Chemical Engineering Journal 203 (2012) 285293

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Chemical Engineering Journal

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Fixed bed adsorption of As(III) on iron-oxide-coated natural rock (IOCNR)

and application to real arsenic-bearing groundwater
Sanjoy Kumar Maji, Yu-Hsuan Kao, Chin-Jen Wang, Guang-Sin Lu, Jia-Jing Wu, Chen-Wuing Liu
Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC

g r a p h i c a l a b s t r a c t

h i g h l i g h t s
" As(III) removed column efciency

"

"
"

"

using IOCNR was evaluated by logit

method.
No oxidizing agent required to
convert As(III) to As(V), in situ two
step mechanism is proposed.
Regenerated bed with NaOH could
be re-usable.
Efuent water quality of the treated
real arsenic-bearing sample could be
usable.
Geochemical model, PHREEQC,
accurately reected the column
experimental results.

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 18 May 2012
Received in revised form 5 July 2012
Accepted 6 July 2012
Available online 15 July 2012

This study examines the efciency of the xed-bed adsorption of As(III) on iron-oxide-coated natural rock
(IOCNR) in a contaminated aquatic environment. We considered a column with a diameter of 2-cm and
varying bed depths, including 10 cm, 15 cm, and 20 cm. The breakthrough (C/Co = 0.016) times were
31.0 h, 49.0 h, and 63.0 h, and the exhaust (C/Co = 0.90) times were 60.0 h, 90.0 h, and 110.0 h, with an
up-ow rate of 8 mL/min, respectively. The volume of the contaminated water treated at the breakthrough points was 14.88 L, 23.52 L, and 30.24 L, and at the exhaust points 28.80 L, 43.20 L, and
52.80 L, respectively when As(III) concentration was 0.6 mg/L. The columns were designed using the logit
method to evaluate the adsorption rate (K) and column efciency (N). The 10-cm exhaust bed was regenerated with 4% NaOH, and its performance was evaluated. This study proposes an in situ two-step mechanism, oxidation of As(III) to As(V), and subsequent adsorption on IOCNR. A column (10 cm) performance
of real arsenic-bearing groundwater was evaluated. Results indicate that the treated efuent water quality is suitable for domestic use. Moreover, the experimental results agreed well with the geochemical
modeling using computer program PHREEQC.
2012 Elsevier B.V. All rights reserved.

Keywords:
As(III)
Column adsorption
Natural rock
Logit model
Real arsenic sample
Geochemical modeling

1. Introduction
Researchers have made numerous attempts to remove arsenic
from aqueous media [18] because of its toxicity to living organisms and concerns of public health. However, the developed methods are superior in removing pentavalent arsenic, arsenate, As(V)
Corresponding author. Tel.: +886 2 33663473; fax: +886 2 23639557.
E-mail addresses: maji.sanjoy@gmail.com
lcw901015@gmail.com (C.-W. Liu).

(S.K.

Maji),

cwliu@ntu.edu.tw,

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.033

than trivalent arsenic, arsenite, As(III) from water medium,

because As(III) is stable at a pH of 0 to 9 as a neutral H3AsO3,
2
3
whereas H2 AsO
3 , HAsO3 , and AsO3 are stable in the pH ranges
of 10 to 12, 10 to 13, and 10 to 14, respectively. By contrast,
As(V), the neutral H3AsO4, the monovalent (H2 AsO
4 ), the divalent
3
(HAsO2
),
and
the
trivalent
(AsO
)
ions
are
stable
at
the pH ranges
4
4
of 0 to 2, 3 to 6, 7 to 11, and 12 to 14, respectively [9]. This
requires the pre-oxidation of As(III) to As(V) using certain toxic
oxidizing agents, such as hypochlorite bleach or potassium permanganate, which subsequently necessitates post-treatment of

