Unprecedented S-34-enrichment of pyrite formed following microbial sulfate reduction in fractured crystalline rocks

• 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 S-34 relative to S-32. As documented by secondary ion mass spectrometry (SIMS) microanalyses, the S-34(pyrite) values are up to +132 parts per thousand V-CDT and with a total range of 186 parts per thousand. The lightest S-34(pyrite) values (-54 parts per thousand) suggest very large fractionation during MSR from an initial sulfate with S-34 values (S-34(sulfate,0)) of +14 to +28 parts per thousand. 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 S-34(pyrite) values were produced by Rayleigh fractionation effects in a diminishing sulfate pool. Large volumes of pyrite with superheavy values (+120 +/- 15 parts per thousand) within single fracture intercepts in the boreholes, associated heavy average values up to +75 parts per thousand and heavy minimum S-34(pyrite) values, suggest isolation of significant amounts of isotopically light sulfide in other parts of the fracture system. Large fracture-specific S-34(pyrite) variability and overall average S-34(pyrite) values (+11 to +16 parts per thousand) lower than the anticipated S-34(sulfate,0) 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 C-13 values in cogenetic calcite suggest that the superheavy S-34(pyrite) 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 S-34-rich pyrite.

Ämnesord

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Geologi (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Geology (hsv//eng)

NATURVETENSKAP  -- Biologi (hsv//swe)

NATURAL SCIENCES  -- Biological Sciences (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Miljövetenskap (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Environmental Sciences (hsv//eng)

Nyckelord

continental crust

deep biosphere

microbial sulfate reduction

pyrite

sulfur isotopes

sulfur isotope fractionation

anaerobic methane oxidation

fatty-acid

biomarkers

reducing bacteria

fennoscandian shield

fluid inclusions

seawater sulfate

sulfide minerals

southern sweden

stable-isotopes

Life Sciences & Biomedicine - Other Topics

Ecology

Geology

ylor j

1985

journal of general microbiology

v131

p631

ambers la

1975

canadian journal of microbiology

v21

p1602

continental crust

Miljövetenskap

The changing Earth

Publikations- och innehållstyp

ref (ämneskategori)

art (ämneskategori)