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Applied Geochemistry 26 (2011) 648654

Contents lists available at ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Natural Red Earth as a low cost material for arsenic removal: Kinetics
and the effect of competing ions
Anushka Upamali Rajapaksha , Meththika Vithanage, Lakmal Jayarathna, Chanaka Kapila Kumara
Chemical and Environmental Systems Modeling Research Group, Institute of Fundamental Studies, Hantana Road, Kandy 20000, Sri Lanka

a r t i c l e

i n f o

Article history:
Available online 6 January 2011

a b s t r a c t
This study investigates the effect of reaction time and competing ions on As retention on Natural Red
Earth (NRE). The initial As [As(III) or As(V)] concentrations were varied between 105 and 104 M
for competitive adsorption studies while samples were spiked with 2.67 lM As for kinetic studies.

2
Batch experiments were performed for solutions with different concentrations of PO3
4 , NO3 and SO4
(5.26  105, 8.06  104, and 2.60  103 M, respectively) as competing ions for the two systems. One
system had controlled conditions (pH 5.5, 0.01 M NaNO3) while the second is uncontrolled (no pH control
and no NaNO3). Kinetic data were best described by a pseudo-second order model demonstrating strong
interaction between As species and >FeOH and AlOH sites on the NRE surface. The equilibrium solid
phase concentrations for As(III) and As(V) were observed as 20 and 12.5 lg/g, respectively. The time
taken to equilibrium was the same (90 min) for both As species. Competitive adsorption isotherm exper2
iments showed a greater effect of PO3
4 on the reduction of adsorption of both As species than with SO4
and NO
.
Arsenic(III)
agreed
with
the
Langmuir
equation
signifying
monolayer
formation
while
As(V)
3
adsorption was in accord with a Fruendlich isotherm indicating multilayer adsorption. FTIR spectra indicated an inner sphere bonding of arsenate and FeO sites with PO3
4 while an outer-sphere weak complexation was observed with NO
3 . The substrate appears to show a potential for a similar rate of
adsorption under both controlled and uncontrolled conditions indicating its possible use in domestic
water lters to remove As from water.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Arsenic is an ubiquitous element found in the atmosphere, lithosphere, hydrosphere and biosphere. A combination of natural processes and a range of anthropogenic activities release As to the
environment. However, most environmental As problems originate
as a result of mobilization under natural conditions. Arsenic
enrichment of surface and groundwater is great in many parts of
the world, including Bangladesh, West Bengal, India, China, Argentina, Taiwan, Vietnam, Mongolia (Smedley and Kinniburgh, 2002;
Smedley et al., 2005; Agusa et al., 2006; Mohan and Pittman, 2007).
Numerous remediation methods have been reported in the literature for removal of As from water, which include coagulation,
adsorption and separation by ion exchange resin (Jakariya, 2000;
Thirunavukkarasu and Viraraghavan, 2003). In the coagulation process, As removal relies on adsorption and co-precipitation of As
into metal hydroxides (Thirunavukkarasu and Viraraghavan,
2003). The ion exchange method is not economically attractive
Corresponding author. Tel.: +94 812232002; fax: +94 812232131.
E-mail addresses: anushka@ifs.ac.lk, upamalirajapaksha@yahoo.com (A.U. Rajapaksha).
0883-2927/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2011.01.021

for water having high total dissolved solids (TDS > 500 mg/L) or
SO2
(>25 mg/L) (US EPA, 1999). The dominant process used to
4
date, is adsorption onto earth materials (Altundogan et al., 2000;
Anderson et al., 1976; Goldberg, 1986; Jain and Leoppert, 2000;
Manning and Goldberg, 1996; Thirunavukkarasu and Viraraghavan, 2003; Weerasooriya et al., 2003; Daus et al., 2004; Gen-Fuhrman et al., 2004; Vithanage et al., 2007b, 2009). However, most of
these studies have been carried out under laboratory controlled
conditions where pH was kept at a prescribed level and background electrolyte was added to activate the surface sites of the solid material. In such cases, adsorption characteristics could be
different from situations where the adsorbent is applied in household lters under natural conditions. This study was carried out to
investigate the effect of laboratory controlled and uncontrolled
conditions on adsorption, to identify the feasibility of using Natural
Red Earth (NRE) as a low cost adsorbent for As removal from potable water. It is important to note that the uncontrolled system was
tested with the objectives of observing any effect of purging with
N2 and addition of NaNO3 in the laboratory on the NRE-As system
since in household lter systems it is impossible to purge N2 and
the use NaNO3. However, use of the uncontrolled system did not
solely simulate a natural household system.

