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.

Potential of high pH and reduced sulfur for arsenic mobilization - Insights from a Finnish peatland treating mining waste water.

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.