Indian Journal of Chemical Technology

Vol. II, July 2004, pp 518-525

Removal of arsenic from water by different adsorbents

Rajeev Goel", S K Kapoor" , Kshipra Misra'" & R K Sharma"
'Centre for Environment & Explosives Safety, Metcalfe House, Delhi 110054, India
hDepartment of Chemistry, University of Delhi, Delhi 110007, India

Received 8 April 2003; revised received 4 March 2004; accepted JO May 2004

Present study is carried out for the removal of As(lII) from water using commonly available adsorbents such as
sand, from Yamuna river (Delhi ), as well as from Ganga river (Kolkata), activated carbon, Hametite ore and sand -iron scrap
mixture. All these adsorbents are used as received but sand and activated carbon which do not show much adsorption for As(lII)
are modified by treating with different metal ions in order to improve their adsorption efficiency. Results of the laboratory
experiments under static conditions have confirmed that iron impregnated granular activated carbon (GAC), spherical activated
carbon (SAC) as well as sand - iron scrap mixture have much promise as a medium for the removal of As(JII) in drinking
water. Various parameters like adsorbent dose, contact time, pH and arsenic concentration are optimized. A simple and
economical domestic arsenic removal kit has been designed and successfully evaluated in the laboratory using sand-iron scrap
mixture as media for the removal of arsenic from water.

IPC Code: C02F 1/28

Keywords: Arsenic removal, hametite ore, activated carbon, sand, adsorption, drinking water

