This study describes the sorption of As(V) and As(III) to schwertmannite as a function of pH and arsenic loading. In general, sorption of As(V) was greatest at low pH, whereas high pH favored the sorption of As(III). The actual pH of equivalent As(V) and As(III) sorption was strongly loading dependent, decreasing from pH approximately 8.0 at loadings <120 mmol(As) mol(Fe)(-1) to pH approximately 4.6 at a loading of 380 mmol(As) mol(Fe)(-1). Sorption isotherms for As(V) were characterized by strong partitioning to the schwertmannite solid-phase at low loadings and sorption capacities of 225-330 mmol(As(V)) mol(Fe)(-1) at high loadings. In contrast, the As(III) isotherms revealed a weak affinity for sorption of As(III) versus As(V) at low loadings yet a greater affinity for As(III) sorption compared with As(V) at high loadings (when pH > 4.6). Sorption of As(V) and As(III) caused significant release of SO(4)(2-) from within the schwertmannite solid-phase, without major degradation of the schwertmannite structure (as evident by X-ray diffraction and Raman spectroscopy). This can be interpreted as arsenic sorption via incorporation into the schwertmannite structure, rather than merely surface complexation at the mineral-water interface. The results of this study have important implications for arsenic mobility in the presence of schwertmannite, such as in areas affected by acid-mine drainage and acid-sulfate soils. In particular, arsenic speciation, arsenic loading, and pH should be considered when predicting and managing arsenic mobility in schwertmannite-rich systems.

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Iron-monosulfide oxidation and associated S transformations in a natural sediment were examined by combining selective extractions, electron microscopy and S K-edge X-ray absorption near-edge structure (XANES) spectroscopy, The sediment examined in this study was collected from a waterway receiving acid-sulfate soil drainage. It contained a high acid-volatile sulfide content (1031 micromol g(-1)), reflecting an abundance of iron-monosulfide. The iron-monosulfide speciation in the initial sediment sample was dominated by nanocrystalline mackinawite (tetragonal FeS). At near-neutral pH and an 02 partial pressure of approximately 0.2 atm, the mackinawite was found to oxidize rapidly, with a half-time of 29 +/- 2 min. This oxidation rate did not differ significantly (P < 0.05) between abiotic versus biotic conditions, demonstrating that oxidation of nanocrystalline mackinawite was not microbially mediated. The extraction results suggested that elemental S (S8(0)) was a key intermediate S oxidation product Transmission electron microscopy showed the S8(0) to be amorphous nanoglobules, 100-200 nm in diameter. The quantitative importance of S8(0) was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S8(0) particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S8(0) to SO4(2-) was mediated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.

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Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).

In acid-mine drainage and acid-sulfate soil environments, the cycling of Fe and As are often linked to the formation and fate of schwertmannite (Fe(8)O(8)(OH)(8-2x)(SO(4))(x)). When schwertmannite-rich material is subjected to near-neutral Fe(III)-reducing conditions (e.g., in reflooded acid-sulfate soils or mining-lake sediments), the resulting Fe(II) can catalyze transformation of schwertmannite to goethite. This work examines the effects of arsenic(V) and arsenic(III) on the Fe(II)-catalyzed transformation of schwertmannite and investigates the associated consequences of this mineral transformation for arsenic mobilization. A series of 9-day anoxic transformation experiments were conducted with synthetic schwertmannite and various additions of Fe(II), As(III), and As(V). X-ray diffraction (XRD) and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy demonstrated that, in the absence of Fe(II), schwertmannite persisted as the dominant mineral phase. Under arsenic-free conditions, 10 mM Fe(II) catalyzed rapid and complete transformation of schwertmannite to goethite. However, the magnitude of Fe(II)-catalyzed transformation decreased to 72% in the presence of 1 mM As(III) and to only 6% in the presence of 1 mM As(V). This partial Fe(II)-catalyzed transformation of As(III)-sorbed schwertmannite did not cause considerable As(III) desorption. In contrast, the formation of goethite via partial transformation of As(III)- and As(V)-sorbed schwertmannite significantly decreased arsenic mobilization under Fe(III)-reducing conditions. This implies that the Fe(II)-catalyzed transformation of schwertmannite to goethite may help to stabilize solid-phase arsenic and retard its subsequent release to groundwater.

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