Journal of Colloid and Interface Science 294 (2006) 265272

www.elsevier.com/locate/jcis

Mechanistic modeling of arsenic retention on natural red earth

in simulated environmental systems
Meththika Vithanage a, , Rohana Chandrajith b , Athula Bandara c , Rohan Weerasooriya a
a Chemical Modeling Laboratory, Institute of Fundamental Studies, Kandy, Sri Lanka
b Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka
c Department of Chemical Physics, Fritz-Haber Institute der Max Planck Gesellshaft Berlin, Berlin, Germany

Received 4 March 2005; accepted 18 July 2005

Available online 16 September 2005

Abstract
Arsenic retention on natural red earth (hereafter NRE) was examined as a function of pH, ionic strength, and initial arsenic loading using both
macroscopic and spectroscopic methods. Proton binding sites on NRE were characterized by potentiometric titrations yielding an average pHzpc
around 8.5. Both As(III) and As(V)NRE surface configurations were postulated by vibration spectroscopy. Spectroscopically, it is shown that
arsenite forms monodentate complexes whereas arsenate forms bidendate complexes with NRE. When 4 < pH < 8 and [total arsenic as As(III)
or As(V)] = 0.385 mol/L both arsenite and arsenate exhibit near 100% adsorption for a 10-fold variation of ionic strength that is ascribed to
inner-sphere complexation of surface bonding. Arsenite exhibits an apparent bond-switching mechanism from inner-sphere to outer-sphere at
excess As(III) loading (total arsenic as As(III) or As(V)] = 38.5 mol/L. Competitive effect of arsenate for arsenite adsorption sites was observed
when [initial As] = 0.385 mol/L. In dual adsorbate systems the As(III) was reduced over 20%, showing a competition of arsenite for arsenate
binding sites (or vice versa). All experimental data were quantified with a 2pK generalized diffused layer model considering two site types for
both protons and anions binding using reaction stoichiometries, as follows:

FeOH + H+ FeOH+ 2, 4.744,

FeOH FeO + H+ , 9.03,
AlOH + H+ AlOH+ 2, 7.229,
AlOH AlO + H+ , 9.316,
FeOH(s) + H3 AsO3(aq) FeHAsO2
3(s) + H2 O, 6.798,
AlOH(s) + H3 AsO3(aq) AlHAsO2
3(s) + H2 O, 5.319,

FeOH(s) + H2 AsO4(aq) FeHAsO2
4(s) + H2 O, 11.88,
AlOH(s) + H2 AsO
4(aq) AlHAsO 2
4(s) + H2 O, 9.061.
2005 Published by Elsevier Inc.

Keywords: Surface complexation; Generalized diffuse layer; Arsenite; Arsenate; Competitive adsorption; Natural red earth

1. Introduction and As(III) species are predominant in natural aquatic environ-

Arsenic is a toxic, carcinogenic element and has a complex
chemistry in the environment due to its contrasting oxidation
states. Although it exists in four major oxidation states, As(V)
* Corresponding author. Fax: +94 0 81 2232131.
E-mail address: meththikav@yahoo.com (M. Vithanage).
0021-9797/$ see front matter 2005 Published by Elsevier Inc.
doi:10.1016/j.jcis.2005.07.026
ments [1]. Arsenic is found in both surface and subsurface water
as a result of rock weathering, industrial waste discharge, vol-
canic emissions, fertilizer applications, mining, and smelting;
however, it is more abundant in groundwater than in surface
water. In oxic environments, arsenate [As(V)] is prevalent and
exists as a monovalent (H2 AsO 2
4 ) or divalent (HAsO4 ) anion.
Arsenite [As(III)] exists as an uncharged molecule (H3 AsO3 )
266 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272
and as an anionic (H3 AsO 3 ) species in a moderately reduc-
ing environment where anoxic conditions persist [2]. Although
As(III) is unstable under aerobic environment, the transforma-
tion of As(III) to As(V) is kinetically controlled [3]. Therefore
both arsenic species can occur in nature.
Naturally occurring arsenic is commonly incorporated into
a large number of minerals such as arsenopyrite, realgar, and
orpiment. On the basis of geochemistry, four probable mecha-
nisms have been proposed to describe the arsenic mobility in
aquifers: (a) mobilization of arsenic due to direct oxidation of
arsenopyrite minerals; (b) reductive remobilization of arsenic-
contaminated iron oxyhydroxides (FeOOH) in the subsurface
as a result of enhanced draw down and recharge of aquifers;
(c) leaching by bicarbonate ion; and (d) desorption of arsenic by
phosphate that migrates into aquifers after fertilizer use [47].
Release of arsenic occurs rapidly once Fe and Mn dissolve un-
der reducing environments or otherwise by desorption, which
occurs after As(V) is reduced to As(III), because As(III) is not
as tightly bound to the sediments [1].
According to recent studies arsenic concentration in surface
and subsurface water is high, particularly in tropical regions,
which include Argentina, Chile, southwestern Taiwan, northern
Mexico, southern Thailand, Inner Mongolia, China, Vietnam,
West Bengal in India, and Bangladesh [1]. Therefore removal
of arsenic from drinking water is extremely important and had
been given much consideration the world over [815].
Natural red earth of Sri Lanka (hereafter NRE) was selected
for our research because it is a well-known fact that iron-
bearing minerals adsorb arsenic efficiently [1,15,16]. The re-
active binding sites of NRE were characterized with H-surface
titrations. The adsorption of As(III) and As(V) on NRE were
examined in batch mode as a function of pH, ionic strength
and adsorbate concentration both in single and dual ion sys-
tems. The proton and arsenic adsorption data were quantified
by a generalized diffuse layer model (DLM) after plausible
arsenicNRE surface complexes were postulated with transmis-
sion FTIR spectroscopy.
The surface-charging properties of the solidsolution in-
terface have been examined in terms of surface complexa-
tion thereby assuming both 1-pK (surface >SOH, species
+1/2
>SOH2 , >SO1/2 ) and 2-pK (species >SOH, >SOH+ 2,
>SO ) approaches [2,813]. When compared to the 1-pK
model, the 2-pK approach is widely used, particularly on
metal (hydro) oxides. In this case the surface is hydrox-
alated in two consequent steps, >SOH + H+ >SOH+ 2 and
>SOH >SO + H+ . The following factors further merit the
selection of DLM for H+ and As(III) and As(V) adsorption data
on NRE. (a) The single-plane modeling approach eliminates the
estimation of several fitting parameters associated with mul-
tilayer models without sacrificing accuracy. (b) The surface
chargepotential relationship is determined by GouyChapman
theory. (c) The combination of high inner layer capacitance
and low outer layer capacitance of multilayer models indicates
that the two planes are embedded in a porous mineral surface
layer of finite thickness, which is in agreement with a gener-
alized single layer of representation incorporated in the DLM.
(d) The generalized DLM is capable of handling several sur-
face sites simultaneously [17]. The DLM is both simpler and
more versatile in that it corrects adsorption for ionic strength
using GouyChapman theory [18], it does not demand an input
capacitance, and it demands the smallest number of input para-
meters [19]. Hence, this provides an excellent platform for the
calculation of interfacial properties of NRE and its adsorption
behaviour.
2. Materials and methods
2.1. Natural red earth
The NRE used for the study was obtained from the north-
western part (latitudes and longitudes of 8 14 50 N and
79 45 45 E) of Sri Lanka. NRE occurs as rounded and well-
sorted quartz sand in a red clayey matrix with accessory il-
menite and magnetite. The brick red color indicates oxidizing
conditions for the formation of red hematite. The NRE con-
tains little Fe2+ (01%). However, Fe3+ content is typically
high (>2.0%), sometimes reaching up to 6% [20]. XRD and
XRF studies were carried out for identification of the miner-
alogical properties and the bulk chemical composition of NRE,
respectively.
Acids, bases, and stock solutions were prepared in deion-
ized, distilled water. Precalibrated solutions of 0.103 M NaOH
and 0.106 M HNO3 were used for pH adjustments. 5 M
NaNO3 was used to regulate electrolytic concentration. Ana-
lytical grade sodium arsenite (Fluka, Switzerland) and sodium
arsenate (Sigma, Australia) were used as sources for stock so-
lutions.
2.2. Experimental procedure
2.2.1. Surface titration
NRE was mechanically sieved prior to the experiments.
Quantification of proton-binding sites was carried out by a con-
ventional potentiometric titration method. A quantity of 20 g/L
of <63 m fraction of NRE suspension was equilibrated well
at the desired ionic strength for 24 h. Prior to the equilibration
and throughout the titration the sample was purged with pure N2
(99.996%) to minimize CO2 contamination. Three titration ex-
periments were performed on the basis of different electrolytic
concentrations (0.1, 0.01, and 0.001 M NaNO3 ). The initial pH
of NRE suspension was 6.0 and it was raised to 9 with
0.103 M NaOH before commencement of titrations. In order to
minimize the solid dissolution the solution pH was kept above
4.0. The surface charge ( H ) was calculated using the equa-
tion [19]
(CA CB + [OH ] [H+ ]) F
H = , (1)
a S
where H is the surface charge (C/m2 ), C A is added acid con-
centration, C B is added base concentration, [OH ] is the hy-
droxyl ion concentration, [H+ ] is the proton concentration, a is
equilibrium OH and H+ ion concentration for a given quantity
of solid used (g/L), F is the Faraday constant (96,500 C/mol),
and S represents the specific surface area (m2 /g).
 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272 267

