Neoarchaean seawater sulphate concentrations from sulphur isotopes in massive sulphide ore

Abstract

The concentration of sulphate in today’s oceans—approximately 28,000 μmol l−1—is maintained by a balance between removal by pyrite burial and evaporite deposition and supply by oxidative weathering and the erosion of sulphate minerals from evaporites1. Oceanic sulphate concentrations were much lower before the rise of atmospheric oxygen about 2.4 Gyr ago2. The limited spread of δ34S values in sedimentary sulphides from 3.85 to 2.5 Gyr ago suggests that microbial sulphate reduction, if it played an important role in the Archaean marine sulphur cycle, must have occurred at sulphate concentrations of 200 μmol l−1 or less3. Here we use sulphur isotope systematics of the 2.7 Gyr old volcanogenic massive sulphide ore deposits from Kidd Creek, Ontario, to provide constraints on seawater sulphate concentrations independent of biological considerations. By comparing these values with metal and sulphur budgets from modern hydrothermal settings, we estimate that seawater sulphate concentrations 2.7 Gyr ago were roughly 80 μmol l−1. At these levels, the residence time of sulphate was on the order of 200,000 years, sufficiently long to make sulphate a conservative compound in the open ocean, but still short enough to suggest that hydrothermal sulphur fluxes were accompanied by a globally significant sink associated with microbial sulphate reduction.

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Figure 1: Mass-independent sulphur isotope signatures of sulphides from Kidd Creek.
Figure 2: Empirical probability distribution of seawater sulphate concentrations in the Neoarchaean Kidd Creek basin.

References

  1. 1

    Halevy, I., Peters, S. E. & Fischer, W. W. Sulfate burial constraints on the Phanerozoic sulfur cycle. Science 337, 331–334 (2012).

    Article  Google Scholar 

  2. 2

    Lyons, T. W. & Gill, B. C. Ancient sulfur cycling and oxygenation of the early biosphere. Elements 6, 93–99 (2010).

    Article  Google Scholar 

  3. 3

    Habicht, K. S., Gade, M., Thamdrup, B., Berg, P. & Canfield, D. E. Calibration of sulfate levels in the Archean Ocean. Science 298, 2372–2374 (2002).

    Article  Google Scholar 

  4. 4

    Vearncombe, S. et al. 3.26 Ga Black smoker-type mineralization in the Strelley Belt, Pilbara-Craton, Western-Australia. J. Geol. Soc. 152, 587–590 (1995).

    Article  Google Scholar 

  5. 5

    Alt, J. C. Sulfur isotopic profile through the oceanic crust - sulfur mobility and seawater-crustal sulfur exchange during hydrothermal alteration. Geology 23, 585–588 (1995).

    Article  Google Scholar 

  6. 6

    Shanks, W. C., Bischoff, J. L. & Rosenbauer, R. J. Sea-water sulfate reduction and sulfur isotope fractionation in basaltic systems—interaction of sea-water with fayalite and magnetite at 200–350 °C. Geochim. Cosmochim. Acta 45, 1977–1995 (1981).

    Article  Google Scholar 

  7. 7

    Woodruff, L. G. & Shanks, W. C. Sulfur isotope study of chimney minerals and vent fluids from 21° N, East Pacific Rise—hydrothermal sulfur sources and disequilibrium sulfate reduction. J. Geophys. Res. 93, 4562–4572 (1988).

    Article  Google Scholar 

  8. 8

    Herzig, P. M., Hannington, M. D. & Arribas, A. Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: Implications for magmatic contributions to seafloor hydrothermal systems. Mineral Depos. 33, 226–237 (1998).

    Article  Google Scholar 

  9. 9

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

    Article  Google Scholar 

  10. 10

    Farquhar, J., Savarino, J., Airieau, S. & Thiemens, M. H. Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO2 photolysis: Implications for the early atmosphere. J. Geophys. Res. 106, 32829–32839 (2001).

    Article  Google Scholar 

  11. 11

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

    Article  Google Scholar 

  12. 12

    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 

  13. 13

    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 

  14. 14

    Ono, S. H., 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. Precambr. Res. 169, 48–57 (2009).

    Article  Google Scholar 

  15. 15

    Ono, S. et al. New insights into Archean sulfur cycle from mass-independent sulfur isotope records from the Hamersley Basin, Australia. Earth Planet. Sci. Lett. 213, 15–30 (2003).

    Article  Google Scholar 

  16. 16

    Shanks, W. C. & Seyfried, W. E. Stable isotope studies of vent fluids and chimney minerals, Southern Juan-de-Fuca Ridge—sodium metasomatism and seawater sulfate reduction. J. Geophys. Res. 92, 11387–11399 (1987).

