Development of a sustainable

material for adsorptive removal of

Arsenic

Seminar on
Sustainable Technologies for water treatment
Madan Mohan Malaviya University of Technology, Gorakhpur
Prof. Bikash Mohanty 8th March, 2019
Dept. of Chemical Engg., IIT Roorkee
 Introduction

Arsenic’s history in science, medicine and technology has been

overshadowed by its notoriety as a poison in homicides. Arsenic is
viewed as being synonymous with toxicity. Dangerous arsenic
concentrations in natural waters is now a worldwide problem and often
referred to as a 20th–21st century calamity.

Arsenic which ranks 20th in natural abundance, is a natural component of

the earth’s crust(0.00005% of the earth’s crust) and is widely distributed
throughout the environment in the air, water and land. It is highly toxic in its
inorganic form

Dinesh Mohana, Charles U. Pittman Jr. ,”Arsenic removal from water/wastewater using adsorbents—A critical review”, Journal of Hazardous Materials 142 (2007) 1–53

2
How Arsenic enters into human system
Arsenic is mobilized by natural weathering reactions, biological activity, geochemical reactions,
volcanic emissions and other anthropogenic activities. Soil erosion and leaching contribute to
612 × 108 and 2380 × 108 g/year of arsenic, respectively, in dissolved and suspended forms in the
oceans
Most environmental arsenic problems are the result of mobilization under natural conditions.
However, mining activities, combustion of fossil fuels, use of arsenic pesticides, herbicides, and
crop desiccants and use of arsenic additives to livestock feed create additional impacts

Fish, shellfish, meat, poultry, dairy products and cereals can also be dietary sources of arsenic, although exposure from
these foods is generally much lower compared to exposure through contaminated groundwater. In seafood, arsenic is
mainly found in its less toxic organic form. Many industrial chemical processes such as processing of glass, pigments,
textiles, paper, metal adhesives, wood preservatives, alloying and ammunition also use Arsenic. Arsenic is also used in the
hide tanning process and, to a limited extent, in pesticides, feed additives and pharmaceuticals

People who smoke tobacco can also be exposed to the natural inorganic arsenic content of tobacco because tobacco
plants can take up arsenic naturally present in the soil. Also, in the past, the potential for elevated arsenic exposure was
much greater when tobacco plants used to be treated with lead arsenate insecticide

3
 Introduction Problem of As contamination
As contamination (Globally)

70
Affected countries: Argentina, Bangladesh,Cambodia, Chile, China, India, Mexico,
Nepal, United States of America, New Zealand, Taiwan, Philippines, Hungary, Romania,
Croatia, Serbia, Vietnam etc.
countries
Estimated population affected: A 2014 study by WHO found that over 200 million
people in more than 70 countries are seriously affected by arsenic poisoning of drinking
water1.

Amini et al 2008 Environ. Sci. Technol. 42(10) 3669-3675.

1Royal Geographical Society, Annual International Conference 2007

4
 Introduction Problem of As contamination (cont.)

As contamination (In India)

153
Affected states of India: West Bengal, 19% of
U.P., Jharkhand, Bihar, Assam and Indians
Manipur, Chhattisgarh etc. drink
Districts

21
About 239 million people across 153 water
districts in 21 states drink water that with
contains unacceptably high levels of lethal
States arsenic . In effect, they are being levels of
239 slowly poisoned. Calculations based
on information provided by the water
arsenic
UP has the largest
Million people resources ministry in response to a
number of
question in the Lok Sabha reveal that people, over 70
65% of Assam’s population, or about million, exposed
21 million people is drinking arsenic- to arsenic-
contaminated water, while it’s 60% in contaminated
in Bihar and 44% in West Bengal. water

https://timesofindia.indiatimes.com/india/19-of-indians-drink-water-with-lethal-levels-of-arsenic/articleshow/62226542.cms

5
 Introduction Arsenic Hazards
Exposure to moderate to high (more than 50 µg/l) levels of arsenic in drinking
water is associated with an increased risk of lung, bladder and skin cancer, as
well as with numerous reproductive, cardiovascular, neurological, skin lesion,
diabetes and respiratory diseases, and with increased all-cause mortality.
Chronic exposure to arsenic is also associated with deficits in children’s cognitive
and motor functions.

As (+3) is more toxic than As (+5) and Inorganic As is generally more toxic than organic As
As (III) can easily bind with specific proteins and transported into the cell. On the other hand,
As(V) cannot reach inside the cell by this mechanism. As(V) get to reduced to +3 state for this
transport to occur. Also, As(III) can bind with -SH group present in many proteins, enzymes, thus
inhibiting their activity. Most forms of organo aresnicals such as arsenobetaine are metabolized
by our body and eliminated via urine. Further, inorganic forms are better absorbed by body than
organic arsenic.

