Monothioarsenate Uptake, Transformation, and Translocation in Rice Plants

Thioarsenates form under sulfur-reducing conditions in paddy soil pore waters. Sulfur fertilization, recently promoted for decreasing total arsenic (As) grain concentrations, could enhance their formation. Yet, to date, thioarsenate toxicity, uptake, transformation, and translocation in rice are unknown. Our growth inhibition experiments showed that the toxicity of monothioarsenate (MTA) was similar to that of arsenate but lower than that of arsenite. Higher toxicity of MTA with lower phosphate availability might imply uptake through phosphate transporters similar to arsenate. To demonstrate direct uptake of MTA by rice plants, a species-preserving extraction method for plant samples was developed. When plants were exposed to 10 μM MTA for 72 h, up to 19% and 4% of total As accumulated in roots and shoots, respectively, was MTA. Monothioarsenate was detected in xylem sap and root exudates, and its reduction to arsenite in rice roots and shoots was shown. Total As uptake was lower upon exposure to MTA compared to arsenate, but root to shoot translocation was higher, resulting in comparable As shoot concentrations. Thus, before promoting sulfur fertilization, uptake and detoxifying mechanisms of thioarsenates as well as potential contribution to grain As accumulation need to be better understood

Experimental Confirmation of Isotope Fractionation in Thiomolybdates Using Ion Chromatographic Separation and Detection by Multicollector ICPMS

Molybdenum ⁹⁸Mo/⁹⁵Mo isotope ratios are a sediment paleo proxy for the redox state of the ancient ocean. Under sulfidic conditions, no fractionation between seawater and sediment should be observed if molybdate (MoO₄^2–) is quantitatively transformed to tetrathiomolybdate (MoS₄^2–) and precipitated. However, quantum mechanical calculations previously suggested that incomplete sulfidation could be associated with substantial fractionation. To experimentally confirm isotope fractionation in thiomolybdates, a new approach for determination of isotope ratios of individual thiomolybdate species was developed that uses chromatography (HPLC-UV) to separate individual thiomolybdates, collecting each peak and analyzing isotope ratios with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Using commercially available MoO₄^2– and MoS₄^2– standards, the method was evaluated and excellent reproducibility and accuracy were obtained. For species with longer retention times, complete chromatographic peaks had to be collected to avoid isotope fractionation within peaks. Isotope fractionation during formation of thiomolybdates could be experimentally proven for the first time in the reaction of MoO₄^2– with 20-fold or 50-fold excess of sulfide. The previously calculated isotope fractionation for MoS₄^2– was confirmed, and the result for MoO₂S₂^2– was in the predicted range. Isotopic fractionation during MoS₄^2– transformation with pressurized air was dominated by kinetic fractionation. Further optimization and online-coupling of the HPLC-MC-ICPMS approach for determination of low concentrations in natural samples will greatly help to obtain more accurate species-selective isotope information

Potential of high pH and reduced sulfur for arsenic mobilization:insights from a Finnish peatland treating mining waste water

Abstract Peatlands, used for purification of mining waste waters, have shown efficient solid-phase sequestration of contaminants such as arsenic (As). However, contaminant re-mobilization may occur related to management changes or chemical alteration of original peatland conditions. For a treatment peatland in Finnish Lapland, we here confirm efficient As retention in near-surface peat layers close to the mining waste water inflow, likely due to binding to FeIII-phases. Seven years into operation of the treatment peatland, there appears to be further retention potential, as large areas downstream still had solid-phase As concentrations at background levels. However, via depth-resolved pore water analysis we observed a hotspot 170 m from the inflow at 10–50 cm depth, where As pore water concentrations exceeded input concentrations by a factor of 20, indicating substantial As re-mobilization. At the same spot, a peak of reduced sulfur (S) species was found. Arsenic species detected were arsenite and up to 26% methylated oxyarsenates, 15% methylated and 7.9% inorganic thioarsenates. We postulate that As mobilization is a result of short-term re-equilibration to a changed inflow chemistry after installation of a process water treatment plant and a long-term consequence of changing pore water pH from acidic to near-neutral, releasing reduced S and As. We infer that the co-occurrence of reduced S and As leads to formation of methylated and/or thiolated As species with known low sorption affinity, thereby further enhancing As mobility. Laboratory incubation studies with two peat cores confirmed a high S-induced As mobilization potential, especially when As-Fe-rich, oxic surface layers were incubated anoxically at near-neutral pH. Highest risk of As re-mobilization from this treatment peatland is expected in a scenario in which mining waste water inflow has stopped but the peatland remains flooded, and near-surface layers transition from oxic to anoxic conditions