2.2.2. Adsorption edges Table 1

A series of batch experiments were carried out to investigate Parameters used for optimization
adsorption characteristics of the NRE. The initial adsorption Parameter Value Reference
experiment was performed with varying NRE concentrations Surface area 350 m2 /g Assumed
to obtain the optimal NRE concentration for maximum ad-
Equilibrium constants
sorption. NRE suspensions of varying solid concentration were H2 AsO +
3 + H = H3 AsO3 9.20 [13]
spiked with arsenite or arsenate to yield a final concentration of HAsO2 +
3 + H = H2 AsO3 14.23 [13]
0.077 mol/L. Based on these preliminary data we found that
AsO3 + H+ = HAsO3
3 2
19.22 [13]
5 g/L NRE showed optimal results, and hence were used in ad-
sorption studies. Both arsenate and arsenite adsorption edges H2 AsO +
4 + H = H3 AsO4 2.30 [14]
HAsO2 + H + = H AsO 6.80 [14]
were constructed in NaNO3 according to the following method. 4 2 4
AsO3 + 2
A 5 g/L NRE suspension was prepared and equilibrated for 4 + H = HAsO4 11.60 [14]
24 h after adjustment of the pH 9 in desired ionic strengths
(0.1, 0.01, and 0.001) by 5 M NaNO3 . Then the batch solution Table 2
was spiked with arsenite or arsenate to yield final concentra- Chemical composition of NRE
tions 0.385 and 38.5 mol/L. The system pH was decremented Sample (%) SiO2 TiO2 Al2 O3 Fe2 O3 MnO MgO CaO K2 O P2 O5
at 1.0 pH intervals up to 4. At each point, a 10-ml sample RE 54.15 5.54 20.73 12.39 0.23 0.3 0.28 1.17 0.13
potion was transferred to a centrifuge tube. These tubes were
Sample (mg/L) Ba Ce Cr Ga Nb Ni Pb Rb Sr Th V Y Zr
equilibrated for 24 h at 100 rpm (EYELA B603 shaker) and
RE 315 826 128 21 81 76 37 58 69 151 345 105 4553
the pH of the suspension was measured again and recorded.
The solidsolution separation was carried out by membrane
filtration (0.45 m pore size) for determination by hydride gen- shown). Therefore only >AlOH and >FeOH sites, which are
erator atomic absorption spectroscopy (Model GBC 933 AA believed to abut from the surfaces of amorphous Fe or Al coat-
Australia). ings, are treated as active. The >SiOH sites, which correspond
to the hydroxylation of the silica phase, were not considered in
2.3. Transmission Fourier transform infrared spectroscopy the calculations, since we envisaged that these sites were not
readily available for surface complexing.
Fourier transform infrared spectra (Model JASCO FTIR
410) of arsenicNRE systems were examined to determine the 3.1. Potentiometric titrations
bonding behavior of single- and dual-ion arsenic on the NRE
after treating them with KBr at a 10:1 ratio. Fig. 1 shows the variation of surface charge of NRE, H sus-
pensions as a function of pH in 0.1, 0.01, and 0.001 M NaNO3 .
2.4. Data modeling As shown in the figure, it is evident that the H is mainly con-
trolled by the H+ and OH ions, which indicates that both
Surface acidity and arsenic binding constants were deter- surface hydroxyl functional groups of NRE, i.e., >AlOH and
mined by the FITEQL computer algorithm of Herbelin and >FeOH, behave amphoterically. The pHZPC of NRE was es-
Westall [21]. According to XRF data the NRE contains both Al timated experimentally as 8.8 (Fig. 1). Either when pH < 4 or
and Fe-derived phases. These sites were active and designated
as >FeOH and >AlOH respectively. The >SiOH, which corre-
sponds to silica phase, was not considered since this phase was
effectively covered with Al and Fe layers at varying degrees of
thickness (the SEM data are not given).
The experiment for the determination of cation exchange
capacity (CEC) was carried out according to a procedure dis-
cussed by Anderson and Ingram [22]. The CEC of NRE was
low (18 meq/100 g of soil). Hence arsenic retention by an ex-
change mechanism was not considered. The parameters used
for data modeling are given in Table 1.

