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Long-term sedimentary recycling of rare sulphur isotope anomalies

Abstract

The accumulation of substantial quantities of O2 in the atmosphere has come to control the chemistry and ecological structure of Earth’s surface. Non-mass-dependent (NMD) sulphur isotope anomalies in the rock record1 are the central tool used to reconstruct the redox history of the early atmosphere. The generation and initial delivery of these anomalies to marine sediments requires low partial pressures of atmospheric O2 (; refs 2, 3), and the disappearance of NMD anomalies from the rock record 2.32 billion years ago1,4 is thought to have signalled a departure from persistently low atmospheric oxygen levels (less than about 10−5 times the present atmospheric level) during approximately the first two billion years of Earth’s history. Here we present a model study designed to describe the long-term surface recycling of crustal NMD anomalies, and show that the record of this geochemical signal is likely to display a ‘crustal memory effect’ following increases in atmospheric above this threshold. Once NMD anomalies have been buried in the upper crust they are extremely resistant to removal, and can be erased only through successive cycles of weathering, dilution and burial on an oxygenated Earth surface. This recycling results in the residual incorporation of NMD anomalies into the sedimentary record long after synchronous atmospheric generation of the isotopic signal has ceased, with dynamic and measurable signals probably surviving for as long as 10–100 million years subsequent to an increase in atmospheric to more than 10−5 times the present atmospheric level. Our results can reconcile geochemical evidence for oxygen production and transient accumulation with the maintenance of NMD anomalies on the early Earth5,6,7,8, and suggest that future work should investigate the notion that temporally continuous generation of new NMD sulphur isotope anomalies in the atmosphere was likely to have ceased long before their ultimate disappearance from the rock record.

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Figure 1: The rare sulphur isotope record through time.
Figure 2: Schematic diagram of the sulphur isotope mass balance model.
Figure 3: Modelled changes to the Δ33S value of seawater sulphate after the onset of oxidative sulphur cycling.

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Acknowledgements

Funding from NSF-EAR and the NASA Exobiology Program supported this research. C.T.R. acknowledges support from an O. K. Earl Postdoctoral Fellowship in Geological and Planetary Sciences at the California Institute of Technology. N.J.P. acknowledges support from NSF-EAR-PDF. Comments and criticism from L. Kump, B. Wing, A. Bekker and K. Konhauser greatly improved the manuscript.

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C.T.R. and N.J.P. designed the model. C.T.R. compiled the sulphur isotope database and performed the modelling and statistical analyses. C.T.R. and N.J.P. wrote the manuscript, with contributions from T.W.L.

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Correspondence to Christopher T. Reinhard.

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The authors declare no competing financial interests.

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Reinhard, C., Planavsky, N. & Lyons, T. Long-term sedimentary recycling of rare sulphur isotope anomalies. Nature 497, 100–103 (2013). https://doi.org/10.1038/nature12021

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