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Cromato y Arsenato en Goethita
Cromato y Arsenato en Goethita
Arsenate and Chromate Retention dominant species in oxygenated systems, and like phosphate,
generally exhibits a low mobility in soils and waters due to
Mechanisms on Goethite. 1. its retention on mineral surfaces. Furthermore, such retention
reactions may also help to restrict reduction of As(V) to As(III)
Surface Structure under reducing conditions (4), a desirable consequence since
As(III) is the more toxic and mobile species.
SCOTT FENDORF,† MATTHEW J. EICK,‡ Chromate is also very toxic to living organisms, being a
P A U L G R O S S L , * ,§ A N D strong oxidant, a potential carcinogen, and corrosive (5).
DONALD L. SPARKS‡ Chromate is more mobile in soils than arsenate, and its
Soil Science Division, University of Idaho, retention mechanism is also unresolved. Modeling efforts of
Moscow, Idaho 83844-2339, Department of Cr(VI) sorption on hydrous oxides of Fe and Al as well as in
Plant and Soil Sciences, University of Delaware, soils suggest that Cr(VI) forms an outer-sphere complex on
Newark, Delaware 19717-1303, and Department of these surfaces (6-9). In contrast to surface complexation
Plant, Soil, and Biometeorology, Utah State University, modeling, competitive ion displacement studies have shown
Logan, Utah 84322-4820 that Cr(VI) is retained much more strongly than anions such
as Cl- or SO42- and that its retention strength approaches
that of phosphate (10, 11). However, these mechanisms are
based on macroscopic data that cannot definitively ascertain
The molecular structure of ions retained on mineral surfaces microscopic information.
is needed to accurately model their sorption process and Because of the hazards invoked by both arsenate and
to determine their stability. Extended X-ray absorption chromate, reactions that remove these species from the
fine structure (EXAFS) spectroscopy was used in this study aqueous phase rendering them immobile and limiting their
to deduce the local coordination environment of two bioavailability are desirable. Hydrous oxides of Fe are one
environmental contaminants, arsenate and chromate, on the of the principle sorbents of these oxyanions in soils and waters.
Knowledge of the oxyanion sorption mechanisms will help
mineral goethite (R-FeOOH). Based on the oxyanion-
in the development of molecular sorption models of such
Fe distances, it was concluded that three different surface reactions, and it will help to evaluate the risk imposed by the
complexes exist on goethite for both oxyanions: a mono- sorbate.
dentate complex, a bidentate-binuclear complex, and a
The local coordination environment of arsenate absorbed
bidentate-mononuclear complex. At low surface coverages, on and coprecipitated with ferrihydrite was previously
the monodentate complex was favored while at higher investigated using extended X-ray absorption fine structure
coverages the bidentate complexes were more prevalentsthe (EXAFS) spectroscopy (12, 13). The presence of a bidentate-
bidentate-binuclear complex appears to be in the greatest binuclear complex was noted by both Waychunas et al. (12)
proportion at these highest surface coverages. Therefore, and Manceau (13) and appears to be the dominant surface
modeling efforts for chromate or arsenate retention on complex. The same type of complex was also observed for
goethite need to consider a monodentate complex at very phosphate (14, 15) and arseante (16, 17) sorption on goethite
low coverages, both the monodentate and bidentate using infrared (IR) spectroscopy. In addition to the bidentate-
complexes at intermediate coverages, and predominantly binuclear complex, Waychunas et al. (12) and Manceau (13)
noted other surface states of arsenate on ferrihydrite; however,
the bidentate complexes at very high coverages.
their conclusions are not consistent. Waychunas et al. (12)
obtained an opitmal fit between predicted and experimental
EXAFS curves by including a monodenate surface complex.
Introduction Manceau (13), on the other hand, proposed a bidenate-
Arsenic and chromium are potential toxins that enter the mononuclear complex that was similar to the surface structure
environment in elevated levels primarily due to anthropogenic observed for selenate adsorbed on goethite (18). Recent wide-
activities. The toxicity of arsenic in biological systems is well angle X-ray scattering (WAXS) data lend further support to
established. The mechanism and degree of toxicity depends the bidentate-binuclear complex but showed no indication
on its speciation. Arsenate (AsO43-) acts as an analog of of a bidenate-mononuclear complex (19); the presence of a
phosphate (PO43-) and can uncouple substrate-level phos- monodentate complex could neither be supported or refuted
phorylation in the glycolytic pathway (1). Arsenite (AsO33-) by the WAXS data.
possesses a high affinity for the sulfydryl groups of amino Although the atomic configuration of arsenate on ferri-
acids such as cysteine and thereby inactivates a wide range hydrite was investigated previously, further information is
of enzymes in intermediate metabolism (2). As a conse- needed on the surface structure of arsenate sorbed on other
quence, arsenite is more toxic than arsenate. Current Federal iron oxides common to soils. No direct information on the
water quality standards indicate that arsenic concentrations surface structure of chromate sorbed on hydrous oxides is
in excess of 50 ppb are hazardous to the welfare of humans published. Accordingly, the objective of this study was to
and domestic animals (3). Fortunately, arsenate is the determine the surface structure of chromate and arsenate
sorbed on a common soil iron oxide, goethite, using EXAFS
* Corresponding author fax: 801-797-3376; e-mail address: grossl@
spectroscopy. This technique is sensitive to the local
cc.usu.edu.
