Redox controls on arsenic enrichment and release from aquifer sediments in central Yangtze River Basin

More than 100 million people in Asia are presently exposed to groundwater with arsenic (As) concentrations exceeding the World Health Organization standard of 10 μg L⁻¹. Arsenic contaminated groundwater within basins of the central portion of the Yangtze River has recently been reported, but the processes controlling arsenic concentrations have yet to be resolved. We examined the hydrologic and geochemical factors controlling arsenic within the Jianghan Plain, an inland sedimentary basin of the Yangtze River, where arsenic concentrations exhibit strong seasonal variability driven by surface and groundwater mixing (Schaefer et al., 2016). Hydrologic fluctuations alter redox conditions in the aquifer, leading to oscillations between arsenic/iron reduction and oxidation. Here we investigate the depth-distribution of solid and aqueous phase iron and arsenic species and, through a series of laboratory manipulations, constrain the biogeochemical processes controlling seasonal changes in groundwater arsenic concentrations. In sediment incubations from ∼20 m below the surface, where solid-phase arsenic concentrations exceed 100 mg kg⁻¹, both unamended and glucose-amended sediment samples result in arsenic release to the aqueous phase. In situ carbon was capable of promoting As release in the sediment. In contrast, sediment batch incubations from other depths resulted in limited As release. Solid phase arsenic in the enriched zone was relatively oxidized but may become reduced over short time periods. In sediments below the As-enriched zone, glucose amendment resulted in arsenic reduction, but arsenic release to the aqueous phase was restricted by the subsequent formation of arsenic sulfide minerals. Buried sedimentary arsenic coupled with anaerobic microbial respiration of subsurface organic carbon within the Jianghan Plain aquifer leads to rapid release of As to groundwater. Arsenic release from sediments at ∼20 m depth is sufficient to explain arsenic concentrations throughout the aquifer, and provides a mechanism to explain how shifts in hydrology result in seasonally variable arsenic concentrations in groundwater.