Arsenic Removal by Adsorption Author(s): Shailendra K. Gupta and Kenneth Y.

Chen Source: Journal (Water Pollution Control Federation), Vol. 50, No. 3 (Mar., 1978), pp. 493-506 Published by: Water Environment Federation Stable URL: http://www.jstor.org/stable/25039577 . Accessed: 04/12/2013 14:45
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Arsenic
Shailendra University

removal
K. Gupta, Kenneth Y. Chen of Southern California, Los Angeles

by

adsorption

Arsenic in natural waters actions, cultural

is a commonly ecosystems. Its may originate waste industrial use of arsenical

occurring

toxic

metal

A variety of methods
for past wastewater. move valent arsenic Major include species, with a

have been used

from water methods

in the
and to re

in natural presence re from geochemical discharges, pesticides. or agri Arsenic

removal treatment

arsenic metal

it has also been to be carcinogenic;1 suspected as a causal factor for HafFs dis is known
3 ease.2' from Acute and chronic of consumption arsenic in poisoning arsenic-contaminated arsenic

coprecipitation into sorption

with complexation poly as ferric and such iron, ad metal hydroxide,11-13 floe,14'15 activated lime soften

ing,16'

17 sulfide precipitation
onto ion

coagulant

(ferrous

sulfide

drinking water
U. S., critical trations waters,

has been
water

reported.4'5
supplies arsenic and is

In the
not concen ground a

beds),19-21 adsorption and and alumina,22 23 Patterson reviewed nology mary for of water treatment

carbon21

Recently exchange.21 treatment arsenic tech wastewater. A and sum

however, problem;6 in wastewaters, surface waters and geothermal

and

methods

removal

frequently criteria.8 is can

exceed
water Arsenic quite

the recommended
standards 7 and 9 water in because chemistry

limits of drinking
quality aquatic the systems element

achieved is listed in Table I. Most of these studies do not

extent of removal of various on

indicate

the of in

arsenic

species. efficiency

Also,
solution

kinetic

data and data on the effects

adsorption

complicated

conditions

be

stable

in four oxidation
different waters, redox surface

states
arsenate

(+5,

+3,
In

required
most

for reactor
This

design
paper

are
presents

lacking
labora

0, '?3) oxidized

under

conditions. species

instances.

(H3As04, H2AsOr,
forms; the under arsenite

HAsOr2)

are

the

stable

moderately species

reducing (H3AS03,

conditions, H2As03",

tory data on the effect of pH, salinity, and type of adsorbents on the kinetics and equi libria of arsenic removal from solution by
adsorption.

HAs03~2) become predominant. When is present, realgar (AsS) and orpiment

occur as stable solids at pH values

sulfide (As2S3)
ap

EXPERIMENTAL
Analysis
samples in order in were to

below

of As (III)
collected study water, the

arid As(V).
from form of various arsenic and

Water
sources present waste

5.5 and proximately values) about 0 volts.

AsS2are the predominant

redox potentials HAsS2 (aqueous)

aqueous

(Eh and

species.

geothermal

freshwater,

The solubility of HAsS2 the order of 106-5 M

mental low be arsenic

is reported to be on Ele (0.025 mg/1).

stable at

is thermodynamically

a low Eh
but formed no

level.
data under

Its solubility
are available. extremely

is undoubtedly
Arsine reducing may condi

water. Samples were collected directly into and stop bottles acid-cleaned polyethylene Each immediately. sample pered air-tight was filtered through a 0.45-/* membrane filter
under a nitrogen environment. Analyses of

tions; it is only
Pash3= 1 arm).

slightly

soluble

(10-5-3 M

at

As (III) and total soluble arsenic were car ried out by selective reduction, at pH 4 and 1
respectively, to arsine. The arsine formed

Arsenic

does form solids with

and solids varies

iron, alumina,
however, than As2S3 accord

was
M

absorbed

in a solution composed
0.5 percent

of 0.005 The
atomic spectro

calcium, magnesium are no arsenic there

nickel; other

mercuric

nitrate,

weight:volume

which
The

have
toxicity

solubilities
of toxic arsenic than

less than 0.05 mg/1.

greatly However,

NiN03
arsenic absorption.

prepared
was

in 0.02 N

nitric

acid.

ing to its oxidation

is far more

state; for example, As (III)

As(V). un reduces a detoxifi

flameless analyzed using An atomic absorption

photometer
background and izer,

equipped
corrector, electrodeless

with
heated

a deuterium
graphite lamp,

arc
atom was

like mercury, methylation greatly as and may be considered toxicity, cation process.10

discharge

used

in this study. March 1978 493

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Gupta TABLE

and Chen I. Summary of arsenic treatment methods Initial

Arsenic Treatment cone.

and efficiency Final

Arsenic cone.

of removal.23
Percent Removal Reference

(mg/ml)
0.2 0.2 0.5

(mg/ml)
0.06 0.03 0.03 0.05 0.003-0.005 0.003-0.006 5 0.05 0.06 15-20 0.05 0.05 26.4

