Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation: New evidence for microbial sulfate reduction in the early Archean

Yuichiro Ueno, Shuhei Ono, Douglas Rumble, Shigenori Maruyama

Research output: Contribution to journalArticle

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Abstract

Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (32S/33S/34S/36S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ34S-Δ33S-Δ36S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ34S = -5 ± 2‰; Δ33S = -3 ± 1‰); (2) MD sulfate (δ34S = +10 ± 3‰); (3) non-MD sulfur (δ34S > +6‰; Δ33S > +4‰); and (4) igneous MD sulfur (δ34S = Δ33S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in 34S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO2. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in 34S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ33S/δ34S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ36S values and steep Δ36S/Δ33S slopes, which deviate from the main Archean array (Δ36S/Δ33S = -0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ36S/Δ33S = -5 to -11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested.

Original languageEnglish
Pages (from-to)5675-5691
Number of pages17
JournalGeochimica et Cosmochimica Acta
Volume72
Issue number23
DOIs
Publication statusPublished - Dec 1 2008
Externally publishedYes

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Sulfur Isotopes
Barium Sulfate
sulfur isotope
Sulfur
barite
Sulfates
Archean
sulfate
sulfur
pyrite
Igneous rocks
sulfur cycle
early Earth
Sulfides
Fractionation
analysis
Aerosols
Isotopes
igneous rock
Minerals

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation : New evidence for microbial sulfate reduction in the early Archean. / Ueno, Yuichiro; Ono, Shuhei; Rumble, Douglas; Maruyama, Shigenori.

In: Geochimica et Cosmochimica Acta, Vol. 72, No. 23, 01.12.2008, p. 5675-5691.

Research output: Contribution to journalArticle

Ueno, Yuichiro ; Ono, Shuhei ; Rumble, Douglas ; Maruyama, Shigenori. / Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation : New evidence for microbial sulfate reduction in the early Archean. In: Geochimica et Cosmochimica Acta. 2008 ; Vol. 72, No. 23. pp. 5675-5691.
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