Large sulfur isotope fractionations associated with Neoarchean microbial sulfate reduction

Science  07 Nov 2014:
Vol. 346, Issue 6210, pp. 742-744
DOI: 10.1126/science.1256211

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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


The minor extent of sulfur isotope fractionation preserved in many Neoarchean sedimentary successions suggests that sulfate-reducing microorganisms played an insignificant role in ancient marine environments, despite evidence that these organisms evolved much earlier. We present bulk, microdrilled, and ion probe sulfur isotope data from carbonate-associated pyrite in the ~2.5-billion-year-old Batatal Formation of Brazil, revealing large mass-dependent fractionations (approaching 50 per mil) associated with microbial sulfate reduction, as well as consistently negative Δ33S values (~ –2 per mil) indicative of atmospheric photochemical reactions. Persistent 33S depletion through ~60 meters of shallow marine carbonate implies long-term stability of seawater sulfate abundance and isotope composition. In contrast, a negative Δ33S excursion in lower Batatal strata indicates a response time of ~40,000 to 150,000 years, suggesting Neoarchean sulfate concentrations between ~1 and 10 μM.

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