This article was downloaded by: [Romanian Ministry Consortium]

On: 7 July 2010

Access details: Access Details: [subscription number 918910071]
Publisher Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-
41 Mortimer Street, London W1T 3JH, UK

Environmental Technology
Publication details, including instructions for authors and subscription information:
http://www.informaworld.com/smpp/title~content=t791546829

Titanium dioxide-mediated photocatalysis of a biorefractory chloroether in

secondary wastewater effluent
Richard J. Wattsa; Sungho Kongb; Margaret P. Orrc; Glenn C. Millerd
a
Department of Civil and Environmental Engineering, Washington State University, Pullman, WA,
USA b Department of Chemical Engineering, Hanyang University, Seoul, South Korea c Dow Chemical,
Midland, MI, USA d Department of Environmental and Resource Sciences, University of Nevada, Reno,
NV, USA

To cite this Article Watts, Richard J. , Kong, Sungho , Orr, Margaret P. and Miller, Glenn C.(1994) 'Titanium dioxide-
mediated photocatalysis of a biorefractory chloroether in secondary wastewater effluent', Environmental Technology,
15: 5, 469 475
To link to this Article: DOI: 10.1080/09593339409385451
URL: http://dx.doi.org/10.1080/09593339409385451

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf

This article may be used for research, teaching and private study purposes. Any substantial or
systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or
distribution in any form to anyone is expressly forbidden.

The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses
should be independently verified with primary sources. The publisher shall not be liable for any loss,
actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly
or indirectly in connection with or arising out of the use of this material.
 Environmental Technology, Vol. 25. pp 469-475
Publications Division Selper Ltd., 1994

TITANIUM DIOXIDE-MEDIATED
PHOTOCATALYSIS OF A BIOREFRACTORY
CHLOROETHER IN SECONDARY WASTEWATER
EFFLUENT

RICHARD J. WATTS 1 *, SUNGHO KONG2, MARGARET P. ORR 3 AND GLENN C. MILLER 4

1
Department of Civil and Environmental Engineering, Washington State University,
Pullman, WA 99164-2910, USA
2
Department of Chemical Engineering, Hanyang University, Seoul, South Korea
3
1078 Building, Dow Chemical, Midland, MI 48667, USA
4
Department of Environmental and Resource Sciences, University of Nevada, Reno, NV 89557, USA

(Received 20 September 1993; Accepted 24 January 1994)

Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010

ABSTRACT

The effects of pH, soluble chemical oxygen demand (COD), suspended solids, and ammonia -
nitrogen on the titanium dioxide (TiO2)-photocatalyzed treatment of l,2-bis(2-
chloroethoxy)ethane (BCEE) were investigated in secondary wastewater effluent. The
photochemical oxidation of BCEE was pH dependent and most rapid at pH 4. Sequential increases
in soluble COD were provided by the addition of filtered wastewater influent, and suspended
solids were varied by adding sonicated mixed liquor. Photocatalysis rates were inversely
proportional to soluble COD concentrations, and the reaction was completely quenched at a
soluble COD of 164 mg l-1. Suspended solids in concentrations up to 90 mg l-1 and ammonia -
nitrogen (0.83-70 mg 1-1) did not affect the photochemical oxidation of BCEE. The results show
that, of the water quality characteristics investigated, only soluble COD affected TiO2-mediated
photocatalysis of the chloroether under the conditions of this study. Therefore, photocatalytic
treatment of biorefractory compounds in complex matrices, such as wastewater effluents, may be
possible if the concentrations of quenching species associated with the soluble COD are not
significantly high.