Charcoal filtration Lime softening Lime softening Precipitation Precipitation Precipitation Precipitation Precipitation Precipitation Precipitation Ferric sulfide Precipitation Precipitation with with with with with with with filter with with lime plus alum ferric ferric ferric ferric ferric sulfate sulfate chloride hydroxide hydroxide iron

70 85 95 85-92 98-99 80 98 94-96 94 80

19 19 18 17 16 16 14 20 15 13 21 22 18

0.35 0.31-0.35 25 3

362
0.8 132.0

bed
sulfide sulfide

Adsorption Adsorbents.
solids were

study. Three
chosen for area the 210

types
present

of

activated
study.

washed, and then rinsed four times with tilled de-ionized water.
Adsorption was prepared tinuous mixing experiment. for each was A datum separate point. during the

dis
batch Con ex

1.
granular, lar,

Activated
surface matter

Alumina: Bauxite:

28 X 48
m2/g.

mesh, granu surface

provided

2. Activated
volatile

30 X 60 mesh, 8 X 30 mesh,
were not

6 percent.

3. Activated Carbon: area 500-600 m2/gm.

These three adsorbents

subjected

to any
adsorption out with times

additional
study.

pretreatment

prior

to the

were carried Experiments ten seawater diluted freshwater, a and seawater (S.W./10), (S.W.), chloride and seawater were co

0.67 M sodium chloride solution. Trace metals

from sodium solids technique

In a total of 100 ml of perimental period. alumina and 2 activated of solution, g/1 bauxite, and 3 g/1 activated carbon were used The initial pH throughout the experiment. values of the solutions were adjusted with either a strong acid (HC1) or a strong base The initial pH value of the solu (NaOH). tions for each adsorbent was adjusted to give the desired final equilibrium pH. All solids were aged in the solution for 12 hours to
minimize pH after change a 12-hour during the experiment.

precipitated
These tion

with
were

ferric hydroxide
removed through an by 0.05-ju. II.

at pH 7.5.
filtra membrane

Figure
sorbent

1 shows

the pH

change
period.

of each ad
In the next

a vacuum

filter.
solutions cases

The
are sodium

chemical
shown meta-silicate and silicate seawater on the

compositions
in Table was to added

of
In to the of

these
some the

48 hours, the pH was found to vary as much as 0.2 to 0.4 units and continued to change
at a lower rate thereafter. The pH changes

freshwater of soluble

evaluate

effect

adsorption

arsenic.

could be caused by re-equilibration with the surrounding solution of small particles formed abrasion during shaking. For by mechanical
this reason results are expressed in terms of

All chemicals used were of analytical reagent All labware used in the experiments grade. was soaked in 6 percent HC1 for 24 hours, TABLE IL Initial chemical Liquid
NaCl Seawater (0.67 M) Diluted

final pH. The initial As (III) and As(V) in the form of NaAs02 and concentrations for adsorption Mg
?

composition Na
15 410

of solutions K
?

experiments S04~
? ?

(in mg/1). Si
?

Ca
?

Cl
23 760

B
?

10 times

/S W \ i-Tjpl Seawater (S.W.)

120 1200

39 390

35 350

120 1200

1940 19 400

270

0.4

0.1 1.0

0.10 1.0

2 700 4.0

494

Journal WPCF

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Arsenic TABLE III. Water

in waters. Arsenic Concentration

Removal

quality criteria for Arsenic

Ac. ALUMINA (2gm/l) Ac. BAUXITE (2gm/l) Ac. CARBON (3gm/D

Source
Drinking water : maximum concentration : irrigation : livestock water 0.10 0.20

(mg/1)

permissible Agriculture Agriculture Calif, ocean

0.05

discharge

50% time 0.01 10% time 0.02

Na2HAs04 were varied (0.4 to 10 mg/1 As).

Samples were shaken test

from 5
continously

to 130
in a

?jM
con 6 INITIALpH in

stant-temperature
Experimental

(25 ? 2?C)
solutions were

bath

shaker. 1. Comparison FIGURE of initial and final pH of the solution containing different con centrations of adsorbents after 12 hours of
shaking.

prepared

250-ml adding
sorbent

glass-stoppered arsenic stock

solution.

flasks by Erlenmeyer to an equlibrated ab

times" was noted

"Zero

after the prepared solution was shaken five times. In experiments for As (III) adsorption, all flasks were flushed with nitrogen gas and
stoppered immediately to prevent the ox

Blanks
were

in the absence on
identically

of activated
to correct

solids
for ad

prepared

to As(V). of As (III) yg?nation Shaking times of 36 hours were used for activated
alumina tivated and carbon. bauxite and 48 hours for ac

sorption
arsenic

the bottles.
were

Initial

and

final
No

concentrations

compared.

At the end of the reaction period, samples filtered were through a 0.45-/A membrane filter using a pressure filtration technique. The filtration technique used in these experi ments was simple and fast. About 40 ml of the sample was filtered through a 0.45-/A
membrane sufficient centrations. in 90 seconds. pH This and volume arsenic was con for measuring

significant arsenic adsorption by the reaction bottles was observed within 60 hours in the pH range from 2 to 11 for concentrations under study. The slight difference observed
was within the was adsorption experimental observed error. on the No 0.45-ju, arsenic mem

brane during filtration.