6
Introduction Effects of As contamination

Effects of
Arsenic

Source: www.aquabrightindia.com Source: www.amitesting.com

Source: www. sengupta-research.web.lehigh.edu

7
 Arsenic Chemistry

Arsenic is present in groundwater as As(III) and As(V) forms in different proportions. Most
treatment methods are effective in removing arsenic in pentavalent form and hence include
an oxidation step as pre-teatment to convert arsenite to arsenate. Arsenite can be oxidized by
oxygen, ozone, free chlorine, hypochlorite, permanganate, hydrogen peroxide and fulton's
reagent but Atmospheric oxygen, hypochloride and permanganate are commonly used for
oxidation in developing countries:

H3AsO3 + ½ O2 = H2AsO4- + 2 H + (1)

H3AsO3 + HClO = HAsO4-- + Cl- + 3H+ (2)
3H3AsO3 + 2KMnO4 = 3HAsO4-- + 2MnO2+ + 2K+ + 4H+ + H2O (3)

Air oxidation of arsenic is very slow and can take weeks for oxidation (Pierce and Moore, 1982)
but chemicals like chlorine and permanganate can rapidly oxidize arsenite to arsenate under wide
range of conditions.

8
Arsenic Chemistry Arsenic exists in the −3, 0,
+3 and +5 oxidation states
Two forms are common in natural
waters: arsenite (AsO3 3−) and
arsenate (AsO4 3−), referred to as
arsenic(III) and arsenic(V).
Pentavalent (+5) or arsenate
species are: AsO4 3−, HAsO4 2−,
H2AsO4− while trivalent (+3)
arsenites include As(OH)3,
As(OH)4−,AsO2OH2−and AsO3 3−.
Pentavalent species predominate
and are stable in oxygen rich
aerobic environments. Trivalent
arsenites predominate in
moderately reducing anaerobic
environments such as
groundwater.
 Comparison of main arsenic removal techniques
Major oxidation /precipitation Advantages Disadvantages
technologies
Air oxidation Relatively simple, low-cost but slow process; in situ Mainly removes arsenic(V)
arsenic removal; also oxidizes other inorganic and and accelerate the
organic constituents in water oxidation process
Chemical oxidation Oxidizes other impurities and kills microbes; relatively Efficient control of the pH
simple and rapid process; minimum residual mass and oxidation step is
needed

Major coagulation /co- Advantages Disadvantages

precipitation technologies
Alum coagulation Durable powder chemicals are available; relatively Produces toxic sludges; low removal
low capital cost and simple in operation; effective of arsenic; pre-oxidation may be
over a wider range of pH required
Iron coagulation Common chemicals are available; more efficient Medium removal of As(III);
than alum coagulation on weigh basis sedimentation and filtration needed
Lime softening Chemicals are available commercially Readjustment of pH is required
Comparison of main arsenic removal techniques contd….
Major sorption and ion- Advantages Disadvantages
exchange technologies
Activated alumina Relatively well known and commercially Needs replacement after four to five regeneration
/Activated Carbon available
Iron coated sand Cheap; no regeneration is required; Not standardized; produces toxic solid waste
remove both As(III) and As(V)
Ion-exchange resin Well-defined medium and capacity; pH High cost medium; high-tech operation and
independent; exclusive ion specific maintenance; regeneration creates a sludge disposal
resin to remove arsenic problem; As(III) is difficult to remove; life of resins

Major membrane technologies Advantages Disadvantages

Nanofiltration Well-defined and high-removal efficiency Very high-capital and running cost, pre-
conditioning; high water rejection
Reverse osmosis No toxic solid waste is produced High tech operation and maintenance
Electrodialysis Capable of removal of other contaminants Toxic wastewater produced
Other techniques: Foam flotation;
Solvent extraction; Bioremediation
 Comparison of some techniques available in India

Type of Principal of
Techniques Remarks Reference
system separation

For Arsenic removal

Available Techniques

Department Coagulation- Fine powder of alum

of public and potash is added,
health Two bucket flocculation- Tahura et
engineering system Unable to reduce up
sedimentation and to desire level 0.05 al. 2001
(DPHE),
Bangladesh filtration mg/L.

As(III) removal is not

Adsorption Jalil and
B.E. College , Adsorption on very good;
column fitted Ahmed
Howrah activated alumina Adsorption capacity:
with tube well 2001.
1.41 g/kg

12
 Comparison of some techniques available in India

Type of Principal of
Techniques Remarks Reference
system separation

For Arsenic removal

Available Techniques

Down flow Adsorption on Cost of chemical is

Pal Trockner
fixed bed granular ferric very high; Capacity: Pal 2001
ADSORPAS®
adsorbent hydroxide (GAFH) 15-30 g/kg

Four
chamber Oxidation-
FeCl3, Red hematite, PHED,
PHED, West filter Coagulation-
quartz, sand, activated West
Bengal attached sedimentation
alumina added Bengal
with tube and filtration
well
 Comparison of some techniques available in India
Type of Principal of
Techniques Remarks Reference
system separation
For Arsenic removal
Cost is high (Rs 443000 +
Available Techniques

Activated
RPM Two 20000 per charge for
enhanced hybrid Ahmed et al.
Marketing chamber treating 200000 liters of
alumina 2005
Pvt. Ltd. ed unit water as in 2001) (Rs
adsorption
2.31 per liter)
Web 2
Anir Fixed bed GFH(granulated Typical residual mass of
(Technology not
Engineers Inc adsorber ferric hydroxide) GFH is 5-25 ppm
disclosed)
SOES-
Tablet
Jadhavpur Consists of mud jar, filter
and filter - Das et al. 2001
University candle and tablet
candle
and CSIR

14
 As contamination in India : Socio-economic status of affected
people and need for cheaper adsorbents

Clay filter can reduce the

arsenic concentration to or
below 50 ppb only when
Aso value < 100 ppb
Clay filter
Dug well
Collection of ground Cheap alternative sources / technique for
water as drinking water drinking water

As (µg/l) F (mg/l) Place (Patel et al., (2015)

148-985 3.7-27 Kourikasa, Rajnandgaon Dist.

