitized
photodegradation under
dichlorophenylp-nitrophenyl ether (2,4-D) oxidation
from processes
simulatedand basic sunlight.
and natural photochemical reactions
chlorination of drinking water and industrial occurring andin the environment.
municipal waste waters by water disinfection Methods
plants, or from agricultural runoff or industrial The study was conducted in a semi-continuous
waste discharges [1,6,7]. 2,4-DCP is also been system in flat reactors (0.060.10 m) of the
The
volumeidea0.01dm
of anchoring
3 the photosensitizer
. Five reactors into an
were symmetrically
Background
reported as an endocrine disruptor [8]. Due to its insoluble carrier was first proposed by Kautsky in
Photosensitized
the high harmful oxidation
compound may occur both
is important in orderin positioned around the xenon lamp (Osram 100W,
1939
E = [2]
324 andEinstein
then by s -1 Merrifield
dm -3
), in 1963 solar
simulating [3].
homogeneous and heterogeneous
to protect the environment against thesystems.
effects ofTheits 0
Immobilization was obtained
disadvantage of the homogenous
action. Unfortunately process
the classic is the
treatment radiation. The reaction mixtureonwas a solid carrier
agitated by
such
gentle as
air silica
or oxygengel, stream.
alumina,Ascelite, cellulose,
photosensitizers
necessity
methods areof removing
not able toof degrade
the photosensitizer
them. Also,from the polysiloxane, copolymers, polydimethylsiloxane,
the
use solution after the
of advanced reaction has
oxidation been completed.
method, which are Rose Bengal and derivative of porphine, aluminum
chitozan or more recently
phthalocyanine and zinc phthalocyanine Nafion were[4-8].
used
On the other hand, water-insoluble chromophores Photensitizers can also be immobilized on the
used in the suspension form have got weak activity
and often undergo aggregation at the specific 202
reactor walls directly or indirectly through an
additional binder [9]. Immobilization of
1
concentration, resulting in a decrease of activity chromophores leads also to the maintenance of
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

MICROPOLLUTANT REMOVAL
Micropollutant removal by HOBY
HO IN LOW-FREQUENCY ULTRASOUND TREATMENT
in low-frequency ultrasound treatment of will be
OF AN AGRO-FOOD INDUSTRY SEWAGE SLUDGE
an agro-food industry sewage sludge filled in by PP3-15
EAAOP4
J.A. Snchez Prez1, G. Rivas-Ibez1, P. Soriano1 , J. L. Casas Lpez1, L. Ponce-Robles1, A. Agera1
(1) Research Centre on Solar Energy (CIESOL), University of Almera-CIEMAT, Almera, Spain, jsanchez@ual.es.

.
This work was aimed at studying the degradation
of the pesticides attached to the sewage sludge
from an agro-food industry WWTP applying an
ultrasound treatment (US) at low-frequency for
excess sludge reduction. The US treatment
applied resulted in a high degradation percentage
for most of the pesticides found the sewage
sludge studied. The mechanisms responsible to
degrade micropollutants was the attack of
hydroxyl radicals (HO) generated during US
exposure.

Introduction dissolved organic carbon increase (DOCincrease) do not

change for higher treatment times reaching a maximum
Huge amounts of excess sludge are produced as a level 0.8 0.04 and 298.24 16.06 respectively. Several
result of both industrial and urban wastewater depuration micropollutants were found attached to the sludge
based on biological processes using activated sludge coming from the cleaning stage of vegetables and fruit to
systems. The most frequently routes for sludge excess be transformed in an agro-food industry. They were
DEGRADATION OF TRICLOSAN
disposal in the European Union areINdewatering,
NATURAL WATER AND(TBZ),
thiabendazole WASTEWATER USING
imazalil (IMZ), KrCl(PIR),
pirimicarb
Degradation of
digestion, incineration,
EXCILAMP Triclosan in Natural
(222 nm) landfill and land use in Water and Wastewater Using PP3-16
prochloraz (PROC), myclobutanil (MYCLO),
KrCl Excilamp
agriculture, which imply(222a nm)
high cost to the industry. acetamiprid (ACTM) and propanocarb (CARB). The
However, an increasing concern about the presence of
N. Garkusheva, N. Vorobeva, G. Matafonova, V. Batoev results of pesticides degradation from the sludge after 2 h
heavy metals and organic pollutants adsorbed to the ofSt.,
sonication treatment
Baikal Institute of Nature Management SB RAS, 6 Sakhyanova Ulan-Ude, Russiaare shown in Table 1.
sludge (due to their hydrophobicity and tendency to be
garcusheva@mail.ru
absorbed to particles) is growing in the scientific
KrClover
communities excilamp
the last (222
yearsnm)
since the sewageA KrCl
sludgeexcilamp (222 nm) has been applied to-1examine the
may Direct
become UV UV/Hand
a source of aquatic 2O2 terrestrialdegradation
pollution Table 1. of Degradation
efficiency triclosan at 1 percentage
mg L in Milli of each
Q
Milli Q water
when it is used in agriculture et al.,Lake micropollutant
water,
or landfill (Maillera Baikal waterattached
(LW) toandsludge from an
diluted agro-food
municipal
2014). Lake water (LW) wastewater (WW) industry.
by direct UV photolysis and the AOP
Wastewater (WW) UV/H2O2. The UV/H2O2 treatment of Milli Q water and LW
Methods
Triclosan more effectively Pesticide Degradation
degraded triclosan compared (%) only.
to UV
US treatments at low-frequencies
UV/H2O2 The degradation rates of triclosan in WW were roughly the
(20-40 kHz)
WWon the generation of acoustic
based cavitation,
UV samehave
for UV andTBZ UV/H2O2 treatments (k = 0.03 cm2 mJ-1).
97.7
proven effective in sludge minimization by disrupting the
The effectiveness of UV/H2O2 in terms of UV fluences
LW flocs and also successful in degradation of
sludge
decreased in the order
IMZ Milli Q > LW > WW. 51.0 The calculated
micropollutant attached to the sludge (Tyagi et al., 2014).
As energy requirements for 90% removal by both UV and
Millisuch,
Q this work was aimed at studying the
degradation of the pesticides attached to theUV/H 2O2 schemes
sewage PIRwere relatively low 41.9
3
for all tested water
sludge from0 an 50agro-food
100 industry
150 wastewater
200 treatment ranging from 0.6 to 1.0 kWh m .
matrices,
plant applying Fluence,
an US treatment
mJ cm at fixed low-frequency
-2 PROC 90.8
(24 kHz) and maximum power (320 W) with a constant
temperature (20C) for excess sludge reduction. Besides, MYCLO
in Background
order to investigate the mechanisms of pesticide treatment plant (Ulan-Ude,55.8Russia), respectively.
degradation with this US treatment, the sonodegradation DOC concentrations in LW and WW were 1.0 and
of Triclosan
a pesticide mixture (TCS, 24 mgACTM 74.8
L-1, respectively (Shimadzu TOC-L CSN).
commonly found 5-Chloro-2-(2,4-
in the agro-food
industry was studied in aqueous is
dichlorophenoxy)-phenol) solution.
an antimicrobial In degradation experiments WW was diluted to 1
agentResults
used in many personal care products and it is mg LCARB
-1
DOC to be comparable 88.9 with DOC level in
and Discussion
considered to be an emerging organic LW. TCS was spiked into the selected waters and
As can be seen
micropollutant, in Figurein1, natural
detected the maximum
watersludge
and its degradation was monitored during both direct
disintegration
wastewater [1].was achieved in 2 hthat
It is known of treatment.
TCS canBoth be UV photolysis and UV/H2O2 oxidation
volatile suspended solids decrease (VSSdecrease) and experiments. The average fluence rate during the
directly photolysed and oxidized via reaction with
OH generated in AOPs (kOH = 5.4 109 M-1s- irradiation was calculated using the Spreadsheet
1
[2]). Direct UV and UV-based AOPs with low 203
available at https://www.iuva.org. The applied1
fluence was obtained by multiplying the average
and medium pressure mercury lamps were widely
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

RF ATMOSPHERIC PRESSURE PLASMA JET FOR SURFACE MODIFICATION OF HIPS

RF Atmospheric Pressure Plasma Jet PP3-17
for Surface Modification of HIPS
J. Pawlat1, P. Terebun1, M. Kwiatkowski1, J. Diatczyk1, H. Stryczewska1, T. Murakami2.
(1) Lublin University of Technology, Nadbystrzycka 38A, 20-618 Lublin, Poland, askmiki@hotmail.com
(2) Seikei University, 3-3-1 Kichijoji-Kitamachi, Musashino-shi, Tokyo 180-8633, Japan

Wettability of rubber-modified styrenic polymers such as high-

impact polystyrene (HIPS) can be modified using RF-powered
atmospheric pressure plasma jet.
45 s treatment of 40 W with argon and oxygen mixture as
substrate gas caused change of surface contact angle from 90 to
18o. Zero dimensional chemical kinetic model was utilized to
identify the dominant particle species generated by our device.
Presence of ozone was confirmed experimentally what is in good
accordance with modelling results.

Surface properties of polymers can be party species. The O3 density gradually increases and
adjusted using physical and chemical techniques reaches a value of 8x1016 cm-3 during 2 ms. The
including ozone and plasma treatment. maximum O2(1D) density at the jet's nozzle is
Treatment of HIPS was performed using 9x1015 cm-3. The O-atom density reaches a value
atmospheric pressure plasma jet. The main part of of 1x1015 cm-3 at the exit of the core region. The
the device, which is presented in Fig. 1, was RF- densities of atomic oxygen metastable O(1S) and
Fluorescence
powered Evolution
changeable EVOLUTION
FLUORESCENCE Of
rod electrode ofOF Humic-Like
tungsten or
HUMIC-LIKE Substances
molecular
SUBSTANCESObtained From
oxygen OBTAINED
metastable 1
2( S) are
OFROM will be filled
smaller
SOLID
1 in by
acid-proof stainless steel. The electrode was
Solid
URBAN Urban
WASTES Wastes
IN In
SOLAR Solar Photochemical
PHOTOCHEMICAL than the O-atom and O2( D) densities by orders
Processes
PROCESSES For Water
FOR WATER TREATMENT
EAAOP4 of PP3-18
powered by a regulated RF supply (AG 1021 RF
Treatment magnitude at the exit of the core. The global
generator, T&C
Ana Mara AmatPower
1 Conversion)
,L. Carlos 2 via impedance
, F.S. Garca model M.Mora,
Einschlag3 , R.Vicente, indicatesAntonio
that the reactive
Arques 1
Garca- H, HxOy,
y S.species,
matching network
Ballesteros1
(Fig. de1B).
. (1) Grupo It was
Procesos possible Avanzada.
de Oxidacin to NODptox and
de HNO
Ing. Textil
x resulting
y Papelera. from
Univ.the humid
Politc. de air
power plasma
Valncia, Pzareactor
Ferrndiz with frequencies
y Carbonell impurity appear
from 10 , aamat@txp.upv.es.
1, 03801-Alcoy during de
(2) Instituto residence
Investigacintimey of 2 ms
kHzDesarrollo
to 20MHz. Temperature
en Ingeniera of sample
de Procesos, even alternativas,
surface y Energas
Biotecnologa at the small humid
PROBIEN air fraction. Those
(CONICET-UNCo),
wasBuenos Airesand
monitored 1400, Neuqun,
kept belowArgentina.
the melting (3)point
Instituto
. de Investigaciones
reactive Fisicoqumicas
species will Tericas
makey Aplicadas
significant
(INIFTA), CCT-La Plata-CONICET, Universidad Nacional de La Plata, Diag 113 y 64, La Plata, Argentina
contributions to the afterglow chemistry. The main
ion species are molecular oxygen ions, i.e. O4+,

Fluorescence O and O4. Achieved
excitation-emission
2 matricesozone
(EEMs)concentrations
were used to
characterize ranged 0.82g/m3 (at 50
the transformation of W theand 40%O2/60%He
humic-like feed
substances
(HLS) obtained gasfrommixture).
urbanAPPJ
wasteswaswhenused
used forasthe treatment
additive of
in the
photo-FentonHIPS surfaces.
processes. Theend,
To this measurements
photochemical of experiments
static water
contact
at different pHs, angle
in the for HIPS
absence and were
presence performed
of H2Ofor the
2 were
operating
performed. Also, voltage, frequency
the interaction between HLS and power of 500was
and Fe(III) V,
studied. 14.355 MHz and 40W, respectively.
Measurements were made for three mixtures of
gases: helium with oxygen, argon with oxygen and
helium with air. A significant influence of distance
from the end of reactor for treatment times less
than one minute was observed. For two minutes
the angle was the same for all distances, which
could allow more freely treatment objects with
more complex surfaces. After one day, the contact
angle started to return to its previous value, which
Figure 1. Experimental set-up.
Introduction is The degradation
particularly evidentofat HLS
longer inexposure
photo-Fenton
times.
processes was studied using
This may indicate that the effect of a solution of 20 mg/L
plasma
The globalsubstances
Humic-like model revealed
(HLS) that the most
obtained from of HLS and
treatment 5 mg/L
in the of isFe(III),
material not toothedeep, system
and was
the
pronounced
urban wastesneutral
are able species
to expandare reactive oxygen
the pH region of studied is
process with (2,2 mmol/L) and without H2O2 and at
reversible.
the photo-Fenton processes until near neutral pHs three different pH values (3, 5 y 7). Experiments
[1]. This effect seems to be ruled by the interaction
between Fe(III) and HLS. On the other hand,
204
were performed in a 250 mL cylindrical Pyrex
vessel irradiated with a solar simulator (Sun 2000, 1
fluorescence spectroscopy is a sensitive technique ABET Technologies) equipped with a 550 W
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

UV-C AND UV-C/H2O2 DEGRADATION OF TWO ARTIFICIAL SWEETENERS,

UV-C and UV-C/H2OSUCRALOSE
ACESULFAME-K AND 2 degradation of two artificial sweeteners,
will be filled
PP3-19
in by
Acesulfame_K and Sucralose
EAAOP4
C.Drosou1, K. Tyrovola1, T. Neromilioti1, E. Kourounioti1, , N.P.Xekoukoulotakis1
(1) Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100
Chania, Greece
edrosou@isc.tuc.gr

In the present study, the degradation of two artificial sweeteners,

acesulfame_K (ACE) and sucralose (SUC) was investigated by
direct UV-C photolysis and H2O2/UV-C photochemical oxidation.
Several parameters as pH, H2O2 dosage, ACE and SUC
concentrations and water matrix were studied. According to the
experimental results, it was obvious that H2O2/UV-C process not
only decomposes the artificial sweeteners but at the same time the
TOC concentration of the solutions was substantially decreased.