RESULTS
There is evidence from the analysis of many water samples that both As (III) and As(V)

TABLE

IV.

Arsenic

concentration
As

ranges.
Concentra tion

Source
of Los Angeles City Surface waters Groundwater Geothermal Seawater Industrial water Wastewater and secondary plant) available. water supply 0.002-0.21

(mg/1)
0.002-0.004

As ail) (mg/1)

As (V) (mg/1)
0 0.002 -0.004

Reference
this study 29

N.A.* -4.0 -3.0 0.002-0.014 0.01 600 0.003-0.01 0.002 -0.003 N.A.* -2.4 0.0005-0.003

N.A.* N.A.* 0.006 -0.50 0.0005-0.004 N.A.* N.A* 0.001 -0.009

5,26,27 4, 19, 28, this study 25, 30 31, this 32, 33

0.01 0.03 0.003effluents

Primary (Hyperion * N.A.?Not

study

March

1978

495

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Gupta

and Chen
30 j-1-1-1-1-1-r

i _i_I 01-'-1-1-1-?_i_i_' 60 20 100 10

200 Time (min.)

600

1000

2000

4000

FIGURE
are

2.

Adsorption
under oxidizing

of As(V)
as well

by different
as mildly

absorbents

at optimum
conditions

pH values.
in most geo calculations present as

present

reducing

conditions.

reducing thermal indicate

encountered be

The data in Table III and IV indicate that in geothermal concentrations fluids As(V) range between 4 and 90 percent of the total
soluble arsenic. concentrations In general, 10 lie between average and 40 As(V) percent

24 con As ( III ). Sergeyeva and Khodskovsky cluded that the most probable form in which
arsenic mildly exists reducing in hydrothermal conditions) solution is arsenious (under acid.

reservoirs, thermodynamie arsenic that should

of the total soluble arsenic.

61-1-1-1-1-1-1-1-1-i-r

Under

the mildly

The

existence

of both

As (III)

and As(V)

FIGURE 496

3.

Adsorption

of As (III)

by different

absorbents

at optimum

pH values.

Journal WPCF

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Arsenic 27
O-O?.

Removal

26

o 4>
g 25 o CO o o O to 24 < 3. 23 A Activated Activated Alumino (2 mg/1) Bauxite ( 2 mg/1)

22

4 Final

5 pH

FIGURE

4. pH effect on adsorption I ? O]. freshwater, ??M;

of AS(V)

[initial As(V)

concentration,

53.4

be a result conditions under these may species to ar arsenate of of reduction incomplete to senite. kinetics of arsenate reduction The are unknown. arsenite

activated

alumina

and

bauxite

were

much

The existence of both As (III) and As(V) forms in surface waters is probably caused by the slow rate of oxyg?nation of arsenite to
arsenate or bacterial reduction of can arsenate to

slower than those of As(V). Within the first 10 minutes, 6 percent of 12.4 /?M As (III) and 2 percent of 12.6 pM As (III) was re moved alumina and bauxite by activated As (III) removal was found to respectively. time in both freshwater and increase with
seawater adsorption as shown and extent in Figure 3. of arsenic The removal rate of de

arsenite
where

at

neutral

pH

in

localized
exist.

areas
The

a reducing

environment

creased with

increasing

salinity.

rate is about dized/1/day was found

8.6 X 10~5 ?M of As (III) oxi in seawater.25 The reaction rate in to decrease with a decrease The results for the on activated alumina,
in freshwater and sea

salinity. kinetics. Adsorption adsorption of As(V)

bauxite, and carbon

water are shown in Figure 2. Figure 3 shows the rate of uptake of As (III) by activated
alumina water. and In all bauxite cases, much in the freshwater adsorption and rate sea is ex

ponential.
from solution

As(V)

was
faster

found
by

to be removed
alumina

activated

the Within than by any other adsorbent. in fresh water, 50 percent of first 10 minutes, was removed by activated 53.4 fxM As(V) alumina (2 g/1); 40 percent of 53.4 ?jM (2 g/1); and 23 As(V) by activated bauxite percent of 26.4 pM As(V) by activated carbon Rates of As (III) adsorption on (3 g/1).

of 5. pH effect on adsorption FIGURE carbon [initial As(V) As(V) by activated 19.4 pMy activated carbon (2 concentration, = 0.66]. g/1 ) seawater matrix; ionic strength March 1978 497

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Gupta

and Chen

<

Activated Activated

Alumina Bauxite

(2gm/l) (2gm/l)

3L

Jl.

