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Formation constants for thioarsenite species have been determined in dilute solutions at 25 uC, SH 2 S from 10 27.5 to 10 23.0 M, SAs from 10 25.6 to 10 24.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH) 3 0 , and a mononuclear thioarsenite with an S/As ratio of 3 : 1. Thioarsenic species with S/As ratios of 1 : 1, 2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations w 10 24.3 M at neutral pH. Conversion from neutral As(OH) 3 0 to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.

The fate and transport of metal ions in soils and sediments may be controlled by sorption to the metastable iron (hydr)oxide, ferrihydrite. The reversibility of metal partitioning to ferrihydrite can be significantly influenced by its transformation to more thermodynamically stable structures such as goethite or hematite. We studied changes in metal partitioning during aging of coprecipitates of ferrihydrite containing Cd(II), Mn(II), Ni(II), or Pb(II) at pH 6 and temperatures of 40 or 70 °C and as a function of metal surface loading. Aqueous metal concentrations as well as the fraction extracted by 0.2 M ammonium oxalate were continuously monitored. At the end of aging, solids were characterized by thermogravimetric analysis and X-ray diffraction. Prior to aging, the extent of metal sorption decreased in the order Pb(II) >> Ni(II) > Mn(II) = Cd(II). However, with ferrihydrite transformation, the extent of sorption increased and apparent sorption reversibility decreased significantly for Mn(II) and Ni(II). Both Pb(II) and Cd(II) demonstrated net desorption with aging, and sorption reversibility remained essentially unchanged. These differences in metal behavior are consistent with structural incorporation of Mn(II) and Ni(II) into the goethite or hematite structure and minimal incorporation of Cd(II) and Pb(II) within these crystalline products at pH 6.

The partitioning of Zn to the pyrophyllite surface was studied as a function of surface loading for periods up to 4 months. Examination of the reaction products using X-ray absorption fine structure spectroscopy (XAFS) indicated the formation of a Zn precipitate at each surface loading. Comparison of the local structure of the surface precipitates to the structure of various hydroxide- and carbonate-bearing phases indicates the formation of a Zn−Al layered double hydroxide (LDH). The solubility of Zn following aging in pyrophyllite systems indicated that the initial Zn−Al LDH precipitates transformed to a more stable form. Increased Zn stability in these experimental systems may be attributed to an increase in LDH crystallinity (Ostwald ripening) or incorporation of Si within the LDH interlayer leading to transformation to a phyllosilicate-like phase. Our results support formation of an LDH precipitate as a precursor to Zn fixation in soils abundant in aluminosilicate minerals. These results augment recent findings that transition metals may form layered hydroxide and phyllosilicate-like precipitates during sorption to clay minerals. Acknowledgment of this process as a potential metal sequestration mechanism in certain soil types is important to assessment of contaminant attenuation. Development of a more comprehensive database of solubilities for these surface precipitates will facilitate more reliable estimates.

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Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 degrees C. Comparison of extraction data and X-ray diffraction results confirmed that hematite and goethite were the primary transformation products. HFO transformation was significantly retarded at or above an arsenate solid loading of 29 455 mg As/kg HFO. However, HFO transformation proceeded at a significant rate for arsenate solid loadings of 4208 and 8416 mg As/kg HFO. At a solid loading of 8416 mg As/kg HFO, XRD results suggested arsenate primarily partitioned to hematite. Comparison of HFO transformation rates observed in this research to rates obtained from the literature at pH 6 and temperatures ranging from 24 to 70 degrees C suggests that arsenate stabilization could be realized in oxic environments with a significantfraction of iron (hydr)oxides. While this process has not been documented in natural systems, the predicted half-life for transformation of an arsenic-bearing HFO is approximately 300 days at 25 degrees C at solid loading < 8415 mg As/kg HFO. The projected time frame for arsenate stabilization indicates this process should be considered during development of conceptual and analytical models describing arsenic fate and transport in oxic systems containing reactive iron (hydr)oxides. The likelihood of this process would depend on the chemical dynamics of the soil or sediment system relative to iron (hydr)oxide precipitation-dissolution reactions and the potential retarding/competing influence of ions such as silicate and organic matter.

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Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-1) in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.