irradiation, either alone or in the presence of H2O2,

Recently, Artificial Sweeteners (ASs) have in aqueous matrices. Several experimental
received the attention of scientists due to their parameters were investigated such as initial
ubiquitous presence in the aquatic environment. artificial sweetener concentration, initial H2O2
They are used as sugar substitutes in foods, concentration, solution pH, and water matrix (i.e.
beverages, personal care products and ultrapure water (UPW), bottled water (BW) and
pharmaceuticals products. Among the ASs used, waste water (WW)).
acesulfame, cyclamate, saccharin and sucralose
have been identified in wastewater effluents [1]. Photolysis experiments were performed in an
PHOTOSENSITIVE
These compounds ChitosanshowCHITOSAN
substantial FOR VISIBLE-LIGHT
resistance toWater WATER
immersion POLLUTANT
well, batch type, DEGRADATION
laboratory scale
Photosensitive For Visible-light Pollutant PP3-20
common wastewater treatment. The mechanical photochemical reactor, consisting of an inner
Degradation
and secondary1 microbial digestion ,1
can partially 1 cylindrical 1
quartz glass vessel housing the lamp
S. Ledakowicz
mineralize and ,remove
M. Olak-Kucharczyk , M. Foszpaczyk
sweetener pollutants. From , M.and
Gmurek an. external double-walled, cylindrical,
(1) above
the Lodz University of Technology,
ASs, acesulfame andFaculty of Process
sucralose have and Environmental Engineering,
borosilicate glass, Department
reaction vessel, ofwhile
Bioprocess
UV-C
Engineering, ul. Wolczanska 213, 90-924 Lodz, Poland, stanleda@p.lodz.pl
been reported as the most persistent sweeteners radiation was provided by an 11 W, low pressure
with removal rates 40% and 20%, respectively [2]. mercury lamp, emitting predominately at 254 nm.
The scientific goal of the studies was to investigate the
Actually, the occurrence of acesulfame and Samples were periodically taken from the
photosensitized oxidation of xenobiotics in aqueous solutions
sucralose in waste water treatment plant effluents photochemical reaction vessel and were analyzed
using photosensitizers immobilized on chitosan carrier particles
has been reported up to 2.5mg/L and 0.119mg/L for residual acesulfame-K and sucralose
and to determine process parameters of degradation through
respectively [3,4]. Due to their incomplete concentration by LC-MS/MS and LC coupled with
photosensitized oxidation in heterogeneous system. The
removal from the waste water treatment plants and a diode array detector (Waters Alliance), while
presented work was focused on determination the dependencies
their presence to the water bodies, the ASs were total organic carbon (TOC) concentration was
between degradation efficiency of selected compounds and
identified as emerging contaminants. Over the past measured with a TOC analyzer (Shimadzu
reaction parameters such as: pH, temperature of reaction
decades, several advanced oxidation processes 5000A).
solution, substrate and oxygen concentration, quantity of
(AOPs) have been
Fig.1. Chitosan beans successfully
with immobilizedemployed for the
different immobilized photosensitizer,
In an initialirradiation intensityexperiments,
set of photolysis and multiplethe
degradation of photosensitizers.
a wide range of micro-pollutants in
re-use of chitosan
direct beans with immobilized
photolysis, under UV-C photosensitizer.
irradiation, of
the aqueous phase. In particular, photolysis under
Moreover the possibility
Acesulfame_Kof solar and
irradiation was investigated.
Sucralose was studied in
UV-C irradiation, either alone or in the presence of
H2O2, has been found very effective for the ultrapure water and at inherent solution pH (which
oxidative degradation of organic micro-pollutants was approximately 6 in both cases), and the results
Thethecontamination
in aqueous phase by [1-4].
xenobiotics
In theofUV-H aqueous are shown in
Hydrogel Figures
beads were 1 and 2, respectively.
produced by the As can
phase
2O2
resources have become a global
process, hydrogen peroxide absorbs UV light andproblem. These been seen
inversion in Figure
method 1,
from UV-C
an irradiation
aqueous was
solution able
of
substances rapid
undergoes oftendecomposition
in an unchanged to formform, hydroxylare to degradeinacesulfame
chitosan acetic acid.inThe
a very short time
chitosan (almost
solution was
discharged into the wastewater treatment plant,
radicals. in few minutes).
dropped However,
by needle to NaOHthe total organic
where carbon
coagulation
whereaimdue
The of the to present
the low work efficiency
was to study of usedthe concentration
was carried out. wasAsstable, indicating
a sensitizer that there
phthalocyanines,
degradation of
degradation methods they getsweeteners
two artificial into the namelysurface were by-products
porphyrin as well as which cannot
rose bengal werebeused.
further
The
water. Photochemical
acesulfame_K oxidation,
(its chemical particularly
formula is giventhisin degraded.
presented workInstead,
was 85%
focusedremoval of TOC was
on determination the
using molecular
Figure oxygen, is
1) and sucralose (itsundoubtedly one of the
chemical formula is achieved
dependencieswith between
the addition of H2O2
degradation after 240
efficiency of
most in
given important
Figure 2), photochemical
under UV-C (i.e. method, since
= 254 nm)it minutes irradiation.
the selected compounds and the reaction
does not liberate any additional chemical oxidant. parameters such as: pH and temperature of
Singlet oxygen is a particularly good candidate for
photodegradation of water contaminants
205 reaction solution, substrate and oxygen
concentration, quantity of immobilized
1
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

MINI GLIDING ARC ATMOSPHERIC PRESSURE PLASMA REACTOR

Mini Gliding Arc Atmospheric Pressure Plasma Reactor PP3-21
J. Diatczyk, J. Pawat, H. D. Stryczewska, P. Terebun, M. Kwiatkowski. Lublin University of Technology,
Nadbystrzycka 38A, 20-618 Lublin, Poland, j.diatczyg@pollub.pl.


The gliding arc (GA) discharge plasma is the example of low
temperature plasma that can be generated in multi-electrode
reactors with enforced fast gas flow at atmospheric pressure.
Plasma generated in the mini-GA reactor is in non-equilibrium
state. This kind of source of high-energy electrons without
heating the plasma gas in the whole volume of plasma reactor
chamber is essential for plasma chemistry and bio-medical
applications.
Developed gliding arc plasma device (mini-GA) can be applied for
surface treatment of industrial materials. Obtained experimental
results show that mini-GA plasma reactor does not change
physical properties of the treated surface.



There are many results of research works that respect to the axis of symmetry of the gas nozzle.
the low temperature plasma generated in the Plasma reactors with gliding discharge are
GlidArc type reactor is an effective method in the supplied with special power supplies. The reactors
process of disposal and treatment of different can be operated at a constant, alternating AC and
gaseous pollutants [1-5]. pulsating current [4]. The mini-GA reactor is
The
Removalbasic reactor
of emerging is composed of two electrodes,
contaminants from supplied
water viaWATER by high voltage power supply with no
REMOVAL OF EMERGING CONTAMINANTS FROM VIA PEROXYMONOSULFATE
between which
peroxymonosulfate an electric discharge
activationIRON takes
with SOURCES place.
various iron separate i gnition
(Fe+2s,ystem Fe+3, (figure 1), which can give
ACTIVATION WITH VARIOUS (Fesources +2
, Fe+3, ZVI) PP3-22
The gas
ZVI) nozzle is placed below the electrodes in certain p ortion o f t he energy in the single cycles of
their axis of
1 symmetry. 1 Gas flows
2 with 2 plasma.
M.G. Antoniou , N. Tsiarta , S. Rodriguez , A. Santos (1) Department of Environmental Science and Technology,
predetermined
Cyprus University speed. The arc
of Technology, initiates
3036 Lemesos, at Cyprus
the maria.antoniou@cut.ac.cy.
(2) Dep. Ingeniera Qumica.
shortest
Fac. CC. gap between
Qumicas. two electrodes,
Universidad Complutense.after 28040which Madrid. Spain.
it elongates by transverse gas flow. At this point in
time, the current in the arc is at its maximum This projectvalue studied the removal of persistent organic pollutants
and the voltage at the lowest (quasi-thermal from water with novel Sulfate Radical-based Advanced
regime). A transverse gas flow is introduced Oxidation that Processes (SR-AOPs). The model contaminants
moves the arc from its initial position included and allows caffeine (stimulant), ibuprofen (analgesic), and diuron
elongation [5-7]. The elongating arc demands and were chosen because of structural
(herbicide)
differentiations
more power to sustain itself, until it reaches the and susceptibility of their functional groups to
maximum that the power supply can provide. the radical At species formed. Chemical oxidation was achieved
through electron transfer activation of peroxymonosulfate
this point the power drop on both plasma and Figure 1. Schemata of equivalent electrical circuit.
(PMS), from different iron sources including the ferrous ion
external resistance is known to be of the 2+ total
(Fe ), the ferric ion (Fe3+) and zero-valent iron (ZVI). In general
power. This is the transition point for the regime of oxidation The reactor has the possibility to work in
ZVI/PMS system was found to be the most efficient
GlidArc operation [5, 6]. Due to continuous gas
oxidation system for all the different circumstances,
different contaminants for example dueusing
to the the
flow, the length of the arc continues to grow, but gases such
continuous and slow release of aqueous iron species. as oxygen, synthetic air and carbon
the power supplied by the source is insufficient to dioxide with different percentage formula.
balance the convective energy losses to the The discharge mechanisms of mini-GA are the
Introduction peroxymonosulfate (PMS) [6-7]. The in-
surrounding gas and discharge disappears. similar like in traditional GlidArc (figure 2). One of
situ generated radical species from SR-AOPs
Mini-GA reactor has pesticides,
small discharge space, the key parameters determining the amount of
The increasing use of pharmaceuticals mainly include sulfate radicals (SO4-), which
where i nitial d istance b etween e lectrodes d istance generated active particles in the plasma, is the
and personal care products in modern societies has have high redox potential for electron abstraction
in ignition
resulted inpoint
the need can be
for equal
applicationto one
oftenth
additionalof a shape
(2.5-3.1 and
V). size
Side of treactions
he arc discharge.
can cause This
thewformation
ork aims
millimetre. The reactor has many adjustment and
treatment of water and wastewater mainly due to to identify the factors
of additional radical species such hydroxyl affecting the length and
setting possibilities,
the recalcitrant nature for of
example distance between
these compounds. Since, duration
radicals o(HO f the
discharge.
) and peroxymonosulfate radicals
electrodes
conventionalcan be changed
treatment processes continuously.
are found toThe be (SO5-).
electrodes
inefficient in move
removing axially, these symmetrically
contaminantswith or In this study, the sulfate radical generating
produce additional hazardous waste [1-2], current oxidant peroxymonosulfate (HSO5-, PMS) was
research activities are focusing on their complete
destruction through advanced chemical oxidation
206 chosen to be activated by various iron sources
(Fe+2, Fe+3, and ZVI), since sulfate radicals have
1
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

Degradation
DEGRADATION OFof endocrineDISRUPTING
ENDOCRINE disruptingCHEMICALS
chemicals by
BY heat-
HEAT-ACTIVATED in by
will be filled

PERSULFATE activated persulfate EAAOP4 PP3-23

N. Potakis1, Z. Frontistis1,D. Mantzavinos1. (1) Department of Chemical Engineering, University of Patras, GR-
26504 Patras, Greece, zfrontistis@chemeng.upatras.gr

In this work, BPA was chosen as a representative

model compound of the EDCs family to investigate its
degradation by heat-activated persulfate oxidation. The main
scope was to evaluate the effect of various operating conditions
such as initial BPA and SPS concentrations, reaction time, pH,
temperature and water matrix on kinetics.
Completed degradation of BPA was observed in 120,
30, 7 and 3 min when the reaction was carried out at 40 C,
50 C, 60 C and 70 C, respectively. The process appears to be
favored at neutral pH. For the range of concentrations studied,
the reaction order with respect to BPA shifts from first to zeroth
as initial concentration increases from 110 g/L to 440 g/L.
The role of water matrix is critical and has a negative effect on
process efficiency, i.e. it decreases with increasing matrix
complexity.

In this work, BPA was chosen as a

The presence of endocrine disrupting representative model compound of the EDCs
compounds (EDCs) at the ng/L-g/L level in family to investigate its degradation by heat-
waters and treated wastewaters has been well- activated persulfate oxidation. The main scope was
documented. EDCs are designed to be bioresistant to evaluate the effect of various operating
and, therefore, they are only partially removed by conditions
FAST DEGRADATION OF ENDOCRINE DISRUPTORS BY Agsuch PO4/TiOas 2 SOLAR
initial BPA and SPS
Fast degradation
biological
PHOTOCATALYSIS
processes. As of Endocrine
a consequence, Disruptors
they are by Ag 3PO4/TiO2 solar
concentrations,
3
reaction time, pH, temperature
will be filled
and PP3-24
released in the water cycle and may pose a in by
photocatalysis water matrix on kinetics.
potential danger to 1 fish and 1 other aquatic 1 EAAOP4
1
M.E.Taherieven , A. Petala , Z.concentrations
Frontistis , D.I. Kondarides Oxidation
1 reactions were conducted in a
organisms, at trace of 0.1-10 , D. 120
Mantzavinos . (1) Department of Chemical
mL thermostated reactor made of pyrex glass.
Engineering, University of Patras,
ng/L [1]. Bisphenol A (BPA) is predominantly GR-26504 Patras, Greece, zfrontistis@chemeng.upatras.gr
The vessel was open to the atmosphere without
used in plastics manufacturing (epoxy and gas sparging sinceBPApreliminary
In this work, was runs chosen showed as thata
polycarbonate resins) as binder, plasticizer and the effect ofmodel aeration on degradation was
hardener, while it may also be employed as representative compound of the EDCs
1 negligible.
family to Certain volumes
investigate its ofdegradation
BPA and by SPS
additive in flame[Ag 3retardants,
PO /TiO (3:1)]=250 brake
4 2 mg/L fluids and stock solutions were mixed to a predefined volume
0.9
thermal papers. BPA
[BPA]=240 g/L
pH=6 is known to have estrogenic
Ag 3 PO 4 /TiO 2 as a catalyst under simulated
0.8 of ultrapure
solar irradiation. water in found
It was order thatto getAg3PO the4/TiO
desired
activity at concentrations as low as 1 ng/L [1,2]. In 2
solar photocatalysis is an efficient method0=110
concentration of each reactant (i.e. [BPA]
0.7
recent
0.6 years, various efforts are being made to for
Visible 440fast
the g/L; [SPS]0=10650
destruction of BPA mg/L).
in aqueous SPSsolutions.
was added
eliminate or effectivelySolar remove xenobiotics in the
C/Co