3. Results and discussion

The XRD analysis confirmed that the crystalline silica phase

is dominant in NRE (details were not shown). The XRF results
(Table 2) showed that Al (as Al2 O3 ) and Fe (as Fe2 O3 ) are also
present in significant proportions, probably existing as an amor-
phous coating around silica grains, to the extent that the surface
properties of silica are masked completely (SEM images are not
Fig. 1. Variation of surface charge, , with pH based on three different ionic
strengths. Solid suspension concentration was 5 g/L. Symbols represent exper-
imental data; solid lines represent model calculations. Titration window ranged
from pH 4 to 9. pHzpc = 8.5.
268 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272

Table 3
Optimized FITEQL results obtained for potentiometric titration
Parameter Value
0.1 M 0.01 M 0.001 M Weighted meana
Site density
FeOH 1.309 102 1.136 103 3.042 102 7.782 103
AlOH 6.600 104 4.217 104 1.160 103 6.423 104
Experimental pHZPC 8.8

log K
FeOH
FeOH+2 4.269 5.303 4.604 4.744
FeO 9.868 8.168 8.874 9.03
AlOH
AlOH+2 7.238 6.979 7.586 7.229
AlO 10.1 8.616 9.567 9.316

FeOH(s) + H3 AsO3(aq) FeHAsO2

3(s) + H2 O 9.769 6.798 6.568
AlOH(s) + H3 AsO3(aq) AlHAsO2
3(s) + H2 O 9.539 5.319 3.506
2FeOH(s) + 2H2 AsO 2
4(aq) 2FeHAsO4(s) + 2H2 O 11.64 11.88 11.46
2AlOH(s) + 2H2 AsO 2
4(aq) 2AlHAsO4(s) + 2H2 O 7.025 9.061 9.314
a Weighted averages were calculated from log K =


wi (log K)i , where wi = (1/log K )i /( (1/log K )i , where log K is the standard deviation obtained from
FITEQL calculations.