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

the efuents [10,11]. Despite these disadvantages, adsorption is a

highly efcient method for removing contaminants from aqueous
media because of its simplicity, ease of operation and handling,
sludge-free operation, and regeneration capacity. Considering the
afnity of arsenic toward iron, various iron-based media have been
developed and used effectively as adsorbents for removing both
As(III) and As(V) from water. However, the ne powdery form of
iron oxides hinder their separation from the aqueous solution following the adsorption activity, and limits their use in column operations. Furthermore, the lack of extensive study, low sorbent
adsorption capacity, high pressure loss during column runs, and
regeneration difculty are additional disadvantages that limit their
use [12].
Among the various forms of arsenic, As(III) and As(V) are
responsible for groundwater contamination, As(III) has greater toxicity and more mobility compared to As(V). However, As(III) readily attacks and denatures the sulfhydryl radicals of proteins and
enzymes, and is a serious global problem [1316]. Though the
leaching of arsenic into groundwater is still not clearly understood,
it is considered relatively geogenic. The oxidation of arsenic rich
iron-pyrites may be a possible mechanism [17]. The biochemical
cycles of iron (Fe), sulfur (S), and arsenic (As) are closely linked
[16,18]. Long-term ingestion of high levels of arsenic-contaminated water, over the maximum contaminant level (MCL) of
0.01 mg/L set by the World Health Organization (WHO) causes dermal problems, headaches, vomiting, cancers in different organs
and, even death. This is why in 1993, in Geneva, the WHO established a guideline for the MCL of arsenic in drinking water at
0.01 mg/L, though different countries have established their own
guidelines [19].
To address this issue, studies have examined the removal of arsenic from aquatic environments using different adsorbents; however, most studies primarily considered batch adsorption [20,21].
Few reports on the removal of arsenic in xe-bed media have been
published [2225]. Observation of xed-bed columns is vital for
predicting the column breakthrough or shape of the wave front,
which determine the operation life span of the bed and the regeneration time. Additionally, the observation of continuous ow systems is also important for obtaining basic engineering data. Batch
studies of adsorption capacities may not provide accurate scale-up
information regarding the column operation system [26] because
of several undetermined factors. To develop an alternative, this
study evaluates the removal of As(III) by a continuous ow xedbed column system with different bed depths, using the developed
adsorbent iron-oxide-coated natural rock (IOCNR), and including
the regeneration and re-adsorption. This study also implements
xed-bed column on real arsenic-bearing potable sample. The arsenic adsorbed beds were designed by the logit method.
General geochemical models have been developed to simulate
the specic scenario of the reactive transport of As [27,28] in the
environment and particularly the modeling of As interaction with
the major redox-active elements, such as carbon, oxygen, nitrogen,
sulfur, and iron is of importance [29] though comprehensive eld
were limited [3032]. The PHREEQC [3335], a computer program
for simulating geochemical reactions and transport processes in
natural or polluted water, is capable for performing complex speciation, batch-reaction, one-dimensional transport, inverse geochemical modeling calculations and has widely been used for
researches involving computational thermodynamic equilibrium
[36,37]. The geochemical model PHREEQC, version 2.18 is adopted
to simulate the arsenic ltration experiments in iron-oxide-coated
natural rock (IOCNR). Finally, this study proposes an in situ twostep mechanism, the oxidation of As(III) to As(V) and subsequent
adsorption on IOCNR.
The granulated natural rock (NR) used in this study is considered to be granite rock. Granite is an igneous rock formed from

magma. Granitic magma has numerous possible origins, but it always intrudes other rocks. Most granite intrusions are typically
at a depth between 1.5 km and 50 km in the thick portion of the
continental crust. Although the elemental composition of granite
is dependent on its source, all types of granite share common elemental constituents [38]. The granulated NR rock used in this
study was crushed and loaded with Fe(III).
2. Materials and methods
2.1. Reagents
All chemicals were of analytical reagent grade, and were used
without further purication. All aqueous solutions were prepared
in Milli Pore (MP) water. The MP water was tested for arsenic,
but the level was not within the detection limit (<5 lg/L). As(III)
stock solution with an arsenic concentration of 20 mg/L was prepared using NaAsO2 (SigmaAldrich) and diluted as required.
Concentrated HCl, NaOH, Fe(NO3)3.9H2O, Na2EDTA.2H2O,
NH4OH, NH4Cl, MgCl2.6H2O, NaBH4, Erichrome black T, and 2methoxy methanol were purchased from J.T. Baker (USA). The
chemicals were used as received. Moreover, appropriately diluted
solutions were prepared when required.
2.2. Apparatus and instruments
The apparatus used in this study was rst soaked in concentrated HNO3 (J.T. Baker) for 12 h, washed in MP water followed
by tap water, and then dried in a hot-air oven. A Perkin Elmer
AAnalyst 200 atomic absorption spectrophotometer coupled with
high-performance liquid chromatography equipment (HPLC,
Perkin Elmer, series 200) was used to quantify arsenic. This study
employed a JEOL JSM-7000F eld scanning electron microscope
(Japan) to perform SEM and EDX, and an electrical balance (A&D
Company Limited, Fx-200i, Japan) was used for weighing. A
mechanical orbital shaker (Deng Yng, D600, Taiwan) was used to
shake all solutions, and a Gilson micropipette with disposable tips
was used to add samples. All the pH values were measured using a
digital pH meter (Suntex pH meter, sp-2300, Taiwan), and an
electrically-operated ow rate-controlled peristaltic pump (Chrom
Tech, Taiwan) was used to charge samples to the column. The total
amount of iron in aqueous media before and after treatment with
IOCNR was measured by the ferrozine method using a spectrophotometer (Thermo, Genesys 10 vis, Japan).
2.3. Adsorbent preparation and characterization
The iron-oxide-coated natural rock (IOCNR) adsorbent used in
this study was prepared by heating 100 g of granulated natural
rock (NR) (0.148 mm) in a solution of Fe(NO3)39H2O, which was
produced by dissolving 50 g Fe(NO3)39H2O in 150 mL of MP water.
The procedure for preparing and characterizing of IOCNR has been
reported previously [9]. Table 1 shows the elemental compositions
of the adsorbent obtained from EDX.
2.4. Batch adsorption study
Batch experiments were carried out at 25 2 C using 50 mL of
synthetic As(III) solution in a mechanical shaker, with an agitation
speed of 180 rpm. The samples were placed in 100 mL polyethylene bottles. Adsorbent doses of 0 to 15 g/L were used to evaluate
the optimal dose. The pH of the medium was 5.7 0.2, and the
As(III) concentration was 0.6 mg/L. The optimal adsorbent dose,
13 g/L, reduced the concentration of As(III) to the MCL of
0.01 mg/L. Thus this dose was used in the observations.