Chhattisgarh
EPA 815-R-00-028, December 2000
Cost of treatment

1400000
1157600
1200000 Plant capacity : 1mgd
1000000
775820
Cost ($)

800000
600000
400000 310500
230845 Activated alumina based well head
129143 Collection of adsorption column in West Bengal
200000
0 groundwater as(S. Sarkar et al. / Water Research 39
Coagulation- Lime Activated Reverse Ion Exchange drinking water(2005) 2196–2206)
filtration softening Alumina (AA) Osmosis (IX)
(LS) (RO) Both As in the ground water of Uttar Pradesh, Assam, West
Bengal, Chattishgarh etc. 15
Cost comparison of BATs (http://www.sos-arsenic.net/)
 Approaches for low cost adsorbent
development
• Surfaces modified activated carbon
• Surface modified soil
• Nano-material based adsorbent
Carbon surface chemistry depends upon the activation conditions and temperatures employed.
Activation refines the pore structure. Mesopores and micropores are formed yielding surface areas up
to 2000 m2/g . Acidic and basic activation carbon exists according to the Steenberg’s classification.
The acidic groups on activated carbons adsorb metal ions. Surface area may not be a primary factor
for adsorption on activated carbon. High surface area does not necessarily mean high adsorption
capacity.

Adsorption capacity depends on activated carbon properties, adsorbate chemical

properties, temperature, pH, ionic strength, etc
 Adsorption of As using Granular Activated Carbon(GAC)
Table Process parameters for optimum removal of arsenic from simulated ground water using
GAC as adsorbent.
Parameters Optimum value Specific % Removal Remarks
uptake (µg/g)
Adsorbent 16 As(III): 2.65 As(III): 45.07 Equilibrium
concentration, As(V): 3.84 As(V): 65.33 reaches at 48 h of
(g/l) As(T): 6.49 As(T): 55.20 agitation. Optimum
Agitation time , 24 removal of As(T) is
h ~98.3 % of the
pH 5-7 for As(V) removal obtained at
9-11 for As(III) equilibrium.
7 for As(T)
Temperature, °C 30 °C

From this table it is clearly evident that GAC is incapable of removing

most of the As so as to make it usable for drinking purpose. Thus the
surface chemistry of the GAC has to be modified.
 Surface Chemistry of GAC at various pH & mechanism of adsorption

(a) (b) (c)

Functional groups on GAC surface; (a) & (b) Ref. Water Research 32(1998) 3414-3424, © Carbon 37 (1999)
1379–1389
Ash composition of GAC Role of ash on surface charge development
SiO2: 54 %, M-OH + H+ M-OH2+ (1)
CaO: 12.5 %, (at a pH < pHZPC of metal oxide)
Al2O3: 7.23 %, M-OH + OH- M-O- + H2O (2)
MgO: 3.25 % (at a pH > pHZPC of metal oxide)
Fe2O3: 2.15 % Where M stands for Al, Ca, Mg, Fe or Si
Acid insoluble: ~ 21 % Above reactions takes place depending upon the solution
pHZPC for SiO2, Fe2O3, Al2O3, CaO, pH and hence produces both positive and negative charges
MgO and are 2.2, 8, 8.3, 11.0 and on GAC surface, which is a function of solution pH
12.4 respectively (Srivastava et al.,
2006).
 GAC as adsorbent and its surface modification
 At neutral pH the arsenic removal efficiency of GAC is very less due to its
predominantly negatively surface charge (In our experiment with 16 g/l
adsorbent dose and 24 h of agitation the arsenic concentration in the treated
water could not be reduced from 188 ppb to 50 ppb)

 Positive charge density on the

δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_
surface of GAC can be
increased at neutral pH by a. Surface charge without impregnation (NPC=2δ+)
impregnating metal ions having
more than one positive ions. Ca+2 δ+ Ca+2 δ+

δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_

b. Surface charge with medium impregnation (NPC=6δ+)

δ+ δ+ δ+

Ca+2 Ca+2 Ca+2

Schematic presentation of the increase in

δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_
positive charge density on adsorbent
surface due to surafce modification Mondal
et al., 2007, Ind. Eng. Chem. Res. 46(8)
c. Surface charge with optimum impregnation (NPC=8δ+)
Equilibrium study: arsenic adsorption capacity of GAC-Fe
Mondal et al., 2009, AIChE J. 55(7)
0.6

0.5

0.4

qe (mg/g)
As(T) for GAC-Fe
0.3 As(III) for GAC-Fe
As(V) for GAC-Fe
0.2

0.1

0
0 1 2 3 4
GAC-Fe before adsorption
Aso (mg/l)