About 70 million people in West Bengal, India and 90
million population of Bangladesh is already exposed to
arsenic contaminated drinking water. Tens of thousands
of people have been showing skin discoloration and other
more serious manifestations of arsenic toxicity. There
are reports of deaths and serious infection relating
arsenic poisoning. A similar comparable problem has
recently been discovered in northern Vietnam also l .
Arsenic is a known human carcinogen and even a minute
quantity consumed can have severe adverse health effects
on living beings 2. Arsenic can cause acute and chronic
toxicity on human health. The severity of toxicity
depends on age and sex of the individual, the dose and
duration of exposure, chemical nature of the compound,
route of entry and the amount of arsenic accumulated
into the body. The predominant symptoms of arsenic
poisoning are skin manifestations which is called
Arsenicosis. Other most common manifestations of
arsenic poisoning are melanosis, keratosis,
leukomelanosis, hyperkeratosis and also in some cases
conjuctivitis, bronchitis and hepatomegally. Severe cases
of skin cancer (squamous cell carcinoma and basal cell
carcinoma) have also been reported' .
Arsenic in drinking/ground water is commonly
"Present address: NMRL, Shil-Badlapur Road, Addl. Ambernath
421506 (E-mail: kmisra99@yahoo.com)
found in +3 (arsenite) and +5 (arsenate)4 0x idation states
and order of toxicity varies as follows:
As(III) > As(V) > organic- As
In anthropogenic polluted waters, other arsenic
species may also be expected. Arsenic concentration
in drinking water normally ranges from ppb to ppm in
different parts of the world 5 . World Health Organization
(WHO) and Environment Protection Agency (EPA)
have established permissible value of 0.01 mg/L
(10 ppb) for arsenic in drinking watd'. According to
Chakraborti 5 arsenic contamination is gradually
increasing in the areas of West Bengal and Bangladesh
where it was not earlier contaminated.
Many physical and chemical treatment techniques
such as oxidation by UV/Sunlighe·Mprecipitation using
iron, manganese and aluminum salts'! , ion exchange and
fixed bed adsorption (using activated alumina, bone char,
sand, polymeric resin and activated carbon)IO·11 and
desalination (reverse osmosis and electrodialysis)1 2, etc
have been tried by different researchers, however none
of these methods has provided a permanent solution to
the problem due to one or more limiting factors in the
technique. These remediation methods have been
proved useful for the removal of As(V) to certain extent,
 GOEL et al.: REMOVAL OF ARSENIC FROM WATER BY ADSORBENTS
but are not successful in removing As(III) to the desired
drinking water limit.
Considering the seriousness of the problem there
is an urgent need to develop a technique which is simple,
economical, environmental friendly and suitable for
treating contaminated water at house hold level, so that
immediate relief could be provided to the poor villagers
who are consuming water with very high concentrations
of arsenic.
Therefore, a comparative study has been carried
out with commonly available adsorbents for the
removal of As(IlI) from water, which is relatively more
toxic and difficult to be removed. Some of these
adsorbents e.g. granular activated carbon (GAC) and
river sand which as such have not shown good
adsorption for arsenic(III) are modified by different
physico-chemical methods in order to increase their
adsorption efficiency. These treated adsorbents are found
to be useful for the removal of arsenic(III) from ground
water and can be very well used for the development
of domestic drinking water treatment kits .
Experimental Procedure
Selection of adsorbents
Various adsorbents such as sand from Yamuna and
Ganga rivers, Hematite ore and iron scrap from steel
plant, three different grades of indigenously available
coconut based granular activated carbons (GAC) from
Mis Active Carbon India Limited, Hyderabad and a
pitch based spherical activated carbon (SAC) obtained
from MIs Krehan, USA are used for adsorption studies.
Surface modification of selected adsorbent
Surface treatment on both the sand samples is
carried out as per reported methods for iron oxide and
manganese dioxide D . '4 .
Metal impregnation on granular activated carbon
grade 60 (GAC-60) of surface area 1100 m2/g is carried
out using iron and manganese salts at alkaline pH.
The details are given below,
100 g of GAC-60 is washed with Milli-Q water
and dried at 105°C ti II the constant weight. 240 mL of 2
M solution of Fe(N0 1),.9H,O is added to the dried
GAC-60 and pH of the solution is adjusted to -12 by
the addition of conc. solution of NaOH. The carbon is
kept in an oven for 24 h at - IIO°C. Treated carbon is
then washed with Milli-Q water till colourless and finally
dried to constant weight.
519
Manganese impregnation on GAC-60 has been
carried out by mixing 100 g of washed and dried carbon
with 200 mL of 0.2 M of KMnO 4 solution. To this about
200 mL solution of 0.3 M MnCI 2 is added slowly. The
pH of the solution is maintained -12 by the addition of
concentrated solution of NaOH. The carbon treated so
is kept in an oven for 24 h, washed, dried and stored in
stoppered bottles.
Adsorption isotherm studies
Static adsorption isotherm studies of I ppm
solution of sodium arsenite (As 1+) and real contaminated
ground water brought from West Bengal (200 ppb) are
carried out using 50 mL solution, with varying doses
( 5-80g/L and 20-80 giL respectively) of the above
mentioned adsorbents in stoppered glass bottles . AIl
the adsorbents are thoroughly washed with Milli -Q
water and dried at 120°C till constant weight before
use. Contents are then shaken for 24 h on a thermostatic
shaker maintained at 30± I dc. The solutions are allowed
to settle and then filtered through Whatman filter paper
No.1 . Arsenic concentration before and after adsorption
is determined as per ASTM method ' 5 using GBC-HG-
3000 atomic absorption spectrophotometer(AAS ).
Metal ion concentration of virgin and impregnated
GACs is carried out using Phillips X-ray fluorescence
(XRF) at Durgapur Steel Plant. Surface area of activated
carbons are measured using Micromeritics ASAP 20 I0
Surface analyzer at CEES. AIl the reagents used are of
AR quality and only Milli-Q water is used for solution
preparation and washings.
Arsenic removal kit
An arsenic removal kit as shown in Fig. I has been
designed and evaluated for its performance for the
removal of arsenic(III) and total arsenic from real
contaminated water. The kit consists of three chambers
made up of stainless steel and placed one over the other
on an iron stand. Dimensions of each chamber are 285
mm (1.0.) X 333 mm (H.T.). The adsorbent (sand-iron
scrap mixture in 50:50 ratio) is kept on a perforated
disc in a sealed bag connected to a mechanical stirrer
which can be operated either mechanically or using a
battery. Twenty liters of sodium arsenite solution I
contaminated water which is placed in the top chamber
is shaken with the optimized dose of adsorbent (-100
g) at a constant speed for the optimized time of 2 h.
The same solution is then filtered through the
virgin sand (-12Dq,g) placed in a bag in the second
520 INDIAN 1. CHEM. TECHNOL., JULY 2004