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

Table 1
Physical and chemical properties of IOCNR.
Properties

Quantitative value (from batch study)

Geometric mean size (mm)

Bulk density (g/cm3)
Surface area (m2/g)
Pore volume (cm3/g)
Al (%)
Fe (%)
Si (%)
C (%)
Na (%)
Mg (%)
Ca (%)
As (%)
O (%)
pHzpc
Cation exchange capacity (CEC)

Before Fe (III) loaded

After Fe(III) loaded

After As(III) loaded

0.148
3.3
15.3120
0.01347
3.14/1.88(w/a)

9.93/5.70(w/a)
18.56/24.92(w/a)
1.42/0.99(w/a)
0.63/0.42(w/a)
1.51/0.61(w/a)
0.21/0.04(w/a)
65.01/65.52(w/a)
5.8
8.6 mequiv/100 g

2.72/1.76(w/a)
11.78/3.69(w/a)
9.29/5.78(w/a)
15.75/22.94(w/a)
0.97/.74(w/a)
0.80/0.58(w/a)

0.40/0.09(w/a)
59.08/64.60(w/a)

1.67/1.01(w/a)
7.67/2.25(w/a)
5.57/3.25(w/a)
20.02/27.29(w/a)
0.70/10.50(w/a)
0.45/0.30(w/a)

0.02/0.00(w/a)
63.90/65.40(w/a)

w = weight%, a = atomic%.

We conducted an equilibrium study of the contact time of an

As(III)-contaminated sample with adsorbent, using an arsenic concentration of 0.6 mg/L. The pH of the medium was 5.7 0.2. The
shaking time varied from 0 to 7 h. The equilibrium time was
found to be 6 h and this duration was used in further experiments. The samples were left to stand for 5 min after shaking,
and were then ltered through Advantec 5C lter paper. The concentration left in the ltrate was subsequently analyzed.
2.5. Fixed bed column studies
Fixed bed column study was conducted using borosilicate glass
columns of 2 cm internal diameter and 55 cm length. The column
was packed with IOCNR between two supporting layers of glass
wool (3 cm) (Fig. 1) to prevent the adsorbent oating from the
outlet. The bed depths were 10 cm, 15 cm, and 20 cm, and the cor-

responding beds were loaded with 48 g, 73 g, and 97 g of

IOCNR, respectively. The column was charged with As(III)-bearing
synthetic water in the up-ow mode, with a volumetric ow rate
of 8 mL/min (1.538 m3/m2 h). The initial As(III) concentration
was 0.6 mg/L and the pH was 5.7 0.2. Samples were collected at
certain time intervals and then analyzed for remaining arsenic
concentrations.
As(III)-exhausted IOCNR packed 10-cm column can be regenerated using 4% NaOH. Exhausted bed was charged using 4% NaOH
solution with the same up-ow rate of 8 mL/min until 99% of
the adsorbed As(III) was recovered. Subsequently, the bed was
reconditioned with MP water for 40 h in the same up-ow mode,
using the same ow rate, until the pH of the efuent water was 7.0.
Then the bed was recharged with the same concentration of As(III),
with the same ow rate, and the performance was evaluated. In all
the cases the temperature was 25 2 C and the pH was 5.7 0.2.

