Environmental Selenium Transformations: Distinguishing Abiotic and Biotic Factors Influencing Se Redox Transformations

Worldwide, selenium (Se) is proving to be a significant environmental concern, with many anthropogenic activities (e.g. coal mining and combustion, phosphate mining and agricultural irrigation) releasing potentially hazardous concentrations into surface and subsurface ecosystems. The US EPA is currently considering aquatic Se regulations, however no guidelines exist for excess soil Se, despite its ability to act as a persistent Se source. Various abiotic and biological processes mediate Se oxidation/reduction (redox) transformations in soils, thus influencing its solubility and bioavailability. In this research we assess (1) the ability of metal-transforming fungal species to aerobically reduce Se (Se (IV and/or VI) to Se(0)), and (2) the relative contribution of biotic and abiotic pathways for aerobic Se transformation. The primary objective of this research is to determine what abiotic and biotic factors enhance or restrict Se bioavailability.

Results indicate that fungal-mediated Se reduction may be quite widespread, with at least 7 out of 10 species of known Mn(II)-oxidizing fungi isolated from metal impacted environments also identified as capable of aerobically reducing Se(IV) and/or Se(VI) to Se(0). Increasing concentrations of selenite (SeO₃^2-; Se(IV)) and selenate (SeO₄^2-; Se(VI)) generally reduced fungal growth rates, although selenate was more likely to inhibit fungal growth than selenite. To study oxidation, Se(0) was combined with Mn(III/IV) (hydr)oxides (henceforth referred to as Mn oxides), Se-transforming fungi (Alternaria alternata), and oxalic acid to mimic Se biogeochemistry at the plant-soil interface. Increased pH in the presence of fungi (7.2 with fungi, 6.8 without fungi after 24 days) was observed. Additionally, a slight decrease in redox potential was measured for incubations without Mn oxides (236 mV with Mn oxides, 205 mV without Mn oxides after 24 days), indicating that Mn oxides may enhance Se oxidation. Elemental Se oxidation rates to Se(IV and/or SeVI) and extent will also be determined by measuring dissolved Se(IV) and Se(VI). Results from this research are key for understanding Se-transforming reactions in soils, and the role of both biotic and abiotic factors in influencing Se bioavailability and mobility within and out of contaminated ecosystems.