Top chamber
...
_ ..... Stirrer

- ~ Ads orbellt bag

-~ .... Perforated disk
,..---,...,
II ~ ... Disk with 0.65 mm
dia. orifice

Sand

.-.. .. Disk with 0.65mm dia

"l..--J' orifice
II

...
--"
Bottom Chamber

C
~
Fig 1- Arsenic removal kit

chamber at an optimized flow rate of2-3 Lph with initial
resistance time of 15 min and finally arsenic free water
is collected in the third chamber. Due to very high
adsorption capacity of sand-iron scrap mixture, this
system is recommended to clean about 60 L of arsenic
contaminated water of about I ppm concentration. If
the arsenic concentration is less it can be used further
for treating more water. No leaching of iron is detected
in the treated water. Results of the tests are given in
Table I.
The kit is simple in operation and economical as
it utilizes iron scrap, a processed waste generated from
steel industry This may prove highly beneficial for the
villagers in arsenic affected areas of West Bengal and
Bangladesh .
Waste utilization of spent adsorbent
Disposal of arsenic laden adsorbent is
unacceptable under growing environmental regulations
due to high toxicity of arsenic. The spent adsorbent is
being disposed off in the form of cement/polymer
matrix 16. The cement matrix can be made in the form of
M-25 standard grade 17 impermeable concrete blocks
used in construction industry resulting into no waste
generation in the process and making the technology
environmental friendly and green.
Results and Discussion
Results of analysis of the selected adsorbents
(Table 2) show 4 and 0.24% impregnation of iron and
manganese, respectively on sand and granular activated
carbon ( GAC) samples. Slight increase in surface area
of the adsorbents (GAC and sand) has been observed
after impregnation/treatment. This can be explained on
the basis of probable opening of pores by heating and
release of gaseous substances during impregnation as
has been observed by other workers previously IX.
 GOEL cl al. : REMOVAL OF ARSENIC FROM WATER BY AOSORBENTS 521

Table I - Results of water analysis after treatment by arsenic removal kit

S.No . Metals EPA's drinking Initial conc. of Initi al conc. of Concentration Final concentration
water limit sodium arsenite real water (j..Ig/L) after first stage after second stage

(j..Ig/L) solution (j..Ig/L) treatment (j..Ig/L) treatment (j..Ig/L)

Sodium Real Soeium Real

arsenite water arsenite water
solution solution

Arsenic 10 120± 2 450 ±3 20 ± 0.2 12 ± 0.2 < IO±O.I BOL*

2 Iron 300 Nil 100±2 365 ± 2 175 ± 2 <300 ± 2 <300 ±2

* BOL: Below Detection Limit, i.e., < 0.003 mg/L

Table 2 - Physical and chemical characteristics of adsorbents

S.No. Adsorbent pH pH Fe (%) AI (%) Mn (%) Si (%) Surface area

(in water) (in As sol) (BET) m2/g

I GAC-50 9.6 10. 1 trace trace trace trace 950

2 GAC-60 9.7 10.0 trace trace trace trace 1117
3 GAC-70 10.2 10.5 trace trace trace trace 1264
4 GAC-Fe 7.9 8.77 4.0 trace trace trace 1306
5 GAC-Mn 10.3 9.8 trace trace 0.24 trace 1300
6 OS 8.7 7.7 5.0 10.7 nd 8(J.0 6
7 CS 8.3 7.6 4.7 11.5 nd 79.8 I
8 OS-Fe 10.2 10.2 8.9 10.7 nd 80.0 7
9 CS-Fe 9.5 9.9 14.0 11.5 nd 79.8 7
10 OS-Mn 8.2 8. 1 5.0 10.7 0.22 80.0 7
II CS-Mn 7.7 7.7 4.7 11.5 0.2 79.8 8
12 IS 8.5 8.8 99 .2 nd 0.42 0. 15
13 Hematite 7.0 7.2 62.6 1.8 1.3 42