Unoccupied
Aso vs specific uptake plot (Aso: 0.188 - 3.2 mg/l)
Occupied
Polynomial> Freundlich > Langmuir> Temkin
qmax = 235 µg/l (Langmuir isotherm) Point of use
appl.
GAC-Fe can treat >> 380 bed volume of
contaminated groundwater in continuous
operation ( Maji et al., 2008)
Arsenic concentration in the regenerating liquid is ~ GAC-Fe after adsorption
100 times more than the Aso in water sample and it
can be treated by lime softening etc.
SEM of GAC-Fe
More research is required for ultimate solution
 90 84 Aso: 188 ppb, Feo: 2.8 ppm,
80 Mno:0.6 ppm
70
60
Ase (ppb)

50
MCL value of As (WHO & Indian
40
standards)
30
20 10
9 9.4 8.5
10
0
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
Adsorbent type
Natural soil based adsorbent

Laterite soil based adsorbent(ABTL)

Laterite is a kind of soil found mainly in the hot and arid regions around the world.
The following properties makes it a good choice to be used as a adsorbent:
• It is rich in oxides of iron, aluminum and silica which possess good potential to
remove many inorganic pollutants and heavy metals.
• It is highly porous in nature and possess large surface area
• It is a naturally available and has almost no material cost.
 Synthesis of adsorbents
Synthesis of ABTL
Step-1: Leaching of Iron and aluminum ions in acidic conditions (with
the help of 200 ml 2N HCl in 50 g thermally treated laterite at 70 °C)

Step-2: Excess amount of HCl was distilled and approximately 70% of

it was recovered by heating at 110 °C and 200 mL distilled
water was slowly added to this acid laterite mixture
Synthesis of ABTL (cont.)

Step-3: Conversion of these aqueous metallic ions to oxy-hydroxides

by addition of base (with the help of approximately 120 ml 4N NaOH)

Surface modification
(Acid-base treatment)

Raw Laterite Acid-base treated Laterite

 Due to the presence of these metal oxy-hydroxides
the adsorbing capacity of laterite is enhanced.
Characterization of ABTL
BET Surface area and Pore volume
31
0.2

dV/dlog(w)…
24 0.2

quantity adsorbed (cm3.g-1 STP)

(cm3.g-1.Å-1)
dV/dlog(w)
22 26
0
20 0
quantity adsorbed (cm3.g-1 STP)

0 10 20
18 0 5 10 15 20 21
pore width (nm)
16 pore width (nm)
14 16
12
10 11
8
6 6
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
relative pressure (P/Po) relative pressure (P/Po)

(TTL) (ABTL)

Adsorbent Surface area (m2/g) Pore volume (m3/g)

Thermally treated laterite (TTL) 31.6037 0.0096

Acid-base treated laterite (ABTL) 36.7004 0.0444

26
 Characterization of ABTL (cont.)
3

466
Raw Laterite
Thermally Treated Laterite
FTIR analysis

474
Treated
Acid-base Laterite
treated laterite

1030

534
542
2

Absorbance

912
3370
3405
3680

790
690
1620
1

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Functional group Wave number (cm-1)

Al-O-H streching 3680
OH group of Fe, Al and Si minerals 3370 to 3405
H-O-H bending 1620
Si-O stretching 1030
Al-OH bond stretching 912
cristobalite (polymorph of quartz) 790, 690
Fe-O bond stretching, Fe2O3 and Si-O-Al stretching 542 to 474
Fe-O bond stretching 534 and 466
Mn2O3 related stretching and bending 750 cm-1 to 450
27
 Characterization of ABTL (cont.)

ABTL
XRD analysis

TTL

Mineral name 2θ
Fe2O3 26, 67
FeO 36
Al2O3 39, 67, 73
SiO2 20, 26, 36, 63, 67
Mn3O4 26, 49, 59, 63, 73, 79
28
Characterization of ABTL (cont.)
FESEM-EDX
analysis

Thermally Treated Laterite Acid-Base Treated Laterite

Element Weight % Element Weight %
CK 23 CK 15.45
NK 1.04 NK 3.65
OK 42.05 OK 42.37
AlK 6.3 AlK 9.93
SiK 15.37 SiK 15.38
FeK 12.23 FeK 13.22

29
 Characterization of synthetic water and real ground water
Synthetic ground water preparation

Stock arsenic and fluoride solutions of 1000 mg/L concentration were made by
adding 1.734 g of NaAsO2 and 2.21 g of NaF in one liter of Millipore water,
respectively, and appropriate dilutions were made to make solutions of desired
concentration.