when pH > 10, the solid shows some dissolution; hence reliable
titration data cannot be obtained in these regions. The titration
data obtained in the pH range 49 were, therefore, taken for cal-
culations. Although operational, the generalized diffused layer
model (DLM) assumed two types of surface sites with equal
affinity for protons [17]. However, H+ -titration data of NRE
cannot be successfully modeled by making such an assump-
tion. Therefore, the proton affinity constants of >ALOH and
>FeOH sites were assumed to be different. These constants
and the site densities of >AlOH and >FeOH were obtained
by numerical optimization using FITEQL [21]. The calculated
data are shown in Table 3. The optimized ratio of >AlOH and
>FeOH sites, i.e., >ALOH/>FeOH, always converged to 10.
As shown in the data (Table 3), the intrinsic acidic constants
of >AlOH sites were almost comparable to that of amorphous
aluminum oxide (AAO), and those of >FeOH sites were similar
to that of amorphous iron oxide (AFO). This is expected since
the surface coating of NRE is thought of forming by entwining
AAO or AFO layers around sand (silica) grains.
The experimentally derived pHzpc value represents a com-
posite effect of all active sites present on the NRE surface, i.e.,
>ALOH and >FeOH. The pHzpc was obtained as 8.5 by data
modeling. The weights used were derived by optimization (Ta-
ble 3). Moreover, the intrinsic acidity constants of different sites
of NRE were averaged according to the procedure shown by
Dzombak and Morel [17]. Table 3 shows final results for the
intrinsic acidity constants and site density values of NRE.
3.2. Adsorption of arsenic species onto NRE
3.2.1. Arsenite adsorption
The adsorption density of arsenite on NRE, As(III) , reached
almost 100% when the pH ranged between 4 and 8.0 at
initial loading [As(III)] = 0.385 mol/L (Fig. 2A). When
pH > 8 the As(III) values showed around 70% reduction. As
shown in Fig. 2B, for excessive initial loadings of As(III), i.e.,
38.5 mol/L, the optimal As(III) values decreased by about
50%. The As(III) was optimal over the range pH 49 and
no significant decrease was observed with further increase of
pH (up to 9). The AFO showed 100% As(III) adsorption for
the same pH range at initial loading of [As(III)] = 20 mol/L
[11]. In this case the solid suspension was 0.5 g/L, which cor-
responds to a site density value of 2.31 sites/nm. Parabolic
behavior was shown for As(III) adsorption on AAO yielding a
maximum around pH 8.5 when initial [As(III)] = 30 mol/L
and solid content 1 g/L was used [11]. However, at an initial
loading of As(III) of 100 mol/L and solid content of 4 g/L,
the adsorption envelopes of both AAO and AFO were similar
to that of NRE [2]. Based on these data it is concluded that the
As(III) removal efficiency was dependent on both initial load-
ing and NRE content used.
According to Hayes et al. [23], the mechanisms of surface
complexation of anions (and cations as well) are postulated
by examining the ionic strength dependence of the adsorption
edges. According to these workers, outer spherically bonded
surface complexes exhibit a marked effect on ionic strength,
yielding distinctly separated adsorption edges. In the case of
inner sphere bonding such a separation of adsorption edges can-
not be readily discerned. However, these observations should be
interpreted with caution. For example, how far should the ad-
sorption edges be separated from a given point to yield 100%
outer sphere or inner sphere complexes? Therefore, by visually
judging the separation of adsorption edges, only the relative de-
gree or dominance of inner- or outer sphere bonding can be
inferred. Accordingly, the arsenite adsorption on NRE (at initial
[0.385 mol/L]) does not show any ionic strength dependency,
which evidences that an inner-sphere bonding mechanism is
dominant (Fig. 2A). As shown in Fig. 2B, at high arsenite
 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272
Fig. 2. Variation of arsenite adsorption on NRE as a function of pH and ionic
strength: (A) 0.385 mol/L; (B) 38.5 mol/L. Suspension density: 5 g/L.
Solid, broken, and dotted lines represent DL model calculations where squares,
circles, and triangles represent experimental data for 0.1, 0.01, and 0.001 M
ionic strength, respectively.
loadings well-separated adsorption edges were obtained, which
signals that outer-sphere bonding is dominant. The relative de-
gree of inner- or outer-sphere bonding of a given surface com-
plex cannot, however, be forecast unambiguously from these
data. Thus the stoichiometries that correspond to inner-sphere
bonding of As(III) on NRE were taken into account in model-
ing.
3.2.2. Arsenate adsorption
Arsenate adsorption on NRE was shown as nearly 100%
for low surface loadings of arsenate (=0.385 mol/L) in the
pH range between 4.0 and 8.0 (Fig. 3A). As(V) adsorption de-
creased to some extent (10%) with the additional increase of
pH. Although the AsV values were reduced by about 30%,
the trends of adsorption edges at high initial As(V) loadings
(38.5 mol/L) were almost similar (Fig. 3B). The decrease of
optimal AsV values at excessive As(V) loadings was ascribed
to the availability of sites for adsorption. In contrast to As(III),
As(V) adsorption edges show indifferent behavior for varia-
269
Fig. 3. Arsenate adsorption on NRE as a function of pH and ionic strength:
(A) 0.385 and (B) 38.5 mol/L. Suspension density: 5 g/L. Solid, broken, and
dotted lines represent DL model calculations where squares, circles, and tri-
angles represent experimental data for 0.1, 0.01, and 0.001 M ionic strength,
respectively.
tions of ionic strength. Thus the As(V) on NRE is dominated
by inner-sphere complexation at all adsorbate loadings exam-
ined.
3.3. FTIR results
FTIR experiments were carried out at pH 4, 6, and 8 to ob-
serve the characteristics of NRE and its adsorption of arsenite
and arsenate. FTIR studies were performed only for 0.01 M
ionic strength. A significant effect in the NRE spectrum is ob-
served at pH 4, whereas the variations of spectra, when com-
pared to those of bare NRE, were minimal at pH 6 and 8 (not
shown).
Attention was given to the region 40003000 cm1 of spec-
tra since most changes are expected to observe in this region
upon the sorption of both arsenite and arsenate. The spectrum
of bare NRE showed a broad peak (Fig. 4A) with no character-
istic peaks for terminal OH groups, which denotes absence of
inner or outer terminal hydroxyl groups located at the surface
of NRE at pH 4.
270 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272

