Neoarchean carbonate–associated sulfate records positive Δ33S anomalies

Dissecting ancient microbial sulfur cycling Before the rise of oxygen, life on Earth depended on the marine sulfur cycle. The fractionation of different sulfur isotopes provides clues to which biogeochemical cycles were active long ago (see the Perspective by Ueno). Zhelezinskaia et al. found negative isotope anomalies in Archean rocks from Brazil and posit that metabolic fluxes from sulfate-reducing microorganisms influenced the global sulfur cycle, including sulfur in the atmosphere. In contrast, Paris et al. found positive isotope anomalies in Archean sediments from South Africa, implying that the marine sulfate pool was more disconnected from atmospheric sulfur. As an analog for the Archean ocean, Crowe et al. measured sulfur isotope signatures in modern Lake Matano, Indonesia, and suggest that low seawater sulfate concentrations restricted early microbial activity. Science, this issue p. 703, p. 742, p. 739; see also p. 735 Positive sulfur isotope anomalies hint at unexpected photochemical processes in Earth’s early atmosphere. [Also see Perspective by Ueno] Mass-independent fractionation of sulfur isotopes (reported as Δ33S) recorded in Archean sedimentary rocks helps to constrain the composition of Earth’s early atmosphere and the timing of the rise of oxygen ~2.4 billion years ago. Although current hypotheses predict uniformly negative Δ33S for Archean seawater sulfate, this remains untested through the vast majority of Archean time. We applied x-ray absorption spectroscopy to investigate the low sulfate content of particularly well-preserved Neoarchean carbonates and mass spectrometry to measure their Δ33S signatures. We report unexpected, large, widespread positive Δ33S values from stratigraphic sections capturing over 70 million years and diverse depositional environments. Combined with the pyrite record, these results show that sulfate does not carry the expected negative Δ33S from sulfur mass-independent fractionation in the Neoarchean atmosphere.

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