XAS versus IC-ICP-MS for arsenic-sulfur speciation analysis

Modern analytical methods have demonstrated that soluble arsenic-sulfur species constitute a major fraction of dissolved arsenic in sulfidic waters. However, an intense debate is going on about the exact chemical nature of these compounds, with X-ray absorption spectroscopy (XAS) data suggesting thioarsenites, ion chromatographic and mass spectroscopic (IC-ICP-MS) data suggesting thioarsenates. We show here by XAS that thioarsenites are the primary reaction products of arsenite and sulfide which convert rapidly to thioarsenates when exposed to atmospheric oxygen. The predominance of dithioarsenate determined by IC-ICP-MS in arsenite-sulfide solutions is thus an analytical artifact. When eliminating oxygen by conducting the chromatographic separation under anaerobic conditions, thioarsenites convert to arsenite as they are instable in the acidic and alkaline pH-range and undergo competitive dissociation at decreasing SH-:OH- ratios when diluting a sample. As thioarsenites were found to be necessary precursor species for thioarsenate formation, their analysis at environmentally relevant concentrations is a necessity for modern arsenic speciation analysis.