Fig. 1. Schematic diagram of small scale column used in laboratory experiment and geochemical modeling.

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

2.6. Analysis of column data

2.6.1. Mathematical analysis
The loading behavior of As(III) removed from a xed bed solution containing IOCNR media is shown by the breakthrough curves
(Fig. 2). The breakthrough curves are expressed using normalized
concentrations, and dened as the ratio of efuent As(III) concentration to the inlet As(III) concentration (C/Co) as a function of time
(t) or volume of efuent (Veff) for a given bed height (h). The volume of the efuent (Veff) can be calculated using the following
equation:

V eff Qttot

where Q is the volumetric ow rate (mL/min) and ttot is the total

time of ow till exhaust (h). The total adsorbed As(III) quantity
(mg) in the column for a given feed concentration (Co) and ow rate
(Q) can be found by calculating the area under the breakthrough
curve (A), which is obtained by integrating the adsorbed As(III) concentration (Cads, mg/L) = inlet As(III) concentration (Co) efuent
As(III) concentration (C) versus time t (h) plot by the following
equation:

qtot

QA
Q

1000 1000

C ads dt

t0

The total amount of As(III) fed to the column (X; mg) is calculated using the following equation:

Fig. 3. Scheme of bed depth.

ttot

C o Q tot
1000

The total removal of As(III) by the column, that is, the column
performance by IOCNR can be calculated using the following
equation:

AsIIItot removal%

qtot
 100
X

QC o
QC
dC
dq
Vp
m

dt
dt
1000 1000

Exhause (90%)
Breakthrough (1.66%)
10 cm real
10 cm reg
10 cm
15 cm
20 cm

2.6.2. Modeling of breakthrough curves

Predicting the breakthrough curve of the efuent is the primary
factor inuencing the successful design of a column adsorption
process. Developing a model that accurately describes the dynamic
behavior of adsorption in a xed-bed system is really difcult. The
process is not performed in a steady state because the adsorbate
concentration changes as the feed moves through the bed. The fundamental transport equations for a xed bed are those of material
balance between solid and uid. Fig. 3 illustrates a variation of this
balance during the reaction. The equation for mass balance material can be stated as follows: input ow = output ow + ow inside
pore + matter adsorbed onto the bed. The mass balance material
equation for this system can be expressed mathematically as
follows:

where QCo is the inlet ow of As(III) in the column (mg/min), QC the

outlet ow of As(III) leaving the column (mg/min), Vp the porous
volume (L) (Vp = (1/(1  e))V where V is the bulk volume (L) and e
is the void fraction in the bed), Vp (dC/dt) is the ow rate through
the column bed depth (mg/min), and m (dq/dt) is the amount of
As(III) adsorbed onto IOCNR (mg/min), where m is the mass of
IOCNR (g) and dq/dt is the adsorption rate (mg/g min). The results
of Eq. (5) show that the linear ow rate (u = Q/Sc, where Sc is the column section, m2), the initial solute concentration, the adsorption
potential, and the porous volume are the factors determining the
balance of a given column bed depth. Therefore, examining these
parameters and estimating their inuence is necessary to optimize
the xed-bed column adsorption process. A number of complex
mathematical equations and numerical models are typically required to estimate these parameters. However, here in this study,
a simple logit model was used to determine the column efciency
[39].

0.8

C/ C 0

0.6

0.4

0.2

3. Results and discussions

3.1. Effect of contact time on adsorption

0
0

40

80

120

Time (h)
Fig. 2. Breakthrough curves of As(IIII) and real sample at different conditions.

In the batch experiments, the equilibrium time (optimal contact

time between the adsorbate and adsorbent) for the uptake of arsenic using IOCNR had to be determined. The initial As(III) concen-

