Depositional influences on porewater arsenic in sediments of a mining-contaminated freshwater lake

Arsenic-containing minerals mobilized during mining activities and deposited to Lake Coeur d'Alene (CDA), Idaho sediments represent a potential source of soluble As to the overlying water. Our objective was to delineate the processes controlling porewater As concentrations within Lake CDA sediments. Sediment and porewater As concentrations were determined, and solid-phase As associations were probed using X-ray absorption near-edge structure (XANES) spectroscopy. Although maximum As in the sediment porewaters varied from 8.4 to 16.2 mu M, As sorption on iron oxyhydroxides at the oxic sediment-water interface prevented flux to overlying water. Floods deposit sediment containing variable amounts of arsenopyrite (FeAsS), with major floods depositing large amounts of sediment that bury and preserve reduced minerals. Periods of lower deposition increase sediment residence times in the oxic zone, promoting oxidation of reduced minerals, SO42- efflux, and formation of oxide precipitates. Depositional events bury oxides containing sorbed As, transitioning them into anoxic environments where they undergo dissolution, releasing As to the porewater. High Fe:S ratios limit the formation of arsenic sulfides in the anoxic zone. As a result of As sequestration at the sediment-water interface and its release upon burial, decreased concentrations of porewater As will not occur unless As-bearing erosional inputs are eliminated.