Adsorption capacity (Fig . 2) of different Although adsorption studies of As(III) and

adsorbents used in present study is calculated from the
results of adsorption isotherm experiments of sodium
arsenite and range from 0.35 to 7Allg/g . It is observed
very clearly that sand and GAC samples as such have
very low value (0.35- 0.81 Ilg/g) of adsorption capacity
for As(III) but after treatment with iron and manganese
compounds it has enhanced drastically and GAC treated
with iron gives maximum adsorption capacity of 2.8
Ilg/g. Similarly sand and iron scrap mixture as well as
spherical activated carbon (SAC) have very high
adsorption capacity of 6.5 and 7 Allg/g respectively and
can remove almost 100% As(III) from water .
As(V) mixture using iron and manganese coated Ganges
sand as carried out by Chaudhuri et at. 13. 14 under
dynamic conditions have shown much promise for the
removal of arsenic from water, however, it is desirable
to study their behaviour under static experimental
conditions also and have comparative data. Strangely,
iron and manganese impregnated sand in the present
case have not given required removal for arsenic(III)
as claimed by previous authors.
Results as shown in Fig. 3 (a,b and c) indicate
that a dose of 35g/L for various sand and GAC samples
is sufficient for the maximum removal of As(II!),
522 INDIAN 1. CHEM. TECHNOL., JULY 2004

80.-----------------------------------------------------------------~--
74.1

70
65 66

Dl 60
OJ
2>
i:' 50
'0
ro
~40
U
C
1530
C.
26.6 27.8
.... 22.8 23.2 23.3 23.5
a(f) 21 .5
~ 20

7.6 8.1

Adsorbents
Fig 2- Adsorption capacity of different adsorbents

whereas a dose of even < 10 giL for sand-iron scrap

mixture as well as for SAC is quite sufficient for almost :
100 % removal of As(III) from the solution . No
significant effect of surface area of GAC has been
observed on adsorption and it also remains unaffected
by the change of sand from Ganga river to Yamuna river, 40 60 8. 100
DosA (oiL)
which further confirms that any river sand can be used ___ GAC-eO ---6--GAC-Fe
for this purpose. _ _ SAC
___ GAe·50
Remarkable increase in the adsorption of As(III) <al
by iron impregnated GAC can be attributed to the
surface complexation reaction of iron impregnated on
carbon surface and aqueous sodium arsenite. In case of •
iron and manganese coated sand, increase in adsorption
efficiency is due to the oxidation of arsenite adsorption
on iron and manganese hydroxide under aqueous
2. 40 60 8. 100
conditions as discussed by Bajpai and Choudhary' 4. Dose (gil)
Removal of arsenite by sand-iron scrap mixture ___ CS _ _ CS-Mn

'-'-CS-Fe _ _ CS-IS
can be easily explained by the reaction of inorganic
arsenic with zero valence iron under aerobic conditions (b)

which in turn forms co-precipitates, mixed precipitates

1200
and finally adsorb on ferric hydroxide solids formed 1000

during the reaction . This is very much in .0.

concurrence with the previous studies carried ~
~
.0. ~
•
400
out by different workers IY - 23 • Higher adsorption "
0
200

efficiency of SAC may be attributed to its shape which 20 40 '0 80 100

provides maximum surface available for adsorption Dose (gil)

compared to the normal GAC of the same surface area 24 . ___ OS _ _ OS_Mn -'-OS-Fe _ _ OS _IS

Effect of contact time has been studied from 4 to (c)

