Thioarsenic Species Associated with Increased Arsenic Release during Biostimulated Subsurface Sulfate Reduction

Introduction of acetate into groundwater at the Rifle Integrated Field Research Challenge (Rifle, CO) has been used for biostimulation aimed at immobilizing uranium. While a promising approach for lowering groundwater-associated uranium, a concomitant increase in soluble arsenic was also observed at the site. An array of field data was analyzed to understand spatial and temporal trends in arsenic release and possible correlations to speciation, subsurface redox conditions, and biogeochemistry. Arsenic release (up to 9 μM) was strongest under sulfate reducing conditions in areas receiving the highest loadings of acetate. A mixture of thioarsenate species, primarily trithioarsenate and dithioarsenate, were found to dominate arsenic speciation (up to 80%) in wells with the highest arsenic releases; thioarsenates were absent or minor components in wells with low arsenic release. Laboratory batch incubations revealed a strong preference for the formation of multiple thioarsenic species in the presence of the r...