Professional Documents
Culture Documents
www.elsevier.com/locate/jcis
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:
Keywords: Surface complexation; Generalized diffuse layer; Arsenite; Arsenate; Competitive adsorption; Natural red earth
and as an anionic (H3 AsO 3 ) species in a moderately reduc- face sites simultaneously [17]. The DLM is both simpler and
ing environment where anoxic conditions persist [2]. Although more versatile in that it corrects adsorption for ionic strength
As(III) is unstable under aerobic environment, the transforma- using GouyChapman theory [18], it does not demand an input
tion of As(III) to As(V) is kinetically controlled [3]. Therefore capacitance, and it demands the smallest number of input para-
both arsenic species can occur in nature. meters [19]. Hence, this provides an excellent platform for the
Naturally occurring arsenic is commonly incorporated into calculation of interfacial properties of NRE and its adsorption
a large number of minerals such as arsenopyrite, realgar, and behaviour.
orpiment. On the basis of geochemistry, four probable mecha-
nisms have been proposed to describe the arsenic mobility in 2. Materials and methods
aquifers: (a) mobilization of arsenic due to direct oxidation of
arsenopyrite minerals; (b) reductive remobilization of arsenic- 2.1. Natural red earth
contaminated iron oxyhydroxides (FeOOH) in the subsurface
as a result of enhanced draw down and recharge of aquifers; The NRE used for the study was obtained from the north-
(c) leaching by bicarbonate ion; and (d) desorption of arsenic by western part (latitudes and longitudes of 8 14 50 N and
phosphate that migrates into aquifers after fertilizer use [47]. 79 45 45 E) of Sri Lanka. NRE occurs as rounded and well-
Release of arsenic occurs rapidly once Fe and Mn dissolve un- sorted quartz sand in a red clayey matrix with accessory il-
der reducing environments or otherwise by desorption, which menite and magnetite. The brick red color indicates oxidizing
occurs after As(V) is reduced to As(III), because As(III) is not conditions for the formation of red hematite. The NRE con-
as tightly bound to the sediments [1]. tains little Fe2+ (01%). However, Fe3+ content is typically
According to recent studies arsenic concentration in surface high (>2.0%), sometimes reaching up to 6% [20]. XRD and
and subsurface water is high, particularly in tropical regions, XRF studies were carried out for identification of the miner-
which include Argentina, Chile, southwestern Taiwan, northern alogical properties and the bulk chemical composition of NRE,
Mexico, southern Thailand, Inner Mongolia, China, Vietnam, respectively.
West Bengal in India, and Bangladesh [1]. Therefore removal Acids, bases, and stock solutions were prepared in deion-
of arsenic from drinking water is extremely important and had ized, distilled water. Precalibrated solutions of 0.103 M NaOH
been given much consideration the world over [815]. and 0.106 M HNO3 were used for pH adjustments. 5 M
Natural red earth of Sri Lanka (hereafter NRE) was selected NaNO3 was used to regulate electrolytic concentration. Ana-
for our research because it is a well-known fact that iron- lytical grade sodium arsenite (Fluka, Switzerland) and sodium
bearing minerals adsorb arsenic efficiently [1,15,16]. The re- arsenate (Sigma, Australia) were used as sources for stock so-
active binding sites of NRE were characterized with H-surface lutions.
titrations. The adsorption of As(III) and As(V) on NRE were
examined in batch mode as a function of pH, ionic strength 2.2. Experimental procedure
and adsorbate concentration both in single and dual ion sys-
tems. The proton and arsenic adsorption data were quantified 2.2.1. Surface titration
by a generalized diffuse layer model (DLM) after plausible NRE was mechanically sieved prior to the experiments.
