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Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation

Abstract

Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past1,2,3,4. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide () in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen5,6. Our results suggest that was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results2. We also find that the 17O isotope anomalies of barites from Marinoan (635 million years ago) cap carbonates display a distinct negative spike (around -0.70‰), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the was at its highest level in the past 750 million years. Our finding is consistent with the ‘snowball Earth’ hypothesis7,8 and/or a massive methane release9 after the Marinoan glaciation.

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Figure 1
Figure 2: How evaporite or barite sulphate records the negative 17 O anomaly of tropospheric O 2 that originated in the stratosphere.
Figure 3: Model-calculated partial pressures of CO 2 based on the lowest sulphate Δ 17 O value for a given period in geological history.

References

  1. Rye, R., Kuo, P. H. & Holland, H. D. Atmospheric carbon dioxide concentrations before 2.2 billion years ago. Nature 378, 603–605 (1995)

    ADS  CAS  Article  Google Scholar 

  2. Berner, R. A. GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2 . Geochim. Cosmochim. Acta 70, 5653–5664 (2006)

    ADS  CAS  Article  Google Scholar 

  3. Ekart, D. D., Cerling, T. E., Montanez, I. P. & Tabor, N. J. A 400 million year carbon isotope record of pedogenic carbonate: implications for paleoatmospheric carbon dioxide. Am. J. Sci. 299, 805–827 (1999)

    ADS  CAS  Article  Google Scholar 

  4. Royer, D. L. et al. Paleobotanical evidence for near present-day levels of atmospheric CO2 during part of the Tertiary. Science 292, 2310–2313 (2001)

    ADS  CAS  Article  Google Scholar 

  5. Yung, Y. L., DeMore, W. B. & Pinto, J. P. Isotopic exchange between carbon dioxide and ozone via O(1D) in the stratosphere. Geophys. Res. Lett. 18, 13–16 (1991)

    ADS  CAS  Article  Google Scholar 

  6. Yung, Y. L. et al. Carbon dioxide in the atmosphere: Isotopic exchange with ozone and its use as a tracer in the middle atmosphere. J. Geophys. Res. 102 (D9). 10857–10866 (1997)

    ADS  CAS  Article  Google Scholar 

  7. Hoffman, P. F., Kaufman, A. J., Halverson, G. P. & Schrag, D. P. A Neoproterozoic snowball Earth. Science 281, 1342–1346 (1998)

    ADS  CAS  Article  Google Scholar 

  8. Pierrehumbert, R. T. High levels of atmospheric carbon dioxide necessary for the termination of global glaciation. Nature 429, 646–649 (2004)

    ADS  CAS  Article  Google Scholar 

  9. Jiang, G. Q., Kennedy, M. J. & Christie-Blick, N. Stable isotopic evidence for methane seeps in Neoproterozoic postglacial cap carbonates. Nature 426, 822–826 (2003)

    ADS  CAS  Article  Google Scholar 

  10. Bao, H. M. et al. Anomalous 17O compositions in massive sulphate deposits on the Earth. Nature 406, 176–178 (2000)

    ADS  CAS  Article  Google Scholar 

  11. Bao, H. M., Thiemens, M. H., Loope, D. B. & Yuan, X. L. Sulfate oxygen-17 anomaly in an Oligocene ash bed in mid-North America: Was it the dry fogs? Geophys. Res. Lett. 30 (16). 1843 1810.1029/2003GL016869 (2003)

    ADS  CAS  Article  Google Scholar 

  12. Howell, K. J. & Bao, H. M. Caliche as a geological repository for atmospheric sulfate. Geophys. Res. Lett. 33 L13816 10.1029/2006GL026518 (2006)

    ADS  CAS  Article  Google Scholar 

  13. Alexander, B. et al. Climate driven changes in the oxidation pathways of atmospheric sulfur. Geophys. Res. Lett. 29 (14). 1685 10.1029/2002GL014879 (2002)

    ADS  Article  Google Scholar 

  14. Bao, H. M. & Marchant, D. R. Quantifying sulfate components and their variations in soils of the McMurdo Dry Valleys, Antarctica. J. Geophys. Res. 111 (D16301). 10.1029/2005JD006669 (2006)

  15. Savarino, J., Lee, C. C. W. & Thiemens, M. H. Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth. J. Geophys. Res. 105 (D23). 29079–29088 (2000)

    ADS  CAS  Article  Google Scholar 

  16. Bao, H. M. Sulfate in modern playa settings and in ash beds in hyperarid deserts: Implication on the origin of 17O-anomalous sulfate in an Oligocene ash bed. Chem. Geol. 214, 127–134 (2005)

    ADS  CAS  Article  Google Scholar 

  17. van Stempvoort, D. R. & Krouse, H. R. in Environmental Geochemistry of Sulfide Oxidation Vol. 550 (eds Alpers, C. N. & Blowes, D. W.) 446–480 (American Chemical Society, Washington DC, 1994)

