Iron-monosulfide oxidation in natural sediments

Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions

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, L. Y. Jang

Research output: Contribution to journalArticle

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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 μ mol 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 O 2 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 (S0 8) 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 SO42- was madiated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.

Original languageEnglish
Pages (from-to)3128-3134
Number of pages7
JournalEnvironmental Science and Technology
Volume43
Issue number9
DOIs
Publication statusPublished - 1 May 2009
Externally publishedYes

Fingerprint

X ray absorption
electron microscopy
Electron microscopy
mackinawite
Sediments
Iron
oxidation
iron
Oxidation
X ray absorption near edge structure spectroscopy
XANES spectroscopy
sediment
acid sulfate soil
soil drainage
support structure
Acids
Sulfides
partial pressure
Partial pressure
Sulfates

Cite this

Burton, E. D. ; Bush, R. T. ; Sullivan, L. A. ; Hocking, R. K. ; Mitchell, D. R G ; Johnston, S. G. ; Fitzpatrick, R. W. ; Raven, M. ; McClure, S. ; Jang, L. Y. / Iron-monosulfide oxidation in natural sediments : Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions. In: Environmental Science and Technology. 2009 ; Vol. 43, No. 9. pp. 3128-3134.
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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 μ mol 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 O 2 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 (S0 8) 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 SO42- was madiated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.",
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Iron-monosulfide oxidation in natural sediments : Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions. / Burton, E. D.; Bush, R. T.; Sullivan, L. A.; Hocking, R. K.; Mitchell, D. R G; Johnston, S. G.; Fitzpatrick, R. W.; Raven, M.; McClure, S.; Jang, L. Y.

In: Environmental Science and Technology, Vol. 43, No. 9, 01.05.2009, p. 3128-3134.

Research output: Contribution to journalArticle

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T1 - Iron-monosulfide oxidation in natural sediments

T2 - Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions

AU - Burton, E. D.

AU - Bush, R. T.

AU - Sullivan, L. A.

AU - Hocking, R. K.

AU - Mitchell, D. R G

AU - Johnston, S. G.

AU - Fitzpatrick, R. W.

AU - Raven, M.

AU - McClure, S.

AU - Jang, L. Y.

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AB - 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 μ mol 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 O 2 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 (S0 8) 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 SO42- was madiated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.

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