Keywords: Titanium dioxide, photocatalysis, l,2-bis(2-chloroethoxy)ethane, wastewater, industrial

wastes

INTRODUCTION to its conduction band. As a result, an electron

Heterogeneous photocatalysis has recently
received widespread attention for the degradation
of biorefractory organics, the oxidation of
disinfection by-products, and the inactivation of
microorganisms (1,2). A number of
photocatalysts have been investigated including
titanium dioxide (TiC^), iron oxides, zinc oxide,
and cadmium sulfide. Titanium dioxide has
received the most attention because to its
photocatalytic activity, conservative nature, and
low cost.
Irradiation of TiC>2 suspensions by near-uv
light, and the subsequent absorption of photons at
the photocatalyst surface, induces the transfer of
an electron from the photocatalyst's valence band
vacancy, or hole, is left in the valence band. This
hole-electron pair process provides a
mechanism by which TiO2 -photocatalysis may
proceed by both electron transfer and hydroxyl
radical mechanisms (3, 4).
Extensive research has focused on the
mechanisms and pathways of TiO 2
photocatalysis. Mechanistic investigations using
trichloroethylene (3, 4), 2-bromo-2-chloro-l,l,l-
trifluoroethane (5), and a variety of refractory
organics (6) have shown that TiC>2 -mediated
photocatalysis has potential for degrading and
mineralizing refractory organics through
various oxidative and reductive processes,
However, most studies have used deionized water
as a matrix, and only one investigation