Jl

_L

7 Final FIGURE
fiM9

8 pH

10

II

12

6.

pH effect on adsorption
matrix].

of As(III)

[initial As(IH)

concentration,

26.0

freshwater

The effect of pH on As(V) pH Effect. adsorption by activated alumina, bauxite, and carbon and As (III) adsorption by activated alumina and bauxite was studied in the pH 2 and 12. The results are range between shown in Figures 4, 5, and 6. Arsenic (V) is effectively adsorbed in the pH range 4 to 7

by activated alumina and bauxite as shown in Figure 4. As(V) adsorption by activated alumina and bauxite was found to decrease above pH 7. Activated carbon adsorbs As(V) better in the acidic pH range between 3 and 5 than in other pH values, as shown in Fig ure 5. Adsorption at is sharply decreased

o?_I_I_I_I_I-1_i-1

8 l/C XI?3

10

12

14

16

FIGURE 7. Langmuir isotherms for adsorption of As(V) = mM of As(V) = mM of As(V)]. adsorbed/g of solids, C 498 Journal WPCF

on activated

alumina

[q?

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Arsenic

Removal

1201-1-1-1-1-i-1-r

Ol_i_i_I_i_i_i_i_i_i_I

01

23456789 1/Cxl?3

10

isotherms for adsorption of As(V) FIGURE 8. Langmuir = mM of As( V) adsorbed/g of solids, C = mM of As(V)]. Variations both lower and high pH values. in As (III) adsorption on activated alumina
and bauxite over the pH range 4 to 9 were sharply above

on activated

bauxite

[q.

pH

9,

as

shown

in Figure

6.

found

to be 300

slight.

Adsorption

decreased

data clearly indicate that activated These better in the acidic carbon adsorbs As(V) pH range; yet it exhibits poor adsorption

250 h

200

3000 9. Langmuir isotherms of adsorption of arsenic(V) FIGURE = mM of As( V)]. = [qe mM As( V) adsorbed/g of solids, C on activated carbon

March

1978

499

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Gupta

and Chen 500

400 h

o-

300

200

100 l/C

1000

1500

10. Langmuir FIGURE isotherms for adsorption of As (HI) on activated = of solids, C = mM of As(III)]. [q. mM of AS (III) adsorbed/g

alumina

600j-1-1-1-'

capacity pH for

in

comparison

to

activated

alumina

and bauxite
/a / s.wV

even

at pH
on carbon).

(the

optimum

adsorption

500

isotherm. Adsorption on activated for As(V)

carbon These are isotherm alumina carbon, shown values and the pH in

isotherms Adsorption alumina, bauxite, and

Figures were 8, 7, obtained and in 9. the

/ /

NqCI / S.W./IO

400- /
300/

pH

range 6 to 7 for adsorption

bauxite, range run in

of As(V)
whereas, was kept the and

on
for be

/ / / // <X/ / /
// /

/,er /* /

activated activated

tween
librium 6.5

and 4.

As (III)

adsorption

equi

were experiments to 8.5 with activated

alumina

range pH bauxite.

Plots of adsorption isotherms shown in Figures 10 and 11.

for As (III) are The adsorption

carried ten out in sea times, solution. chloride

200-

equilibrium

/ //y

freshwater, water, and

experiments seawater 0.67 M

were diluted sodium

100'-?-1-'

25

500 l/C

750

1000

The best fit was obtained with the Langmuir found The Freundlich type plot. plot was to fit equally well for the As (III) and As(V)
concentration culated Table range under study. The listed range. cal in Langmuir V for the are parameters concentration specified

11. Langmuir isotherms for ad on activated of As (III) bauxite sorption = of solids, [qe mM of As (III) adsorbed/g C = mM of As(III)]. 500 Journal WPCF

FIGURE

These
reactions coverage

adsorption
are is monolayer.

isotherms

indicate

that the
and the

reversible

phenomena

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TABLE V.

Parameters

in Langmuir
Activated Bauxite

adsorption

equation.
Bauxite Activated Alumina Activated

Activated

Alum

As (V)
Solvent Conc.

As (HD
Conc. ?7o Range 0.004 ..0.03

As (V)
Conc.

As (III) b #o

Matrix

b*

cot

Range
0.042

q0

Range
0.042

Water

2 480

0.052

0.107 mM
0.032

146

0.016

7 140

0.067

mikf
0.004

0.134 mM
0.032

350

0.014

S.W. 10

0.00

1 190 0.044

0.107 mM
0.032

107

0.016

0.03 mM
0.004

203

0.23

0.107 mM
0.032

96

0.019

NaCl

370

0.059

0.107 mM
0.032

86

0.017

0.03 mM
0.004

290

0.14

0.017 mM
0.011

238

0.014

S.W.

390

0.033

0.08 mM

128 0.01

0.03 mM

44

0.33

0.08 mM

63

0.018

b t qo ?

1/mJlf. mAf/g.

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Gupta

and Chen (V) removal by different

Activated

TABLE V. Efficiency of arsenic different solution conditions.

