Title

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

Document Type

Article

Publication details

Burton, ED, Bush, RT, Sullivan, LA, Hocking, RK, Mitchell, DRG, Johnston, SG, Fitzpatrick, RW, Raven, M, McClure, S & Jang, LY 2009, 'Iron-monosulfide oxidation in natural sediments: Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions', Environmental Science & Technology, vol. 43, no. 9, pp. 3128-3134.

The publisher's version of this article is available at http://dx.doi.org/10.1021/es8036548

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.