Dissolved selenium(VI) removal by zero-valent iron under oxic conditions: Influence of sulfate and nitrate

Abstract

Dissolved Se(VI) removal by three commercially-available zero-valent irons (ZVIs) was examined in oxic batch experiments under circumneutral pH conditions in the presence and absence of NO3- and SO42-. Environmentally relevant Se(VI) (1 mg/L), NO3- ([NO3-N] = 15 mg/L) and SO42- (1800 mg/L) were employed to simulate mining-impacted waters. Ninety percent Se(VI) removal was achieved within 4 to 8 h in the absence of SO42- and NO3-. Similar Se(VI) removal was observed after 10 to 32 h in the presence of NO3-. Dissolved Se(VI) removal rates exhibited the greatest decrease in the presence of SO42-; 90% Se(VI) removal was measured after 50 to 191 h for SO42- and after 150 to 194 h for SO42- plus NO3- depending on the ZVI tested. Despite differences in removal rates among batches and ZVI materials, Se(VI) removal consistently followed first-order reaction kinetics. Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction analyses of reacted solids showed that Fe(0) present in ZVI undergoes oxidation to magnetite [Fe3O4], wüstite [FeO], lepidocrocite [γ-FeOOH], and goethite [α-FeOOH] over time. X-ray absorption near edge structure spectroscopy indicated that Se(VI) was reduced to Se(IV) and Se(0) during removal. These results demonstrate that ZVI can be effectively used control Se(VI) concentrations in mining impacted waters.