Activatec Bauxite

adsorbents

under
Activated Carbon (3 mg/1) A8(V)

Alumina

(2g/D)
Solvent Matrix As(V) (mM) 24.7 60.1 104 24.7 60.1 105.4 25.3 60.1 106.8 22 48.7 72.1 12.3 30.0 52.0 12.35 30.0 52.7 12.65 30 53.2 11.0 24.3 36.0 <7t 12.3 29.76 50.2 12.0 28.8 48.9 12.3 28.8 49.2 10.4 21.8 31.2 100 99 97 97.3 96 93 97.5 96.0 92.5 94.0 90 87 pH 6.5 6.7 6.8 6.8 6.7 6.7 6.5 6.7 6.6 6.7 6.8 6.7 As(V) (mM) 32 66.7 133 32 66.7 107 32 66.7 107 32 53.4 80

(2 g/1)
9100 16.0 33.4 66.5 15.9 33.2 53.4 15.9 33.2 53.4 15.9 26.7 40 16.0 33.3 65.9 15.8 32.8 52.2 15.7 32.8 52 15.4 25.6 38.3 100 99.7 99.0 99.0 98.8 98.0 99 99 97 97 96 95.8 pH 6.9 6.8 6.9 6.8 6.8 6.9 6.7 6.8 6.8 6.7 6.8 6.9 12.8 25.4 34.7 13.3 25.4 34.7 13.3 25.4 34.7 13.1 24.0 33.6

9100 4.26 8.46 11.6 4.43 ^8.46 11.54 4.43 8.46 11.57 4.36 8.0 11.2 4.11 7.82 9.69 4.21 7.20 8.57 4.11 7.0 8.23 3.91 6.01 7.0

%
96.5 92.4 83.5 95.0 85.1 74.3 92.8 82.7 71.1 89.7 75.1 62.6

PH
3.1 3.1 3.2 3.5 3.5 3.4 3.7 3.7 3.6 3.6 3.3 3.5

Water

S.W. 10

NaCl

S.W.

* gioo = Adsorption density at 100% removal, ~ t q Adsorption density (nM/gm of solids). Effect The change of solution composition in percentage of on arsenic adsorption. removal The adsorption chemical capacities of various are ab

sorbents
of various

was found to vary significantly in solutions of different chemical Ar compositions. senic removal is greatly affected by the pH. con The effect of initial As (III) and As(V) centrations on the efficiency of removal is shown in Tables VI and VII. The percentage of As (III) removal was greatly affected by the initial As (III) concentration. However, removal was only slightly affected by As(V) the initial concentration level. TABLE VIL Efficiency of arsenic different solution conditions.
Activated

for As (III)

and As(V)
compositions

in solution
shown

in Table VIII with a residual arsenic concen tration of 50 jug/1 at equilibrium. The data indicate that the adsorption capacity in fresh
water cent and in seawater cases. varied The as much adsorption as 80 per some capacity

on activated alumina was found to for As(V) to 0.81 vary from 4.11 (sea (freshwater) removed per gram of ab water) mg As(V)
sorbent. The silica effect .on arsenic removal

(III) removal by different

adsorbents

under

Bauxite

Activated

Alumina

(2 g/1)
Solvent Matrix As (III) As (III) (jiM) o/ioo* 6.54 13.4 26.7 6.34 ' 13.0 25.0 6.67 13.0 25.9 5.60 10.0 24.0
= <Zioo Adsorption

(2
% 79.6 73.0 70.0 74.7 69.2 66.8 72.0 68.2 62.9 70.3 61.3 57.0
removal,

g/1)
Ojoo 3.26 6.66 13.3 3.27 6.56 12.5 2.94 6.56 12.6 3.00 5.83 11.7 q 2.9 5.53 10.5 2.53 4.82 8.47 2.50 5.29 9.38 2.00 3.69 6.45 pH % 88.8 83.0 79.3 77.6 73.6 67.9 85.2 80.7 74.2 66.7 63.4 55.4 8.47 8.04 8.20 7.70 7.20 7.68 7.77 7.63 7.75 7.63 7.65 7.64

q] 2.6 4.86 9.31 2.36 4.51 8.32 2.4 4.44 8.13 1.96 3.06 6.82
100%

pH 7.99 7.69 7.80 7.23 7.30 7.38 7.41 7.45 7.49 7.52 7.48 7.56

(jiM) 6.65 13.4 26.7 6.54 13.15 25.0 5.87 13.2 25.4 6.00 11.7 23.4

Water

3.27 6.65 13.3 3.16 6.51 12.4 3.33 6.51 12.9 2.79 5.00 12.0
density at

S.W. 10

NaCl

S.W.

= t q Adsorption density (tiM/g of solids). 502 Journal WPCF

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Arsenic

Removal

TABLE VIII. Removal of arsenic achieved for 50 /xg/1 residual arsenic concentration.

by various

adsorbents
Arsenic Removed

at optimum

pH

(mg/g of Solids)
Solvent Matrix Residual Concentration Activated Alumina Activated Bauxite Activated Carbon

mg/1
0.05 0.05

As(V)
4.1 2.0

As (III)
0.2 0.10

As(V)
2.0 1.3

As (III)
0.12 0.09

As(V)
0.34 0.32

Water S.W. 10

NaCl (0.67M)
S.W.