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

3.2. Column study

The adsorbate (As(III)) plot of exit concentration, as a function
of lapse time or volume of treated water, is the breakthrough
curve. The point on the breakthrough curve where arsenic concentrations reaches its maximum allowable value of 0.01 mg/L (corresponding to C/Co = 0.016) was set as the breakthrough point, and
the corresponding to 90% of the inuent concentration as the
point of exhaustion. We selected three bed depths, 10 cm,
15 cm, and 20 for column studies and evaluated their efciency towards As(III). An MP water-spiked As(III) solution was charged
through the columns in an up-ow mode with a volumetric ow
rate of 8 mL/min (1.538 m3/m2 h). The marginal ow rate selected had an adequate amount of efuent water for practical purpose after a period. This range is also common in column design
[23]. The up-ow mode was employed to avoid unnecessary column logging. The As(III) concentration was 0.6 mg/L, optimized
from batch studies. The breakthrough times (Fig. 2) were determined to be 31.0 h, 49.0 h, and 63.0 h for the columns in bed
depths of 10 cm, 15 cm, and 20 cm, respectively, and the exhaust
times were 60.0 h, 90.0 h, and 110.0 h. The volume of contaminated water treated at the breakthrough points for the corresponding bed depths was 14.88 L, 23.52 L, and 30.24 L, respectively. In
contrast, the volume of the contaminated water treated at the exhaust points was 28.80 L, 43.20 L, and 52.80 L, respectively.
Different parameters for the column studies, such as the time
required for the exchange zone to move its own height (tz), height
of the exchange zone (hz), exchange zone moving rate (Uz), bed saturation (%), empty bed contact time (EBCT), and minimum bed
depth required by the breakthrough concentration (xo), have been
calculated using mathematical equations [23,40]. The results are
shown in Table 2.
Column design parameters are crucial for implementing columns practically. In this study, the columns were designed using
the logit method [39,41,42]. The linearized logit equation can be
written as follows:


ln


C
KNx

KC o t
Co  C
V

x0



V
Co
ln
1
KN
CB

where x0 is the minimum column height required to produce an

efuent concentration CB (breakthrough concentration, 0.01 mg/L).
The plot of ln[C/(Co  C)] versus time t, provides a straight line
producing KCo as the slop and KNx/V as the intercept, from which
K and N can be calculated. Table 3 shows the linearized logit equations for different bed depths (10 cm, 15 cm, and 20 cm). The calculated K values were 0.38 L/mg h, 0.23 L/mg h, and 0.16 L/mg h
and the N values were 454.44 mg/L, 483.87 mg/L, and 426.55 mg/
L for the minimum bed depths of 3.83 cm, 5.75 cm, and 9.20 cm,

Table 3
Logit equation of different bed depths.
R2

Bed height

Equation

10 cm
15 cm
20 cm
10 cm
10 cm

y = 0.2281x
y = 0.1407x
y = 0.0944x
y = 0.3453x
y = 0.3491x

1st cycle
1st cycle
1st cycle
2nd cycle
1st cycle real sample

0.9975
0.9938
0.8976
0.9223
0.9867

11.228
10.854
8.8748
5.7995
3.9823

80

60

40

20

0
0

200

600

800

1000

Volume of NaOH (mL)


ln


C=C o
KNx

KC o t
V
1  C=C o

where C is the solute concentration at any time, Co is the initial solute concentration (0.6 mg/L), V is the approach velocity (153.8 cm/
h), x is the bed depth (10 cm, 15 cm, and 20 cm), K is the adsorption
rate constant (L/mg h), and N is the adsorption capacity of the column (mg/L). By rearranging Eq. (6), we obtained the following:

Desorbed As (III) (mg /L)

tration was set at 0.6 mg/L, the adsorbent dose was 13 g/L, and the
adsorbent particle size was 0.148 mm. The pH of the medium was
5.7 0.2. The shaking time varied between 0 and 7 h, and the agitation speed was 180 rpm. Within 1 h of shaking, 56% As(III) was
adsorbed on IOCNR. Shaking for another 5 h removed 98.5%
As(III) from the aqueous medium. A contact time of 6 h was selected to ensure that the removal of As(III) achieved equilibrium.
(Notably, only 30% As(III) was removed using an adsorbent dose
(adsorbent without Fe(III) loaded) of 20 g/L, when the initial As(III)
concentration was 0.5 mg/L, in a contact time of 6 h, when all other
experimental conditions were held constant).
Batch adsorption studies were conducted using various adsorbent doses for optimization. The initial As(III) concentration was
0.6 mg/L. Other experimental conditions were kept constant. The
adsorbent dose was varied between 0 and 15 g/L. Approximately
98.5% As(III) was removed at an adsorbent dose of 13 g/L, which
was selected as the optimal dose.

Fig. 4. Recovery prole of As(III).

