Large sulfur isotope fractionations associated with Neoarchean microbial sulfate reduction

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 similar to 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 Delta S-33 values (similar to -2 per mil) indicative of atmospheric photochemical reactions. Persistent S-33 depletion through similar to 60 meters of shallow marine carbonate implies long-term stability of seawater sulfate abundance and isotope composition. In contrast, a negative Delta S-33 excursion in lower Batatal strata indicates a response time of similar to 40,000 to 150,000 years, suggesting Neoarchean sulfate concentrations between similar to 1 and 10 mu M.