0.05 0.05

1.7 0.80

0.17 0.07

1.0 0.60

0.08 0.07

0.30 0.25

of efficiency seawater and moval

various is listed was of on silica.

adsorbents in Table

in IX.

freshwater In gen

on

amorphous

iron

hydroxide

and

aluminum

eral, in comparison with

efficiency amounts ing concentrations

As(V),

As (III)
by of arsenic

re

hydroxide
Anderson.9 the solely is arsenic

was
The

first studied by Ferguson

general conclusion was

and
that be

affected greatly effect The removal of

vary silica

cannot mechanism adsorption terms in of molecule-surface explained electrostatic interaction, or occlu

the

not

significantly

influenced
the removal.

by

the matrix
background

interaction,

background; does affect

however, the arsenic

matrix

sion.

The

reported

zero

point

of

charge

4.5

As(V) As(V)

DISCUSSION
Little anism bauxite, to the of is known arsenic and about the adsorption on activated species carbon. The mechanism of arsenate and mech alumina, \ \

ON Ac. ALUMINA ON Ac BAUXITE

adsorption

relating arsenite ions

a as(V) ON Ac.CARBON ? As(lli) ON Ac ALUMINA \ ? As(IH) ON Ac BAUXITE \ \ \ \ \ \ \ \ \ \ \

i.of

?-A

WATER PH SM 10 NoCI (0.67M.)

--=1 S.W.

FIGURE for As
adsorbents senic

13.
at

Removal
optimum concentration.

of arsenic by various
pH for 50 ?ig/1 ar

12. Predominance FIGURE diagram (IH) and As(V) as a function of pH.

residual

March

1978

503

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Gupta TABLE

and Chen IX. Silica effect on arsenic removal efficiency.

Water Matrix Seawater Matrix g8i(x)

Initial
Adsorbent Arsenic Concentration

Initial Si (mg/1)
Concentration

gSi(s)t

tfot
26.45 25.1 22.8 5.5 4.45 3.6 16.3 25.25 23.65 4.75 3.1 2.5 7.85 7.68 7.40

X 100

X 100

Activated Alumina

As(V)
53.4 ?iM at pH 6.4-6.9

0 30 70 0 30 70 0 30 70 0 30 70 0 30 70

100 95 86 100 81
65.5

25.6 24.6 23,6 3.6 3.2 2.65 25.25 23.65 21.4 4.35 3.2 2.6

100 96 92 100 89 74 100 94 86 100 74 60

(2g/D
Activated Alumina

As(III)
13.3 tiM at pH 7.2-7.8

(2g/D
Activated Bauxite

As(V) 53.4 MM
at pH 6.0-6.6

100 96 90 100
65.3 52.6

( 2g/l)
Activated Bauxite

As(III)
13.3 nM at pH 6.8-7.0

(2g/D
Activated Carbon

As(V)
26.7 txM at pH 3.1-3.3

100 98 94

(3g/D
* q ?

adsorption density (pM/g). = in the absence of silica. t ffo adsorption density ? at x ppm of silica concentration. t <Zsi(*) adsorption density

values A

for

activated for

alumina

and

bauxite

are

tion

onto

goethite,36

for

adsorption

of

arsenate

slightly basic.34
diagram predominant arsenic species

as a function of pH is shown in Figure 12. is the predominant For As(V), H2AsOr in the species pH range between 3 and 6.5. It is apparent is the major that H2AsOr removed by activated It carbon. species would not be surprising if this is a result of
the the reaction oxo-function of the monovalent on the groups with species surface carbon

and arsenite points species, should result around pK values

interactions and specific

of inflection if electrostatic
mecha

adsorption

nisms are important. Figures 4 and 6 clearly indicate points of inflection around pH 7 and 9, which are the pK2 and pKi values of arsenic
and arsenious are by acids, respectively. mechanisms alumina and It seems

that electrostatic
sorption removal

interaction

and specific
for bauxite.

ad

important activated

arsenic

as suggested by Huang and Wu.35 There is probably little affinity between carbon surface and the nonionic, divalent and trivalent forms For As (III), H3As03 is the pre of As(V). dominant species in the pH range from 0 to 9. Figures 4 and 12 indicate that for As(V)
adsorption, negatively charged molecules were

The adsorption study was solutions of different chemical

evaluate the effect of sodium,

carried
calcium,

out
chlo

composition

in to

ride and total ionic strength. Figures 2 and 3 illustrate the effect of ionic strength on the
rate of arsenic are sorption adsorption. to be shown The slower rates in of ad seawater

removed effectively onto the slightly positive or neutral charge surfaces. For As (III) ad
sorption, moved neutral on relatively on previous H3As03 molecules charged were re neutral surfaces

than in freshwater. rates were Although reduced with salinity or ionic increasing
strength, the adsorption was reduced by no

more

(could be slightly positive

Based studies

or negative).
of anion adsorp

than 5 percent. The effect of chemical composition on adsorption capacity for 50 yxg/1
residual arsenic equilibrium concentration is

504

Journal WPCF

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Arsenic shown in Figure 13. As much as 80 percent reduction in the adsorption capacity of acti to vated alumina in seawater (as opposed
freshwater) conditions was observed. A vary

Removal of

a project engineer with Los Angeles County.