Fi g 3- Optimization of adsorbent dose: (a) Granular activated
32 h using a fixed dose (35 gIL) of activated carbon
carbon; (b) Kolkata Ganga sand; (c) Delhi Yamuna sand
 GOEL el at.: REMOVAL OF ARSENIC FROM WATER BY ADSORBENTS 523

1200 (a)
• •
1000

'""'- 800
..J
C.
.«::::! : 1200

1000
..;!, 600
Q)
:::I 800
U
400
~ }
200 • • • CIl
()
600

0
·0

-+-GAC-Mn
10 20
TIme (h)
_ _ GAC-Fe
30

--.-SAC
40
400

200

0
.II
.- •
_ _ GAC-70 _ _ GAC-60 -+-GAC-50 4 6 10 12

(a) pH
-+-SAC _ _ GAC_Fe
--'-GAC-Mn
-tl-GAC-70 -tl-GAC-60 -+-GAC-SO

220
200 (b)
180 200

::;-
160
140
180
160
ts
• • •
C. 120 140
20
Q) 100 ::;-
U 120
80 "0>
§ 100
60 Q)
U 80
40
20
0
.. • ------
I I I
60
40
0 10 15 20 25 30 20

_ _ GAC-60
Time(h)
4
• • • 10 12
-+-GAC-SO --.-GAC-70
_____ SAC
pH
_ _ GAC-60-Fe _ _ GAC-60-Mn
-+-GAC-SG _ _ GAC-60 --.-GAC-70
_ _ GAC-60-Fe _ _ GAC-60-Mn _ _ SAC
(b)

Fig 4- Optimization of contact time of adsorbents: (a) Sodium Fig. 5- Effect of pH on adsorption
arsenite; (b) Real water (a) Sodium arsenite ; (b) Real water

with I ppm solution of sodium arsenite and a real water between equilibrium concentration Ce and initial
sample collected from West Bengal (India). A time of concentration Co in case of untreated GACs and
about 15 h is found to give optimum removal of arsenic manganese impregnated GAC, while Ce is only
by all the activated carbons used (Fig. 4 a & b). marginally affected by Co in the case of iron impregnated
Results of effect of pH on adsorption of sodium GAC and SAC. This further confirms higher adsorption
arsenite as well as arsenic in real water by different of arsenic(III) on iron impregnated GAC and SAC.
activated carbon as depicted in Fig. 5 (a and b), reveal
that adsorption increases with increase in pH of the Conclusions
solution from 4-7 and remains almost unchanged in 7- It is evident from the work carried out so far that,
II pH range, though is comparatively better in alkaline (i) iron impregnated GAC, SAC and sand-iron
pH. This conforms with the earlier studies carried out scrap mixture can be successfully used for the
by Satpathy et.alY removal of arsenic from drinking water.
Adsorption isotherms of aqueous sodium arsenite (ii) technology can be used for the development of
solution in different concentration (0.5 to 6 mg/L) are cost-effective, simple and environment friendly
carried out with a fixed dose (35 gIL) ofGAC and SAC. arsenic removal kits.
Results as presented in Fig. 6 show a direct relationship (iii) Field trials in arsenic affected areas should be
524 INDIAN J. CHEM. TECHNOL., JULY 2004

6 0 0 0 r - - - - - - - - - - - - - - - - -_ _ _ _ _ _ _ __

5000

4000

..-..
...J
..... 3000
Cl
E
'-'
Q)
()
2000

1000

4
Co(mg/L)

-+-SAC -+-GAC·Fe ......... GAC·Mn

-+-GAC·70 ...... GAC-60 -+-GAC·50

Fig.6 - Effect of arsenic concentration on adsorption

carried out with the developed kits to study the
practical feasibility of the technology.
Acknowledgements
Authors wish to record their sincere gratitude to
Dr. A.K. Datta, former CCR&D(M), DRDO and Dr.
S.K . Salwan, former Director, CEES , for giving
opportunity to work on this problem. Authors are also
thankful to Mr. Satish Kumar, Mr. Vivek Kumar, Mr.
Ashok Rawat and Mr. Naveen Saxena for their help
during the course of this work.
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