Iron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions

Iron-monosulfide oxidation and associated S transformations in a natural sediment were examined by combining selective extractions, electron microscopy and S K-edge X-ray absorption near-edge structure (XANES) spectroscopy, The sediment examined in this study was collected from a waterway receiving acid-sulfate soil drainage. It contained a high acid-volatile sulfide content (1031 micromol g(-1)), reflecting an abundance of iron-monosulfide. The iron-monosulfide speciation in the initial sediment sample was dominated by nanocrystalline mackinawite (tetragonal FeS). At near-neutral pH and an 02 partial pressure of approximately 0.2 atm, the mackinawite was found to oxidize rapidly, with a half-time of 29 +/- 2 min. This oxidation rate did not differ significantly (P < 0.05) between abiotic versus biotic conditions, demonstrating that oxidation of nanocrystalline mackinawite was not microbially mediated. The extraction results suggested that elemental S (S8(0)) was a key intermediate S oxidation product Transmission electron microscopy showed the S8(0) to be amorphous nanoglobules, 100-200 nm in diameter. The quantitative importance of S8(0) was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S8(0) particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S8(0) to SO4(2-) was mediated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.E. D. Burton, R. T. Bush, L. A. Sullivan, R. K. Hocking, D. R. G. Mitchell, S. G. Johnston, R. W. Fitzpatrick, M. Raven, S. McClure and L.Y. Jan