Mechanistic Insight into the Abiotic Interactions of Selenate and Selenite with Natural Organic Matter

Natural organic matter (NOM) decreases the selenium (Se) mobility in soil and sediment. Biotic dissimilatory reduction of selenate and selenite and assimilation of the reduced Se species into biomolecules are thought to be primarily responsible for this decreased Se mobility. However, the possibility of Se immobilization due to the abiotic interaction of Se species with NOM is still poorly understood. Equilibrating selenate and selenite with a model NOM (Pahokee peat soil), followed by X-ray absorption spectroscopic analysis, this study shows that the NOM can abiotically reduce highly mobile selenate into relatively less mobile selenite. NOM can sorb Se species, especially selenite, considerably. Preloading of the NOM with Fe(III) increases the sorption of selenite and selenate by several orders of magnitude. Modeling of the Se and Fe K-edge EXAFS data revealed that Se species are sorbed to NOM due to indirect complexation with the organically complexed Fe(O,OH)6 octahedra through the corner- (2C) and edge-sharing (1E) and direct complexation with the oxygen-containing functional groups of the NOM. This study concludes that the abiotic reduction and complexation of the Se species with NOM can be the additional or alternative route of Se immobilization in the NOM-rich soil and sediment.