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654


2
The effect of competing ions such as NO
and PO3
for
3 , SO4
4
both As(III) and As(V) adsorption was also examined in these
conditions. These three anions were selected since they are the
common co-existing anionic components in natural waters, which
may affect As mobility (Katsoyiannis and Zouboulis, 2002). High
concentrations of anionic species have been used in many previous
studies (Frau et al., 2008; Guan et al., 2009) that aim to verify the
prevalence of a particular mechanism, thereby minimizing the possible interference of a secondary parallel mechanism.

2. Materials and methods


2.1. Solid material
Natural Red Earth (NRE) is a naturally-occurring Fe coated
quartz sand, which is a mixture of different minerals such as
ilmenite, rutile, zircon and others (Dahanayake and Jayawardana,
1979). It has been shown that NRE is composed of high Fe3+, up
to 6%. NRE was selected for this experiment because of its As
adsorption capacity (Vithanage et al., 2006, 2007a, 2009). The mineralogical composition of NRE was determined using XRD, XRF and
SEM, show Fe2O3 and Al2O3 present in signicant proportions,
masking crystalline the silica phase (Vithanage et al., 2006). Red
earth has been shown to have >FeOH and >AlOH reactive sites,
with variable surface charge (Vithanage et al., 2006) for As adsorption. Quantication of proton-binding sites for NRE was carried out
using the potentiometric titration method of Vithanage et al.
(2006) and obtained the point of zero charge (pHzpc) as 8.5 with
surface sites positively charged below pHzpc. With equal concentrations (0.385 lmol/L) of arsenite and arsenate in a single sorbate
system, arsenite adsorption was higher (>98%) than that of arsenate (9895%) under pH conditions found in natural groundwater
(Vithanage et al., 2006). The authors previous modeling data
showed that arsenite forms monodentate complexes whereas arsenate forms bidendate complexes (Vithanage et al., 2007a). Desorption studies have demonstrated that arsenate desorption is less
than that of arsenite and desorption is pH dependant (Vithanage
et al., 2009). When compared to gibbsite and goethite, arsenite
adsorption was higher in NRE while arsenate adsorption did not
show a signicant difference with three adsorbents (Vithanage
et al., 2007b).
Mechanically sieved, <63 lm, NRE, 5 g/L, was used for the
experiments. Two sets of experiments were conducted, one with
the pH of the NRE solid solution adjusted to 5.5 and purged with
N2 to keep the pH constant, as well as with 0.01 M NaNO3 as the
ionic strength adjuster to activate NRE surface sites (hereafter controlled condition). Since arsenite and arsenate adsorption on NRE
recorded maximum values between pH 4 and 7 an average pH
was selected for the controlled experiment (Vithanage et al.,
2006). A second set of experiments were carried out with a natural
pH of NRE solid/solution (pH  6.5), without N2 and NaNO3 (hereafter uncontrolled condition).

649

2.3. Isotherm experiments


The initial As(III) and As(V) concentrations were varied between
105 and 104 M. The solid suspensions (5 g/L) were equilibrated for 3 h in both conditions. The 10 mL aliquots of red earth
suspension were transferred to capped, polypropylene tubes. Batch
experiments were performed for solid solutions with specied
concentrations of 5.26  105, 8.06  104, and 2.60  103 M (5,