The synthetic solution containing arsenic and fluoride used for the
batch adsorption experiments was taken as follows:

Element Range of concentration of contaminant for ABTL

Arsenic (µg/L) 100 to 1000

Fluoride (µg/L) 5000 to 15000
Batch studies and uptake capacities
of the adsorbents
• In batch mode, 50 mL of solution of either arsenic and fluoride or both is taken in 250
mL LDPE bottles (Tarsons) and kept in orbital shaker incubator (Metrex Scientific
Instruments, New Delhi, India) at 150 rpm.
• The concentration of arsenic was determined by ICP-MS (PerkinElmer, ELAN DRCe Axial
Field Technology)
• The concentration of residual fluoride was measured by the help of ion meter (Orlab
Instruments Pvt. Ltd., India, model OR 930) coupled with a fluoride ion selective
electrode (Cole Parmer, USA).
Clamps Sample bottles

Horizontally shaking stand @ 150 RPM

Optimum conditions
Experimental setup
 Batch studies and uptake capacities of the adsorbents

Adsorption isotherms of ABTL : Parametric evaluation

arsenic fluoride

model R2 isotherm constants R2 isotherm constants

RL = 0.568 - 0.929 RL = 0.04 – 0.12

Langmuir
0.996 qo (µg.g-1) = 769 0.995 qo (µg.g-1) = 526
isotherm

bL (µg-1) = 0.000759 bL (µg -1) = 0.0014

KF ((µg.g-1)(L.µg-1)1/n) = KF ((µg.g-1)(L. µg -1)1/n) =

Freundlich
0.986 0.755 0.980 32.75
isotherm

1/n = 0.912 1/n = 0.317

32
Table 5.7 Removal of arsenic and fluoride from real groundwater by ABTL

Percentage
Contaminant Initial concentration Final concentration
removal

Arsenic (µg/L) 512 5 99.02

Fluoride (µg/L) 6300 1000 84.13

Dose: 20 g/l

33
Nano material based adsorbent Synthesis of AHNP

Step 1. Synthesis of AHNP through electrolysis of Al electrode (Carried out at current

density of 195 A/m2 for 2 hours and NaCl (1 g/L) as electrolyte)

Millipore water + NaCl (as electrolyte)

Aluminum (At anode): Al → Al3+ + 3e‾
Anode Aluminum
(At cathode): 2H2O + 2e‾ → H2 + 2OH‾
(oxidation) Cathode
The overall reaction is:
(reduction)
2Al + 3H2O → 2Al(OH)n(solid) + H2

Fresh aluminum hydroxide nanoparticles (AHNP)

AHNP
Step 2. Calcination of aluminum hydroxide at 700 °C to based
produce aluminum hydroxide nanoparticles(AHNP) adsorbent
adsorbent for use
 Invention Characterization of AHNP

BET Surface area analysis

Adsorbent Surface area (m2/g) Pore volume (m3/g)

Aluminum hydroxide 210.5 0.35

nanoparticles
35
 Invention Characterization of AHNP (cont.)
2.2

2
Al_EC
1.8
FTIR analysis
1.6

1.4

1.2

1
Absorbance

0.8

0.6

0.4

0.2

-0.2

-0.4

-0.6
400 900 1400 1900 2400 2900 3400 3900
Wavelength [nm]

Functional group Wave number (cm-1)

Al-O-H streching 3680
OH group of Al mineral 3370 to 3405
H-O-H bending 1620
Al-OH bond stretching 912
36
 Invention Characterization of AHNP (cont.)

Counts
Al_EC Converted.CAF

1600
XRD analysis

900

400

100

0
10 20 30 40 50 60 70 80
Position [°2Theta]

Mineral name 2θ
Nordstrandite (Al(OH)3) 18.46, 20.18, 20.50, 21.11, 22.78, 27.91, 37.52,
39.66, 44.98, and 55.26
Aluminum oxide hydroxide (AlO(OH)) 13.69, 27.91, 38.43, 49.12, 55.26, and 64.79
bayerite (Al2O3) 18.46, 20.50, 38.43, 40.51, 49.12, and 64.79
Corundum (Al2O3) 60.13

37
Invention Characterization of AHNP (cont.)

FESEM-EDX
analysis

38
 Characterization of synthetic water and real ground water
Invention Synthetic ground water preparation

Stock arsenic and fluoride solutions of 1000 mg/L concentration were made by
adding 1.734 g of NaAsO2 and 2.21 g of NaF in one liter of Millipore water,
respectively, and appropriate dilutions were made to make solutions of desired
concentration.

The synthetic solution containing arsenic and fluoride used for the
batch adsorption experiments was taken as follows:

Range of concentration of Range of concentration of

Element
contaminant for ABTL contaminant for AHNP

Arsenic (µg/L) 100 to 1000 100 to 1000

Fluoride (µg/L) 5000 to 15000 5000 to 30000
 Batch studies and uptake capacities of the adsorbents

Adsorption isotherms of AHNP: Parametric evaluation

Arsenic Fluoride
Model
R2 Isotherm constants R2 Isotherm constants

RL = 0.1492 to 0.6369 RL = 0.033 to 0.169

Langmuir
0.995 qo (µg/g) = 833.33 0.988 qo (µg/g) = 2000
isotherm

bL (µg-1) = 0.0057 bL (µg-1) = 9.819×10-4

KF ((µg/g)(L/µg)1/n) = KF ((µg/g)(L/µg)1/n) =
Freundlich 9.1632 71.5145
0.961 0.971
isotherm

1/n = 0.745 1/n = 0.365

40
Table 5.15 Removal of arsenic and fluoride from real groundwater by AHNP

Percentage
Contaminant Initial concentration Final concentration
removal

Arsenic (µg/L) 512 7 98.63

Fluoride (µg/L) 6300 1000 84.13

Dose: 2 g/l for As, 8 g /l for F

Introduction Problem of As and F contamination (cont.)