0.5

environment;
0.4 among them, advanced oxidation Process performance was affected by severalthe
after the working BPA solution had reached
desired such
factors, temperature (i.e. uptime
as irradiation to and70C). type,All
processes
0.3 (AOPs) are a viable alternative option experiments were performed un-buffered atand their
for water/wastewater treatment [2]. The sulfate
0.2 catalyst concentration, BPA concentration,
0.1 inherent matrix.
water pH. Samples The periodically
optimum drawnratiofromofthe
radical-AOP has recently been discussed in the reactor were immediately cooled down at 4C in
Ag 3PO4/TiO2 was found to be 3:1. In addition
0
literature
0 as
2 an 4efficient 6 and8 affordable
10 12 process.
14
an ice bath for about runs5 mintheto silver
quenchleaching
the reaction
Time, min
Sodium persulfate (SPS) (Na2S2O8) has attracted after five sequential as
and then analyzed
determined by to assess
flame the degradation
atomic absorption of
the attention of the scientific community as a BPA by means below of high performance liquid
promising source of sulfate radicals because of its spectrometry.was 10%.
chromatography (Waters Alliance 2695).
moderate cost (i.e. the wholesale price is in the In order to demonstrate the effect of temperature
Endocrine disrupting compounds
order of 1000 USD/tn) and its high redox potential (EDCs)
constitute Photocatalytic
on BPA (200 experiments were conducted
g/L) degradation, a seriesin ofa
of 2.01 V an important
[3].Other class of such
advantages contaminants,
of persulfate over cylindrical pyrex
experiments were glass reactor
conducted at (V=120
an initialmL). Solar
persulfate
which pose an increasing threat
other oxidants include the fact that it is solid at to aquatic
organisms, as well asthus to facilitating
human health. EDCs irradiation
concentration was of emitted
625 mg/L by an
and Oriel
an LCS
initial pH - 100
of 6
ambient temperature, its storage Watt
in the solar simulator
temperature rangesystem.
of 4070Changes
C. in BPA
Increasing
include naturally
and transport, as occurring
well as itsestrogens, synthetic
high stability and
estrogens, phyto-estrogens and xeno-estrogens (i.e. concentration
the were followed
reaction temperature fromby high
40 C performance
to 70 C
aqueous solubility. liquid
enhanced chromatography
BPA conversion(HPLC).
significantly. Complete
pesticides, plasticizers, persistent organochlorines,
organohalogens, alkyl phenols, heavy metal. The optimum ratio of Ag3PO4/TiO2 was found to
Bisphneol A (BPA) was chosen as a representative be 3:1 (Figure 1). BPA removal follows a pseudo- 1
xeno-estrogen typically used in the manufacturing
of numerous chemical products [1,2].
207
first order reaction kinetics with respect to initial
concentration, whereas the kinetic constant
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

SOLAR PHOTOCATALYTIC DEGRADATION AND ANTIBIOTIC INACTIVATION willOF be filled

Solar photocatalytic degradation and antibiotic inactivation of
SULFAMETHOXAZOLE BY TUNGSTEN-MODIFIED TiO2 PP3-25
in by
sulfamethoxazole by tungsten - modified TiO2
EAAOP4
E. Ioannidou1, Z. Frontistis1, D. Venieri2, D.I. Kondarides1, D. Mantzavinos1. (1) Department of Chemical
Engineering, University of Patras, GR-26504 Patras, Greece, zfrontistis@chemenupatras.gr (2) School of
Environmental Engineering, Technical Univerity of Crete, GR-73100 Chania, Greece

The efficiency of tungsten modified TiO2 as a catalyst for the

photocatalytic degradation of sulfamethoxazole under
simulated solar irradiation in environmentally relevant matrices
was investigated. It was found that solar photocatalysis is an
efficient method for the degradation of SMX in aqueous
solutions. Process performance was affected by several factors,
such as irradiation time and type, catalyst concentration, SMX
concentration, pH and water matrix. The optimum catalyst was
found to be 4% tungsten modified TiO2 calcined at 700 C.
SMX removal efficiency was slightly higher at alkaline pH.
The presence of bicarbonates and humic acid resulted in
decrease process, while the presence of electron acceptors
promotes the decomposition of SMX. The removal of SMX
was significantly lower in secondary treated wastewater.

The occurrence of pharmaceuticals and their Another is the overt use of additional
metabolites and transformation products in the semiconductors, such as CdS or WO3, coupled to
environment is becoming a matter of concern TiO2 [2.3].
because these compounds, which may have
adverse effects In on Heterogeneous
living organisms, are The aim of this work was to will study, in a
New Pathways And Homogeneous systematicNear-Neutral
way, the efficiency of
be filled
tungsten
NEW PATHWAYS
extensively IN HETEROGENEOUS
and increasingly used in human AND HOMOGENEOUS NEAR-NEUTRAL in by
Photo-Fenton
PHOTO-FENTON Bacterial
BACTERIAL Inactivation
INACTIVATIONByandIron Oxides
BYmodified
IRON And
TiO Iron
OXIDES Citrate
2 catalyst
ANDand IRONthe CITRATE
effect EAAOP4
of various
veterinary
Complexes medicine and are released continuously PP3-26
COMPLEXES
into the environment [1]. process parameters such as catalyst loading, initial
SMX concentration, solution pH, the presence of
S.Sulfamethoxazole
Giannakis1, C. Ruales-Lonfat
(SMX) , C.isPulgarin
1 1
a synthetic electron acceptors or radicals scavengers and the
1
SB, ISIC,and
antibiotic Group of Advanced
belongs to the Oxidation
group of Processes,
sulfonamidecole Polytechnique
water matrix Fdrale
(i.e. de Lausanne water,
ultrapure (EPFL),bottled
Station 6,and
1015 Lausanne, Switzerland, stefanos.giannakis@epfl.ch
antibiotics. It is the most commonly employed treated wastewater) on the kinetics of SMX
antibiotic of this group and it is extensively used in degradation under simulated solar irradiation . In
both human and veterinary medicine In this [1].
work, the use of iron
addition oxides existing
antibiotic in natural
inactivation was watersstudied
Semiconductor photocatalysis and iron
using citrate determining
solar complex was investigated,
the on their contribution
Minimum Inhibitory
irradiation as the source of photonsin the for solar-assisted
the photo-Fenton
Concentration (MIC) in drinking
of residualwater. The anti-
antibiotic with
microbial activity
activation of the catalyst has received considerable of hematite,
microtiter broth goethite, wstite
dilution and magnetite,
method, regarding
attention over the past few years. However, with or the H2O2 as electron
without microbial growthacceptor was studied,
of specific bacterialyielding
strains
widespread technological use of a heterogeneous a TiO2 photo-Fenton
susceptible to or thea semiconductor action MIC
selected antibiotic. mode is
photocatalyst has been hampered by its action mode, respectively.
wide band defined asThe theuselowest
of iron citrate in neutralof(oran
concentration
gap and the fast recombination of electrons higher) andpH wasantimicrobial
explored, withthata inhibits
demonstration
the growthof prevailing
of at least
holes. homogeneous photo-Fenton pathways.
50% of a microbial Hydroxyl radicals (OH)
population.
and superoxide radicals (O2-) were the main reactive oxygen
Mostly studied TiO2 photocatalyst isspecies Degussa responsible Photocatalytic
for bacterialexperiments
inactivation.were The conducted
presence of in a
P25 (Aeroxide), which contains adjoining anatase cylindrical pyrex glass reactor
NOM and DOM did not hinder the disinfection process, and (V=150 ml). Solar
and rutile microcrystalline regions. Thisbacterial extended regrowthirradiation
was neverwas emitted by an Oriel LCS - 100 W
observed.
functionality is due in large part to the extended solar simulator system. Changes in SMX
near-visible absorption of the rutile phase, concentration were followed by high performance
followed by rapid electron transfer between the liquid chromatography (HPLC).
The problem
phases, leadingof to
drinking
enhanced water scarcity
charge is without
separation and efficiency of the heterogeneous or homogeneous
doubt one of
reduced the greatest
energy wastagechallenges
by of the present
electronhole Figuremode,
action 1shows the firstbyorder
initiated the kinetic
differentconstant
forms forof
times, especially for developing countries
recombination [2,3]. One approach to enhance [1]. The the
iron.degradation
The of 350
heterogeneous g/L SMX. As
photocatalyticseen 4% or
development
activity is to of cheap multi-component
building and sustainable solutions
catalysts WO3-TiO2 shows
semiconductor a significant
efficiency of theimprovement
iron (hydr)oxides solar
for increase
to bacterial physical
inactivation
charge andseparation
the subsequent
and/or photocatalytic
was studied withactivity comparing
the addition to commercial
of 0.6 mg/L iron,
elimination of related diseases is a
visible light absorption include nanodeposits of necessity in Degusssa
without (Aeroxide)
or with theP25.
addition of 10 mg/L of
countries
noble metalwith
poolsinexistent or inadequate
on the exterior of TiO2 treatment
particles. hydrogen peroxide, to act as electron
SMX removal follows a pseudo-first order acceptor. The
facilities. Solar-aided Advanced Oxidation iron citrate was assayed in a 0.1-2.0 mg/L range in
Processes (AOPs) are a potential solution, since
the aforementioned regions coincide with the areas
208presence of H2O2 and its efficiency was compared
with goethite and FeSO4. Irradiation experiments
1
with the highest solar illumination periods around took place under a solar simulator emitting > 290
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

ECOTOXICITY EVALUATION OF SECONDARY EFFLUENT TREATED BY SOLAR

Ecotoxicity evaluation of secondary effluent treated by solar photo- will be filled
PP3-27
PHOTO-FENTON AT NEUTRAL PH IN A RACEWAY POND REACTOR in by
Fenton at neutral pH in a raceway pond reactor
EAAOP4
J.A. Snchez Prez1, A.M. Freitas2, G. Rivas1, A. Cabrera1, M.C. Campos-Maas1, J.L. Casas Lpez1, A. Agera1
(1) Research Centre on Solar Energy (CIESOL), University of Almera-CIEMAT, Almera, Spain, jsanchez@ual.es.
(2) Department of Chemistry and Biology, Federal University of Technology-Paran, Curitiba, Brazil.

Micropollutants (ng L-1 - g L-1) can be persistent even after

wastewater treatment, becoming a risk to aquatic and terrestrial
biota. In this work, different ecotoxicity tests were used to
evaluate the secondary effluent toxicity before and after
treatment by solar photo-Fenton at neutral pH in a raceway
pond reactor. Preliminary analysis detected the presence of 39
micropollutants in the effluent, especially pharmaceuticals, with
a total concentration of 80 g L-1. After 90 min of treatment, a
toxicity reduction was observed as well as a contaminant
degradation rate about 99%. The organisms showed different
sensitivity levels: T. themophyla > D. magna > L. sativa > S.
polyrhiza V. fischeri.

toxicity with various organisms is an important

Background way to monitor processes and reduce operating
Some organic compounds may resist costs, especially when dealing with
conventional treatments, remaining in the WWTP micropollutants [6]. The objective of this work
secondary effluents. Even at low concentrations, was to evaluate the acute and chronic ecotoxicity
these microcontaminants, usually pharmaceuticals, of a secondary effluent before and after tertiary
SIMULTANEOUS
pesticides, personal SOLAR DISINFECTION
careDisinfection
products, among AND PHOTOCATALYTIC
others, treatment TREATMENT
by solar photo-Fenton OFbepH
at neutral in a
Simultaneous
CONTAMINATED
Solar
DRINKINGrisk WATER
and Photocatalytic Treatment of will filled
PP3-28
represent a major environmental especially to raceway pond reactor. in by
Contaminated Drinking Water
aquatic biota [1]. Therefore, it is strongly EAAOP4
Methods
A.J. Expsito, J.M.
recommended bothMonteagudo, A. Durn, I.of
the development Sanmore
Martn, A.M. Acevedo. University of Castilla-La Mancha, Avda.
Camilo Jos tertiary
efficient Cela, 1. 13071, Ciudad Real, Spain,
treatments and AntonioJose.Exposito@uclm.es
the Effluent sample was collected after secondary
ecotoxicological monitoring of these compounds treatment in a municipal wastewater treatment
in the environment [2]. Regarding alternative plant located in Almera (south-east of Spain). The
treatment options, advanced oxidation The present study
processes dealswas
sample with the simultaneous
stored at 4oC in the Escherichia
dark until use. ColiThe
(AOPs) have been investigated for the removal inactivation
of and degradation process
photo-Fenton of organics wassuch as antipyrine
performed in a PVC in
emerging contaminants from urban wastewater drinking waterraceway by means pond of reactor,
a new solarwith 18 photocatalytic
L capacity and and 5
effluents. Among AOPs, the solar photo-Fenton pasteurization cm combined system.A This
liquid depth. installation
paddlewheel has to
attached notan
process has been proven to be efficient associated
in the electricity and maintenance
engine allows the solution costs.
remained On homogeneous
one hand,
removal of microcontaminants [2]. different Recently,reactive and oxygen speciesthe
mixed. Before (mainly
treatment,HOpH ) produced
was set atby6.5
raceway pond reactors have been proposed TiO irradiation
2 for not only destroy antipyrine
to partially remove bicarbonates. but alsoReagents
cause
damage
solar photo-Fenton due to their low cost, capability to E. Coli. On the other hand, the High-Temperature-
concentration used were: 50 mg L H2O2 and 3 x -1

of changing the liquid depth to take advantage Short-Time of treatment

20 mg L kills
-1 bacteria.
Fe2+, at 0, The5 and system has Temperature,
15 min. achieved a
-1
most of photons reaching the reactor surface and peak flow rate of 16 L h of treated water
pH, solar irradiation, at andissolved
turbidity, incident UV-A organic
2
their high treatment capacity [3, 4]. solar They power
are of 37.1 asW/m
carbon well .asThe totaleffects
iron andofH2the antipyrine
O2 consumption
extensive non-concentrating photoreactors concentration,
and solar irradiance
were monitoredandthroughout
catalyst on the the treatment
treatment.
efficiency
consist of channels where water is set in motion by were determined.
Micropollutant analyses and ecotoxicity tests were
a paddlewheel system. Regarding the toxicity of performed before and after treatment. Chemical
wastewater containing micropollutants, there are analysis was performed by liquid chromatography
few studies evaluating sublethal and chronic coupled to hybrid quadrupole-linear ion trap
Experimental:
Background
effects. Acuteandtoxicity
Objectives: assays in organisms tandem mass spectrometry (LC-QqLIT-MS/MS).
belonging to different trophic levels predominate Photocatalytic
Wastewater samples and were
Pasteurization
previously experiments
enriched by
One of the most important problems affecting have been carried out in usingan experimental
relatively to chronic ones [5]. Moreover,
people in developing countries is the inadequate AOPs not solid phase extraction OasisTM setup HLB
always reach the total mineralization of pollutants, (Figure 1) consisting
cartridges (200 mg,of a6 tank cc). of For
50 litres, a solar
ecotoxicity
access to disinfected drinking water, resulting in a CPC (area= 0.25the m2), samples
a heat exchanger, and a solar
and
highercanrisk
generate more toxicdisease
of waterborne intermediates
transmision[2]. measurements, were collected 2
at
Thus, the toxicity evaluation at different stages of pasteurization
initial (0 min), system
intermediate(area= (20 0.5
min) mand ). final
The
[1,2]. On the other hand, emerging micropollutants installation is ina continuous flow system where
advanced oxidation treatment
such as pharmaceuticals have using
been bioassays
identified of in time (90 min) previously washed glass flasks.
water flows through CPC formed by four pipes
drinking water [3]. Therefore, new technologies
are required to eliminate both kinds of 209
filled with immobilized TiO2, and then it flows
through the pasteurizer that heats the water.
1
contamination in drinking water and, in addition, Temperature and water flow are controlled by a
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

COST
Cost ANALYSIS
analysis ofOF PHOTO-FENTON
photo-Fenton DISINFECTION
disinfection IN REAL
in real municipal MUNICIPAL WASTEWATER
wastewater. will be
filled in by PP3-29
EAAOP4
I.M. Romn Snchez1, M. Segura 1, J.A. Snchez Prez1, E. Ortega-Gmez 1, P. Fernndez Ibez1
(1) Research Centre on Solar Energy (CIESOL), University of Almera-CIEMAT, Almera, Spain, iroman@ual.es

.
An economic assessment of photo-Fenton process applied
to wastewater disinfection is presented. Different
strategies were analyzed and compared with other studies.
The lowest estimated cost to treat 4200 m3/year, 0.21
/m3, was obtained in a 30 m2 CPC plant dosing 50 mg/L
of H2O2 and 20 mg/L of Fe. This operation condition
allowed achieving the inactivation of total coliform
required in the Spanish Royal Decree 1620/2007 to
reclaimed wastewater used for agriculture irrigation.