2
50 and 250 ppm, respectively) for PO3
4 , NO3 and SO4 as competing ions. Arsenic and competing anions were spiked into the system, the tubes were equilibrated for 24 h at 100 rpm (EYELA
B603 shaker), and then pH was measured and recorded. After centrifugation, the supernatant was transferred by membrane ltration (0.45 lm) for As determination. Determination of As was
performed ame atomic absorption spectrometry (GBC 933,
Australia).
2.4. FTIR studies
The transmission spectra were obtained between 400 and
4000 cm1, with 4 cm1 resolution using a FTIR spectrometer
(Nicolet 6700, USA). Sample pellets were prepared for FTIR by mixing vacuum dried samples with fused-KBr. Spectral analyses were
performed using OMNIC (version 7.3) software tools (Nicolet 6700,
USA). FTIR experiments were carried out for Natural Red Earth, red
earth treated with arsenite and arsenate, and the isotherm experiments with competing ions to observe the changes on the NRE.
3. Results and discussion
3.1. Adsorption kinetic study
The study of adsorption kinetics describes the solute removal
rate which controls the residence time of As at the solidsolution
interface including the diffusion process (Naiya et al., 2009).
Kinetic data is shown in Fig. 1. The equilibrium solid phase concentration (qe) for As(III) and As(V) was observed to be 20 and
12.5 lg/g, respectively. A distinct reduction of As adsorption
was apparent under uncontrolled conditions for both As(III) and
As(V) (Fig. 1). Arsenic(III) adsorbed better to NRE than As(V) in
all experiments; however the time taken to reach equilibrium
was the same (90 min) for both species. Fig. 1 demonstrates that
adsorption of arsenite and arsenate onto NRE was rapid in the
beginning, followed by a slower process to reach a plateau. The ki-

2.2. Kinetic experiments


Arsenic adsorption kinetic studies were carried out for both laboratory controlled (denoted as C henceforth) and uncontrolled conditions (denoted as UC henceforth) for As(III) and As(V). The solid
suspensions (5 g/L) were equilibrated for 3 h under both conditions
following which 2.67 lM of arsenite and arsenate were spiked
into the system. Ten mL aliquots of suspension were taken at
known time intervals, ltered through a membrane lter
(0.45 lm), and analyzed for As with an Atomic Absorption Spectrometer with hydride generation (GBC 933, Australia).

Fig. 1. Adsorption kinetic data for As species in controlled and uncontrolled


conditions, qt denotes the amount adsorbed per gram of adsorbent at time t.

650

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654

netic experimental data were analyzed using pseudo-rst order,


pseudo-second order, and intra-particle diffusion models (Naiya
et al., 2009; Srivastava et al., 2006).
3.1.1. Pseudo-rst order model
The pseudo-rst order equation, also known as, the Lagergren
equation can be written as in Naiya et al. (2009) assuming non-dissociating molecular adsorption onto NRE:

dq
k1 qe  qt
dt

where qt = amount adsorbed per g of adsorbent at time t (lg/g);


qe = amount adsorbed per g of the adsorbent at equilibrium (lg/
g); k1 = Lagergren rate constant (min1); t = time (min).
The integrated form of Eq. (1) can be written as below.

logqe  qt log qe 

k1 t
2:303

The kinetic parameters as well as correlation coefcient (R2)


and chi square (v2) were obtained from the plot log(qeqt) vs t.
Eq. (2) was used for data tting. It was observed that the rst order
kinetics does not represent the experimental data (not shown in
gure).

Table 1
Kinetic parameters.
qexp (lg/g)

Exp
Pseudo-rst
As(III) UC
As(III) C
As(V) UC
As(V) C

order model
19.516
22.944
10.948
14.109

qcal (lg/g)
12.434
10.522
8.320
3.462
k2 (lg/g min0.5)

Pseudo-second order model


As(III) UC
19.516
0.004
As(III) C
22.944
0.007
As(V) UC
10.948
0.005
As(V) C
14.109
0.022
kid (lg/g min0.5)
Intra-particle diffusion model
As(III) UC
19.516
1.131
As(III) C
22.944
0.649
As(V) UC
10.948
0.a708
As(V) C
14.109
0.289

k1 (min1)
0.024
0.038
0.036
0.026

R2

v2

0.903
0.953
0.880
0.889

41.538
10.719
4.628
31.289

0.996
0.999
0.984
0.999

1.344
0.454
2.483
0.757

0.888
0.723
0.675
0.826

2.932
1.533
8.190
0.327

h (lg/g min)
1.728
4.232
0.713
4.535
C
7.232
15.104
4.060
10.778

3.1.2. Pseudo-second order model


The pseudo-second order adsorption kinetic rate equation is
based on the assumption of chemisorption of the adsorbate on
the adsorbents and expressed as below (Ho and McKay, 1999; Srivastava et al., 2006):

