Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

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


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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others


  1. Farquhar, J., Bao, H. & Thiemens, M. Atmospheric influence of Earth’s earliest sulfur cycle. Science 289, 756–758 (2000).

    Article  Google Scholar 

  2. Luo, G. et al. Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago. Sci. Adv. 2, e1600134 (2016).

    Article  Google Scholar 

  3. Pavlov, A. & Kasting, J. Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere. Astrobiology 2, 27–41 (2002).

    Article  Google Scholar 

  4. Labidi, J., Cartigny, P. & Moreira, M. Non-chondritic sulphur isotope composition of the terrestrial mantle. Nature 501, 208–211 (2013).

    Article  Google Scholar 

  5. Wing, B. A. & Farquhar, J. Sulfur isotope homogeneity of lunar mare basalts. Geochim. Cosmochim. Acta 170, 266–280 (2015).

    Article  Google Scholar 

  6. Farquhar, J. & Wing, B. A. Multiple sulfur isotopes and the evolution of the atmosphere. Earth Planet. Sci. Lett. 213, 1–13 (2003).

    Article  Google Scholar 

  7. Reinhard, C. T., Planavsky, N. J. & Lyons, T. W. Long-term sedimentary recycling of rare sulphur isotope anomalies. Nature 497, 100–103 (2013).

    Article  Google Scholar 

  8. Cabral, R. A. et al. Anomalous sulphur isotopes in plume lavas reveal deep mantle storage of Archaean crust. Nature 496, 490–493 (2013).

    Article  Google Scholar 

  9. Keller, C. B. & Schoene, B. Statistical geochemistry reveals disruption in secular lithospheric evolution about 2.5 Gyr ago. Nature 485, 490–493 (2012).

    Article  Google Scholar 

  10. Partridge, M. A., Golding, S. D., Baublys, K. A. & Young, E. Pyrite paragenesis and multiple sulfur isotope distribution in late Archean and early Paleoproterozoic Hamersley Basin sediments. Earth Planet. Sci. Lett. 272, 41–49 (2008).

    Article  Google Scholar 

  11. Ono, S., Beukes, N. J. & Rumble, D. Origin of two distinct multiple-sulfur isotope compositions of pyrite in the 2.5 Ga Klein Naute Formation, Griqualand West Basin, South Africa. Precambrian Res. 169, 48–57 (2009).

    Article  Google Scholar 

  12. Farquhar, J. et al. Pathways for Neoarchean pyrite formation constrained by mass-independent sulfur isotopes. Proc. Natl Acad. Sci. USA 110, 17638–17643 (2013).

    Article  Google Scholar 

  13. Fischer, W. W. et al. SQUID–SIMS is a useful approach to uncover primary signals in the Archean sulfur cycle. Proc. Natl Acad. Sci. USA 111, 5468–5473 (2014).

    Article  Google Scholar 

  14. Gaillardet, J., Viers, J. & Dupré, B. Trace elements in river waters. Treatise Geochem. 5, 225–272 (2003).

    Article  Google Scholar 

  15. Johnson, J. E., Gerpheide, a, Lamb, M. P. & Fischer, W. W. O2 constraints from Paleoproterozoic detrital pyrite and uraninite. Geol. Soc. Am. Bull. 126, 813–830 (2014).

    Article  Google Scholar 

  16. Li, L. et al. Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks. Nat. Commun. 7, 13252 (2016).

    Article  Google Scholar 

  17. Turchyn, A. V., Tipper, E. T., Galy, A., Lo, J. K. & Bickle, M. J. Isotope evidence for secondary sulfide precipitation along the Marsyandi River, Nepal, Himalayas. Earth Planet. Sci. Lett. 374, 36–46 (2013).

    Article  Google Scholar 

  18. Johnston, D. T. Multiple sulfur isotopes and the evolution of Earth’s surface sulfur cycle. Earth Sci. Rev. 106, 161–183 (2011).

    Article  Google Scholar 

  19. Bekker, A. et al. Atmospheric sulfur in Archean komatiite-hosted nickel deposits. Science 326, 1086–1089 (2009).

    Article  Google Scholar 

  20. Goodwin, A. M. Principles of Precambrian Geology (Academic Press, London, San Diego, 1996).

  21. Halevy, I., Johnston, D. T. & Schrag, D. P. Explaining the structure of the Archean mass-independent sulfur isotope record. Science 329, 204–207 (2010).

    Article  Google Scholar 

  22. Paris, G., Sessions, A. L., Subhas, A. V. & Adkins, J. F. MC-ICP-MS measurement of δ 34S and Δ33S in small amounts of dissolved sulfate. Chem. Geol. 345, 50–61 (2013).

    Article  Google Scholar 

  23. Paris, G., Adkins, J. F., Sessions, A. L., Webb, S. M. & Fischer, W. W. Neoarchean carbonate-associated sulfate records positive 33S anomalies. Science 346, 739–742 (2014).

    Article  Google Scholar 

  24. Stallard, R. & Edmond, J. Geochemistry of the Amazon 1. Precipitation chemistry and the marine contribution to the dissolved load at the time of peak discharge. J. Geophys. Res. 86, 9844–9858 (1981).

    Article  Google Scholar 

  25. Price, J. R. & Szymanski, D. W. The effects of road salt on stream water chemistry in two small forested watersheds, Catoctin Mountain, Maryland, USA. Aquat. Geochem. 20, 243–265 (2014).

    Article  Google Scholar 

  26. Baroni, M., Thiemens, M. H., Delmas, R. J. & Savarino, J. Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions. Science 315, 84–87 (2007).

    Article  Google Scholar 

  27. Nriagu, J. O. & Coker, R. D. Isotopic composition of sulfur in precipitation within the Great Lakes Basin. Tellus A 2826, 365–375 (1978).

    Google Scholar 

  28. Caron, F., Tessier, A., Kramer, J. R., Schwarcz, H. P. & Rees, C. E. Sulfur and oxygen isotopes of sulfate in precipitation and lakewater, Quebec, Canada. Appl. Geochem. 1, 601–606 (1986).

    Article  Google Scholar 

Download references


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.

Author information

Authors and Affiliations



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

Corresponding author

Correspondence to Mark A. Torres.

Ethics declarations

Competing interests

The authors have no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing