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Title: Iron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions.
Authors: Burton, ED
Bush, RT
Sullivan, LA
Hocking, RK
Mitchell, DRG
Johnston, SG
Fitzpatrick, RW
Raven, M
McClure, S
Jang, LY
Keywords: Iron
Transmission Electron Microscopy
Oxidation
Sediments
Transformations
Extraction
Issue Date: 1-May-2009
Publisher: American Chemical Society
Citation: Burton, E. D., Bush, R. T., Sullivan, L. A., Hocking, R. K., Mitchell, D. R. G., Johnston, S. G., et al. (2009). Iron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions. Environmental Science & Technology, 43(9), 3128-3134.
Abstract: 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 μmol 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 O2 partial pressure of 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 (S08) was a key intermediate S oxidation product. Transmission electron microscopy showed the S08 to be amorphous nanoglobules, 100−200 nm in diameter. The quantitative importance of S08 was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S08 particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S08 to SO42− 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. © 2009, American Chemical Society
URI: http://dx.doi.org/10.1021/es8036548
http://apo.ansto.gov.au/dspace/handle/10238/3020
ISSN: 0013-936X
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