dq
ks qe  qt 2
dt

where qt = amount adsorbed per g of adsorbent at time t (lg/g);


qe = amount adsorbed per g of the adsorbent at equilibrium (lg/
g); ks = pseudo-second order constant (g/lg min); t = time (min).
The integrated form of the above equation becomes:

t
1
t

qt ks q2e qe

The initial sorption rate, h (mg/g min), as t ? 0 can be dened

Fig. 2. Pseudo-second-order plot for the adsorption of As species in controlled and


uncontrolled conditions.

as:

h ks q2e

3.1.3. Intra-particle diffusion model


A process is diffusion controlled if its rate is dependent upon the
rate at which components diffuse towards one another and that
was explored by the intra-particle diffusion model (Eq. (6))
(Srivastava et al., 2006).

qt kid t 1=2 C

where qt = mass adsorbed per g of adsorbent at time t (lg/g); ki1/2


); C = constant
d = intra-particle diffusion rate constant (lg/g min
(lg/g). Different kinetic parameters obtained for different models
are listed in Table 1.
The best t model was chosen from all three analyzed models
by considering the calculated correlation coefcient (R2). The
kinetic data were best described by the pseudo-second order
model (Fig. 2). According to Ho and McKay (1999), since the sorption system is pseudo-second order, the rate limiting factor is
chemical sorption in nature involving valency forces through
sharing electrons between sorbate and sorbent, it is valid for the
AsNRE systems investigated. Hence, both arsenite and arsenate
indicate a strong interaction on >FeOH or >AlOH of NRE surface.

3.2. Adsorption isotherms


The arsenic adsorption was modelled with Langmuir (Eq. (7))
and Freundlich (Eq. (8)) adsorption isotherm.
Langmuir adsorption isotherm is given by,

Cads

kMCmax
1 kM

where Cads = concentration of adsorbate adsorbed per unit area of


surface (mol m2); [M] = equilibrium solution concentration
(mol dm3) of adsorbate; Cmax = maximum adsorption density(mol m2); k = equilibrium constant for the overall adsorption
process (dm3 mol1).
The Langmuir model assumes that all adsorption sites have
equal afnity for the adsorbate and therefore only monolayer
adsorption occurs.
The following equation (Eq. (8)) was used to calculate Cads.

Cads

Asini  Asfin
AS

where [As]ini = initial As concentration (mol dm3); [As]n = nal As


concentration (mol dm3); [A] = surface area (m2 g1); [S] = solid
content (g L1).

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654

651

The Freundlich adsorption isotherm has the form,

Cads kf M1=n

where Cads = adsorption density (mol m2); M = equilibrium As


concentration (mol dm3); n = afnity of the adsorbent for the
adsorbate; kf = Freundlich coefcients related to the absorbent
capacity (mol m2/(mol dm3)1/n). The linear form of Freundlich
adsorption isotherm takes the following form:

log Cads log kf

1
log M
n

10

The Freundlich isotherm applies to solid surfaces with different


afnities. Therefore the model tting with the Freundlich isotherm
can be considered to have multilayer adsorption as well as surface
heterogeneity (Ho et al., 2002).
Arsenic(III) adsorption with NO
3 did not show a signicant
difference between laboratory controlled and uncontrolled
conditions (Fig. 3) and the maximum adsorption density was
9.75  108 mol m2. However, As(V) showed a considerable
difference between laboratory controlled and uncontrolled conditions (Fig. 4) reaching a maximum adsorption density of 7.67 
108 mol m2 and 4.92  108 mol m2, respectively, with the
NO
3 present in the system. The Langmuir isotherm model assumes
monolayer adsorption while the Freundlich isotherm is based on
the assumption of heterogeneous surfaces as well as multilayer
adsorption (Ho et al., 2002). In this system As(III) adsorption data
tted well with the Langmuir isotherm model (Fig. 5) while the
As(V) adsorption isotherm (Fig. 6), was nearly linear on a loglog
scale with a Fruendlich isotherm, suggesting a multilayer formation of adsorption in the presence of all the anions. Nitrate is considered as an anion to activate the surface area and could increase
the rate of adsorption of monodentate complexes and may not act
as a competing ion.
Both As(III) and As(V) demonstrated a greater reduction of
adsorption with PO3
as a competing ion compared to SO2
and
4
4
NO
in
the
system.
Similar
to the presence of NO
3
3 , As(V) showed
a greater effect than As(III) on the reduction of adsorption with
PO3
in the system. Also the adsorption of As(V) is less when
4

