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Unprecedented 34 S-enrichment of pyrite formed following microbial sulfate reduction in fractured crystalline rocks.
- Source :
-
Geobiology [Geobiology] 2018 Sep; Vol. 16 (5), pp. 556-574. Date of Electronic Publication: 2018 Jun 27. - Publication Year :
- 2018
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Abstract
- In the deep biosphere, microbial sulfate reduction (MSR) is exploited for energy. Here, we show that, in fractured continental crystalline bedrock in three areas in Sweden, this process produced sulfide that reacted with iron to form pyrite extremely enriched in <superscript>34</superscript> S relative to <superscript>32</superscript> S. As documented by secondary ion mass spectrometry (SIMS) microanalyses, the δ <superscript>34</superscript> S <subscript>pyrite</subscript> values are up to +132‰V-CDT and with a total range of 186‰. The lightest δ <superscript>34</superscript> S <subscript>pyrite</subscript> values (-54‰) suggest very large fractionation during MSR from an initial sulfate with δ <superscript>34</superscript> S values (δ <superscript>34</superscript> S <subscript>sulfate,0</subscript> ) of +14 to +28‰. Fractionation of this magnitude requires a slow MSR rate, a feature we attribute to nutrient and electron donor shortage as well as initial sulfate abundance. The superheavy δ <superscript>34</superscript> S <subscript>pyrite</subscript> values were produced by Rayleigh fractionation effects in a diminishing sulfate pool. Large volumes of pyrite with superheavy values (+120 ± 15‰) within single fracture intercepts in the boreholes, associated heavy average values up to +75‰ and heavy minimum δ <superscript>34</superscript> S <subscript>pyrite</subscript> values, suggest isolation of significant amounts of isotopically light sulfide in other parts of the fracture system. Large fracture-specific δ <superscript>34</superscript> S <subscript>pyrite</subscript> variability and overall average δ <superscript>34</superscript> S <subscript>pyrite</subscript> values (+11 to +16‰) lower than the anticipated δ <superscript>34</superscript> S <subscript>sulfate,0</subscript> support this hypothesis. The superheavy pyrite found locally in the borehole intercepts thus represents a late stage in a much larger fracture system undergoing Rayleigh fractionation. Microscale Rb-Sr dating and U/Th-He dating of cogenetic minerals reveal that most pyrite formed in the early Paleozoic era, but crystal overgrowths may be significantly younger. The δ <superscript>13</superscript> C values in cogenetic calcite suggest that the superheavy δ <superscript>34</superscript> S <subscript>pyrite</subscript> values are related to organotrophic MSR, in contrast to findings from marine sediments where superheavy pyrite has been proposed to be linked to anaerobic oxidation of methane. The findings provide new insights into MSR-related S-isotope systematics, particularly regarding formation of large fractions of <superscript>34</superscript> S-rich pyrite.<br /> (© 2018 The Authors. Geobiology Published by John Wiley & Sons Ltd.)
Details
- Language :
- English
- ISSN :
- 1472-4669
- Volume :
- 16
- Issue :
- 5
- Database :
- MEDLINE
- Journal :
- Geobiology
- Publication Type :
- Academic Journal
- Accession number :
- 29947123
- Full Text :
- https://doi.org/10.1111/gbi.12297