Peaks observed between 1250 and 650 cm1 are ascribed to

metal oxide bonds such as >AlO and >FeO vibrations.
Arsenite-treated NRE showed a characteristic peak in the region
40003000 cm1 (Fig. 4B) and the peak intensities are low in
arsenate-treated NRE (Fig. 4C) samples. As(III)-treated NRE
showed high-intensity peaks in the region 40003000 cm1 ,
which are ascribed to monodentate surface complexes. Decon-
volution of the spectral data of arsenate resulted in seven dis-
tinct components (peak/width) at 3265/155, 3409/113, 3482/67,
3553/76, 3621/22, 3650/23, and 3697/16. However, the spec-
trum of arsenite treated NRE is reproduced with six peaks alto-
gether, with the peak at 3650/23 disappearing.
Myneni et al. [24] presented an arsenate reaction with
freshly prepared hydrous iron oxide, which produced peaks at
700, 802, and 875, and for goethite 719, 730, 810, 838, and
938 cm1 . Only a few bands of these were observed in the
arsenic-treated NRE (700900 cm1 ). The peak at 914 cm1
can be assigned as >AlOH vibration and it was intense in
treated samples, which indicates >AlOAs bond formation.
Peaks recorded in the region 600900 cm1 by Goldberg and
Johnston [2] for Fe oxides did not appear in bare and treated
NRE samples, but peaks in the region 1200900 cm1 were
present, which can be assigned to surface complex formation.
Sun and Doner [25] have shown that arsenate was adsorbed
on goethite inner-spherically, forming strong bidentate binu-
clear complexes. This is proved by our sorption studies and the
peak intensities observed at the 40003000 cm1 region in the
FTIR studies. Therefore it can be postulated that the arsenate
forms bidentate complexes on natural NRE.

3.4. Data modeling

The modeling of both As(III) and As(V) adsorption onto

NRE was carried out with the generalized diffuse-layer model
with the modifications stated in Section 3.1. In analogy to
Dzombak and Morel [17], Bradbury and Baeyen [26] and Hoch
and Weerasooriya [27], densities of >AlOH and >FeOH site
ratio were kept around 1:100. The CEC of NRE was compara-
bly low to that of swelling clays and hence not incorporated into
the model. According to vibrational spectroscopic data it is pos-
tulated that As(III) forms monodentates, whereas As(V) form
bidentate complexes with >AlOH and >FeOH sites on NRE.
Ionic strength dependence data on adsorption support chemical
bonding of both As(III) and As(V) on NRE. Collating all infor-
mation, we introduced the following reaction stoichiometries to
model both As(III) and As(V) adsorption data:
FeOH(s) + H3 AsO3(aq) FeHAsO2
3(s) + H2 O, (2)