Sanitation Districts

REFERENCES
1. Arguello, Chronic the R. A., et Endemic of Rve. al., "Cutaneous Cancer Re Univ. in in Regional Arsenicism Province Argentine Cordoba, Fac. Cienc. Med.

for ing degree of salt effect was observed and As (III) adsorption on different As(V) In general, As(V) adsorbents. adsorption was affected much more by chemical composition than was As (III). in Posselt et al37 reported the reduction
Ca2+ creasing on adsorption ionic strength. oxides in on manganese with oxide 38 demon Lockwood

Cordoba, 8, 409 (1950) Proc. Conf. on Physiological Aspects of Water Quality, Public Health Service (1960).
2. Burgers, gelehrt. J., "Haff Sickness." Ges. Naturw. Kl, "Chemical Criticism Biochem. "An in Sehr. 11 Konigsb. (1934);

public."

strated that the rate of adsorption

manganese was reduced

of mercury
in the

Poll. Ams. 9 (Dec. 1936).

3. Lockemann, G., Haff Sickness, Hypothesis." 4. Wyllie, J., Arsenic of Investigation of the Arsenic Z., the 207, Source Can. 194 of Pub.

solutions. ionic strength of high presence 39 out that the Stumm and pointed Morgan role of ionic strength in decreasing adsorption of ions such as calcium might be that of the The change in of particles. agglomeration surface properties along with the possibility
of Na+ and Ca2+ ion adsorption on these ad

(1929), Water Poll. Abs., 5 (July 1932).

of Investigation a Well Water."

Health Jour., 28, 128 (1937), Jour. Amer. Water Works Asm., 29, 1202 (1937).
5. Fairhall, Drinking 6. McCabe, Water L. L. T., Water." J., "Toxic Jour. Contaminants New Eng. Water of

sorbents would reduce the availability of ad cause a change sorption sites. This would in the adsorption rate and adsorption capacity as the diffusion to partly covered sites would
progress.

Works Asm., 55, 400

et al, Supply

(1941).

of Community "Survey Jour. Amer. Water System."

that data from this study indicate As (III) is less effectively removed than As(V). The
Oxidation to achieve of arsenite to arsenate removal. effective arsenic is necessary Oxida

Works Asm., 62, 670 (1970). 7. 1962 USPHS Drinking Water

PHS Publ. No. D. National Documents, Washington, 8. Environmental Programs, ing Water 956, Government C. 20402. Agency, Protection Interim Printing

Standards,
of Office, "Water

Superintendent

tion of arsenite
been used

to arsenate
to

by
remove

chlorine
arsenic.

has

successfully40

Regulations."

Drink Primary Federal Register,

40, (248)

(Dec. 24, 1975).

CONCLUSIONS
The results of this study show that arsenic in many is a commonly occurring pollutant natural waters and that arsenic acid (H2AsOr) and arsenious acid (H3As03) species are ef fectively adsorbed in the pH range from 4
to 7.

M. A., "Chem 9. Ferguson, J. F., and Anderson, in Water of Arsenic ical Forms Supplies In "Chemistry of Their Removal." and and Distribution." Treatment Water Supply,

Alan J. Rubin (Ed.), Ann Arbor Science Publishers (1974).

S. A., A.C.S. "Review of Arsenical Series Pesti Symposium, American Editor, 7, E. A. So Chemical

10.

Peoples, cides." Woolson,

indicate Laboratory adsorption experiments that arsenic removal can be best accomplished in the As(V) state. Removal of arsenic from
wastewaters to meet water quality criteria

ciety (1975). 11. Cherkinski, S. N.,

"Purification 12. Buswell, Analysis A. M., and R. from of et

and Ginzburg,
Arsenious

F.

L,

Wastewaters."

is technically

feasible.

Water Poll Abs. 14, 315-316

"Water al, Treatment." I., "Removal Water

(1941).
Problems Jour. of Amer. in

ACKNOWLEDGMENTS
Credits. This study was supported by Grants No. ENV 75-09957 and 09957-AO1 from National RANN Science Foundation
program. 13.

Water Works Assn., 35, 1303-1311

Berezman, Arsenic Drinking

(1943). 185

Inorganic under Field

Conditions." (1965).
14. Logsdon, Metals G.

Water

Poll

Abs.,

29,

is Associate Authors. Kenneth Y. Chen Professor and Director of the Environmental at the University of Program Engineering Southern California, Los Angels. At the time of this study, Shailendra K. Gupta was a graduate student in that program. He is now

of Heavy "Removal S., et al, In Treatment." Conventional by 111 16th Water 16, Conf, Proc, Qual. of Illinois, Illinois, 133, University Urbana,

Feb.
15. Skripach, Arsenic

13-14
T,

(1974).
of Fluoride of the and Rare

et al, "Removal the Wastewater from

March

1978

505

This content downloaded from 128.189.90.141 on Wed, 4 Dec 2013 14:45:01 PM All use subject to JSTOR Terms and Conditions

Gupta

and Chen
Earth Conf. Industry." Water Poll. In Proa, 2, 5th 111-34 Internat. (New Conf, Univ. of Illinois, Urbana, Cham

Res.,

York: Press, Pergamon 16. Rosehart, R., and Lee, L., Arsenic of Removal Wastes/* Canad. M., Possible K., Water 2nd 1964). L. Mining et al,

1971). "Effective from Jour., "Arsenic and

paign, 17 (1974). "New 28. Mohler, H,

Swiss

Regulation
Waters." 31, 1421 "Chronic Region."

for
Jour.