F contamination (Globally)
Affected countries: China, India, Sri Lanka, South Africa, United States of America,
central Europe, Mexico, Argentina, etc.

Estimated population affected: Over one hundred million people in more than 25
countries are probably affected by excessive fluoride in drinking water.

Amini et al 2008 Environ. Sci. Technol. 42(10) 3662-3668.

Amini et al 2008 Environ. Sci. Technol. 42(10) 3669-3675.

46
 Introduction Problem of As and F contamination (cont.)
F contamination (In India)

Affected states: Andhra Pradesh,

Bihar, Gujarat, Karnataka, Haryana,
Kerala, Madhya Pradesh,
Maharashtra, Orissa, Punjab,
Rajasthan, Tamil Nadu, U.P., West
Bengal, etc.

Estimated population affected: In

2017, approximately 11.5 million
people in more than 19 states are
probably affected by excessive
fluoride in drinking water.

1Royal Geographical Society, Annual International Conference 2007

47
Introduction Problem of As and F contamination (cont.)
As and F contamination (In India)

Affected states: Assam, Bihar, Chhattisgarh, Karnataka, Haryana,

Jharkhand, Punjab, U.P., West Bengal, etc.

TARGET AREA

48
21 countries are affected by groundwater
arsenic contamination
USA Taiwan Canada The WHO
CHINA Mexico Hungry provisional
Chile Argentina Japan guideline of
Bangladesh Poland India 10 ppb (0.01
mg/L) has
largest population at risk been
is in Bangladesh followed adopted as
by West Bengal in India the drinking
Long term drinking water exposure causes skin, lung, water
bladder, and kidney cancer as well as pigmentation standard.
changes, skin thickening (hyperkeratosis) neurological
disorders, muscular weakness, loss of appetite, and
nausea.
Redox potential (Eh) and pH control arsenic speciation. H2ASO4
− dominates at low pH (less than about pH 6.9) in oxidizing
conditions. At higher pH, HAsO4 2− is dominant (H3AsO4 0 and
AsO4 3− may be present in strong acid or base conditions,
respectively). Under reducing conditions at pH < ∼9.2, the
uncharged H3AsO4 0 predominates (Fig. 1).
 Mechanism of arsenic adsorption on GAC-Fe
 Surface modification Manju et al., 1998; Gu et al., 2005.
MOH + OH- MO- + H2O (at a pH above the pHzPC of MOH)
MO- + Fe(OH)2+ (MO)-Fe(OH)2
2MO- + Fe(OH)2+ (MO)2-Fe(OH)
Some part of As(III) is converted
2(C-XH) + Fe(OH)2+ (C-X)2-Fe(OH)2+ + 2H+
2(C-XH) + Fe(OH)2+ (C-X)2-Fe(OH)2+ + 2H+ to As(V)
2(C-XH) + Fe(OH)3 (C-X)2-Fe(OH)3 + 2H+
59

58

57 GAC-Fe before adsorption

56

55

54

1634.23
745 cm-1 , As(III)
53

52
3819.52

51
%T

50

49
GAC
3436.16
48

47

46
820 cm-1 ,
As(V)
45

1700.13
44

860 cm-1 , As(V)

3820.65

43

42 GAC-Fe after adsorption

41

4 00 0 3 50 0 3 00 0 2 50 0 2 00 0 1 50 0 1 00 0 5 00

Wave number Wa ven umb ers (cm-1)

FTIR of GAC-Fe before & after adsorption of Arsenic
 Possible reactions
(M-O)-Fe(OH2+)2 + 2 HAsO4- (M-O)-Fe(HAsO4)2 + 2H2O
(M-O)2-Fe(OH2+) + H2AsO4- (M-O)2-Fe(H2AsO4) + H2O FTIR spectra supports the capture of
(C-X)2-Fe(OH)2+ + HAsO42- (C-X)2-Fe(AsO4) + H2O arsenic by exchange with hydroxyl ions
(C-X)-Fe(OH)2+ + H2AsO4- (C-X)-Fe(OH)HAsO4 + H2O
Mondal et al., 2009, AIChE J. 55(7)
(C-X)2-Fe(OH)3o + H2AsO4- (C-X)-Fe(OH)2H2AsO4 + OH-
(C-X)-Fe(OH)2+ + H2AsO3- (C-X)-Fe(OH)HAsO3 + H2O Mondal et al. 2008, Hazmat, 150(3)
(C-X)2-Fe(OH)3o + H2AsO3- (C-X)2-Fe(OH)2H2AsO3 + OH-
Kinetics study : Rate limiting step & adsorbent design
Pseudo 2nd order model more suitably Mondal et al., 2009, AIChE J. 55(7)
explains the kinetics of adsorption (r2 =1)
0.02
0.0195
Determination of rate limiting step 0.019
0.0185
P1
P2 P3

