During a time of negligible atmospheric pO2, Earth's early sulfur cycle generated a spectacular geological signal seen as the anomalous fractionation of multiple sulfur isotopic ratios. The disappearance of this signal from the geologic record has been hypothesized to constrain the timing of atmospheric oxygenation, though interpretive challenges exist. Asymmetry in existing S isotopic data, for example, suggest that the Archean crust was not mass balanced, with the implication that the loss of S isotope anomalies from the geologic record might lag the rise of atmospheric O2. Here, we present new S isotopic analyses of modern surface and groundwaters that drain Archean terrains in order to independently evaluate Archean S cycle mass balance. Natural waters contain sulfur derived from the underlying bedrock and thus can be used to ascertain its S isotopic composition at scales larger than typical geological samples allow. Analyses of 52 water samples from Canada and South Africa suggest that the Archean crust was mass balanced with an average multiple S isotopic composition equivalent to the bulk Earth. Overall, our work supports the hypothesis that the disappearance of multiple S isotope anomalies from the sedimentary record provides a robust proxy for the timing of the first rise in atmospheric O2.

Supplement to: Torres, Mark A; Paris, Guillaume; Adkins, Jess F; Fischer, Woodward W (2018): Riverine evidence for isotopic mass balance in the Earth's early sulfur cycle. Nature Geoscience, 11(9), 661-664