    Article  Google Scholar 

  17. 17

    Farquhar, J. et al. Mass-independent sulfur of inclusions in diamond and sulfur recycling on early earth. Science 298, 2369–2372 (2002).

    Article  Google Scholar 

  18. 18

    Ono, S., Shanks, W. C., Rouxel, O. J. & Rumble, D. S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides. Geochim. Cosmochim. Acta 71, 1170–1182 (2007).

    Article  Google Scholar 

  19. 19

    Peters, M. et al. Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach. Chem. Geol. 269, 180–196 (2010).

    Article  Google Scholar 

  20. 20

    Humphris, S. E. & Cann, J. R. Constraints on the energy and chemical balances of the modern TAG and ancient Cyprus seafloor sulfide deposits. J. Geophys. Res. 105, 28477–28488 (2000).

    Article  Google Scholar 

  21. 21

    Bischoff, J. L. & Seyfried, W. E. Hydrothermal chemistry of seawater from 25 °C to 350 °C. Amer. J. Sci. 278, 838–860 (1978).

    Article  Google Scholar 

  22. 22

    Seyfried, W. E. Jr, Ding, K., Berndt, M. E. & Chen, X. in Volcanic-Associated Massive Sulfide Deposits—Processes and Examples in Modern and Ancient Settings: Reviews in Economic Geology Vol. 8 (eds Barrie, C. T. & Hannington, M. D.) 181–200 (1999).

    Google Scholar 

  23. 23

    Hannington, M. D., Galley, A. G., Herzig, P. M. & Petersen, S. in Proc. ODP, Sci. Results Vol. 158 (eds Herzig, P. M., Humphris, S. E., Miller, D. J. & Zierenberg, R. A.) 389–415 (Ocean Drilling Program, 1998).

    Google Scholar 

  24. 24

    Hannington, M., Bleeker, W. & Kjarsgaard, I. in Sulfide Mineralogy, Geochemistry, and Ore Genesis of the Kidd Creek Deposit: Part I. North, Central and South Orebodies 163–224 (Econ. Geol. Monograph, Vol. 10, 1999).

    Google Scholar 

  25. 25

    Blount, C. W. & Dickson, F. W. Solubility of anhydrite (CaSO4) in NaCl-H2O from 100 to 450 °C and 1 to 1000 bars. Geochim. Cosmochim. Acta 33, 227–245 (1969).

    Article  Google Scholar 

  26. 26

    Knauth, L. P. Salinity history of the Earth’s early ocean. Nature 395, 554–555 (1998).

    Article  Google Scholar 

  27. 27

    Stüeken, E., Catling, D. & Buick, R. Contributions to late Archaean sulphur cycling by life on land. Nature Geosci. 5, 722–725 (2012).

    Article  Google Scholar 

  28. 28

    Zahnle, K., Claire, M. & Catling, D. The loss of mass-independent fractionation in sulfur due to a Palaeoproterozoic collapse of atmospheric methane. Geobiology 4, 271–283 (2006).

    Article  Google Scholar 

  29. 29

    Walker, J. C. G. & Brimblecombe, P. Iron and sulfur in the pre-biologic ocean. Precambr. Res. 28, 205–222 (1985).

    Article  Google Scholar 

  30. 30

    Sleep, N. H. & Zahnle, K. Carbon dioxide cycling and implications for climate on ancient Earth. J. Geophys. Res. 106, 1373–1399 (2001).

    Article  Google Scholar 

Download references

Acknowledgements

Data measured for this study are available in the Supplementary Information. The National Science and Engineering Research Council of Canada made this study possible through fellowships to J.W.J. and a Discovery grant to B.A.W. Analytical costs at the Stable Isotope Laboratory at the University of Maryland were supported by the National Science Foundation.

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This study was conceived by J.W.J. and B.A.W. Samples from Kidd Creek, and interpretation of their depositional environment were provided by M.D.H. Sulphur isotope analyses were performed by J.W.J. Analysis and interpretation of the data were completed by J.W.J., B.A.W. and J.F. The paper was written by J.W.J. and B.A.W.

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Correspondence to J. W. Jamieson.

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The authors declare no competing financial interests.

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Jamieson, J., Wing, B., Farquhar, J. et al. Neoarchaean seawater sulphate concentrations from sulphur isotopes in massive sulphide ore. Nature Geosci 6, 61–64 (2013). https://doi.org/10.1038/ngeo1647

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