Table 2
Constant parameters of logit model for different bed depths.
Arsenic (III), bed height (cm)

tz (h)

K (L/mg h)

hz (cm)

N (mg/L)

Uz (cm/h)

EBCT (min)

xo (cm)

Sat (%)

10
15
20
10
10

29
41
47
17
10

0.38
0.23
0.16
0.58
8.73

5.52
5.01
4.81
9.0
6.13

454.44
483.87
426.55
153.80
7.02

0.19
0.12
0.10
0.53
0.62

4.10
6.20
8.25

3.83
5.75
9.20
7.03
2.80

92.86
95.03
93.76
81.22
70.29

(1st cycle)
(1st cycle)
(1st cycle)
(2nd cycle)
(1st cycle, real sample)

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

respectively for the corresponding bed depths of the column (Table

2). This study compared the column efciencies with that of previous studies [22,23]. No signicant leaching of the component from
the adsorbent was noticed. The iron concentration of the efuent
was less than 0.1 mg/L, and the hardness was 20 mg/L.
The As(III)-exhausted (after 60 h) 10-cm bed depth column was
regenerated using 4% NaOH, with the same experimental conditions. The eluents were collected with respect to bed volume
(31 times), and the As(III) contained was quantied. After recovering 99% of the adsorbed As(III) (Fig. 4), the bed was reconditioned by washing with MP water, using the same up-ow rate
for 40 h to achieve a pH of 7.0. Then, the reconditioned bed
was recharged again using MP water-spiked As(III) solution with
the same concentration of 0.6 mg/L and the same up-ow mode.
The breakthrough time occurred after 8.0 h, and the exhaust time
occurred after 25.0 h, and the corresponding volumes of As(III)
contaminated water treated were 3.84 L and 12.0 L, respectively.
The adsorption rate constant, K (L/mg h), and the adsorption capacity of the column, N (mg/L), were calculated using the logit model
(Table 2). The adsorption efciency of the regenerated bed decreased to 34% in the second-cycle. Alkaline treatment of the exhausted IOCNR with NaOH removes the coated Fe(III) as Fe(III)
hydroxide from the adsorbent surfaces, which may reduce the arsenic removal efciency of IOCNR [9].
3.3. Application to the real arsenic bearing water
More than 34 samples of real arsenic-bearing groundwater
were collected from different wells in the Lanyang Plain, a severely
arsenic-affected area, in north eastern Taiwan, during May 2010. A
highly arsenic-contaminated groundwater found at Loug-de well
(40 lg/L) was taken for the treatment. Table 4 lists the characteristics of the groundwater (before and after treatment with IOCNR
at breakthrough time) supplied by the Agricultural Engineering Research Centre, Tao-Yuan, Taiwan.
IOCNR packed 10-cm bed depth column was considered for the
study. The column was charged with the sample water. The upow rate was 8 mL/min. The arsenic(tot) concentration was 40 lg/
L, and the pH was 7.5. All the other experimental conditions were
xed. The breakthrough (C/Co = 0.25) and exhaust (90%) times were
16 h and 26 h, respectively. For the times, the corresponding volumes of water treated were 7.68 L and 12.48 L, respectively. The
bed was designed using the logit method, and the K and N were
calculated (Table 2). The results reveal that the column efciency
(7.02 mg/L) of the method used in this study was lower than that
of the synthetic sample (10-cm bed depth of synthetic As(III) sample). The combined effects of sulfate, phosphate, bicarbonate, and
total organic carbon (TOC) present in the real sample (Table 4)

Table 4
Water quality of the real arsenic-bearing water (before and after treatment).
Parameter

Before treatment

After treatment (at breakthrough)

pH
EC (ls/cm)
Fetot (mg/L)
Cl (mg/L)

7.50
928.00
0.123
9.00
10.00

6.80
830.00
<0.20
8.00
8.60

PO3
4

0.022
2.44
3.56
8.00
1.54

0.02
2.40
3.64
7.80
1.40

CO2
3

40.00
845.00
19.20

<10.00
800.00
18.00

30.00

25.00

SO2
4 (mg/L)
Mn (mg/L)
Mg (mg/L)
Ca (mg/L)
TOC (mg/L)
(mg/L)
As(total) (lg/L)
HCO
3 (mg/L)
(mg/L)
Hardness (mg/L)

