Inhibition of methanogenesis leads to accumulation of methylated arsenic species and enhances arsenic volatilization from rice paddy soil

Flooded soils are important environments for the biomethylation and subsequent volatilization of arsenic (As), a contaminant of global concern. Conversion of inorganic to methylated oxyarsenic species is thought to be the rate-limiting step in the production and emission of volatile (methyl)arsines. While methanogens and sulfate-reducing bacteria (SRB) have been identified as important regulators of methylated oxyarsenic concentrations in anaerobic soils, the effects of these microbial groups on biovolatilization remain unclear. Here, microcosm and batch incubation experiments with an Arkansas, USA, rice paddy soil were performed in conjunction with metabolic inhibition to test the effects of methanogenic activity on As speciation and biovolatilization. Inhibition of methanogenesis with 2-bromoethanesulfonate (BES) led to the accumulation of methylated oxyarsenic species, primarily dimethylarsinic acid (DMAs(V)), and a four-fold increase in As biovolatilization compared to a control soil. Our results support a conceptual model that methanogenic activity suppresses biovolatilization by enhancing As demethylation rates. This work refines understanding of biogeochemical processes regulating As biovolatilization in anaerobic soil environments, and extends recent insights into links between methanogenesis and As metabolism to soils from the mid-South United States rice production region.