PO3
4 is present as a competing ion than with NO3 . This could be
due to the formation of bidentate complexes of arsenate as well
as PO3
4 with the NRE surface which greatly reduces the available
sites for adsorption. Generally As(III) forms monodentate complexes with Fe hydroxide while As(V) or PO3
4 form both monoden-

2
3
Fig. 5. Langmuir adsorption isotherm for As(III) with NO
3 , SO4 and PO4 at 0.01 M
NaNO3, pH = 5.5 Symbols represent experimental results and the solid line
represents calculated results using a non-linear least square t.

3
Fig. 3. Experimental results of adsorption isotherms for As(III) with NO
3 and PO4
constructed under controlled and uncontrolled conditions.

2
3
Fig. 6. Freundlich adsorption isotherm for As(III) with NO
3 , SO4 and PO4 at 0.01 M
NaNO3, pH = 5.5.

3
Fig. 4. Experimental results of adsorption isotherms for As(V) with NO
3 and PO4
constructed under controlled and uncontrolled conditions.

652

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654

tate in addition to bidentate complexes (Ler and Stanforth, 2003).


When adsorption occurs as bidentate complexes the adsorbed concentrations are much less than that of monodentate adsorption,
which may be the reason for the greater reduction of As(V) adsorption than As(III) in the presence of PO3
4 .
Neither controlled conditions nor uncontrolled conditions
reached maximum adsorption of As(V) with PO3
4 in the solution
(Figs. 3 and 4) while As(III) reached maximum adsorption at the
adsorption density of 5  108 mol m2. This could be explained
using multi layer formation of anions attached to the surface of
the NRE. The As (V) competitive system with PO3
4 was in agreement with the Freundlich isotherm equation (Fig. 6), which indicated a heterogeneous surface as well as multilayer adsorption.
Slopes of the Freundlich isotherm >1 were for all experiments except for the SO4As(III) uncontrolled system. The present ndings
seem to be consistent with previous observations on isotherm
modeling of arsenite and arsenate adsorption on different sorbents
(Dutta et al., 2004; Vithanage et al., 2007a; Streat et al., 2008).
Vithanage et al. (2007a) have reported that As(III) adsorption ts
with a Langmuir isotherm indicating monolayer formation while
As(V) is ts with Freundlich demonstrating multilayer adsorption.
When pH 5.5 NRE surface sites tend to be positively charged as
NREs pHzpc = 8.5. At the low initial concentrations, As species
tend to react with the most reactive surface site, >FeOH2+ (Vithanage et al., 2006). After the adsorption reaches its maximum surface coverage, the next reactive sites, >AlOH2+, appear for
adsorption. This may lead to an increase of adsorption with loading
increases. Similarly, adsorption of As(V) to the NRE surface, in the
same way as an electrical double layer, may increase adsorption
proportional to the loading.
The PO3
4 ion is similar to that of arsenate in structure and deprotonation constants, and, therefore, PO3
4 is considered as a possible competing ion for arsenate. Also PO3
4 forms a strong innersphere surface complex with Fe hydroxides, which reduces the
available adsorption sites and inhibits the adsorption of As (Jain
and Leoppert, 2000; Su and Puls, 2001; Zhao and Stanforth, 2001;
Guan et al., 2009). Similarly, precipitation of PO3
4 on the soil surface
might also promote the formation of negatively charged surface
sites and reduce surface potential (Goh and Lim, 2004). Therefore,
the competition between PO3
4 and As on adsorption sites is probably caused by all these different reactions on surfaces of NRE.
Jain and Leoppert (2000) and Meng et al. (2000) demonstrated
that there is no inuence of SO2
on arsenate adsorption on fer4
rihydrite over the pH range of 310. However, in the present
experiments an effect on arsenate adsorption was observed in
the presence of SO2
4 . However, the effect is not as strong as competition of PO3
on NRE and this corroborates the ndings of Su
4
and Puls (2001). The adsorption density reached for As(V) and
As(III) in the presence of SO2
4 was higher than the As adsorption
observed with PO3
.
This
could
be due to the lower negative charge
4
3
of SO2
4 than that of PO4 (Goh and Lim 2004). The reduction in As
removal potential caused by the presence of SO2
4 is mainly associated with the competition between SO2
4 and As for the adsorption
sites. Similar observations were made by Stollenwerk (2003) using
macroscopic chemical evidence showing SO2
4 adsorbs via electrostatic attraction as an outer-sphere complex and, therefore, demonstrate less effect on As adsorption than inner-sphere complex
formers such as PO3
4 . Table 2 shows the Cmax, and k values for
As(III) in competitive anion systems. Arsenite adsorption is better
2
3
in the presence of NO
3 than with SO4 and PO4 when considering
the rate of adsorption in the concentration range studied.
The values of Freundlich constants and correlation coefcients
(R2) for the adsorption process are presented in Table 3. Initial
adsorption is higher under controlled conditions for all the competing ion systems compared to that of uncontrolled systems (Figs.
3 and 4).

