In Planta Arsenic Thiolation in Rice and Arabidopsis thaliana.

Inorganic and methylated thioarsenates have recently been reported to form in paddy soil pore waters and accumulate in rice grains. Among them, dimethylmonothioarsenate (DMMTA) is particularly relevant because of its high cytotoxicity and potential misidentification as nonregulated dimethylarsenate (DMA). Studying DMMTA uptake and flag leaf, grain, and husk accumulation in rice plants during grain filling, substantial dethiolation to DMA was observed with only 8.0 ± 0.1, 9.1 ± 0.6, and 1.4 ± 0.2% DMMTA remaining, respectively. More surprisingly, similar shares of DMMTA were observed in control experiments with DMA, indicating in planta DMA thiolation. Exposure of different rice seedling varieties to not only DMA but also to arsenite and monomethylarsenate (MMA) revealed in planta thiolation as a common process in rice. Up to 35 ± 7% DMA thiolation was further observed in the shoots and roots of the model plant Arabidopsis thaliana. Parameters determining the ratio and kinetics of thiolation versus dethiolation are unknown, yet, but less DMA thiolation in glutathione-deficient mutants compared to wild-type plants suggested glutathione concentration as one potential parameter. Our results demonstrate that pore water is not the only source for thioarsenates in rice grains and that especially the currently nonregulated DMA needs to be monitored as a potential precursor of DMMTA formation inside rice plants.

Long-term paddy use influences response of methane production, arsenic mobility and speciation to future higher temperatures.

Anaerobic microbial metabolisms make flooded paddy soils a major source of the greenhouse gas methane (CH4) and mobilize toxic arsenic (As), threatening rice production and consumption. Increasing temperatures due to climate change enhance these microbially mediated processes, increasing their related threats. Chronosequence studies show that long-term paddy use ("age") changes soil properties and redox biogeochemistry through soil organic carbon (SOC) accumulation, its association to amorphous iron (Fe) phases, and increased microbial activity. Using paddy and non-paddy soils from a chronosequence as proxies of soil development and incubating them at different temperatures, we show that paddy soil age influences the response of paddies to changes in temperature. Older paddies showed up to a 6-fold higher CH4 production with increasing temperature, compared to a 2-fold increase in young ones. Contrarily, changes in As mobility were higher in non-paddies and young paddies due to a lack of Fe-SOC-sorption sites. Temperature increased the formation of phytotoxic methylated As in all paddies, posing a risk for rice production. Mitigation strategies for future maintenance, abandonment, or management of paddy soils should include the consideration that history of use shapes the soils' biogeochemistry and microbiology and can influence the response of paddy soils to future temperature increases.