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Riverine evidence for isotopic mass balance in the Earth’s early sulfur cycle

Abstract

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, although interpretive challenges exist. Asymmetry in existing S isotopic data, for example, suggests that the Archaean 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 Archaean terrains in order to independently evaluate Archaean 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 Archaean 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.

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Fig. 1: Maps showing the location, sampling localities and bedrock geology of the Superior Craton study area.
Fig. 2: Sulfur isotope measurements of Canadian Rivers.
Fig. 3: Inferred Δ33SAC from analyses of Canadian Rivers.

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Acknowledgements

M.A.T. acknowledges support from the Caltech Texaco Postdoctoral fellowship and the California Alliance for Graduate Education and the Professoriate (AGEP). This work was supported from funds supplied by the David and Lucile Packard Foundation, a Caltech GPS Division Discovery Award (W.W.F), and a grant from the National Science Foundation (EAR-1349858) to W.W.F and J.F.A. This project benefited from the use of instrumentation made available by the Caltech Environmental Analysis Center. All authors acknowledge helpful comments provided by B. Wing on an earlier draft of this manuscript.

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G.P. and M.A.T conducted the laboratory analyses. All authors contributed to the sample collection, data analysis and manuscript preparation.

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Correspondence to Mark A. Torres.

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Torres, M.A., Paris, G., Adkins, J.F. et al. Riverine evidence for isotopic mass balance in the Earth’s early sulfur cycle. Nature Geosci 11, 661–664 (2018). https://doi.org/10.1038/s41561-018-0184-7

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