Table 2
2
3
Langmuir isotherm constants for As(III) with NO
3 , SO4 and PO4 .
k (dm3 mol1)

Experiment
NO
3
PO3
4
SO2
4

Cmax (mol m2)

R2

As(III) C
As(III) UC

3.530  10
2.867  103

7

1.478  10
1.607  107

0.974
0.915

As(III) C

0.404  103

2.456  107

0.952

As(III) UC

0.375  103

3.017  107

0.961

As(III) C

0.670  103

3.002  107

0.966

As(III) UC

0.505  103

3.736  107

0.949

Table 3
2
3
Freundlich isotherm constants for As(V) with NO
3 , SO4 and PO4 .
kf (mol m2/(mol dm3)1/n)

R2

NO
3

As(III) C
As(III) UC

2.606  104
2.973  104

0.937
0.973

PO3
4

As(III) C

3.893  103

0.989

As(III) UC

1.273  103

0.990

As(III) C

1.029  105

0.989

As(III) UC

8.113  103

0.969

Experiment

SO2
4

3.3. FTIR results


Due to overlapping with the IR vibrational mode of metalO
bonds and As-O bonds, it was very difcult to characterize the
interaction between As(III) or As(V) with the NRE surface. However, detailed FTIR characterization of As(III) and As(V) adsorption
on NRE was given in a previous study (Vithanage et al., 2006). Similar to that, small spectral changes can be observed in region 600
670 cm1 and 36003770 cm1 (Figs. 7 and 8). A peak at 631 cm1
disappeared after As adsorption. Two peaks at 645 and 656 cm1
were broadened and shifted after As(III) adsorption.
In the presence of As(III) and PO3
4 , red-shifting (shifting to low
wavenumber) was observed; however in the presence of NO
3 blueshifting occurred. For SO2
the shift was less signicant. Corre4
spondingly, in the region 3600 to 3770 cm1 similar observations
can be made. Peaks at 3647 and 3651 cm1 were broaded and
shifted to low wavenumber for PO3
4 indicating inner-sphere complexation (Figs. 7 and 8).
Peaks at 3647 and 3651 cm1 correspond to the out of plane
stretching mode of structural OH sites in NRE and peaks at 631,
645 and 656 cm1 correspond to the bending mode of structural
OH sites (Madejova 2003; Ece et al., 1999; Mervat 2008). The

Fig. 7. The FTIR spectra of As(III) adsorbed on NRE with competing ions for 600
670 cm1.

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654

653

Fig. 8. The FTIR spectra of As(III) adsorbed on NRE with competing ions for 3600
3720 cm1.