may have caused the slow adsorption rate. At a low pH (<7), sulfate
ion competes with arsenic removal because it forms an outersphere complex on the surfaces of the adsorbent surfaces [43].
The presence of PO3
4 affects arsenic removal substantially because
it binds with the adsorbent components (Al, Fe). Bicarbonate forms
inner-sphere complexes with the adsorbent components (Al, Fe).
The organic carbons (TOC), which are macromolecular compounds,
scavenge the adsorbent sites and slow the adsorption process [9].
The efuent water quality (Table 4) suggests that the arsenic removed water could be used for household purposes.
3.4. Postulated geochemical model
PHREEQC, the computer program, version 2.18 is widely used
for simulating geochemical reactions and transport processes in
natural or polluted water. The program is based on the equilibrium
chemistry of aqueous solutions interacting with minerals, gases,
solid solutions, exchangers, and sorption surfaces. PHREEQC has
the capability to model varied one-dimensional transport processes, including diffusion, advection, and dispersion. These processes can be combined with equilibrium and/or chemical kinetic
reactions. Fig. 1 shows the conceptual model of xed-bed column
used in geochemical modeling. Several processes have been accounted for the basic calculations in this study, including equilibrated speciation, equilibrium phases, surface sorption, ion
exchange and forward transport modeling that are similar to that
of the control conditions of laboratory xed-bed experiments.
The conceptual model assumed that As(III)-contained synthetic
water/groundwater (solution 0) initially charged in different
depths of the xed-bed column. The xed-bed columns are assumed to have Fe oxyhydroxides (@FeOOH) and goethite with cation exchange capacity and sorption sites (solution 1). Initially, the
ion exchange and surface sorption were equilibrated between the
solid and aqueous phases. Different composition of recharged
water (As(III)-contained synthetic water and As-bearing groundwater) was continuously purged into the single cell and then equilibrated with the minerals by ion exchange and surface sorption.
The advection and dispersion transport of PHREEQC with single
cell representing the groundwater ow in aquifer.
The experimental conditions like, arsenic concentration, bed
depths, and ow-rate were the input data in PHREEQC to perform
the computational programme. The IOCNR is assumed to be = FeOOH and goethite and were considered as the initial conditions for
all cases of 1to -3 (10 cm, 15 cm, 20 cm) and 4 (10 cm, real sample)
(SOLUTION 1). In all 4 cases, the cation exchange sites and surface
sites were dened with EXCHANGE 1 and SURFACE 1, respectively
[44]. The initial exchange and surface compositions were determined by the equilibration of Fe-oxides at different recharges.
The database, WATEQ4F.dat included the element arsenic and surface complexation constants from Allison [45] (Table 5). After the
equilibrium calculation of geochemical reactions, the different
recharges (As (III)-contained synthetic water and As-bearing

Table 5
Reaction and thermodynamic constant for calculation of surface-complexation
reactions in PHREEQC.
Adsorption reaction
Case 1 to -3

H3AsO4 +
H3AsO4 +

Case4

Hfo_wOH = Hfo wOHAsO3

4
Hfo_sOH = Hfo sOHAsO3
4 +

LogK (kJ/mol)
+ 3H

3H+

+
H3AsO4 + Hfo_wOH = Hfo wHAsO
4 + H + H2O
H3AsO4 + Hfo_wOH = Hfo_wH2AsO4 + H2O
+
H3AsO4 + Hfo_wOH = Hfo wOHAsO3
4 + 3H
+
H3AsO4 + Hfo_sOH = Hfo sOHAsO3
4 + 3H

Hfo = Oxidized iron.

10.12
10.12
2.81
8.61
10.12
10.12

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

Table 6
Summary of simulated and column experimental result.
Bed depths

10 cm
15 cm
20 cm
10 cm(real)

Experimental data

Table 7
As(III) removal with pH variation.

Simulated data

Breakthrough
time (h)

Exhaust
time (h)

Breakthrough
time (h)

Exhaust
time (h)

31
49
63
16

60
90
110
26

33
50
66
15

60
90
120
26

groundwater) were purged into the cells in 4 cases by advection

and dispersion. The dispersivity was assumed to 0.015 m for IOCNR
in the transport modeling. A total of 2308, 1539 and 1154 shifts
were specied, which were equal to the different pore volumes because only one cell system was used (case 1, 2, and 3) and the corresponding time step was 0.065, 0.0975, and 0.013 h, respectively.
Hence the entire simulation time was 150 h. The shift and time
step in case 4 were 770 and 0.065 h, respectively, while the entire
simulation time was 150 h. Table 6 shows the simulated results of
all 4 cases. All of the breakthrough times in the simulated result are
very similar to that of the xed-bed column studies. Fig. 5 shows
the coefcient of determinant in 4 cases and are higher than 75%.
In contrast, our simulation results indicate that the models to use

pH

As(III) removal(%)

3.0
4.12
5.70
7.30
8.30

83
93
98.5
98
96

the scaling approach succeed to make good predictions. This proposed scaling approach offers a promising method for surface complexation models.
3.5. Effect of pH and probable mechanism
The chemical characteristics of both adsorbent and adsorbate
may vary with pH. Neutral and different As(III) oxyanions are present in aqueous media at various pH values. Hence, the adsorption
study must be carried out at various pH of the media, because pH
signicantly inuences the arsenic uptake capacity and the effect
of solution pH on the adsorption of As(III) by IOCNR. In the batch
study, the pH of the medium varied from 3.0 to 8.3, with all other
experimental conditions xed. Table 7 presents the As(III) removal

Fig. 5. Comparison of the simulated results and experimental results in cases 14.