Fig. 4. FTIR spectra of aqueous suspension of bare NRE and arsenic-treated AlOH(s) + H3 AsO3(aq) AlHAsO2
3(s) + H2 O, (3)
NRE at pH 4 for the region 40003000 cm1 . (A) Bare NRE; (B) curve de-
composition for arseniteNRE; (C) curve decomposition for arsenateNRE. FeOH(s) + H2 AsO 2
4(aq) FeHAsO4(s) + H2 O, (4)
Arsenite and arsenate were at equimolar concentration of 0.385 mol/L. Sus-
pension concentration of 5 g/L for 0.01 M NaNO3 . AlOH(s) + H2 AsO 2
4(aq) AlHAsO4(s) + H2 O. (5)
The model calibrations were carried out using the experimental
When compared to the bare spectrum of NRE, a marked dif- data set obtained for initial As(III) = As(V) = 0.385 mol/L.
ference of the peak intensities was observed in arsenite- and The mass action coefficients of reactions (2)(5) were ob-
arsenate-treated NRE samples, particularly in the spectral re- tained by optimization. The modeled data fitted well with ex-
gions 40003000, 17501250, 1100900, and 800650 cm1 . perimental values (solid, broken, and dotted lines in Figs. 2A
 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272
Fig. 5. Competitive adsorption of arsenic on NRE as a function of pH and
ionic strength. Dual ion systems: equimolar concentration, As(III) = As(V) =
0.385 mol/L. Suspension concentration, 5 g/L. Solid, broken, and dotted lines
represent DL model calculations; experimental data represented by symbols.
and 3A), and the optimized anion binding constants are re-
ported in Table 3. The model validations were carried out using
average mass action coefficients reported in Table 3 together
with experimental data shown in Figs. 2B and 3B. As shown in
Figs. 2B and 3B (solid, broken, and dotted lines), both As(V)
and As(III) adsorption curves fitted well for high adsorbate
loading (38.5 mol/L).
3.5. Modeling competitive adsorption
Further validations of the model were done using data gen-
erated from dual-sorbate systems. The competitive adsorption
of anion species was obtained by spiking arsenite and arse-
nate into NRE suspension at an equimolar concentration of
0.385 mol/L. Nearly 100% adsorption was obtained for arsen-
ate, while arsenite adsorption was decreased by about 5% in the
pH range from 4 to 8. When pH > 8 both arsenite and arsenate
showed decreases in adsorption (Fig. 5). In this pH range arsen-
ite adsorption decreased up to 80% with the increase of pH and
arsenate showed 40% decrease. However, the arsenic adsorp-
tion showed no distinct shifts with the ionic strength changes,
which indicates dominance of inner-sphere complexes. The to-
tal site concentration of solids used is 1.58 103 mol/L; both
arsenic species covered only onto 8.37 106 mol/L, show-
ing that the NRE surface is largely undersaturated with respect
to As(III) or As(V) adsorption. Under these circumstances the
presence of As(III) affects the adsorption density of As(V);
hence it can be assumed that As(V) and As(III) ions are com-
peting for the same NRE sites. To model this competitive effect
between As(V) and As(III) species, the same model was used to
quantify the adsorption data using the mass action coefficients
shown in Tables 1 and 3. As shown in Fig. 5 the competitive
adsorption of As(III) and As(V) on NRE can be modeled well
(solid, broken, and dotted lines) using single sorbate parame-
ters obtained independently. Therefore it is concluded that this
model is valid for competitive adsorption behavior of arsenic
species as well.
271
4. Summary
Natural NRE has both >FeOH and >AlOH sites for surface