PO3
4 ion could have affect on structural OH sites and form innersphere surface complexation (Tyrovola et al., 2006). This could lead
to formation of a strong bond with surface OH sites and show a
shifting to the low wavenumbers (Figs. 7 and 8). Nitrate facilitates
orientation of surface OH sites and, therefore, bond strength decreases resulting in a shift to a high wavenumber. In the presence
of AlOH surface sites, Al should strongly distort the symmetry of
As and the AsOAl vibration is shifted to very low wavenumbers
when comparing AsOH vibration. However, in the presence of Fe
OH surface sites, the AsOFe band exhibits a small shift for AsOH
vibration. Therefore, in the presence of PO3
4 , As interacts with both
surface AlOH and FeOH sites however, in the presence of SO2
4 , it
is only the FeOH sites.
3.4. Possible sorption mechanisms
Prior studies have suggested that As(V) and As(III) is bound to
the Fe oxide minerals by forming an inner-sphere complexes, in
which the As(III) or As(V) exchange with surface-OH or -OH2
groups that are directly coordinated to structural Fe(III) at the Fe
oxide surface (Escudero et al., 2009). However, considering the
characteristics of NRE, the presence of different functional groups
on the NRE surface and the As species present at the particular
pH, the authors propose the mechanisms for As(III) and As(V)
adsorption on NRE in the presence of PO3
4 as given in Fig. 9ac.
In the case of As(V), similar to PO3
4 , the absorbed arsenate anion is usually coordinated to two adjacent structural Fe3+ cations
on the NRE surface (Fig. 9a) which is called a bidentate binuclear-bridging complex. Based on the observations from the Freundlich isotherm tting, a further multilayer complex formation
of As(V) in the presence of PO3
is proposed (Fig. 9b). Although
4
both bidentate binuclear-bridging complexes and monodentate
complexes have been postulated for As(III) adsorption in previous
studies (Manning et al., 1998; Su and Puls, 2001; Escudero et al.,
2009), the present authors postulate a monodentate complex for
the As(III)-NRE system in the presence of PO3
considering the
4
reduction of adsorption (Fig. 9c).
4. Conclusions
Arsenic retention on NRE demonstrated a pseudo-second order
behavior while arsenite and arsenate reach maximum adsorption
around 90 min for both uncontrolled and controlled conditions.
However, As(III) adsorbed better onto NRE than As(V) with all

Fig. 9. Postulated models for As adsorption on NRE in the presence of PO3


as a
4
competing ion. (a) Bidentate model for As(V) adsorption, (b) multilayer adsorption
of As(V) with PO3
4 in the system and (c) Monodentate adsorption of As(III) on NRE
in the presence of PO3
4 .

the competing ions. The maximum adsorption capacity of As(III)


in controlled conditions were recorded as 1.06  107,
2
3
9.43  108, 5.73  108 mol m2 for NO
respec3 , SO4 and PO4
tively. From the investigation of the effect of competitive anions,

2
it was found that the effect is in the order of PO3
4 > NO3 > SO4 .
In terms of adsorption isotherms, a Langmuir isotherm could better
represent equilibrium adsorption of As(III), while a Freundlich was
the best t for As(V) for both controlled and uncontrolled conditions indicating multilayer adsorption in the presence of competing anions. However, the presence of NO
in the system
3

654

A.U. Rajapaksha et al. / Applied Geochemistry 26 (2011) 648654

increased the rate of adsorption of both As(III) and As(V), the existence of PO3
signicantly reduced As adsorption capability and
4
rate. The ndings of this study suggested that the laboratory
uncontrolled condition had a small effect on As adsorption on
NRE and that could be due to the absence of an ionic strength adjuster in the system. The results show that the ability of NRE to absorb As does not appear to be affected much by the high
concentration of anions. Therefore, in natural systems, the presence of anions will not reduce the effectiveness of NRE to absorb
As. As a consequence, it is concluded that the NRE could be potentially effective in removing As from potable water, and could be
effectively used in making domestic lters.
Acknowledgements
We would like to extend our thanks for the support given by
Prof. Prosun Bhattacharya and Prof. Jean Jiin-Shuh. Reviewers and
editorial comments helped to improve the manuscript quality
and clarity.
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