† University of Idaho. coordination environment of the oxyanion, yielding direct
‡ University of Delaware. information on the distances and number of ions about As
§ Utah State University. or Cr. The surface structures derived here are used in the
S0013-936X(95)00653-5 CCC: $14.00 1997 American Chemical Society VOL. 31, NO. 2, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 315
TABLE 1. Reaction Conditions for Arsenate and Chromate
Sorption on Goethite and Resulting Surface Coverage
oxyanion concn (mM) pH log Γa
AsO4 3- 1 9.0 -2.27
8.0 -2.15
6.0 -2.05
CrO42- 2 6.0 -1.90
3 6.0 -1.67
5 5.0 -1.45
a Surface excess based on the quantity of the oxyanion sorbed per
FIGURE 3. k3 weighted, backtransformed higher distant peaks from TABLE 2. Parameters Defining Local Coordination Environment
the FT spectra of As on goethite showing the fit (dashed line) of the of Arsenate Sorbed on Goethite as Determined by EXAFS
theoretical curve to the experimental curve (solid line). Spectroscopy
surface excess, log Γ shell distance (Å) CN σ2 (Å2)
Based on the fit of the theoretical to the experimental
spectra, the first peak in the FT curve was composed of -2.05 As-O 1.66 3.8 0.0018
approximately four oxygen atoms at an average distance of As-Fe 2.85 1.3 0.0022
1.66 Å from the central As atom. Peaks occurring at greater 3.24 1.6 0.0031
distances in the FT spectra were also isolated and fit. The 3.59 0.41 0.0055
more distant peaks resulted from backscattering induced by -2.15 As-O 1.66 3.7 0.0019
Fe atoms, and the CN and R values varied with the different As-Fe 2.84 0.92 0.0026
surface loadings. At the highest loading, a shell at 3.24 Å 3.23 1.3 0.0029
dominated the backtransformed curve, with the fits being 3.59 0.67 0.0062
significantly improved by the addition of shells at 2.85 and -2.27 As-O 1.67 3.9 0.0019
3.59 Å. The highest distant Fe backscatter was much more As-Fe 2.85 0.61 0.0017
3.24 0.96 0.0038
prominant at the lowest surface loading. The fit of a
3.60 1.05 0.0050
backtransformed second peak is shown in Figure 3. After
each of the peaks in the FT spectra were fit, the parameters
were used to model the backtransformed curve composed of to that of arsenate: for all three surface coverages ap-
the full spectra out to approximately 4 Å. The fits of the full proximately four oxygen atoms coordinate the central Cr atom
spectra for each arsenate loading are shown in Figure 4. The at an average distance of 1.68 Å. This distance and coor-
local coordination parameters determined by this procedure dination number are in agreement with values reported for
for As are summarized in Table 2. the chromate ion (28). Beyond the first shell composed of
In Figure 5, the experimental EXAFS spectra for Cr(VI) oxygen, multiple Fe shells are apparent. Fitted backtrans-
sorbed on goethite are shown for three different surface formed spectra of the isolated peaks in the FT spectra and
loadings. Chromate exhibited a similar first shell environment the full backtransformed spectra from 0 to 4 Å (Figure 6)
coordinate surface functional groups leads to the formation the sorbate will be dependent upon its molecular configu-
of a binuclear-bidentate surface complex. The bidentate- ration. EXAFS spectroscopy indicates that three surface
binuclear complex appears to be the most prevalent at all but complexes of both arsenate and chromate exist on goethite.
very low surface coverage. This observation is in agreement At very low surface loadings, a monodentate complex must
with WAXS (19), IR spectroscopy (17), and other EXAFS be considered. At high surface coverages, the sorption of
spectroscopy (12, 13) studies. A recent IR study (17) indicates these oxyanions is dominated by the formation of bidentate
that only singly coordinated surface groups of goethite are surface complexes. It appears that the bidentate-binuclear
reactive with arseante at coverages below log Γ ) -1.75 (200 complexes are the most significant at all but very low surface
mmol/kg). Moreover, a bidentate-binuclear complex of coverage.
arsenate on the (110) face of goethite was predicted as the
dominant surface species based on the surface coverage that
results in complete dissapperance of the singly coordinated
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