Contributions to late Archaean sulphur cycling by life on land


Evidence in palaeosols suggests that life on land dates back to at least 2.76 Gyr ago1,2. However, the biogeochemical effects of Archaean terrestrial life are thought to have been limited, owing to the lack of a protective ozone shield from ultraviolet radiation for terrestrial organisms before the rise of atmospheric oxygen levels several hundred million years later3. Records of chromium delivery from the continents suggest that microbial mineral oxidation began at least 2.48 Gyr ago4 but do not indicate when the terrestrial biosphere began to dominate important biogeochemical cycles. Here we combine marine sulphur abundance data with a mass balance model of the sulphur cycle to estimate the effects of the Archaean and early Proterozoic terrestrial biosphere on sulphur cycling. We find that terrestrial oxidation of pyrite by microbes using oxygen has contributed a substantial fraction of the total sulphur weathering flux since at least 2.5 Gyr ago, with probable evidence of such activity 2.7–2.8 Gyr ago. The late Archaean onset of terrestrial sulphur cycling is supported by marine molybdenum abundance data and coincides with a shift to more sulphidic ocean conditions5. We infer that significant microbial land colonization began by 2.7–2.8 Gyr ago. Our identification of pyrite oxidation at this time provides further support for the appearance6 of molecular oxygen several hundred million years before the Great Oxidation Event.

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Figure 1: Total inferred weathering flux Fw to continental margins over time.
Figure 2: Contribution of different sulphur sources to continental margin sediments.
Figure 3: Molybdenum concentrations in the late Archaean and early Proterozoic.


  1. 1

    Rye, R. & Holland, H. D. Life associated with a 2.76 Ga ephemeral pond?: Evidence from Mount Roe #2 paleosol. Geology 28, 483–486 (2000).

  2. 2

    Watanabe, Y., Martini, J. E. J. & Ohmoto, H. Geochemical evidence for terrestrial ecosystems 2.6 billion years ago. Nature 408, 574–578 (2000).

  3. 3

    Cockell, C. S. The ultraviolet history of the terrestrial planets - implications for biological evolution. Planet. Space Sci. 48, 203–214 (2000).

  4. 4

    Konhauser, K. O. et al. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event. Nature 478, 369–373 (2011).

  5. 5

    Reinhard, C. T., Raiswell, R., Scott, C. T., Anbar, A. & Lyons, T. W. A late Archean sulfidic sea stimulated by early oxidative weathering of the continents. Science 326, 713–716 (2009).

  6. 6

    Buick, R. When did oxygenic photosynthesis evolve? Phil. Trans. R. Soc. B 363, 2731–2743 (2008).

  7. 7

    Canfield, D. E. The evolution of the Earth surface sulfur reservoir. Am. J. Sci. 304, 839–861 (2004).

  8. 8

    Williamson, M. A. & Rimstidt, J. D. The kinetics and electrochemical rate-determining step of aqueous pyrite oxidation. Geochim. Cosmochim. Acta 58, 5443–5454 (1994).

  9. 9

    Catling, D. C. & Claire, M. W. How Earth’s atmosphere evolved to an oxic state: a status report. Earth Planet. Sci. Lett. 237, 1–20 (2005).

  10. 10

    England, G. L., Rasmussen, B., Krapez, B. & Groves, D. I. Palaeoenvironmental significance of rounded pyrite in siliclastic sequences of the Late Archaean Witwatersrand Basin: Oxygen-deficient atmosphere or hydrothermal alteration? Sedimentology 49, 1133–1156 (2002).

  11. 11

    Rasmussen, B. & Buick, R. Redox state of the Archean atmosphere: evidence from detrital heavy minerals in ca. 3250–2750 Ma sandstones from the Pilbara Craton, Australia. Geology 27, 115–118 (1999).

  12. 12

    Holland, H. D. When did the Earth’s atmosphere become oxic? A Reply. Geochem. News 100, 20–22 (1999).

  13. 13

    Taylor, S. R. Abundance of chemical elements in the continental crust: a new table. Geochim. Cosmochim. Acta 28, 1273–1285 (1964).

  14. 14

    Eggins, S. M. et al. A simple method for precise determination of >40 trace elements in geological samples by ICPMS using enriched isotope internal standardisation. Chem. Geol. 134, 311–326 (1997).

  15. 15

    Strauss, H. in Precambrian Sedimentary Environments: A Modern Approach to Ancient Depositional Systems (eds Altermann, W. & Corcoran, P. L.) (Blackwell Science, 2002).

  16. 16

    Farquhar, J. et al. Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry. Nature 449, 706–709 (2007).

  17. 17

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

  18. 18

    Walker, J. J. & Pace, N. R. Endolithic microbial ecosystems. Annu. Rev. Microbiol. 61, 331–347 (2007).

  19. 19

    Buick, R. The antiquity of oxygenic photosynthesis: Evidence from stromatolites in sulphate-deficient Archean lakes. Science 255, 74–77 (1992).

  20. 20

    Pavlov, A. A., Brown, L. L. & Kasting, J. F. UV shielding of NH3 and O2 by organic hazes in the Archean atmosphere. J. Geophys. Res. 106, 23267–23287 (2001).

  21. 21

    Wolf, E. T. & Toon, O. B. Fractal organic haze provided an ultraviolet shield for early earth. Science 328, 1266–1268 (2010).

  22. 22

    Canfield, D. E. The early history of atmospheric oxygen: Homage to Robert M. Garrels. Annu. Rev. Earth Planet. Sci. 33, 1–36 (2005).

  23. 23

    Knauth, L. P. & Kennedy, M. J. The late Precambrian greening of the Earth. Nature 460, 728–732 (2009).

  24. 24

    Shen, Y., Buick, R. & Canfield, D. E. Isotopic evidence for microbial sulphate reduction in the early Archaean era. Nature 410, 77–81 (2001).

  25. 25

    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).

  26. 26

    Poulton, S. W. & Canfield, D. E. Ferruginous conditions: A dominant feature of the ocean through Earth’s history. Elements 7, 107–112 (2011).

  27. 27

    Liang, M-C., Hartman, H., Kopp, R. E., Kirschvink, J. L. & Yung, Y. L. Production of hydrogen peroxide in the atmosphere of a Snowball Earth and the origin of oxygenic photosynthesis. Proc. Natl Acad. Sci. USA 103, 18896–18899 (2006).

  28. 28

    Emerson, S. & Hedges, J. Chemical Oceanography and The Marine Carbon Cycle (Cambridge Univ. Press, 2008).

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We thank H. Strauss for sharing his sulphur database. This study was financially supported by NSF EAR-0921580. D.C.C. also acknowledges support from NASA Astrobiology grant NNX10AQ90G and the NAI Virtual Planetary Laboratory.

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E.E.S. and D.C.C. designed and analysed the model, and all authors contributed to the collection of literature data and the composition of the manuscript.

Correspondence to Eva E. Stüeken.

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

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