complexation. The experimentally derived pHzpc is 8.5. Both
arsenite and arsenate showed a strong affinity for NRE, having
100% adsorption between pH 4 and 7.5 at a solid concentration
of 5 g/L. No pH or ionic strength dependency was observed
in the pH range 47.5, suggesting an inner-sphere binding
mechanism for low surface loads (0.385 mol/L). At excess
adsorbate loads (38.5 mol/L), arsenite adsorption showed
outer-sphere complex formation. Surface titration and adsorp-
tion data were modeled well with DLM. These findings showed
that both arsenite and arsenate species are efficiently ad-
sorbed on natural NRE surfaces and therefore natural NRE is a
promising sorbent for developing an arsenic removal unit proc-
esses.
Acknowledgments
Professor Kazunari Domen (Tokyo University Japan) gave
the JASCO FTIR spectra to Athula. We thank Professor
N.W. Jern for providing SEM. Dharshani helped in the labora-
tories. Thanks go to Devika, Kushani Mahesh, and Madhu for
their support given. Valuable comments made by anonymous
reviewers significantly improved the manuscript.
References
[1] P.L. Smedley, D.G. Kinniburgh, Appl. Geochem. 17 (2002) 517.
[2] S. Goldberg, C.T. Johnston, J. Colloid Interface Sci. 234 (2001) 204.
[3] P.H. Masscheleyn, R.D. DeLaune, W.H. Patrick, Environ. Sci. Technol. 25
(1991) 1414.
[4] R.T. Nickson, J.M. McArthur, P. Ravenscroft, W.G. Burgess, K.M. Ah-
med, Appl. Geochem. 15 (2000) 403.
[5] A.B. Mukherjee, P. Bhattacharya, Environ. Rev. 9 (2001) 189220.
[6] M.H. Anwar, J. Akai, H. Sakugawa, Chemosphere 54 (2004) 753.
[7] P. Bose, A. Sharma, Water Res. 36 (2002) 4916.
[8] M.A. Anderson, J.F. Ferguson, J. Gavis, J. Colloid Interface Sci. 54 (1976)
391.
[9] S. Goldberg, Soil Sci. Soc. Am. J. 50 (4) (1986) 1154.
[10] A. Jain, R.H. Loeppert, J. Environ. Qual. 29 (2000) 1422.
[11] S. Goldberg, Soil Sci. Soc. Am. J. 66 (2002) 413.
[12] B.A. Manning, S. Goldberg, Soil Sci. Soc. Am. J. 60 (1996) 121.
[13] R. Weerasooriya, H.J. Tobschall, D. Wijesekara, E.K.I.A.U.K. Arachige,
K.A.S. Pathirathne, Chemosphere 51 (9) (2003) 1001.
[14] O.S. Thirunavukkarasu, T. Viraraghavan, K.S. Subramanian, Water Qual.
Res. J. Can. 36 (2001) 55.
[15] H. Gen-Fuhrman, J.C. Tjell, D. McConchie, Environ. Sci. Technol. 38
(2004) 2428.
[16] K.P. Raven, A. Jain, R.H. Loeppert, Environ. Sci. Technol. 32 (1998)
344.
[17] D.A. Dzombak, F.M.M. Morel, Surface Complexation Modelling, Wiley,
New York, 1990.
[18] W. Stumm, J.J. Morgan, Aquatic Chemistry, WileyInterscience, New
York, 1996.
[19] D. Langmuir, Aqueous Environmental Geochemistry, PrenticeHall, En-
glewood Cliffs, NJ, 1997.
[20] K. Dahanayake, S.K. Jayawardana, J. Geol. Soc. India 20 (1979) 433.
[21] A.L. Herbelin, J.C. Westall, FITEQL: A Computer Program for Deter-
mination of Equilibrium Constants from Experimental Data, Report 99-
272 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272

01, Department of Chemistry, Oregon State University, Corvallis, OR,
1999.
[22] J.M. Anderson, J.S.I. Ingram, Tropical Soil Biology and Fertility, CAB
International, Wallingford, 1993.
[23] K.F. Hayes, C. Papelis, J.O. Leckie, J. Colloid Interface Sci. 115 (1988)
564.
[24] S.C.B. Myneni, S.J. Traina, G.A. Waychunas, T.J. Logan, Geochim. Cos-
mochim. Acta 62 (19/20) (1998) 3285.
[25] X. Sun, H. Doner, Soil Sci. Soc. Am. J. 161 (1996) 865.
[26] M.B. Bradbury, B. Baeyen, Geochim. Cosmochim. Acta 66 (2002)
2325.
[27] M. Hoch, R. Weerasooriya, Chemosphere 50 (2005) 743.