469
 documented the use of TiO2 -mediated
photocatalysis in wastewater (7). If TiO2
photocatalysis is to achieve widespread use, its
effectiveness in more complex matrices
requires investigation. Therefore, the purpose of
this research was to determine the effects of
common wastewater constituents (pH, soluble
chemical oxygen demand, suspended solids, and
NH3-N) on the TiC>2 -mediated photocatalytic
treatment of a biorefractory organic
contaminant.
MATERIALS AND METHODS
Materials
Anatase (n-TiC>2), obtained from Fisher
Scientific, was used without modification. 1,2-
Bis(2-chloroethoxy)ethane (BCEE) was purchased
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010
from Aldrich; it was chosen as a model
contaminant because of its biorefractory nature,
low volatility, and high water solubility.
Unchlorinated effluent was obtained from the
secondary clarifiers at the city of Stead, Nevada
wastewater treatment plant, an extended aeration
activated sludge facility with Q = 3790 m3 day 1 . It
was stored at 4C and used within two days. The
effluent was aerated for 15 min and brought to
room temperature 24 h prior to each experiment.
Routine nutrient analyses were performed (8),
and the average concentrations are listed in
Table 1.
Preparation of TiO2 Suspensions
Anatase (20 g) was added to 1 1 of water
drawn from a Milli-Q ion exchange system
(Millipore Corporation) and then sonicated for
30 min. The suspension was concentrated by
evaporation (103'C) for 24 h and allowed to settle
for 2 h. The supernatant was decanted, and the
Table 1. Nutrient data for the unchlorinated
secondary effluent.
Parameter Value
pH 7.1
Total Alkalinity 65 mg I"1 as CaCO3
Suspended Solids 42 mg I"1
Total Dissolved Solids 313 mg I"1
Ammonia-N 0.83 mg I' 1
Nitrite-N 1.3 mg I"1
Nitrate-N 13.4 mg I"1
Orthophosphate 1.2 mg I' 1
470
concentration of the stock titanium dioxide was
determined as total solids (8). Aliquots of 1 ml of
the suspension were added to the wastewater
effluent (100 ml) to provide a final titanium
dioxide concentration of 250 mg I" 1 . The
suspensions were not sonicated during
photocatalytic experiments.
Light Source
Wastewater-TiC>2 suspensions were
irradiated with Westinghouse F40BL lights,
which have an emission spectrum below 400 nm
(the range at which TiO2 absorbs most strongly)
that corresponds to the solar spectrum. The light
intensity was monitored using a Spectroline long
wave (320-380 nm) UV intensity meter to insure a
uniform and constant light flux under the bank of
lamps. The lights were placed 11.3 cm above the
surface of the water.
Kinetic Studies with l,2-bis(2-chloroethoxy)
ethane
The photocatalytic treatment of 40 mg I' 1
BCEE was investigated in unchlorinated
secondary effluent containing TiO2 (250 mg I' 1 )
under F40BL lights. The reactions were
conducted in 10 cm diameter x 4 cm deep
borosilicate glass dishes using 100 ml of
effluent; the resulting water depth was 1.3 cm.
The pH, soluble chemical oxygen demand (COD),
suspended solids (SS), and ammonia-nitrogen
(NH3-N) were varied to determine their effects
on BCEE photocatalysis rates.
The effect of pH on BCEE photocatalysis
rates was determined by adjusting the pH of the
effluent containing BCEE (40 mg I"1) and TiO2
(250 mg I'1) from 4 to 10 by 1-pH unit intervals
using HC1 or NaOH. The effect of soluble COD on
BCEE photocatalysis rates was investigated using
tap water or GF/C-filtered effluent spiked with
filtered wastewater influent to provide soluble
COD concentrations up to 90 mg I' 1 . To determine
the effect of suspended solids, mixed liquor from
the city of Stead wastewater treatment plant was
added to GF/C-filtered effluent in concentrations
up to 90 mg I' 1 . The mixed liquor solids were
resuspended and washed three times with
deionized water, and the final suspension was
sonicated for 30 min prior to adding the solids to
the effluent. The effect of ammonia was
determined by adding NH3-N (as NH4C1) at final
concentrations from 0.83 to 70 mg I"1 to the
filtered secondary effluent.
Aliquots were collected during all
 experiments at 0, 15, 30, 60, and 90 min. The
aliquots were extracted with ethyl acetate and
analyzed by gas chromatography. Control
samples without anatase and dark controls with
anatase were run in parallel.
Analyses
Ammonia-nitrogen concentrations were
monitored using low- and high-level indophenol
methods (9). Chemical oxygen demand was
analyzed by the low-level closed reflux procedure
(8). Ethyl acetate extracts were analyzed for
BCEE with a Hewlett-Packard 5890 gas
chromatograph fitted with a 15 m x 0.53 mm DB-1
capillary column and flame ionization
detection. The nitrogen carrier gas flow rate was
10 ml min" 1 ; chromatographic conditions
included an initial oven temperature of 60C,
final oven temperature of 180cC, program rate of