1. Introduction 2. Materials and methods

The global fresh water shortage is currently one 2.1. Experimental procedure
of the main environmental problems because of
the increasing demand for different uses in the last For carrying out this study we have analyzed a
decades. One option AND this problem is EFFICIENCYwork
previous of the group dealing with real
Photocatalytic andtoAntimicrobial
PHOTOCATALYTIC avoid
ANTIMICROBIAL Efficiency of TiO2-Based
wastewater OF Interior
[1] TIO
where
2
-BASED INTERIOR
the experimental procedure
wastewater
PAINTS reclaiming. PP3-30
Paints of the optimized disinfection process by photo-
Agriculture produces 60 % of global food and Fenton was described. Three different reactant
1 1 1
consumes
G. Skouras 70% , G. of fresh
Tatsi , M.water
Tsoulfaand, C.there is 1a, S.need
Nannou Tsafou1, A.
dosages for1, CPC
Mitsionis N. Todorova 2
disinfection plant1,were
, T. Albanis C. Trapalis 2
proposed:,
1
and T. Vaimakis .
of new water sources such as reclaimed 2+
(1) University
wastewater with of Ioannina, Department
high quality standards. of Chemistry, 45110, Ioannina,1. Greece,
[H2O2]gskouras@cc.uoi.gr.
= 50 mg/L and [Fe ] = 20 mg/L
(2) Institute of Material Science, NCSR, Demokritos, 15310, Ag. Paraskevi, Athens, Greece.
For use in irrigation of crops, different 2. [H2O2] = 50 mg/L and sequential
legislative frameworks have been developed in additions of [Fe2+] = 20 mg/L, 10 mg/L
order to regulate the content of microorganism in Summary and 10 mg/L
water. In Spain, the Royal Decree 1620/2007 2+
This study presents a3.TiO[H 2O2] = 100 mg/L and [Fe ] = 20
2-based paint for the consolidation of
includes regulations for this use, limiting the mg/L
crowded places like hospitals, schools, companies, etc., where dirt
occurrence of microorganism. For example, limits
and
for Escherichia coli are 100 CFU/ 100 mL for the
microbes are at
Forhigh rates.
comparison Thepurposes
titania used in thisthepaint
between was
different
Spanish regulation and 1 CFU/ 100 mL for the
made by the sol-gel technique.
reactant The catalyst
dosages, characterized
the accumulated solarusing the
energy
WHO.
BET model, UV-Vis,
was used DRS
and spectroscopy,
calculated accordingXRDto Eq.and(1): SEM
techniques. The photocatalytic activity of the TiO2-based paint was
investigated
As an alternative to traditional treatments in with antibacterial tests of the bacteria Staphylococcus
water disinfection, Advanced Oxidation Aureus (Newman Strain).
Processes [1]
(AOPs) were studied. One of the new approaches
for wastewater disinfection is the photo-Fenton where QUV,n and QUV,n1 are the UV energy
Introduction
process, which produces hydroxyl radicals via a accumulated per unit volume (kJ/L) at times n and
series catalyst, in a 24-wellUV
n 1, respectively, cell culture
G,n is plate. The
the average cell
incident
The of catalyticofcycle
influence reactions
indoor with iron,
air quality H2O2
on human culture plateonwastheplaced under area,
a lighttn emitting
and UV-vis radiation. irradiation irradiated is the
health is increasingly considered, since people diode (LED) array
experimental time atof 400nm
samplefor n,photocatalytic
Ar is the
spend
In this their
work, amajority of time
cost assessment for theindoors.
photo- reaction,
illuminatedwhilecollector area (m2)took
illumination and Vplace fortotal
t is the 24
Photocatalysis
Fenton process is now seen astoa valuable
applied option for
real wastewater hours.
volume The colonies
of treated waterof(L). survival bacteria were
de-polluting
disinfection purposes.
is presented considering the determined by standard plating method,
inactivation of total coliform bacteria as an
Materials and Methods immediately after appropriate dilution on agar
indicator of fecal contamination of reclaimed plates and overnight incubation, so that the
The reagents
wastewater to be used for irrigation
used for the fabrication of the
in agriculture. number of viable colony forming units (CFUs) can
catalyst were ethanol (EthOH) and methanol be calculated.
(MetOH), docusate sodium (AOT), titanium
isopropoxide Ti(iPrO)4 and acetic acid (AA). In
210
Results and Discussion
1
200ml solution of methanol and ethanol of equal
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

PHOTOCATALYTIC INACTIVATION
Photocatalytic inactivation of theOFwaterborne
THE WATERBORNE PROTOZOAN
protozoan parasite PARASITE
will be filled
CRYPTOSPORIDIUM PARVUM USING
Cryptosporidium parvum using TiO2/HTiO /H
2 2O
O UNDER
2 2 2 under
SIMULATED AND
simulated and NATURAL in by
PP3-31
SOLAR CONDITIONS EAAOP4
natural solar conditions
M.J. Abeledo-Lameiro1, A. Reboredo-Fernndez1, M. I. Polo-Lpez2, P. Fernndez-Ibez2, E. Ares-Mazs1,
H. Gmez-Couso1.
(1) Department of Microbiology and Parasitology, Faculty of Pharmacy, University of Santiago de Compostela,
Campus Vida, 15782 Santiago de Compostela, A Corua, Spain.
(2) Plataforma Solar de Almera-CIEMAT, Carretera Sens km 4, 04200 Tabernas, Almera, Spain.

The enhancement in the effectiveness of the photocatalytic TiO2

disinfection against Cryptosporidium parvum by the addition of
low concentrations of H2O2 was evaluated. Distilled water
containing 100 mg l-1 of TiO2 and 50 mg l-1 of H2O2 was spiked
-2
UV dose (kJ m )
with C. parvum oocysts and exposed to simulated and natural
0 100 200 300 400

38
solar radiation. The oocyst global viability was determined by
100
36 inclusion/exclusion of the fluorogenic vital dye propidium
iodide and spontaneous excystation. The results prove the
34
80 32
Oocyst global viability (%)

30
enhancement in the effectiveness of solar disinfection
Temperature (C)

60 28

40
Dark
Solar radiation
Dark/TiO2
26
24
procedures against C. parvum when TiO2 is incorporated,
Solar radiation/TiO2
Dark/H2O2
22
20
decreasing the time needed to reach the oocyst inactivation.
However, the addition of H2O2 at low concentrations did not
20 Solar radiation/H2O2
Dark/TiO2/H2O2 18
Solar radiation/TiO2/H2O2

improve the photocatalytic TiO2 disinfection.

16
0 Average temperature
14

00:00 02:30 05:00

Exposure time (h)

pyramid of resistance to disinfectants) makes that

Background conventional methods of treatment for drinking or
THE ANTIBACTERIAL
Cryptosporidium PROPERTIES
is aproperties
genus of enteric OF CONCRETES
protozoan SUPPLEMENTED
regenerated waters WITH TITANIUM
are not sufficient to be
eliminate
The antibacterial
PHOTOCATALYST UNDER
of
VISIBLE
concretes
IRRADIATION
supplemented with titanium will filled
PP3-32
parasites of medical and veterinary importance their presence [3]. Thus, an outbreak in by of
photocatalyst under visible irradiation
that infects a wide range of human and animal Cryptosporidium hominis infection EAAOP4 transmitted
M. Janus1,2, P.Disease
Rokicka1,O.severity
Stelmach1 , ranges from , A.through the public , K.water
Zajc1, J.supply
Zatorskaaffecting
1 1 1
worldwide. E. Kusiak-Nejman Markowska-Szczupak ,
1 1
A. Czyewski , A.W. Morawski . (1)
asymptomatic or mild to severe, intractable Institute of Chemical and Environment Engineering, West Pomeranian
approximately to 27000 inhabitants of stersund
University with
diarrhoea of Technology,
wastingSzczecin,
depending ul. Puaskiego
on immune 10, 70-322(Sweden)
Szczecin, Poland, mjanus@zut.edu.pl
in November 2010 (2)was reported
Department of Sanitary Engineering, West Pomeranian University of Technology,
recently, being the Szczecin, al. Piastwof50,waterborne
largest outbreak 70-310
status, nutrition,
Szczecin, Poland.
and age. In developing countries,
cryptosporidiosis is estimated to be responsible for cryptosporidiosis in Europe [4].
UV-Vis The antimicrobial properties of concrete plasters, containing co
30-50% of the deaths in children under five years Advanced oxidation were processes (AOPs)against are a
modified TiO /N,C photocatalysts evaluated
of age and is considered the second agent causing 2
Escherichia coli undergroupUV-Vis
of related processes
irradiation. Theor technologies
impact of treatment that
diarrhoeal disease and dead in children after
temperature, as lead well toas the generationpresence
non-metals of radical in oxygen
the TiOspecies 2/N,C
rotavirus [1].
additives on the which result abilities
antimicrobial in the oxidative
of concretedegradation
plasters wasof
Transmission occurs by the faecal-oral discussed. route pollutants and inactivation of several waterborne
either by person toPetri persondishor animal to human or pathogens. Heterogeneous photocatalysis with
by ingestion concrete
of contaminated
plate water or food. In TiO2 is one of these processes which has received
developed countries,
suspension waterborne transmission is
of E. coli
most research attention in recent years for
considered the main mode of transmission and wastewater
forming treatment
units purposes
on the plates. [5].the
In all Moreover,
experiments, it is
Introduction
Cryptosporidium was the main aetiological agent known that the addition of low concentrations
negative control tests in darkness conditions and of
in 60.3% of the waterborne protozoan parasitic H2O2 cancontrol
positive enhance the efficacy
under UV-Vis of photocatalytic
irradiation (one
Outdoor and indoor pollutions caused by
outbreaks TiO2 300W
disinfection [6]. Ultra Vitalux) were carried
road trafficreported
and industryworldwide between as
are considered 2004twoandof bulb OSRAM
2010 [2].
the worlds worst problems in metropolitan and outObjective
simultaneously.
urban
Due areas.
to therapy The options
use of ofTiO 2 photocatalyst are
cryptosporidiosis in
Results
The aim and discussion
of this work is to study the
combination
limited, appropriatewith construction
hygiene and materialsproper water has
shown a favourable synergetic effectmeasures
in the enhancement
It has been of the clearlyphotocatalytic
demonstrated TiO that2
management and treatment are the main disinfection against thewith resistance forms to of
removal of air pollutants. Driven
of prevention. However, Cryptosporidium is an by the need to mixing concrete powder TiO 2 contributed
use solar waterborne
light moreenteropathogen
completely, which many Cryptosporidium parvum (oocysts)
developing additive selling points of the final by the addition
emerging
investigations have nature
been performed to makeforms TiO2 of low concentrations
product. All examined of Hconcretes
2O2 under (16 simulated
samples) and
particular resistant of the infectious natural solar radiation.
photocatalytically
(second after the active beyond itsagent
prion infectious absorption
in the supplemented with commercial titania (P25),
threshold of 400 nm. Although there are outdoor nitrogen and carbon co-modified TiO2-N,C
applications of TiO2 photocatalysis, in the exhibited antimicrobial properties. What
literature there is lack of information on the
interaction between concretes supplemented with
important, to activation of photocatalyst, visible
light was used. The higher bacteria inactivation
211 1
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

SOLAR PHOTOCATALYSIS
Solar Photocatalysis AS DISINFECTION
as Disinfection TECHNIQUE:
Technique: InactivationINACTIVATION
of OF will be filled
KLEBSIELLA PNEUMONIAE IN SEWAGE AND INVESTIGATION
Klebsiella pneumoniae in Sewage and Investigation of Changes in OF CHANGES IN in by PP3-33
ANTIBIOTIC RESISTANCE PROFILE EAAOP4
Antibiotic Resistance Profile
D. Venieri1, I. Gounaki1, M. Bikouvaraki1, V. Binas2, 3, A. Zachopoulos2, G. Kiriakidis2, 3, D. Mantzavinos4.
(1) School of Environmental Engineering, Technical Univerity of Crete, GR-73100 Chania, Greece,
danae.venieri@enveng.tuc.gr. (2) Institute of Electronic Structure and Laser (IESL), FORTH, Vasilika Vouton, GR-
71110 Heraklion, Greece. (3) Quantum Complexity & Nanotechnology Center (QCN), Department of Physics,
University of Crete, GR-70013 Heraklion, Greece. (4) Department of Chemical Engineering, University of Patras,
Caratheodory 1, University Campus, GR-26504 Patras, Greece.
The objectives of the present work were (i) to investigate the
efficiency of cobalt- and manganese-doped titania materials to
inactivate K. pneumoniae in real wastewater under solar radiation
and (ii) under natural sunlight, (iii) to compare inactivation rates
among solar photocatalysis, UV-C irradiation and chlorination
and (iv) to study possible changes in bacterial antibiotic resistance
profile through treatment. Dopants significantly enhanced the
photocatalytic activity of TiO2 under solar irradiation, in terms of
K. pneumoniae inactivation, while the process was retarded under
natural solar light. Catalysts with the binary dopant exhibited the
best photocatalytic activity in all cases. Chlorine concentrations of
1 and 5 mg/L proved to be satisfactory for an overall 7-Log
reduction of K. pneumoniae population after 30 min of treatment.
The effect of disinfection on bacterial antibiotic resistance profile
and on MICs varied, depending on the tested antibiotic and on the
applied treatment method.