arsenicNRE surface complexes were postulated with transmis- Quantification of proton-binding sites was carried out by a con-
sion FTIR spectroscopy. ventional potentiometric titration method. A quantity of 20 g/L
The surface-charging properties of the solidsolution in- of <63 m fraction of NRE suspension was equilibrated well
terface have been examined in terms of surface complexa- at the desired ionic strength for 24 h. Prior to the equilibration
tion thereby assuming both 1-pK (surface >SOH, species and throughout the titration the sample was purged with pure N2
+1/2
>SOH2 , >SO1/2 ) and 2-pK (species >SOH, >SOH+ 2, (99.996%) to minimize CO2 contamination. Three titration ex-
>SO ) approaches [2,813]. When compared to the 1-pK periments were performed on the basis of different electrolytic
model, the 2-pK approach is widely used, particularly on concentrations (0.1, 0.01, and 0.001 M NaNO3 ). The initial pH
metal (hydro) oxides. In this case the surface is hydrox- of NRE suspension was 6.0 and it was raised to 9 with
alated in two consequent steps, >SOH + H+ >SOH+ 2 and 0.103 M NaOH before commencement of titrations. In order to
>SOH >SO + H+ . The following factors further merit the minimize the solid dissolution the solution pH was kept above
selection of DLM for H+ and As(III) and As(V) adsorption data 4.0. The surface charge ( H ) was calculated using the equa-
on NRE. (a) The single-plane modeling approach eliminates the tion [19]
estimation of several fitting parameters associated with mul-
(CA CB + [OH ] [H+ ]) F
tilayer models without sacrificing accuracy. (b) The surface H = , (1)
chargepotential relationship is determined by GouyChapman a S
theory. (c) The combination of high inner layer capacitance where H is the surface charge (C/m2 ), C A is added acid con-
and low outer layer capacitance of multilayer models indicates centration, C B is added base concentration, [OH ] is the hy-
that the two planes are embedded in a porous mineral surface droxyl ion concentration, [H+ ] is the proton concentration, a is
layer of finite thickness, which is in agreement with a gener- equilibrium OH and H+ ion concentration for a given quantity
alized single layer of representation incorporated in the DLM. of solid used (g/L), F is the Faraday constant (96,500 C/mol),
(d) The generalized DLM is capable of handling several sur- and S represents the specific surface area (m2 /g).
M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272 267
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
when pH > 10, the solid shows some dissolution; hence reliable pH > 8 the As(III) values showed around 70% reduction. As
titration data cannot be obtained in these regions. The titration shown in Fig. 2B, for excessive initial loadings of As(III), i.e.,
data obtained in the pH range 49 were, therefore, taken for cal- 38.5 mol/L, the optimal As(III) values decreased by about
culations. Although operational, the generalized diffused layer 50%. The As(III) was optimal over the range pH 49 and
model (DLM) assumed two types of surface sites with equal no significant decrease was observed with further increase of
affinity for protons [17]. However, H+ -titration data of NRE pH (up to 9). The AFO showed 100% As(III) adsorption for
cannot be successfully modeled by making such an assump- the same pH range at initial loading of [As(III)] = 20 mol/L
tion. Therefore, the proton affinity constants of >ALOH and [11]. In this case the solid suspension was 0.5 g/L, which cor-
>FeOH sites were assumed to be different. These constants responds to a site density value of 2.31 sites/nm. Parabolic
and the site densities of >AlOH and >FeOH were obtained behavior was shown for As(III) adsorption on AAO yielding a
by numerical optimization using FITEQL [21]. The calculated maximum around pH 8.5 when initial [As(III)] = 30 mol/L
data are shown in Table 3. The optimized ratio of >AlOH and and solid content 1 g/L was used [11]. However, at an initial
>FeOH sites, i.e., >ALOH/>FeOH, always converged to 10. loading of As(III) of 100 mol/L and solid content of 4 g/L,
As shown in the data (Table 3), the intrinsic acidic constants the adsorption envelopes of both AAO and AFO were similar
of >AlOH sites were almost comparable to that of amorphous to that of NRE [2]. Based on these data it is concluded that the
aluminum oxide (AAO), and those of >FeOH sites were similar As(III) removal efficiency was dependent on both initial load-
to that of amorphous iron oxide (AFO). This is expected since ing and NRE content used.