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010
15C min' 1 , injector temperature of 180C, and
detector temperature of 190C.
RESULTS AND DISCUSSION
Experimental data obtained throughout this
study showed exponential loss of BCEE. Plots of
the natural logarithm of BCEE concentration as a
function of time yielded straight lines with r 2 >
0.90 which indicates pseudo first-order kinetics.
0.01-
0.008 -
0.006-
0.004 -
0.002 -
1 1.
3 4 5 6 7
Figure 1. First-order rate constants for BCEE degradation as a function of pH.
Other studies (4, 6) have shown empirical first-
order loss of organic substrates during
heterogeneous photocatalysis, and such
experimentally-determined rate constants were
used in this study to compare the treatment of
BCEE in the presence of different wastewater
constituents.
The effect of pH on the photocatalytic
treatment of BCEE is shown in Figure 1. These
data show that the removal of BCEE was dependent
on pH; the most effective treatment was at the
lower pH regimes with the highest rate constant
for BCEE loss (0.009 min"1) at pH 4. Other studies
have shown that photocatalysis rates are pH
dependent; for example, the Ti02-photocatalyzed
oxidation of phenol was also greatest at pH 4 (10).
The alkalinity of the effluent was 65 mg I' 1 as
CaCO3 (0.65 mM) which consists primarily of
HCO3- at neutral pH (Table 1). The higher
photocatalysis rates at the lower pH regimes may
be due to the loss of HCO3' as CO2 because the
equivalence point between the two species is at a
pH of approximately 4.5. Bicarbonate is an
important hydroxyl radical quencher that can
significantly lower TiO2 -mediated
photocatalysis rates (1, 11). In addition, other
species commonly found in wastewater, such as
weak organic acids (in which the pKa varies as a
function of chain length), may also affect the pH
response of photocatalytic activity (11, 12).
1 1 I I I
8 9 1 0 11
PH
471
 The recovery of BCEE in control solutions
was greater than 95%, indicating that the loss of
BCEE by volatilization or sorption was minimal.
A pH of 6 was chosen for subsequent experiments
because it provided a relatively high rate of
reaction (Figure 1) and is representative of the
pH of industrial and municipal waste streams.
First-order rates for BCEE degradation as a
function of soluble wastewater COD are shown in
Figure 2. Photocatalytic rates of BCEE
degradation were inversely proportional to
soluble COD concentrations. 1,2-Bis(2-
chloroethoxy)ethane degraded most rapidly at the
lower COD concentrations (k = 0.029 min'1 with
COD of 10 mg I"1), and the oxidizing species
generated by the illumination of titanium dioxide
were completely quenched at a soluble COD
concentration of 164 mg I' 1 (Figure 2). The
effects of hydroxyl radical quenchers have been
well documented (11-13). Common quenchers,
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010
such as organic acids, alcohols, ascorbic acid,
and amino acids, react with hydroxyl radicals at
rates > 109 M'1 sec -1 (14). These species are
commonly found in municipal and industrial
wastewaters, and may affect the oxidative
treatment of these waste streams if they are
present in high enough concentrations.
A reduction of 50% in total organic carbon
(TOC) and BCEE was observed within 15 min
(Figure 3). After 90 min, the oxidation of BCEE to
0.03-
I
0 50
Soluble COD (mg I 1 )
Figure 2. Effect of soluble COD on the TiO 2 -mediated photocatalysis of BCEE.
472
below its detection limit with over 60% reduction
in TOC were observed, which is expected because
of the nonspecific nature of the hydroxyl radical
oxidations.
The TiO2 -mediated photocatalytic treatment
of BCEE was unaffected by suspended solids
concentrations up to 90 mg I'1 (Figure 4). These
data show that suspended solids did not
significantly reduce the available light, quench
the titanium dioxide excited states, or reduce the
availability of the photochemically-produced
reactants which oxidize BCEE when short light
paths (e.g., 1.3 cm) are used. Although suspended
solids concentrations up to 90 mg I' 1 were
evaluated, the soluble COD concentrations were
nearly equal (80-100 mg I"1) because the COD
added through the addition of the sonicated mixed
liquor suspended solids was primarily in the
particulate state. The rate constants for BCEE
removal shown in Figure 4 range from 0.004 to
0.006 min'1. These results are in agreement with
the first-order rate constant of 0.006 min' 1
obtained for the soluble COD concentration of 92
mg I"1 without the addition of suspended solids
(Figure 2).
Figure 5 describes rates of TiO2-mediated
BCEE photocatalysis as a function of NH3-N
concentration. These data show that the
photocatalytic degradation of BCEE was
unaffected by NH3-N concentrations up to 70 mg
100 150 200
 300" -[ 50