1. Introduction perspective, the objectives of the current study

In recent years considerable
INACTIVATION attention has been
OF STAPHYLOCOCCUS AUREUS were
IN (i) to investigate
WATER BY MEANS the efficiency
OF SOLAR ofwill
cobalt- and
Inactivation
drawn towards ofmany
PHOTOCATALYSIS
Staphylococcus
opportunistic
USING
aureus
METAL pathogens
in Water by means of Solar
DOPED TiO2 manganese-doped
SEMICONDUCTORS titania materials which inwere
be filled
PP3-34
by
Photocatalysis
contained in raw and using Metal
treated Doped TiO
wastewater, among 2 Semiconductors
prepared in previous work [5], to inactivate K.
EAAOP4
which Klebsiella
D. Venieri 1 pneumoniae
, F. Tournas, I. Gounaki1,isV. Binas
prominently
2, 3 pneumoniae
, A. Zachopoulos 2 in real
, G. Kiriakidis 2, 3
, D. wastewater
Mantzavinos4. under solar
included
(1) School[1]. The frequency
of Environmental of reports
Engineering, concerns
Technical radiation
Univerity and (ii) under
of Crete, GR-73100 Chania,natural
Greece,sunlight, (iii) to
mainly the multi-drug resistance
danae.venieri@enveng.tuc.gr. of this
(2) Institute specific Structure
of Electronic compareand Laser inactivation
(IESL), FORTH, rates
Vasilikaamong
Vouton, GR-solar
strain,
71110while equally
Heraklion, significant
Greece. is theComplexity
(3) Quantum resistance&ofNanotechnology
photocatalysis,Center UV-C
(QCN), irradiation
Department of andPhysics,
chlorination
K.University
pneumoniaeof Crete, GR-70013
isolates Heraklion, Greece.
to environmental stressed(4) Department
and (iv) of Chemical
to study Engineering,
possible University
changes of in Patras,
bacterial
Caratheodoryand
conditions 1, University Campus,
deleterious GR-26504
agents, suchPatras, as Greece.
antibiotic resistance profile through treatment.
disinfectants. Conventional The aim of the present study was to investigate inactivation rates
wastewater
disinfection involves chlorination, which of isStaphylococcus
widely 2. aureus
Materials in water
and methodsby means of heterogeneous
used to remove effectively an extendedphotocatalytic variety of treatment
The bacterial understrain simulated
used in the andpresent
naturalstudysolar
was
Metal doped TiO
microorganisms 2 materials
[2]. Another as approach irradiation.
towardsFor this K. purpose
pneumoniae Fe-, Al-NCTC and Cr-doped
5056. Solar catalysts
TiO2irradiation
photocatalytic
seems to besemiconductors
the application of photocatalysis were preparedwith and assessed
experiments were in carried
terms out of in their disinfection
a solar radiation
metal doped TiO2 [3]. Completeefficiency. bacterial The simulator
effect of varioussystem operating (Newport, conditions
model such as
96000)
inactivation, mostly desired,metal-doping
which isaureus
Staphylococcus is highly concentration,
equipped withbacterial a 150 Wconcentration,
xenon ozone-free treatment
lamp
dependent upon operating parameters timeof and eachtoxic and
effectsan on Air bacteria
Mass 1.5 were Filter S.(Newport,
examined.
Global aureus
sewageSimulated
disinfection& natural solar that usesproved
process naturalto or be readily
model inactivated during photocatalytic
81094), simulating solar radiation treatment of
reaching
simulated solar irradiation
irradiation. However, even the aquatic
in the samples, since disinfection
the surface of the earthoccurred at a zenithrapidly
angle(i.e. aftero.
of 48.2
case of residual cells post treatment, the 20 extent
min ofoftreatment).UV-CMoreover,
irradiationit was was provided
observed by thata inactivation
11 W lamp
DNA damage and the induced oxidative of thestress bacteria is attributed
(Philips, TUV, to 11
solar
W, photocatalytic
PL-S). Air wasoxidationcontinuouslyof
Satisfactory disinfection their cells isand not to potential
sparged metal-doped
into the liquid, thecatalystreaction toxicity
mixture of the
was
may have various consequences,
rates in aquatic samples among which
the alteration of the microbial antibioticsemiconductors.
resistance The overall process
continuously stirred was and retarded under natural
the temperature was
profile. The conditions in wastewatersolar light. Chemical
treatment dopingatmay
maintained 251actoCaswith a satisfactory
a temperature means for
control
plants (WWTPs) are favourable sensitization for the of TiO unit.2 in the visible light
Photocatalytic region. were also carried
experiments
proliferation of antibiotic resistant bacteria (ARB). out under natural sunlight within the period of
A significant
1. Introductionproportion of these pathogens, June - July
catalyst 2014catalyst
loading, at the type Technical University
and initial of
bacterial
carried
Water may in water/wastewater,
serve as the passivedevelopcarrier ofresistance
diverse Crete campus located
concentration, which at 38o31 N and 24oinfluence
typically 04 E, in
mechanisms
bacterial groups and remain presentwhich
and species, either have
in water the clear sunny days. effectiveness.
disinfection During those runs the recorded
Disinfection
supplies,
potential tooractinas treated
infectiouseffluents
agents of[4]. In this
waterborne ranges of solar
experiments wereirradiance
performedand temperature
under simulatedwere and
diseases. In recent years considerable attention has natural solar irradiation.
been drawn towards many highly resistant
pathogens contained in water, among which
212
2. Materials and methods
1

Staphylococcus aureus is prominently included. A co-precipitation method was used to prepare

 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

ENHANCING PHOTOCATALYTIC DEGRADATION OF CYANOTOXINS WITH THE

EnhancingOF
ADDITION photocatalytic degradation
SULFATE-RADICAL of cyanotoxins
PRODUCING with the
OXIDANTS PP3-35
addition of sulfate-radical producing oxidants
M.G. Antoniou1, I. Boraei1, C.M. Kyriakou1, M. Abhishek2, C. Edwards,2, L.A. Lawton2 (1) Department of
Environmental Science and Technology, Cyprus University of Technology, 3036 Lemesos, Cyprus
maria.antoniou@cut.ac.cy. (2) School of Pharmacy and Life Sciences, Robert Gordon University, Aberdeen, UK.

This study focused on the removal of the hepatotoxic

cyanotoxins microcystin-LR and nodularin with enhanced
photocatalytic oxidation (PCO) by the addition of the sulfate-
radical producing oxidants persulfate (PS) and
peroxymonosulfate (PMS). Initially the optimum experimental
conditions were established. The average photon flux at =365
nm of the UVA lamp used was determined at 35.58 3.06 W.
Oxidant addition showed great enhancement in the PCO rates for
both toxins and reduced the treatment times by 1/20 and 3/10, for
PS and PMS, respectively. Quenching studies with methanol and
tetra-butyl alcohol asserted the role of sulfate radicals during
treatment. Toxicity studies based on the inhibition of the PP1
enzyme showed reduction of toxicity in the treated samples.

Introduction any harmful residuals. In this study the sulfate

radical generating oxidants persulfate (S2O82-, PS),
Cyanobacteria(blue-green algae) are peroxymonosulfate (HSO5-, PMS) were chosen
phototrophic microorganisms and represent an instead, since sulfate radicals have higher redox
essential component of the food web in all aquatic potential for electron abstraction than hydroxyl
ecosystems. However, certain strains form radicals and can cause selective oxidation. To the
ASSESSMENT Assessment
Cyanobacteria harmful of algal
Supporting
OF SUPPORTING blooms Electrolytes
ELECTROLYTES
(Cyano- on
best CO
ON 2 Reduction
ofCOour
2
REDUCTION
knowledge, by this is the will
BY PHOTO- be filled
first study
in by PP3-36
HABs) directlyPhotoelectrocatalysis
ELECTROCATALYSIS affect water Ti/TiOat
AT quality by Ti/TiO
/CuOproducing
N-P 2 /CuO n-p Heterojunction
investigating
HETEROJUNCTION the coupling of
SEMICONDUCTOR TiO 2 /UVA with these
2 EAAOP4
undesirable color, taste, odor andSemiconductor by releasing oxidants for the removal of cyanotoxins.
harmful
J. F. decyanotoxins
Brito1, M.V. B. into
Zanonithe
2
. (1) water. Human
Institute of Materials
Chemistry, UNESP- Univ and Methods
Estadual Paulista, Rua Prof. Francisco
activities
Degni 55,(i.e., sewerBrazil,
Araraquara, runoffs, overuse of
jfbrito@ymail.com Reagent grade cyanotoxins were ontained from
fertilizers) and global warming have resulted in an Enzo Life Sciences (Lausen,
increasing prevalence and persistence of Cyano- This work presents the usewas
Switzerland).Analysis of photoelectrocatalysis
performed using
HABs globally [1-2]. Cyano-HABs in Lake Taihu toreversed-phase convert CO2 into HPLC addedwithvalue products. array
photodiode The
in China, (2007) and Lake Erie in USA (2014) Ti/TiO 2/CuO
detection [3].n-pTheheterojunction
PCO experimental semiconductor
set up
have forced restrictions on water availability for shown curves
consisted of of photocurrent
a UVA lamp at vs potential
a set distancewith of 20 a
more than 2 million people combined. good
cm, aresponse
continouslyin presence
stirred 30ofmL 2. Ti/TiO2/CuO
CObrosilicated glass
Cyanotoxins are categorized based their semiconductor reactor vessel,wasand useda ascooling
workingfan electrode
to keep underthe
chemical structure and the way they affect UV-Vis solutionlight and biasbelow
temperature potential
T=35ofC. +0.2V
During forPCO the
mammalian health. Cyclic polypeptides consisting CO the2 reduction presenting
treated solution (V=10 a good
mL)performance.
was also aerated. The
sually of hepta- and pepta- amino acids can cause effect of supporting
The toxicity removal electrolyte
of the treatedwassamples
crucial was to
hepatotoxicity. Two very characteristic examples generate measured different
based on quantities of methanol,
the inhibition of the ethanol
protein
of these groups are microcystin-LR (MC-LR) and and acetone, confirming
phosphatases enzymes (PP1).the electrode is a promising
nodularin (NOD), respectively. material forand
Results photoelectrochemical
Discussion CO2 reduction.
Based on the above, current research efforts are Preliminary experiments indicated that the best
focusing on establishing appropriate treatment
Introduction treatmentwhenconditions
because were istoxin
the semiconductor activated initial
by
strategies to deal
The interest with
in the CO2persistent
conversion blooms. In this
is crescent [1] concentration
light, electrons ~5 and mg/L, TiO2(e-10
holes pairs /h+) mg/L,
are created and
study,
and lightpromisor
the most activated advanced
technique oxidation
for this propose is distance
inside both of TiO
reactor vessel from UVA 2+
2 and CuO surface. Cu
lamptrapsat the
20
processes (AOPs) based the activation
the photoelectrocatalysis [2]. Copper and copper of oxidants, cm, which resulted into an average
electron generated in the TiO2 surface and, photon flux at
catalysts,
oxides areand
thetheir
mostcombination
known p-type weresemiconductor
tested for the = 365 nm ofthe35.58
consequently, Cu2+specie
3.06 W. Our data
is reduced to also
Cu+
removal
used of2 reduction,
for CO MC-LR and NOD.
however hadPhotocatalytic
demonstrated indicated
specie. Thethat CO2 the susceptibility
reduction occurs onofthe the Cu+ two site
oxidation
lack (PCO)[2].
of stability with
In titanium dioxide (TiO
order to improve 2) was
the copper hepatotoxins
reoxidizing the towards
Cu+ speciePCO to treatment
Cu2+ holding did nota
chosen because ita is
oxides stability, p-na TiO
green technology with
2/CuO heterojunction
significantly
TiO2/CuO highdiffer even
stability, at changing
as shown catalyst
in the Graphical
high efficiencies for water
semiconductor was evaluated in this work.detoxification. To loadings.
Illustration.Though the molecular mass of MC-LR
enhance PCO degradation most studies use (heptapeptide) is ~170 amu CO
The photoelectrocatalytic higher than NOD
2 reduction was
hydrogen peroxide
Experimental methods (HP) because it does not leave (pentapeptide) both toxins contain
carried out in different supporting electrolyte. similar
The
The p-n Ti/TiO2/CuO semiconductor was made results show that supporting electrolyte with K+
with 6 thin films deposited by dip-coating in
solution with 3:1 proportion of TiO2:CuO and
213
promotes ethanol formation while supporting 1
electrolyte with Na+ promotes a higher methanol
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

MIXED OXIDE AS PHOTOCATALYST: TiO2-FexOy FOR H2 PRODUCTION BY WATER will be filled

Mixed oxide as photocatalyst: TiO2-FexOy for H2 production by water
SPLITTING METHOD
splitting method in by PP3-37
EAAOP4
A.Prez-Larios1,2,3,4, R. Gomez3, R. Zanella4, J. Bedia5
1
Universidad de Guadalajara, Centro Universitario de los Altos, Depto. Ciencias Biologicas, Carretera a Yahualica
km. 7.5, Tepatitln de Morelos, Jalisco, Mxico. 47600.
2
Instituto Tecnolgico Superior de Arandas, Depto. Ing. Ambiental, Libramiento Sur km 2.7 carretera Arandas-
Len, Arandas, Jalisco, Mxico. 47180.
3
Universidad Autnoma Metropolitana-Iztapalapa, Depto. de Qumica, rea de Catlisis, Grupo ECOCATAL, Av.
San Rafael Atlixco No 189, D.F., Mxico 09340.
4
Centro de Ciencias Aplicadas y Desarrollo Tecnolgico, Universidad Nacional Autnoma de Mxico (UNAM),
04510, Ciudad Universitaria, D.F. Mxico.
5
Seccion de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid, Campus Cantoblanco, E-
28049 Madrid, Spain.
alarios@cualtos.udg.mx

TiO2-FexOy (metal load: 1.0, 3.0, 5.0, 10.0 wt. % Fe) samples
were prepared by the sol-gel method and were evaluated for
the photocatalytic water splitting reaction for hydrogen
production, using a mixture of methanol-water (1:1). The
mixed oxide combination effectively increased the hydrogen
production (~5586 mol/h) obtained by 10.0 wt % Fe. Were
attributed to an enhancement of the electron charge transfer
from TiO2 to the FexOy.

