Arsenic and Selenium Chemistry as Affected by Sediment Redox Potential and pH

Abstract The influence of sediment redox potential and pH on As and Se speciation and solubility was studied. Hyco Reservoir (North Carolina) sediments were equilibrated under controlled redox (500, 200, 0, and −200 mV) and pH (5, natural, and 7.5) conditions. Redox potential and pH affected both speciation and solubility of As and Se. Under oxidized conditions As solubility was low and 87% of the As in solution was present as As(V). Upon reduction, As(III) became the major As species in solution, and As solubility increased. Total As in solution increased approximately 25 times upon reduction to −200 mV. No organic arsenicals were detected. In contrast to As, Se solubility reached a maximum under highly oxidized (500 mV) conditions and decreased significantly upon reduction. Selenium(VI) was the predominant dissolved Se species present at 500 mV. At 200 and 0 mV, Se(IV) became the most stable oxidation state of Se. Under strongly reduced conditions (−200 mV) oxidized Se species were no longer detectable and Se solubility was controlled by the formation of elemental Se and/or metal selenides. Biomethylation of Se was important under oxidized and moderately reduced conditions (500, 200, and 0 mV). More alkaline conditions (pH 7.5) resulted in both greater As and Se concentrations in solution. Dissolved As and Se increased up to 10 and 6 times, respectively, as compared to the more acidic equilibrations.