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S.K. Maji et al. / Chemical Engineering Journal 203 (2012) 285293

Fig. 6. Proposed two-step mechanism of As(III) removal.

efciency of the medium at various pH. As stated previously, trivalent arsenic is stable at a pH of 0 to 9 as neutral H3AsO3; whereas
2
3
H2 AsO
3 , HAsO3 , and AsO3 are stable in the pH ranges of 10 to 12,
10 to 13, and 10 to 14, respectively. As(III) adsorption is highest
at a pH of 7.0. In this study, the zero point charge (ZPC) of IOCNR was
5.8. Bellow ZPC, the surface charge is positive, whereas above Zpc, it
is negative. The neutral As(III) species was, therefore, assumed to
adsorb onto IOCNR through weak van der Waals forces of attraction,
a form of physical adsorption [46]. The As(III) removal efciency
gradually decreased with increases in the pH (>7.0) of the medium
because of the repulsion between the negative de-protonated arsenite species and the negative surfaces of the adsorbent.
This phenomenon can be explained further by postulating a
simple in situ two-step reaction mechanism that involves in the
adsorption of As(III) on Fe(III) oxide-coated adsorbent. Fig. 6 displays this proposed reaction mechanism. In a water medium (acting as an oxidant), the surfaces of Fe(III) oxide-coated adsorbents
oxidized to = FeOOH, exhibiting higher active surface areas than
the simple oxides of iron do. Dynamic electrochemical studies have
shown that water is the primary oxidant for iron. Examinations
using infrared spectroscopy (IRS) and extended X-ray absorption
ne structure (EXAFS) have revealed that As(III) and As(V) form
bidentate, bimolecular surface complexes with = FeOH (or = FeOOH or hydrous ferric oxide, HFO), as the primary species tightly
immobilized on the iron surface. In the rst step, oxyanions of
As(III) in the water medium are oxidized to oxyanions of As(V) in
the presence of dissolved oxygen on the IOCNR surfaces. In the second step, the converted As(V) oxyanions (chemical moiety) are attracted to the iron-oxide-coated surfaces and bound with the
active sites (AOH groups), through weak intermolecular H-bondings. Finally they are bound with the surfaces, eliminating water
molecules. Therefore, pretreating As(III) with external oxidizing
agents, such as hypochlorite bleach or potassium permanganate,
is not required [10,11,47].

4. Conclusion
The developed adsorbent IOCNR was used to remove As(III)
from aqueous media by column study. This study used three bed
depths namely, 10 cm, 15 cm, and 20 cm with borosilicate glass
columns. The columns were treated with an As(III) concentration
of 0.6 mg/L and an up-ow rate of 8 mL/min. The breakthrough
times occurred after 31.0 h, 49.0 h, and 63.0 h, and exhaust times
occurred after 60.0 h, 90.0 h, and 110.0 h, respectively, for the corresponding bed depths. The beds were designed using the logit
method. The column efciencies (N) were 454.44 mg/L,
483.87 mg/L, and 426.55 mg/L for the bed depths of 10 cm,

15 cm, and 20 cm respectively. In the second-cycle, the column

(10 cm) efciency of the NaOH-regenerated bed decreased to
34%. An in situ two-step mechanism, the oxidation of As(III) oxyanions to As(V) oxyanions and subsequent adsorption on IOCNR is
proposed. The column observation (10 cm), using real arsenicbearing groundwater, was conducted in the same experimental
conditions. The obtained experimental results were well simulated
in the geochemical model. Finally the quality of the efuent water
was sufcient for the use of practical purposes.
Acknowledgments
Authors are thankful to National Science Council, Government
of Taiwan for the nancial support for this study under the contracts of NSC 96-2628-B-002-021-MY3 and NSC 99-2628-B-002042-MY3. Also we are thankful to National Central University,
Tao-Yuan, Taiwan for assisting the SEM and EDX studies.
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