PHOTOCATALYTIC ACTIVITY OF TiO2-CoO AS MIXED OXIDE FOR IMPROVEDwill H2 be filled

Photocatalytic activity of TiO2-CoOMETHOD
INTRODUCTION
PRODUCTION BY WATER SPLITTING
as mixedmetal
oxide oxide
for improved
have been H2 recently reported as
PP3-38
in by
production by water splitting efficient method catalysts for photoreforming of alcohol
The most studied processes 3at the present for the5 solutions [5]. EAAOP4
A.Prez-Larios
hydrogen
1,2,3,4
, R. Gomez , R. Zanella
production are electrochemical, steam
4
, C. Belver
1
Universidad
reforming of de Guadalajara,
alcohols Centro Universitario
or hydrocarbons de los Altos, Depto. Ciencias Biologicas, Carretera a Yahualica
and water
km. 7.5, Tepatitln de Morelos, Jalisco, Mxico. 47600.
splitting. Thus, the water splitting using EXPERIMENTAL
2
Instituto Tecnolgico Superior de Arandas, Depto. Ing. Ambiental, Libramiento Sur km 2.7 carretera Arandas-
semiconductors materials had
Len, Arandas, Jalisco, Mxico. 47180. recently acquired
great
3 relevance
Universidad because
Autnoma of the low cost for Depto.
Metropolitana-Iztapalapa, the de The nanomaterials
Qumica, 2 and ECOCATAL,
of TiOGrupo
rea de Catlisis, TiO2-FexOy Av. (metal
hydrogen production.
San Rafael Atlixco No 189,The principle
D.F., Mxico 09340. of this load: 1.0, 3.0, 5.0, 10.0 wt. % Fe) samples were
technique
4
Centro deisCiencias
based Aplicadas
on the photoexcitation
y Desarrollo Tecnolgico, prepared by
of the Universidad the sol-gel
Nacional Autnoma method using
de Mxico titanium
(UNAM),
semiconductor using a UV or
04510, Ciudad Universitaria, D.F.visible light sources.
Mxico. alkoxide and Iron nitrate, followed by the
5
The Seccion de Ingenieriapairs
electrons-hole Quimica, Facultad
formed are decapable
Ciencias,toUniversidad Autonoma
annealing of detheMadrid, CampusatCantoblanco,
samples 500C. E- The
28049
split waterMadrid, Spain. into gaseous oxygen and
molecules semiconductors were characterized by nitrogen
alarios@cualtos.udg.mx
hydrogen[1]. adsorption, UV-Vis spectrophotometry and X-Ray
The alternative method of photocatalytic water diffraction techniques.
splitting is promising since it involves TiO2the The photoactivity
-CoO (metal load: 1.0, 3.0,was
5.0,evaluated
10.0 wt. for the generation
% Co) samples
absorption of light to produce hydrogen were bypreparedof by
hydrogen using
the sol-gel a made
method andhome
werePyrex reactor
evaluated for of
irradiating oxide semiconductors. Photocatalytic 200 ml water
the photocatalytic containing an aqueous
splitting reactionsolution methanol-
for hydrogen
systems for water splitting may contain sacrificial production, water
using (1:1 molar ratio)
a mixture and 0.1 g of catalysts.
of methanol-water (1:1). The The
reagents, as methanol, commonly used mixed in theoxidephotoirradiation was made
combination effectively using athe
increased high pressure
hydrogen
photocatalytic evolution of H2 from water, since
production Hg lamp
(~2400 (with aobtained
mol/h) radiation byof10.0
254wt nm%andCo.intensity
Were
its hydroxyl group captures photogenerated holes to of
attributed 4.4 mW) encapsulated
an enhancement of the electron in charge
a quartz tube
transfer
-/h+ [2]. The
and minimizes the probability of e immersed
from TiO2 to the CoO. in the water solution.
incorporation of metals or metal oxide
nanoparticles on the surface of semiconductors as MAIN RESULTS AND DISCUSSION
co-catalysts has proved to enhance the
photoactivity for the water splitting reaction [3,4]. The textural properties of the prepared materials
These photocatalysts must be efficient, stable,
INTRODUCTION EXPERIMENTAL
are presented in Table 1. It can be seen that the
harmless, abundant and inexpensive. In that way, metal content as mixed oxide has a significant
The need to develop new alternatives for The nanomaterials of TiO2 and TiO2-CoO (metal
sustainable energy has drawn the attention to
emergent clean renewable technologies, since they 214 load: 1.0, 3.0, 5.0, 10.0 wt. % Co) samples were
prepared by the sol-gel method using titanium 1
proceed from natural and lasting source like solar alkoxide and Cobalt nitrate, followed by the
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

VISIBLE LIGHT ACTIVE HYBRID CORE-SHELL TiO2 PHOTOCATALYSTS FOR THE

Visible Light Active Hybrid Core-Shell TiO2 Photocatalysts For The will be filled
PRODUCTION OF USEFUL HYDROCARBONS FROM CO2 in by PP3-39
Production Of Useful Hydrocarbons From CO 2
EAAOP4
P. Falaras1, N.G. Moustakas1, F. Katsaros1, A. Papavasiliou1, E. Kouvelos1, A.G. Kontos 1, T. Steriotis1, G.Em.
Romanos1. (1) Institute of Nanoscience and Nanotechnology, National Center for Scientific Research
Demokritos, 153 10 Aghia Paraskevi, Attiki,, Greece, p.falaras@inn.demokritos.gr

As the pursuit for an environmental pollution and energy crisis

remediation procedure becomes a more and more pressing
topic, artificial photosyntesis seems to be a viable candidate
solution. In this work a core/shell structured TiO2 nanomaterial
(m-TiO2) was immobilized on the surface of glass beads and
tested for its efficiency and selectivity towards producing useful
hydrocarbons from CO2 using water and light. The experiments
took place under UV and visible irradiation, in a specially
designed and constructed photocatalytic reactor. The m-TiO2
material was fully characterized using TEM, SEM, micro-
Raman, IR, XPS, EPS and UV Vis spectroscopy. Significant
CO2 conversion rates were identified using mass spectroscopy
(MS) and gas chromatography (GC) techniques.

The main limitations lie on its wide band gap (3.2

Background eV for the anatase phase) that allows absorption
only up to 387.5nm, leaving all the visible part of
Due to the continuously growing concern of the
world for energy safety and independence the solar unused. As the UV part of the solar
spectrum is limited to about 4%, many research
combined
H PRODUCTION with theFROMremediation of the global
BIO-ALCOHOLS VIA PHOTO-REFORMING USING Au/TiO AND
H2 production from bio-alcohols groups tryusing to modify TiO 2 nanomaterials in filled
order
warming
2
phenomenon, scientists over thevialastphoto-reforming
few Au/TiO 2 will2 be
PP3-40
Pt/TiO AS HETEROGENEOUS CATALYSTS to enhance its absorption domain and shift in the
by
and Pt/TiO
decades 2
2 as heterogeneous
are intensively searching for catalysts
novel, clean
activity to longer wavelengths, deep in the visible
EAAOP4
and sustainable sources and methods to produce
part 1,of
J. Hidalgo1, A. Marinas1, F.J. Tenllado1, V. Montes1, F.J. Urbano J.M.the spectrum.
Marinas 1
, L. IlievaIn2, T.addition,
Tabakova2to reduce
, A.Diaz-
energy.
Lozano1 recombination, some of the most common
(1) Organic Chemistry
Artificial Department,
photosynthesis is University of Cordoba, approaches
a sustainable E-14014 Crdoba, Spain,at
also target alberto.marinas@uco.es
the efficient separation of
(2) Institute
procedure thatofmimicks
Catalysis,natural
Bulgarian Academy of Sciences,
photosynthesis. In 1113 the Sofia, Bulgaria
photogenerated elector hole pairs that
natural photosynthesis, plants convert carbon includes: metal or anion doping; semiconductors
dioxide (CO2), which is a major greenhouse gas,
H2 production coupling; and sensitization
through alcohols photo-reforming with light harvesting
was studied on
Biomass
into glucose used to Alcohols power the plants several Au/TiOdyes
vital 2 and [3-5];
Pt/TiOThese
2 solidsapproaches
(metal loadings can in
betheefficiently
0.5-3%
functions and oxygen that gives life to the planet.
range used not
by weight). only for pollutant
Experimental H2/COdecomposition
2 ratio for glucose, but also
The whole transformation process takes place fructose for photocatalytic
intoand glycerol was quite fuel
close generation,
to the as discussed
theoretical valuein
h Pt/TiO2
the chloroplasts using as inputs water, assuming
CO2 and complete some decomposition
reviews published into CO in2 the
and Hpast few years
2, whereas in
Au/TiO2
solar energy. In the same way, the artificial [6,7].
case of propanols higher values were obtained. This was
photosynthesis uses water, CO2 and solar energyto the formation of some other by-products such as
ascribed
to convert the otherwise valueless or harmful
ethane COand Objectives
2 acetone for propan-1-ol and propan-2-ol, respectively.
Study of:
into valuable hydrocarbons that can be Moreover, reused as propan-2-ol For this wasworkthe an only substrate
inorganic not leading
/ organic core /shell to
fuels.Noblemetal
The role of the chloroplasts is played catalystby deactivation
TiO with time-on-stream.
nanomaterial (m-TiO ) [8] was employed as
Metalloading
specially synthesizedCO2semiconducting
+H2+ nano- 2 2
Substrate organics a visible light active photocatalyst (E g=2.19 eV)
materials (photocatalysts) that have the ability to for the conversion of CO2 into hydrocarbons. The
absorb light. The absorbed energy induces the materials photocatalytic properties have been
formation of charge carrier pairs generating extensively tested in our group in various
hydroxyl and anionic oxygen radicals from water. incorporation
applications of small amounts
concerning treating of metals,
polluted suchwater
Au,
Background
These radicals in turn facilitate the breaking of the Pt, Pd,into
Rh,powder
Cu, Feform or Ni.
either [8,9]Among the different
or immobilized into
very stable double covalent bonds of CO2 and the options, noble ceramic
ultrafiltration metals have been the [10].
membranes most The studiedm-
The problem of the treatment of waste generated
subsequent forming of new hydrocarbon chains due
TiO2 tomaterial
their immobilized
high activityoncompared the surfacewith the
of glass
in different industries and the deficiency in raw
closing the carbon cycle in the environment [1]. transition
beads), was elements
tested [2]. Several
for its papersand
efficiency reported that
selectivity
materials has led to the search for ways to valorize
Titanium dioxide (TiO2) is a low cost, non-toxic, for the same
towards metal amount,
hydrocarbons modification
production from withCO2,Ptinora
waste. In this sense, biomass with an estimated
environmental friendly and abundant widely used Pd resulteddesigned
specially in higher photocatalytic
hydrogen production reactorthan Au
under
annual production of 1011 tonnes (only 3% of which
photocatalyst with a variety of applications [2]. and much more than Rh [2-3]. However, not only
is cultivated, harvested and used in food and non-
food applications) has a tremendous potential.
Therefore, the utilization of biomass for sustainable 215
metal content but also metal particle sizes should be
considered. 1
production of fuels and chemicals is one of the main Regarding the metal loading, it is commonly
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y
Photoelectrocatalytic hydrogen production using nitrogen containing will be filled
in by
water soluble wastes
PHOTOELECTROCATALYTIC HYDROGEN PRODUCTION USING NITROGEN EAAOP4
CONTAINING WATER SOLUBLE WASTES PP3-41

Iosif Tantis1, Lucian-Cristian Pop1, Panagiotis Lianos1,2

(1)Department of Chemical Engineering, University of Patras, 26500 Patras, Greece, e-mail: iosif8@yahoo.com,
(2)FORTH/ICE-HT, P.O. Box 1414, 26504, Patras, Greece

Hydrogen has been produced by photoelectrocatalytic

degradation of model nitrogen-containing water soluble
wastes
(1) FORTH/ICE-HT, P.O. Box 1414, 26504, urea,
Patras, formamide and aqueous ammonia. Hydrogen
Greece
. production was monitored in a simple reactor using a
Photoelectrocatalytic Leaf as functional component, i.e.
an FTO electrode bearing both photocatalyst and
electrocatalyst. Np-titania was used as photocatalyst while
a combination of commercial carbon paste with dispersed
Pt nanoparticles was used as electrocatalyst. Urea
produced the largest quantity of hydrogen, which could be
accelerated by application of an external electric bias.
Current-voltage measurements provided an indication of
current-doubling in the case of formamide.

