Lawrence Berkeley National Laboratory

Elemental selenium [Se(0)] is the dominant species of selenium present in anoxic sediments. The forms of Se in sedimentary rocks similarly contain high proportions of Se(0), but much of the Se is also in the form of metal selenides, Se(-II). It is not clear if the occurrence of these selenides is due to microbial reduction of Se(0), or a purely chemical process. In this study, we examined the Se redox state of San Francisco Bay sediments that were amended with chemically-formed amorphous Se(0) [Se(0)Chem], biologically-formed amorphous Se(0) [Se(0)Biol], chemically formed black crystalline Se(0) [Se(0)Black] and selenite [Se(IV)] by analyzing the Se XANES spectra in the region 12620-12700 eV. Additions of lactate were used to stimulate activity, while formalin was used as a poisoned control. Samples of the sediment slurries were taken over a period of 95 d. The sediments were centrifuged and loaded into acrylic sample holders in an anaerobic chamber. The sample spectra were fitted with up to three standards with the R-Space X-ray Absorption Package. The standards providing the best fits to the samples were the Se(0) form added to the sediments, selenocystine, FeSe(-II), and Se(IV). For samples amended with Se(0)Chem, first order Se(0) reduction rate constants ranged between 0.11 to 0.025 d-1, and only slight stimulation was found in lactate amended samples. A slightly higher initial reduction rate constant was found for samples amended with Se(0)Biol, while rapid reduction of Se(IV) to Se(0) and selenocystine was observed in the sample with Se(IV). No change in the Se(0) spectrum was observed for samples killed with formalin. The significant proportion of sedimentary Se(-II) as revealed by Se XANES spectra compared to freely soluble Se(-II) concentrations measured by ICP-MS or acid volatile Se(-II) indicates most of the reduced Se was present in the solid form. These results confirm our earlier findings that bacteria are capable of reducing Se(0) to Se(-II), and giv