    Google Scholar 

  18. Balci, N., Shanks, W. C., Mayer, B. & Mandernack, K. W. Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite. Geochim. Cosmochim. Acta 71, 3796–3811 (2007)

    ADS  CAS  Article  Google Scholar 

  19. Bender, M., Sowers, T. & Labeyrie, L. The Dole effect and its variations during the last 130,000 years as measured in the Vostok ice core. Glob. Biogeochem. Cycles 8, 363–376 (1994)

    ADS  CAS  Article  Google Scholar 

  20. Luz, B. et al. Triple-isotope composition of atmospheric oxygen as a tracer of biosphere productivity. Nature 400, 547–550 (1999)

    ADS  CAS  Article  Google Scholar 

  21. Young, E. D., Galy, A. & Nagahara, H. Kinetic and equilibrium mass-dependent isotope fractionation laws in nature and their geochemical and cosmochemical significance. Geochim. Cosmochim. Acta 66, 1095–1104 (2002)

    ADS  CAS  Article  Google Scholar 

  22. Miller, M. F. Isotopic fractionation and the quantification of 17O anomalies in the oxygen three-isotope system: an appraisal and geochemical significance. Geochim. Cosmochim. Acta 66, 1881–1889 (2002)

    ADS  CAS  Article  Google Scholar 

  23. Luz, B. & Barkan, E. The isotopic ratios 17O/16O and 18O/16O in molecular oxygen and their significance in biogeochemistry. Geochim. Cosmochim. Acta 69, 1099–1110 (2005)

    ADS  CAS  Article  Google Scholar 

  24. Blunier, T., Barnett, B., Bender, M. L. & Hendricks, M. B. Biological oxygen productivity during the last 60,000 years from triple oxygen isotope measurements. Glob. Biogeochem. Cycles 16 (3). 1029 10.1029/2001GB001460 (2002)

    ADS  CAS  Article  Google Scholar 

  25. Gamsjäger, H. & Murmann, R. K. in Advances in Inorganic and Bioinorganic Mechanisms Vol. 2 (ed. Sykes, A. G.) 317–381 (Academic, London, 1983)

    Google Scholar 

  26. Jiang, G. Q. et al. Stratigraphy, sedimentary structures, and textures of the late Neoproterozoic Doushantuo cap carbonate in South China. J. Sediment. Res. 76, 978–995 (2006)

    ADS  CAS  Article  Google Scholar 

  27. Kasemann, S. A. et al. Boron and calcium isotope composition in Neoproterozoic carbonate rocks from Namibia: evidence for extreme environmental change. Earth Planet. Sci. Lett. 231, 73–86 (2005)

    ADS  CAS  Article  Google Scholar 

  28. Bao, H. M. Purifying synthetic barite for oxygen isotope measurement by dissolution and reprecipitation in a chelating solution. Anal. Chem. 78, 304–309 (2006)

    CAS  Article  Google Scholar 

  29. Bao, H. M. & Thiemens, M. H. Generation of O2 from BaSO4 using a CO2-laser fluorination system for simultaneous analysis of δ18O and δ17O. Anal. Chem. 72, 4029–4032 (2000)

    CAS  Article  Google Scholar 

  30. Mauersberger, K., Krankowsky, D., Janssen, C. & Schinke, R. in Advances in Atomic, Molecular, and Optical Physics Vol. 50 1–54 (Elsevier Academic, San Diego, 2005)

    Book  Google Scholar 

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Acknowledgements

We thank numerous colleagues who have contributed evaporite and barite samples over the years, including W. T. Holser, M. Tucker, C. Spötl, R. Denison, C. Laughrey, S. C. Morris, S. P. Das Gupta, K. Benison, B.–H. Fu, S. Xiao, G. Retallack, W.-L. Zang, J. Hanor, B. Ellwood, D. Henry, B. Dutrow and A. J. Kaufman. One important barite sample, collected by G. P. Halverson, P. F. Hoffman and A. C. Maloof in Mauritania, West Africa, was obtained from M. H. Thiemens and D. P. Schrag. We thank Huifeng Bao for field assistance, M. Khachaturyan for laboratory assistance, and NSF, LSU, NASA (Planetary Atmospheres), the NNSF of China, the Chinese Academy of Sciences and the Chinese Ministry of Science and Technology for financial support.

Author Contributions H.B. designed the research, developed analytical procedures and performed measurements. J.R.L. did one-dimensional photochemical modelling and C.M.Z. directed fieldwork in South China. H.B. and J.R.L. wrote the manuscript.

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Correspondence to Huiming Bao.

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The file contains Supplementary Data with Supplementary Tables S1-S2, Supplementary Figures S1-S5 and additional references. (PDF 1180 kb)

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Bao, H., Lyons, J. & Zhou, C. Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation. Nature 453, 504–506 (2008). https://doi.org/10.1038/nature06959

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