the surface coating of NRE is thought of forming by entwining According to Hayes et al. [23], the mechanisms of surface
AAO or AFO layers around sand (silica) grains. complexation of anions (and cations as well) are postulated
The experimentally derived pHzpc value represents a com- by examining the ionic strength dependence of the adsorption
posite effect of all active sites present on the NRE surface, i.e., edges. According to these workers, outer spherically bonded
>ALOH and >FeOH. The pHzpc was obtained as 8.5 by data surface complexes exhibit a marked effect on ionic strength,
modeling. The weights used were derived by optimization (Ta- yielding distinctly separated adsorption edges. In the case of
ble 3). Moreover, the intrinsic acidity constants of different sites inner sphere bonding such a separation of adsorption edges can-
of NRE were averaged according to the procedure shown by not be readily discerned. However, these observations should be
Dzombak and Morel [17]. Table 3 shows final results for the interpreted with caution. For example, how far should the ad-
intrinsic acidity constants and site density values of NRE. sorption edges be separated from a given point to yield 100%
outer sphere or inner sphere complexes? Therefore, by visually
3.2. Adsorption of arsenic species onto NRE judging the separation of adsorption edges, only the relative de-
gree or dominance of inner- or outer sphere bonding can be
3.2.1. Arsenite adsorption inferred. Accordingly, the arsenite adsorption on NRE (at initial
The adsorption density of arsenite on NRE, As(III) , reached [0.385 mol/L]) does not show any ionic strength dependency,
almost 100% when the pH ranged between 4 and 8.0 at which evidences that an inner-sphere bonding mechanism is
initial loading [As(III)] = 0.385 mol/L (Fig. 2A). When dominant (Fig. 2A). As shown in Fig. 2B, at high arsenite
M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272 269
Fig. 2. Variation of arsenite adsorption on NRE as a function of pH and ionic Fig. 3. Arsenate adsorption on NRE as a function of pH and ionic strength:
strength: (A) 0.385 mol/L; (B) 38.5 mol/L. Suspension density: 5 g/L. (A) 0.385 and (B) 38.5 mol/L. Suspension density: 5 g/L. Solid, broken, and
Solid, broken, and dotted lines represent DL model calculations where squares, dotted lines represent DL model calculations where squares, circles, and tri-
circles, and triangles represent experimental data for 0.1, 0.01, and 0.001 M angles represent experimental data for 0.1, 0.01, and 0.001 M ionic strength,
ionic strength, respectively. respectively.
loadings well-separated adsorption edges were obtained, which tions of ionic strength. Thus the As(V) on NRE is dominated
signals that outer-sphere bonding is dominant. The relative de- by inner-sphere complexation at all adsorbate loadings exam-
gree of inner- or outer-sphere bonding of a given surface com- ined.
plex cannot, however, be forecast unambiguously from these
data. Thus the stoichiometries that correspond to inner-sphere 3.3. FTIR results
bonding of As(III) on NRE were taken into account in model-
ing. 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
3.2.2. Arsenate adsorption ionic strength. A significant effect in the NRE spectrum is ob-
Arsenate adsorption on NRE was shown as nearly 100% served at pH 4, whereas the variations of spectra, when com-
for low surface loadings of arsenate (=0.385 mol/L) in the pared to those of bare NRE, were minimal at pH 6 and 8 (not
pH range between 4.0 and 8.0 (Fig. 3A). As(V) adsorption de- shown).
creased to some extent (10%) with the additional increase of Attention was given to the region 40003000 cm1 of spec-
pH. Although the AsV values were reduced by about 30%, tra since most changes are expected to observe in this region
the trends of adsorption edges at high initial As(V) loadings upon the sorption of both arsenite and arsenate. The spectrum
(38.5 mol/L) were almost similar (Fig. 3B). The decrease of of bare NRE showed a broad peak (Fig. 4A) with no character-
optimal AsV values at excessive As(V) loadings was ascribed istic peaks for terminal OH groups, which denotes absence of
to the availability of sites for adsorption. In contrast to As(III), inner or outer terminal hydroxyl groups located at the surface
As(V) adsorption edges show indifferent behavior for varia- of NRE at pH 4.
270 M. Vithanage et al. / Journal of Colloid and Interface Science 294 (2006) 265272
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 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-
Fig. 5. Competitive adsorption of arsenic on NRE as a function of pH and esses.
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 Acknowledgments
represent DL model calculations; experimental data represented by symbols.
01, Department of Chemistry, Oregon State University, Corvallis, OR, [24] S.C.B. Myneni, S.J. Traina, G.A. Waychunas, T.J. Logan, Geochim. Cos-
1999. mochim. Acta 62 (19/20) (1998) 3285.
[22] J.M. Anderson, J.S.I. Ingram, Tropical Soil Biology and Fertility, CAB [25] X. Sun, H. Doner, Soil Sci. Soc. Am. J. 161 (1996) 865.
International, Wallingford, 1993. [26] M.B. Bradbury, B. Baeyen, Geochim. Cosmochim. Acta 66 (2002)
[23] K.F. Hayes, C. Papelis, J.O. Leckie, J. Colloid Interface Sci. 115 (1988) 2325.
564. [27] M. Hoch, R. Weerasooriya, Chemosphere 50 (2005) 743.