0.018
(Michelson et al., 1975) 0.0175

q t(mg/g)
0.017
 0.030r / D
As(V)
2
t 1 / 2  p
0.0165
0.016 As(III)
0.0155

t 1 / 2   0.230r / D f  (Co / Ce ) 0.015

0.0145
P’2
P’3
0.014

t 1 / 2    [ln( 0.5)] / K1
0.0135 P’1
0.013
0 5 10 15 20 25 30 35 40 45 50
For film diffusion control process Df t
1/2 1/2
(min )
should lie within 10-6 - 10-8 cm2/s
Weber Morris plot
For pore diffusion control process Dp
should lie within 10-11 and 10-13 cm2/s Design of adsorbents
Micro pore vol., cm3/g : GAC- 0.2044 ; GAC-Fe 0.1746, (15 %)
In the present case:
-6 2 Meso pore vol., cm3/g : GAC- 0.0495; GAC-Fe- 0.0212, (57%)
Dp of As(III) : 4.11× 10 cm /s
Macro pore vol., cm3/g: GAC-0.0036 ; GAC-Fe-0.0020, (44%)
Dp of As(V): 2.27 × 10-6 cm2/s
Size of arsenite: 48 nm ; Arsenate: 43 nm
Df of As(III): 2.46 × 10-7 cm2/s
Df of As(V):5.44 × 10-6 cm2/s Adsorbents with more macro pore vol. is suitable
for surface modification and arsenic removal
The over all adsorption process is film diffusion control
Influence of Aso, Fe and Mn on As removal : Models to predict sp. uptake

Mondal et al., 2009, AIChE J. 55(7)

q As(T )  0.172  Aso  0.0013  Feo  0.0084  Mno  0.0003  Feo  Mno  0.0029  Aso  Feo
 0.0056  Aso  Mno  0.0048  Aso  Feo  Mno R 2  0.99 (19)

q As(V )  0.0893  Aso  0.0007  Feo  0.0044  Mno  0.0002  Feo  Mno  0.0018  Aso  Feo
 0.0046  Aso  Mno  0.0032  Aso  Feo  Mno R 2  0.99 (20)

q As( III )  0.0827  Aso  0.0006  Feo  0.0040  Mno  0.0001  Feo  Mno  0.0011  Aso  Feo
 0.0009  Aso  Mno  0.0015  Aso  Feo  Mno R 2  0.99 (21)

0.2

q(mg/g) ExperimentalAs(V)
q(mg/g) Experimental As(III)

0.2
0.18
0.15 0.16
0.14
0.12
0.1 0.1
0.08
0.06
0.05 0.04
0.02
0
0
0 0.05 0.1 0.15 0.2 0 0.05 0.1 0.15 0.2

q(mg/g) Predicted As(III) q(mg/g) Predicted As(V)

As(III) As(V)
 Major outcome

 Arsenic removal capacity of GAC was increased 5.5 times due to impregnation
of Fe ions on its surafce

 GAC-Fe is suitable to produce arsenic free water from contaminated

groundwater of West Bengal and Jharkhand, India

 GAC-Fe can be used in both POU and POE application

 The present adsorbent is highly competitive to some recent adsorbents

 GAC-Fe may treat >> 380 bed volume of contaminated groundwater in

continuous operation (comparison made with Maji et al., 2008)
 Removal of arsenic from simulated
groundwater

(Surface modification of GAC by impregnating

Fe, Mn, Cu and Ca and removal of arsenic from
simulated groundwater of West Bengal &
Jharkhand: batch reactor study)
 Experimental Mondal et al., 2009, AIChE J. 55(7)

Composition of Simulated Experimental scheme

groundwater

As(T) As(III) As(V) Fe Mn pH Remov al of arsenic from

simulated ground water
188 94 94 2.8 0.6 7.1 ±
μg/l μg/l μg/l mg/l mg/l 0.1

Source: Chakraborty et al., 2002 & Adsorptive remov al

Bhattacharjee et al., 2005

Adsorption Adsorption on surface

Batch on GAC modified GACs
reactors in
incubator- Batch study
shaker

Full factorial design of the 3 factors (As, Fe and Mn )

with different levels( 4, 3 and 3 respectively)
GAC-Fe GAC-Mn GAC-Cu GAC-Ca
As : 1 = 0.167 mg/l, 2 = 0.333 mg/l, 3 = 0.5 mg/l 4 = 2
mg/l Batch study Batch study Batch study Batch study
Fe: 1 = 0.9 mg/l, 2 = 1.8 mg/l and 3 = 2.7 mg/l

Mn: 1 = 0.2 mg/l, 2 = 0.4 mg/l and 3 = 0.6 mg/l)

 GAC as adsorbent and its surface modification
 Although adsorption on activated alumina is least cost amongst the BATs for
As removal, it is still not affordable by the poor people of India & Bangladesh

 GAC has wide application in water treatment due to its low cost and its
capacity to remove various types of pollutants including colour & odour etc.

