Bisulfide Reaction with Natural Organic Matter Enhances Arsenite Sorption: Insights from X-ray Absorption Spectroscopy

Terrestrial ecosystems rich in natural organic matter (NOM) can act as a sink for As. Recently, the complexation of trivalent As by sulfhydryl groups of NOM was proposed as the main mechanism for As-NOM interactions in anoxic S- and NOM-rich environments Here we tested the molecular scale interaction of bisulfide (S(-II)) with NOM and its consequences for arsenite (As(III)) binding. We reacted 0.2 mol C/L, peat and humic acid (HA) with up to 5.8 mM SOD at pH 7 and 5, respectively, and subsequently equilibrated the reaction products with 55 M As(III) under anoxic conditions. The speciation of S and the local coordination environment of As in the solid phase were studied by X-ray absorption spectroscopy. Our results document a rapid reaction of S(-II) with peat and HA and the concomitant formation of reduced organic S species. These species were highly reactive toward As(III). Shell fits of As K-edge extended X-ray absorption fine structure spectra revealed that the coordination environment of trivalent As was progressively occupied by S atoms. Fitted As-S distances of 2.24-2.34 angstrom were consistent with sulfhydryl-bound As(III). Besides As(III) complexation by organic monosulfides, our data suggests the formation of nanocrystalline As sulfide phases in HA samples and an As sorption process for both organic sorbents in which As(III) retained its first-shell oxygens. In conclusion, this study documents that S(-II) reaction with NOM can greatly enhance the ability of NOM to bind As in anoxic environments.