Hydrogen production by photocatalytic and rather neglected. However, these compounds are
photoelectrocatalytic procedures has been one of typical animal wastes, they are found in large
the most popular subjects of research. Hydrogen quantities in both urban and agricultural wastes
VISIBLE
canVisibleLIGHTinRESPONSIVE
be produced BiVO4 PHOTOANODES
a photoelectrochemical FOR HYDROGEN
andhydrogen
cell by for they make PRODUCTION
an interesting willtarget
be filledfor
light responsive BiVO photoanodes
4 production PP3-42
in by
water splitting, however, hydrogen yield is higher photo(electro)catalytic hydrogen production. For
EAAOP4
when an Lianos
Panagiotis organic
a,b
or inorganic
, Olivier material
Monfortc, Lucian isPopa,this
Cristian reason,
Stavroula in the
Sfaelou a
present work, we are studying
a
photo(electro)catalytically decomposed
Department of Chemical Engineering, to yield
University hydrogen
of Patras, 26500 Patras, production
Greece by photoelectrocatalytic
b
FORTH/ICE-HT, P.O. Box 1414, 26504 Patras, Greece
hydrogen.
c If this
Department sacrificial
of Inorganic agent is aFaculty
Chemistry, waste,ofthen
Natural degradation
a Sciences, of University
Comenius the lowest molecularMlynsk
in Bratislava, weight
Dolina, 84215 Bratislava, Slovakia
double environmental benefit may be made by the representatives of this category of wastes, namely,
production of a valuable solar fuelAbstract
and the aqueous ammonia, formamide and urea.
Nanocrystalline
simultaneous decomposition of a harmful material. bismuth vanadate was deposited by a simple wet
chemistry procedure on FTO electrodes in order to construct visible
Most of the so far published works deal with responsive
light the Experimental
photoanodes, which were employed for
photoelectrochemical hydrogen production by water splitting. The
photo(electro)catalytic decomposition of specific surface area of the films was controlled by of
ethanol, The configuration a hydrogen-
the presence of a
surfactant
methanol, glycerol and other similar oxygenates. template (Triton X-100). It was, however, found
producing photoelectrochemical cell comprises that when a
the quantity of surfactant was relatively high, the stoichiometry of the
The reason is that these substances can be obtained as well
photocatalyst photoanode electrode
as its activity was lost.carrying a light
The obtained absorbing
material was
characterized by SEM, XRD, AFM, BET and UV-Vis spectroscopy.
as products of biomass and they offer the Optimized oxidation
highestphotoanodes were photocatalyst, a cathode (counter)
employed in photoelectrochemical cells
Figure 1. Schematic representation of for water splitting and hydrogen production under electric and chemicalan
hydrogen yieldreactor
the H-shaped of allemployed
studiedformaterials. Another electrode carrying a reduction electrocatalyst,
bias. Maximum hydrogen production rate was 0.15 mmol/h under
categoryhydrogen
of highproduction.
hydrogen yield compounds is of 1.4electrolyte
electric bias V vs Ag/AgClwhereplusthe
0.37target substance
V chemical bias. is dissolved
sulfide containing wastes. There is still a third and possibly a reference electrode, which is useful
category of waste materials that can be used for for analytical studies. Typical photocatalyst, also
Introduction
hydrogen production: nitrogen, amide and prepared
used in thesol was work,
present sonicated for 3 additional
is nanoparticulate titania
BiVO4 is a promising material which has minutes and deposited on FTO glass by doctor
carbamide-based
attracted attentioncompounds,
as a visiblewhich
light have been
responsive (np-TiO
blading.2).The
Typical electrocatalyst
obtained is a mixture
film was annealed up of
to
photocatalyst for water splitting applications [1]. 500 C for 10 min by using a heating ramp of
The most common and the only active polymorph 20 C/min. This deposition-annealing procedure
of BiVO4 takes a monoclinic scheelite-like was repeated six times to make a film of about 350
crystalline structure with a band gap of 2.4 eV [2].
BiVO4 has a conduction band edge located close
216
nm thick.
For the construction of the electrocatalyst, a
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

AA sol-gel method
SOL-GEL METHODforFOR
preparation of nanostructured
PREPARATION WO 3 photoanodes
OF NANOSTRUCTURED will be filled
WO3 PHOTOANODES
USED FOR PHOTOELECTROCHEMICAL WATER in by PP3-43
used for photoelectrochemical waterSPLITTING
splitting
EAAOP4
S. Sfaelou1, L. C. Pop1, O. Monfort2, P. Lianos1,3
(1) Department of Chemical Engineering, University of Patras, Karatheodori 1, 26500 Patras, Greece,
e-mail:sfaelou@upatras.gr
(2) Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, 84215
Bratislava, Slovakia
(3) FORTH/ICE-HT, Stadiou Str., Platani, P.O. Box 1414, 26504 Patras, Greece.

Abstract
In recent years, various techniques have been developed for
preparation of nanostructured WO3 thin films in order to be
used for photo-electrochemical (PEC) water splitting. In the
present study, WO3 photoelectrodes were synthesized by a
simple sol-gel method and the structural, morphological and
photoelectrochemical properties concerning current and
hydrogen production were studied.

under sonication. The excess of H2O2 was

Introduction catalytically decomposed by a Pt foil [5, 6] and
BORON-DOPED DIAMOND
In recent years,diamond ANODIC
various techniques OXIDATION
have been OF3CONTAMINANTS
then ml ethanol and 0.3gOF EMERGING
triton were willadded. The
Boron-doped
CONCERN
anodic oxidation of contaminants of emerging
WO3 photoanode was prepared by coating the
be filled
PP3-44
developed for the preparation of WO3 thin films in in FTO
by
concern electrode with the above solution by doctor blade
order to be used for photoelectrochemical water EAAOP4
splitting. WO1,3 M.
Z. Frontistis is Yazrda
an n-type2, semiconductor method and
and has1, D. Mantzavinos
Z. Klnc2, A. Katsaounis 1
. (1)the films of
Department were annealed for 10
Chemical
Engineering,
been suggested University of Patras, GR-26504
as an apropriate material Patras,
for PEC Greece,minutes at 500 C (heating rate(2)
zfrontistis@chemeng.upatras.gr. of 20 C/min). For
Kocaeli
cells University,
because of itsDepartment
narrow band of Chemical Engineering,
gap (Eg=2.7 eV), 41380,the Kocaeli,Turkey
construction of the cathode a commercial
which enables utilization of a portion of visible Endocrine
carbon disrupting
paste (Elcocarb compounds (EDCs) are an
C/SP (Solaronix)) was
0.3
spectrum. Moreover, it is stable against applied
importanton class FTO ofby emerging
doctor blading and was
environmental
o
photocorrosion and has satisfactory photoelectron contaminants
annealed at 450 posing
C. Onantheincreasing
top, Pt wasthreat in
deposited
0.25
transport properties [1-3]. aquatic
from a organisms
solution ofand micro-organisms, as well
Diamminedinitritoplatinum(II)
Many methods have been reported for preparing as ethanol
in to human and cast health.
on warm In FTO.this Thework, film thewas
0.2
nanocrystalline WO3 including hydrothermal, wet subsequently
electrochemical annealed
oxidation of oBisphenol
at 450 C. The quantity A and of
k min-1

2
organic
0.15 and inorganic routes, and thermal
Ethyl
Pt wasParaben on BDD
0.1 mg/cm . anode was investigated.
The photoelectrochemical
methods. In the present study, nanostructured WO3 The efficiency
measurements increases
were conductedwithincurrent density
a three-electrode
photoelectrodes
0.1 were synthesized by a simple sol- while the
configuration effect
using of
0.5M initial
NaClO pH4 as is almost
electrolyte.
gel method. The optical, structural, and Illumination
insignificant. was Themade in all cases
process favouredby a in Xe the
lamp
0.05
morphological properties of the films were providing
presence ofanchloride
intensitydueofto 100 mWcm-2 at ofthe
electrogeneration
analyzed by Diffuse Reflectance Spectroscopy position of the photoanode.
active chlorine species. Finally For the range of
(DRS),0 Scanning Electron Microscopy (SEM), and The surface morphology,
concentrations studied, the phase composition
reaction order with and
ultrapure water (XRD).
X-Ray Diffraction Humic acidIn addition,
wastewater the the optical
respect to band gap of
pollutant WO3 nanostructures
concentration shifts from were
photoelectrochemical (PEC) properties of the WO3 measured by SEM,
first to zeroth XRD,
as initial and DRS respectively.
concentration increases.
coatings were studied both for current and
hydrogen
Endocrineproduction.
disrupting compounds (EDCs) are an Results
stability and durability. The development of
important class of emerging environmental boron-doped diamond (BDD) has allowed these
Experimental
contaminants posing an increasing threat in The IV characteristics
drawbacks to be overcome, of theandWO 3 films were
electrochemical
aquatic organisms and micro-organisms, as well as studied bothtoin be
oxidation the dark
appliedand under simulated
effectively for solar
the
toHigh
humanpurity
health.tungsten
EDCs have powder
been shownwith to average
cause illumination.ofThe
degradation organicdark current doesnt deviate
contaminants
particle decline
cancer, sizes upinto sperm
10 microns
counts,(0.4abnormalities
g) was reactedin from the zero
In this work, potential until water electrolysis
the electrochemical oxidationthat of
with aqueous
male hydrogen
reproductive tract,peroxide (3 ml, 30%) [4]
slow development in occurs around
Bisphenol A and 2.2Ethyl
V vs. Ag/AgCl
paraben on BDD (Figureanode1).
infants and increase in the rate of testicular and was investigated.
breast cancer. EDCs are released into the More specifically the effect of current density,
environment from the urine and feces of humans
who take it as a medication. In light of these
217
supporting electrolyte concentration, electrolysis
duration, initial concentration, pH and water
1
 P O S T E R P R E S E N TA T I O N S - 3 rd D A Y

Oxidative Degradation
OXIDATIVE DEGRADATIONof Triton X-45 Using
OF TRITON Zero Valent
X-45 USING ZEROAluminum willIN
VALENT ALUMINUM be THE
filled
PRESENCE OF HYDROGEN PEROXIDE in by PP3-45
in The Presence of Hydrogen PeroxideAND
and PERSULFATE
Persulfate
EAAOP4
I. Arslan-Alaton1, T. Olmez-Hanci1, S. Khoei1, H. Fakhri1. (1) Istanbul Technical University, Environmental
Engineering Department, 34469 Maslak, Istanbul, Turkey, arslanid@itu.edu.tr

The oxidative degradation of aqueous nonionic surfactant Triton X-

45 by hydrogen peroxide (HP) and persulfate (PS) activated
Oxidative degradation in the presence of PS
nanoscale zero-valent aluminum (nZVAl) treatment systems was
SO4 - + studied. Triton X-45-spiked raw freshwater sample and domestic
wastewater treatment plant (DWTP) effluent were also subjected to
S2O82-
nZVAl/HP and nZVAl/PS treatments to study the effect of different
water matrices on Triton X-45 removal. Triton X-45 could be
nZVAl
efficiently degraded using HP and PS activated with nZVAl. Triton
H2O2
X-45 removal in pure water was complete after 90 min nZVAl/PS
treatment in pure water whereas only 76% removal was obtained by
+ HO nZVAl/HP treatment after 120 min (Triton X-45=2 mg/L;
nZVAl=1g/L; HP=0.25 mM; PS=0.5 mM; pH=3). Triton X-45
Oxidative degradation in the presence of HP
degradation was considerably retarded in the raw freshwater (TOC:
6.5 mg/L) sample and DWTP effluent (TOC: 10.1 mg/L) for both
treatment systems most probably due to their organic matter content.

Introduction contaminants. Several treatability studies have

Alkylphenol ethoxylates (APEOs) belong to the already demonstrated that HO - and SO4 --based
class of nonionic surfactants and are being used in AOPs are promising options for the efficient
the formulations of cleaning products, paints, ink treatment of aqueous APEOs [3, 4].
dispersants, textile and leather processing In recent years, innovative AOPs using zero-
STUDY OF HYDROGEN OXIDATION USING DIFFERENTIAL ELECTROCHEMICAL MASS
Study of hydrogen
(preparation,
SPECTROSCOPY
dyeing and
(DEMS) oxidation using Differential
finishing), pulp and paper valent metal,Electrochemical
such as zero-valent iron (ZVI) and
PP3-46
manufacturing, metal processing, cosmetics and zero-valent aluminum (ZVAl) to generate reactive
Mass Spectrometry (DEMS)
personal care products. Although their production oxygen species (ROS) such as HO and SO4 to -

hasJ.been
Vakros, A.within
restricted Katsaounis.
the EuropeanUniversity
Union due of Patras,
degrade and Department
even mineralize of Chemical
refractory organic
to concerns regarding their environmental safety pollutants have received increasing interest. For
Engineering, Patras, Greece, vakros@chemistry.upatras.gr.
and ecological impacts, APEOs are still known as instance, Stieber and coworkers [5] have reported
one of the most frequently used and commercially
In that
the pharmaceuticals
present study and the diagnostic agents of
model reaction were hydrogen
important surfactant groups. It has recently been effectively (indegraded
oxidation a by ZVI in theelectrolyte
polymer presence of O membrane
2
postulated that the anaerobic and/or aerobic at pH 3.0. Similar to ZVI,
electrocatalytic cell) wasit also
usedhastobeendemonstrate
reported the
metabolites of APEOs (namely alkyl phenols) are that ZVAlofpossessed the setcapacity to was
oxidize
functionality a new DEMS up which built up at
more estrogenic and/or mutagenic than the original organic of pollutants
University Patras (aintypicalacidicsetcondition
up is shown in onthethe left,
APEOs [1]. Due to their widespread use in a vast presence of O [6], and ZVAl/O showed a higher
adapted from [1]). During anodic overpotentials, the
2 2
variety of household and industrial applications, oxidationfaradaic
capacitycurrent
compared to that ofbyZVI/O 2 due of the
increased is followed a decrease
their concentrations in water, soil sediments and to the stability of aquo-complexed Al 3+
over a proton
ion signal of m/z=2 (hydrogen) most likely due to the
sewage sludge is well documented and has wider pH range. Lin et al. [7] have studied the
increased to significant levels in the recent past transfer through the Nafion membrane and an increase of the
oxidation efficiency, the influencing factors, the a sharp
signal of m/z=32 (oxygen). On the other hand,
[2]. The elimination of APEOs by chemical, degradation pathways and the reaction mechanism
increase of the signal of m/z=44 (CO2) was observed at
physical and biochemical (activated sludge) for 2,4-dichlorophenol
potentials higher than 1V using ZVAl/O2tointheacidic
and attributed oxidation of
treatment systems is rather slow and inefficient; condition.
hence alternative, advanced abatement processes the carbon cloth which is part of the anodic electrode.
The choice of alternative zero-valent metals with
are currently being suggested. Among these, higher efficiency of producing ROS depends
ozonation
DifferentialhasElectrochemical
been most extensively studied for
Mass Spectrometry crucially
Various onhydrogen-oxygen
the facile transfer of(H electrons
2:O2) to O2 or
mixtures
the oxidation
(DEMS) is of
a APEO-bearing
new techniquewaterswhichfollowed by
has been to initiallywith
saturated added H2oxidants
O were fed to the reaction
at the anodicsolution
part of
the application
developed of the
during advanced oxidation
last decades [1-3]processes
and used (i.e.
the hydrogen peroxide;
cell (catalyst: HP and
Pt/C with persulfate;
loading PS). In
0.5 mg/cm -2)
(AOPs).
to studyThese areelectrocatalytic
various enhanced chemical
systems.oxidation
DEMS this
with regard,
a totalZVAl can between
flowrate provide a100far and greater
400
processes
allows forinvolving the production
the on line detection ofof reaction
highly thermodynamic
cm3/min. Pure driving helium force for electron
saturated with watertransfer
was
reactive and hence non-selective species
products using mass spectrometry during (such as compared
used to feed to ZVI because Anode
the cathode. the reduction potential
and cathode was
hydroxyl radical; processes.
electrochemical HO and sulphate radical;
The typical SO4 -)
response of aluminum
separated withis a-1.67 V (Al
Nafion 1173+membrane
/Al), whereas whilethatboth
of
reacting
times of with organicduring
the systems as well
DEMS as studies
inorganic
are iron
wereis only -0.44 Vto(Fea2+/Fe).
connected The mechanism of
potentiostat/galvanostat
very short (<1 sec) giving the opportunity for safe (Autolab, PGSTAT 302 N). A mass spectrometer
conclusions on the reaction mechanistic steps. The
term differential is used to emphasize the ability 218
(Extrel, MAX 300-LG) was used to analyze the
anodic gases. The ion currents of m/z 2, 4, 18, 28,
1
of the technique to provide kinetic information. 32 and 44 were recorded during no reaction (by-
 D I S IN FE CTION ELE C TROC H E MIC A L P ROC E SS E S A OP S F OR E N E RG Y P ROD U C TI ON
R A D IA TION P ROC E S S E S

BENEFIT AND RISKS FROM ELECTROCHEMICAL ADVANCED OXIDATION PROCESSES

Benefit and risks from Electrochemical Advanced Oxidation
(EAOP) IN WATER TREATMENT THE (PER)BROMATE PROBLEM
will be filled
PP3-47
in by
Processes (EAOP) in water treatment The (per)bromate problem
EAAOP4
M.E.H. Bergmann1, J. Rollin1, T. Iourtchouk1, A.S. Koparal2. (1) Anhalt University, Bernburger Str. 55, 06366
Kthen/Anh., Germany, h.bergmann@emw.hs-anhalt.de. (2) Anadolu University, Eskiehir, Turkey.

