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Süß, Elke ; Scheinost, Andreas C. ; Bostick, Benjamin C. ; Merkel, Broder J. ; Wallschläger, Dirk ; Planer-Friedrich, Britta:
Discrimination of Thioarsenites and Thioarsenates by X-ray Absorption Spectroscopy.
In: Analytical Chemistry.
Bd. 81
(2009)
Heft 20
.
- S. 8318-8326.
ISSN 1520-6882
DOI: https://doi.org/10.1021/ac901094b
Abstract
Soluble arsenic-sulfur compounds play important roles in the biogeochemistry of arsenic in sulfidic waters but conflicting analytical evidence identifies them as either thioarsenates (AsV-sulfur species) or thioarsenites (AsIII-sulfur species). Here, we present the first characterization of thioarsenates (mono-, di-, and tetrathioarsenate) by X-ray absorption spectroscopy and demonstrate that their spectra are distinctly different from those of AsIII-sulfur species, as well as from arsenite and arsenate. The absorption near edge energy decreases in the order arsenate > thioarsenates > arsenite > AsIII-sulfur species, and individual thioarsenates differ by 1 eV per sulfur atom. Fitted AsV-S and AsV-O bond distances in thioarsenates (2.13-2.18 Å and 1.70 Å, respectively) are significantly shorter than the corresponding AsIII-S and AsIII-O bond distances in AsIII-S species (2.24-2.34 Å and 1.78 Å, respectively). Finally, we demonstrate that thioarsenates can be identified by principal component analysis in mixtures containing AsIII-sulfur species. This capability is used to study the spontaneous reduction of tetrathioarsenate to AsIII-sulfur species (possibly trithioarsenite) upon acidification from pH 9.5 to 2.8.