250 -,
40

200"
09
- 30
I 150"
3
0Q
- 20
100"

50" - 10
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010

0 20 40 60 80 100
Time (min)
Figure 3. Titanium dioxide-mediated photocatalysis of BCEE and total organic carbon in secondary
wastewater effluent.

0.008 -1

0.007 -

0.002-

0.001 "

0 I I 1
20 40 60 80 100
Suspended Solids (mg I'1)
Figure 4. Effect of suspended solids on TiO2-mediated BCEE photocatalysis in secondary
wastewater effluent.

I' 1 . The concentrations of NO3-N and NO2-N did provided similar results; for example, Langlais
not increase during these reactions, which et al. (15) reported that ozone-generated hydroxyl
confirms that NH3-N was not oxidized during the radicals reacted slowly with NH3-N, especially
photocatalytic treatment. Other studies have at neutral pH--the regime at which the

473
 0.008 -

0.007 -

0.006 -

0.005 -

0.004 -

0.003 -

0.002 -

0.001 -

0
i I
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010

0
I I
10 20 30 40 50 80
60 70

Figure 5. Effect of NH3-N on BCEE photocatalysis by TiO2 suspensions in secondary wastewater

effluent.

concentration of NH4+ predominates over NH3.
The results of this research show that
significant rates of TiO2 photocatalysis may be
achieved in dilute wastewater at neutral pH,
although higher rates were found at acidic pH
regimes. Soluble COD, which is common to
nearly all municipal and industrial waste
streams, significantly affected the TiO2 -
photocatalyzed treatment of BCEE. Alcohols,
organic acids, ascorbic acid, and other quenchers
and scavengers of oxidants are common to
municipal wastewater, and probably caused the
decrease in BCEE removal with increased
soluble COD concentrations. If a photocatalysis
reactor is designed with a short pathway for light
absorption, suspended solids will not
significantly affect heterogeneous photocatalysis
rates. In addition, NH3-N concentrations to 70
mg I' 1 did not affect the rate of photocatalytic
BCEE removal when the reaction is conducted at
near-neutral pH.
If TiO2 photocatalysis is to be applied to
more complex matrices than previously
investigated, the results of this study show that
soluble COD is the most significant water quality
characteristic that controls TiO2 -mediated
photocatalysis. Therefore, TiO 2 -mediated
photocatalysis of biorefractory compounds in
complex matrices, such as wastewater, may be
practical if the quenching and scavenging
compounds characteristic of soluble COD are
present in low concentrations.
ACKNOWLEDGEMENTS
Funding for this research was provided by
the U.S. Geological Survey through Grant No. 14-
08-0001-G1238.

REFERENCES

1. Ollis D.F., Contaminant degradation in water. Environ. Sci. Technol., 19, 480-484 (1985).
2. Matsunaga T., Tomoda R., Nakajima, T., Nakamura N. and Komino T., Continuous-sterilization
system that uses photosemiconductor powders. Appl. Environ. Microbiol., 54, 1330-1333 (1988).
3. Pruden A.L. and Ollis D.F., Degradation of chloroform by photoassisted heterogeneous catalysis
in dilute aqueous suspensions of titanium dioxide. Environ. Sci. Technol., 17, 628-631 (1983).

474
 4. Glaze W.H., Kenneke J.F. and Ferry J.L., Chlorinated byproducts from the TiO 2 -mediated
photodegradation of trichloroethylene and tetrachloroethylene in water. Environ. Sci. Technol.,
27, 177-184 (1993).
5. Bahnemann D.W., Monig J. and Champman R., Efficient photocatalysis of the irreversible one-
electron reduction of halothane on platinized colloidal titanium dioxide in aqueous suspension. J.
Phys. Chem., 91, 3782-3788 (1987).
6. Matthews R.W., Solar-electric water purification using photocatalytic oxidation with TiO2 as a
stationary phase. Solar Energy, 38, 405-413 (1987).
7. Carey J.H. and Oliver G.B., The photochemical treatment of wastewater by ultraviolet irradiation
of semiconductors. Water Pollut. Res. Canada, 15, 157-184 (1980).
8. Standard Methods for Examination of Water and Wastewater, 18th ed., American Public Health
Association/American Water Works Association/Water Environment Federation, Washington
D.C. (1992).
9. Adams V.D., Water and Wastewater Examination Manual. Lewis Publisher, Inc. Chelsea,
Michigan (1990).
10. Wei T., Wang Y. and Wan C., Photocatalytic oxidation of phenol in the presence of hydrogen
peroxide and titanium dioxide powders. J. Photochem. Photobiol. A: Chem., 55, 115-126 (1990).
11. Okamoto K., Yamamoto Y., Tanaka H., Tanaka M. and Itaya A., Heterogeneous photocatalytic
decomposition of phenol over TiO2 powder. Bull. Chem. Soc. Jpn., 58, 2015-2022 (1985).
12. Okamoto K., Yamamoto Y., Tanaka H. and Itaya A., Kinetics of heterogeneous photocatalytic
Downloaded By: [Romanian Ministry Consortium] At: 09:24 7 July 2010

decomposition of phenol over anatase TiO2 powder. Bull. Chem. Soc. Jpn., 58, 2023-2028 (1985).
13. Matthews R.W., Kinetics of photocatalytic oxidation of organic solutes over titanium dioxide.
Water Res., 24, 653-660 (1988).
14. Dorfman L.M. and Adams G.E., Reactivity of the hydroxyl radical in aqueous solutions. NSRDS-
NBS 46 (1973).
15. Langlais B, Reckhow D.A. and Brink D.R., Ozone in Water Treatment: Application and
Engineering. Lewis Publishers, Inc. Chelsea, Michigan (1991).

475