The Graphical Illustration

(Figure, Scheme, etc.) should
not exceed the size of this area.
Seawater, several process waters and even drinking water may
contain bromide ions known for their high reactivity on mixed
metal oxide electrodes. It could be shown recently that, in addition,
boron doped diamond (BDD) anodes excellently oxidize traces
lower than 1 mg dm-3 or higher amounts of bromide ions to
bromine and bromate at a current density range up to 700 A m-2. In
case of bromine occurrence, formation of brominated organics
(THM, AOX, HAA etc.) is highly probable. Therefore, if treatment
processes are environmentally sensitive, bromide concentration
must be checked prior to applying the EAOP. If bromate
concentration is limited by law, analysis for bromate has to be
carried out. On the other hand, new bromate and perbromate
synthesis technologies can be easily performed using BDD anodes.

Focusing on methods of water treatment it was

found a few years ago that BDD anodes have the
ability to oxidize chloride to chlorate and
perchlorate [1,2]. Later it was found that formation
ofPHOTOCHEMICAL
bromate and perbromate is another option
DEGRADATION OF THEfor CARBAPENEM ANTIBIOTICS IMIPENEM AND
Photochemical
applying
MEROPENEM Degradation
these electrodes
IN AQUEOUS ofEspecially
the Carbapenem
[3]. SOLUTIONS anUNDERAntibiotics Imipenem
SOLAR IRRADIATION PP3-48
electrochemical
and Meropenem production
in Aqueous of perbromate
Solutions Under has Solar Irradiation
significant advantages
N.P. Xekoukoulotakis 1
, Y.compared
Bertakis2, A.with Agerachemical
,2
, A.B. Martnez-Piernas2, J.A. Snchez Prez2, A. Cabrera2 (1)
methods. On the ofother
Technical University Crete,hands,
Department chlorine- and
of Environmental Engineering, University Campus, Chania, Greece,
bromine-based by-products cannot
nikos.xekoukoulotaki@enveng.tuc. be accepted
(2) Research Centre at on Solar Energy (CIESOL), University of Almera-
higher
CIEMAT, Almera, Spain.in the form ClOx-. The
concentration
formation of halogenated organic by-product is an
additional problem when drinking water is treated
forOHHdisinfection NH
as well as in otherThe Advanced
photochemical Figureand1. the
Concentration behaviour
TiO 2 -assisted of the four
photocatalytic
main species in antibiotics,
discontinuous electrolysis (20C).
HN

Oxidation Processes [4,5]. This poster opposes

H

S degradation of two carbapenem namely imipenen and

advantages and disadvantages of BDD anodes for
N
O
OH meropenen, where studied in aqueous solutions
around 1%. Higher current density and higherunder solar
watersImipenem
containing bromide ions in the irradiation range 0.04-in a pilot plant. Both compounds were degraded
O

-3 bromide concentration accelerated bromate but not

1000 mg dm . relatively fast, perbromate
and these formation.
photochemical This istechniques wereon
an indication
effective for theirlimiting
elimination in aqueous solutions.
steps in the series of reactions shown as a
A 0.1 dm thermostatedMeropenem cell with rotating BDD
1,0

anode was used [1] at different temperatures (5 possible mechanism in Eq. 1.

0,8

Imipenem

35 C) and constant current densities. Typically,

0,6

(1)
C/C0

the rotation rate was 300 rpm. Real and synthetic

0,4

drinking water were used, partially with addition

0,2

of bromide. An expanded mesh mixed oxide

0,0
Similar limitation in the last steps from chlorate to
cathode served as counter electrode 4 mm below perchlorate was also detected in chloride oxidation
0 2 4 6 8 10
Quv, kJ/L

the rotating anode. Inorganic and organic by- on BDD.

products were analysed by IC/HPLC.
1. Introduction Surprisingly,
environment, it was found that
including at the same
surface waters,
Fig.In1 recent
shows years,
a typical time-dependent
a large number of compounds picture of molaric concentration the bromate-to-perbromate
groundwater and sediments [2]. Indeed, WWTPs
species
have concentration
been pointed during out as electrolysis
environmental of reaction yielded concern
are of particular to aslowerpotentialperbromate
hot spots for
sodium bromide without
contaminants of emerging concern (CEC) [1]. Theany supporting concentrations compared with the bromide[3].
the release of antibiotics into the environment
electrolyte.
incomplete Bromine forms of
elimination a maximum because it in electrolysis,
these contaminants In recent although
years severalbromatestudies
polarizes
have the been
reacts to bromate.
conventional Perbromate
wastewater is continuously
treatment plants has electrode performedmuch on higher than bromide.
the occurrence So,
and fate of changes
antibiotics
formed
provokedbut at relatively low current
their widespread efficiency of
distribution in the in mechanisms
in environmentalmust be concluded.
aqueous matrices and various
environment. However, scarce information is still classes of antibiotics have been detected in
available about the fate and environmental impact
of many of these contaminants.
219 concentrations in the range of ng/L to g/L [2-7].
Therefore, advanced treatment methods have been
1
 C O N F E R E N C E PA R T I C I PA N T S
Aguilar, Claudia Mexico
Alqabandi, Heba Kuwait
CO N F E Amat, Ana M
An, Taicheng
Spain
China
REN C E Andr onic, Luminita
Anschuetz, Franz iska
Romania
Germany
PART I Antoniou, Maria G . Cyprus
Greece
CI PAN T S
Antonopoulou, Maria
Ar e valo Per ez, Juan Carlos Mexico
Arslan Alaton, Idil Turkey
Autin, Oli vier United Kingdom
Aydin, Iberia Turkey
Batista Brandao, Yana Brazil
Bedia, Jor ge Spain
Belver, Car olina Spain
Berberidou, Chr ysanthi Greece
Ber gmann, Henr y Germany
Bianchi, Claudia Italy
Bianco, Angelica France
Bor ges, M.E. Spain
Bottr el, Sue Ellen Brazil
Bouhelassa, Mohammed Algeria
Brienza, Monica France
Brito, Juliana Fer r eira De Brazil
Br os, Paw el Poland
Byr ne, Tony United Kingdom
Byr ne, John United Kingdom
Cabr era, Alba Spain
Canonica, Silvio Switzerland
Capucci, Valentino Italy
Car ra, Ir ene United Kingdom
Casas Lopez, Jose L Spain
Chiha, Mahdi Algeria
Cotillas, Salvador Spain
Cr ousier, Clair e France
Cr uz Gonzalo, Angel Spain
Da vididou, Konstantina United Kingdom
De Coster, Jonas Belgium
De La Cr uz, Dur vel Mexico
De Luca, Antonella Spain
Dewil, R af Belgium
Diatczyk, Jar oslaw Poland
Diller t, R alf Germany
Ding , Wei China
Dionysiou, Dionysios D Usa
Dominguez, Sara Spain
Dostanic, Jasmina Serbia
DraSinac, Nina Slovenia
Dulova, Niina Estonia
Er ja vec, Bostjan Slovenia
Esplugas, Santiago Spain
Exposito, Antonio Jose Spain
Falaras, Polycar pos Greece
Farhat, Ali Australia

220
 EAAOP 2015
Faria, Joaquim Portugal
Fer nandez Ibanez, Pilar Spain
Fer nandez Mohedano, Angel Spain
Fer rari-Lima, Ana Maria Brazil
Fer r o, Giovanna Italy
Fior entino, Antonino Italy
Fotiou, Theodora Greece
Fr ontistis, Zacharias Greece
Fuentes Camar go, Iliana Mexico
Gar cia, Sara Spain
Gar cia-Munoz, Patricia Spain
Garkushe va, Natalya Russia
Gar rido, Isabel Spain
Giannakis, Stefanos Switzerland
Gimenes, Mar celino Brazil
Gmur ek, Mar ta Poland
Goncalves, Alexandra Portugal
Graca, Catia Brazil
Guimaraes, Jose Rober to Brazil
Haspulat, Bir can Turkey
Her mosilla, Daphne Spain
Hidalgo-Car rillo, Jesus Spain
Hobbs, Matthew United Kingdom
Houeida, Issa Hamoud France
Huang , W inn-Jung Taiwan
Ier volino, Giuse ppina Italy
Ince, Nilsun Turkey
Ioannou, Lida Cyprus
Janus, Magdalena Poland
Kala vr ouz iotis, Ioannis Greece
Kamis, Handan Turkey
Karaolia, Popi Cyprus
Karapati, Sofia Greece
Kitsiou, Vaso Greece
Klamer th, Nikolaus Canada
Klauson, Denis Estonia
Klein, Kati Estonia
Klementova, Sarka Czech Republic
Kondarides, Dimitris Greece
Konstantinou, Ioannis Greece
Konyar, Mehmet Turkey
Kriche vskaya, Marina Estonia
Kr ysa, Josef Czech Republic
Lambr opoulou, Dimitra Greece
Ledakowicz, Stanislaw Poland
Leong , Kah Hon Malaysia
Lianos, Panagiotis Greece
Liu, Fuzhen China
Liu, Huiling China
Lopez-Munoz, Maria-Jose Spain
Lua, Shun Kuang Singapore
Lucas, Mar co United Kingdom
Lyson-Sypien, Barbara Poland
Mac yk, Wojciech Poland

221
 C O N F E R E N C E PA R T I C I PA N T S
Madeira, Luis Miguel Portugal
Malato, Sixto Spain
Manier o, Milena Brazil
Mantza vinos, Dionissios Greece
Mar ce Escale, Mir eia Spain
Mar celino, R afaela Brazil
Marinas, Alber to Spain
Marinho, Belisa Portugal
Mar tin De Vidales, Maria Jose Spain
Mar tinez Castillejo, Fer nando Spain
Mar ugan, Ja vier Spain
Mason, Timothy United Kingdom
Matvee va, Valentina Russia
Medina, Juan Mexico
Meric, Sur eyya Turkey
Meshr ef , Mohamed Canada
Mohammadi Aghdam, Alir eza Italy
Molina, R aul Spain
Morales-Mejia, Julio Cesar Mexico
Morawski, Antoni Poland
Morsy, Mohamed Saudi Arabia
Moz ia, Sylwia Poland
Muf f , Jens Denmark
Nguyen, Hoang Australia
Ning , Xunan China
Oh, Wen-Da Singapore
Or ellana, Maria Argentina
Or ge, Carla Portugal
Ozkal, Can Burak Turkey
Pandiri, Manjula Israel
Papailias, Ilias Greece
Par rino, Francesco Italy
Pawlat, Joanna Poland
Pazdz ior, Katarzyna Poland
Paz os, Mar ta Spain
Pintar, Albin Slovenia
Plakas, Konstantinos Greece
Poulios, Ioannis Greece
Pr onina, Natalja Estonia
Pulgarin, Cesar Switzerland
R ace, Mar co Italy
Rey, Ana Spain
Ribeir o, R ui S . Portugal
Ri ver o, Maria J. Spain
Rizz o, Luigi Italy
Rodrigo, Manuel Andr es Spain
Rodrigues-Silva, Caio Brazil
Rodriguez, Ser gio Spain
Roman-Sanchez, Isabel Maria Spain
Rosa-F., Ver cher Per ez Spain
Rosmaninho, Mar celo Brazil
Sable, Shailesh S . Spain
Saez, Cristina Spain
Sag gior o, Enrico Brazil

222
 EAAOP 2015
Sakkas, Vasilios Greece
Salgado, Pablo Chile
Salomatova, Victoria Russia
Sanchez Per ez, Jose Antonio Spain
Sanchis, Sonia Spain
Sanr oman, Ma Angeles Spain
Sans Maz on, Car men Spain
Segura, Yolanda Spain
Selcuk, Huseyin Turkey
Selishche v, Dmitr y Russia
Sfaelou, Sta vr oula Greece
Shahzad, Naeem Pakistan
Silahua, Adib Mexico
Silva, Mar cela Brazil
Skalska, Kinga Poland
Skouras, Geor gios Greece
Solymosi, Frig yes Hungary
Stucchi, Mar ta Italy
Subr t, Jan Czech Republic
Sz eto, Wai Hong Kong
Tantis, Iosif Greece
Tijani, Jimoh Oladejo South Africa
Tisler, Tatjana Slovenia
Tobajas, Montser rat Spain
Todor ova, Nadia Greece
Tor r es Tor r es, Jose Gilber to Mexico
Tor r es-Palma, Ricardo A. Colombia
Trapalis, Christos Greece
Trapido, Marina Estonia
Tsoumachidou, Sophia Greece
Urbano, Vanessa Brazil
Ur tiaga, Ane Spain
V A, Sijumon India
Vakr os, John Greece
Van Eyck, Kwinten Belgium
Vasilaki, Evangelia Greece
Venieri, Danae Greece
Ver ma, Anoop India
Villegas, Paola Colombia
Villota, Natalia Spain
Wan Mansor, Wan Salida United Kingdom
Wei, Zhishun Japan
Wohlmuth Da Silva, Salatiel Brazil
Xekoukoulotakis, Nikolaos Greece
Yu, Jung-Hoon Korea
Zer efos, Christos Greece
Zhang , Ying Canada
Zielinska-Jur ek, Anna Poland
Ziylan Ya vas, Asu Turkey

223
 Conference Program & Book of Abstracts
CONFERENCE PROGRAM
AND BOOK OF ABSTRACTS
w w w.e aaop4.com
CONFERENCE
PROGRAM AND
BOOK OF ABSTRACTS

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EAAOP