Methods Mine Gold lune, 53 29.

Mineral and Drinking Amer. Water Works Asm., et al, L. C, Alvarado, Poisoning in the Lake

( 1939). Arsenic Water

57 (1972).
17. Magnusen, gents: in Deter Pollutions 30. Danger

Poll. Abs., 39, 430-431

A. I, Ryabinin, and Antimony Atlantic of In

(1965).

Hazard."
18. Irukayama, Black-Foot Drinking Proa,

Science,
Disease

168, 389-390
and

(1970).
between 31.

"Discussion-Relation

A. S, "Arsenic and Romanov, Zone in the Tropical of the Ocean." 2, 257-269 Geokhimiya, and Yoneyama, H, "Treatment

by Arsenic Internat. Conf. Water

the Pollution in Taiwan." Poll.

(1973).
Ohsako, N,

Res.,

Tokyo,
Press, 19.

1. 185-187

(New York: Pergamon

S., "Relation and the Be Pollu 32.

of Arsenic Containing Sulfuric Acid Waste Solutions from Sulfuric Acid Producing Plant." Chem. Abs., 78, 61988 K. (1973).
Prater, B. persion Effluent 33. "The Metal E, Characteristics to Discharges Content of the Steel Tree and Dis Works Estuary."

C. Y. S., and Chen, Shen, tween Disease Black-Foot

tion
Water

of Drinking Water
In Proa, 2nd

by Arsenic
Internat. Conf.

in

Taiwan." York:

Water Poll Cont., 74, 63 (1975).

et H. Larsen, P, of Metal-Bearing Treatment "Chemical al, Mine Jour. Drainage."

20.

Poll. Res., Tokyo, (New 1, 173-190 Press, 1964). Pergamon N. A. and Methodology Curry, "Philosophy of Metallic Presented Waste Treatment." at 27th Purdue Purdue Industrial University Waste Con Re ference, (1972). R. G., "Arsenic from Metallurgical

Water Poll. Control Fed., (1973).

34. Parks, G. A, "The Solid Complex Isoelectric Hydroxides, System." Oxides, Hydroxo 35.

45,
Points and

1682-1695
of Solid

21.

Lee, J. Y., and Rosehart, Process moval by Sorption waters." Canad. Mining Beilack, Water." Patterson, Technology." Inc., Ann E., "Arsenic Journal J. W.,

Aqueous Chem. Rev.,

Waste

65,177(1965).
and Wu, Min-Hwang, Chin-Pao, Huang, Removal "Chromium Carbon Adsorp by Poll. Control tion." Jour. Water 47, Fed.,

(CIM) Bull., 65, 11, 33-37

22. Removal Amer. Water

(1972).
from Works Potable Assn., 36.

2437-2446
Hingston, Goethite Posselt, Hydrous 38. Lockwood, Oxides." H. F.

(1975).
"Ani?n J, et al, and Gibbsite." S, et al, "Cation Dioxides." Adsorption Jour, of Sorption Env. by Soil on Sei.

63, 454-458
23.

(1971).

Treatment Water "Waste Ann Arbor Science Publ., 1-11 pp. (1975). Arbor, Mich., I., and

Science, 23, 2 (1972).

37. Manganese R. A, Env. and Sei.

24.

Sergeyeva,

I. L., Khodskovsky, Conditions of Formation "Physiochemical in Hydrothermal De of Native Arsenic

E.

Tech., 2, 1807-1903 tion of Hg(II)

(1968).
Chen, Tech., K. 7, Y, "Adsorp 1028-1033

posits."
25. Johnson, water." D.,

Geokhimiya,
"Arsenate Ph.D. Thesis,

7, 846
and

(1969).
in Sea 39. Con Limi Micro

by Hydrous

Manganese

Arsenite University

(1973).
Stumm, and Morgan, W, J. J, "Aquatic Introduction Chemistry?An Emphasizing in Natural Chemical Waters." Equilibria

films, Ann Arbor, Michigan

26. Silker, W. centration B., in "Variation the Columbia

(1972).
River." of Some and

in Elemental

nology Oceanography,
27.

9, 540-545 16th Water

(1964).
Trace Ground 40.

Wfiey-Interscience
Shen, Y. S. Drinking "Study Water."

Publ, New York (1970).

of Arsenic Jour. Removal Amer. from Water

W. "Occurrence H., Durum, in Waters Metals Surface

Waters."

In Proa,

Quality

Works Assn., 65, 543-548

(1973).

506

Journal WPCF

This content downloaded from 128.189.90.141 on Wed, 4 Dec 2013 14:45:01 PM All use subject to JSTOR Terms and Conditions