 At neutral pH the arsenic removal efficiency of GAC is very less due to its
predominantly negatively surface charge (In our experiment with 16 g/l
adsorbent dose and 24 h of agitation the arsenic concentration in the treated
water could not be reduced from 188 ppb to 50 ppb)

 Positive charge density on the δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_

surface of GAC can be a. Surface charge without impregnation (NPC=2δ+)

increased at neutral pH by Ca+2 δ+ Ca+2 δ+
impregnating metal ions having
more than one positive ions. δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_

b. Surface charge with medium impregnation (NPC=6δ+)

δ+ δ+ δ+
Schematic presentation of the increase in Ca+2 Ca+2 Ca+2
positive charge density on adsorbent
surface due to surafce modification Mondal δ+ δ_ δ+ δ+ δ+ δ_ δ+ δ_
et al., 2007, Ind. Eng. Chem. Res. 46(8)
c. Surface charge with optimum impregnation (NPC=8δ+)
 Changes in properties of GAC due to surface modification
583.23

Sp. Surface area

Metal content (%)

600 6 4.78
532.25 3.92 4.29
550

(cm 2/g)
488.24 501.93 4
481.31
500 1.89
450 2
400
0
0
GAC GAC-Fe GAC- GAC-Cu GAC-Ca
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
Mn
Adsorbent type
Ads orbe nt type

65 Sp. Surface area Metal content impregnated

418.59
60

55

50
GAC
45 GAC-Fe Mondal et al., 2009, AIChE J.
55(7)

1653.11
1558.47
1652.89 1647.23
40
%T

35
Mondal et al., 2007, Hazmat

1653.60
30
3400 144(1-2)
1650
25
cm-1
20
cm-1
GAC-Ca
15
GAC-Mn FTIR spectra
10
GAC-Cu
3468.64
3448.43
3446.36
3439.00
3437.10

5
4 00 0 3 50 0 3 00 0 2 50 0 2 00 0 1 50 0 1 00 0 5 00
Wa ven umb er s ( cm- 1)

4000 Gu et al., 2005

GAC

Lin(Counts)
3000 GAC-Fe
2000 GAC-Mn

1000 GAC-Cu
GAC-Ca
0
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca 10 20 30 40 50 60 70

SEM micrograph 2-Theta Scale XRD plot

 Optimum conditions for removal

Effect of parameters Range Optimum value

GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
Adsorbent concentration 0-40 16 5 5 6 8
(g/l) g/l
pH

As(T) 5-11 6-8 6-7 7-9 7-11

As(V) 2-12 5-7 5-7 5-7 7-9 7-11

AS(III) 9-11 9-11 9-11 9-11 9-11

Temperature oC 30-60 29 ± 1 29 ± 1 29 ± 1 29 ± 1 29 ± 1
Agitation period (h) 0-52 48 42 36 24 24
Aso ( mg/l) 0-3.2 Specific uptake increases with increase in Aso value

Fixed parameter: Agitation speed : 180 rpm ; Feo : 2.8 mg/l; Mno: 0.6 mg/l
 Selection of best adsorbent amongst various adsorbents
40
35.8 35.7
35
90 84 Aso: 188 ppb, Feo: 2.8 ppm, 29.9
80 30
Mno:0.6 ppm

Specific uptake (μg/g)

70 25 22.2
60 MCL value of As (Indian standard)

Ase (ppb)
20 18.5 18.3 17.4
17.3
50 15.5
14.4
15
40 11.6
10.6
30 MCL value of As (WHO standard) 10
6.5
20 10 5 3.6 2.9
9 9.4 8.5
10
0
0

As(III)

As(III)

As(III)

As(III)

As(III)
As(V)

As(V)

As(V)

As(V)

As(V)
As(T)

As(T)

As(T)

As(T)

As(T)
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
Adsorbent type Adsorbent type

Ase at optimum adsorbent concentration Specific uptake with suitable adsorbent

concentration and 24 h agitation
(pH: 7.1 ± 0.1, temp. 29 ± 1 oC, Agitation : 24 h)

120 97 96
98.5 96 95
100 95

% Regeneration
94
% removal of Mn

94 93
80
63 93
60 92 91
44 40
35 91
40
90
20 89
88
0
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
GAC GAC-Fe GAC-Mn GAC-Cu GAC-Ca
Adsorbent type
Adsorbent type

% removal of Mn % regeneration of spent adsorbents

Mondal et al. 2009, CJCE, In Press
 Mechanism of adsorptive removal
Step-1. Transport of adsorbate/arsenic from bulk to the surface of adsorbent

Step-2. Diffusion of adsorbate/arsenic into the interior part of adsorbent

Step-3. Adsorption of adsorbate/arsenic by the following possible routes

OH
OH OH
Fe
Fe
Fe O

O O O C O
-

Physical adsorption OH-

H2AsO4-1, HAsO4-2

- - O AsO3 O AsO3
O AsO3
Fe
Fe
Fe O

+ O O O C O
+ H

Chemisorption Attachment through exchange of

Mondal et al., 2007, Ind. Eng. Chem. Res. 46(8)
hydroxyl ion
Arsenic contamination of drinking water can occur naturally or
as a consequence of human activities such as mining. A study
performed in the Rímac river basin showed that mine tailings
resulted in elevated arsenic, copper and lead concentrations in
the river and its tributaries.