Skip to main content

Thank you for visiting nature.com. 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:

A seawater oxygen oscillation recorded by iron formations prior to the Great Oxidation Event

Nature Geoscience volume 18, pages 417–422 (2025) Cite this article

Subjects

Abstract

Earth’s atmosphere underwent permanent oxidation during the Great Oxidation Event approximately 2.45–2.22 billion years ago (Ga) due to excess oxygen (O2) generated by marine cyanobacteria. However, understanding the timing and tempo of seawater oxygenation before the Great Oxidation Event has been hindered by the absence of sensitive tracers. Nitrogen (N) isotopes can be an indicator of marine oxygenation. Here we present an ~200 Myr nitrogen isotope oscillation recorded by Neoarchaean and Palaeoproterozoic banded iron formations from the Hamersley Basin, Western Australia, that were deposited in relatively deep marine shelf environments. Paired with the Jeerinah Formation shale record, our data from the Marra Mamba Iron Formation suggest that oxic conditions expanded to banded iron formation depositional environments from ~2.63 to 2.60 Ga. Subsequently, a positive δ15N excursion occurred in the ~2.48 Ga Dale Gorge Member, marking a decline in seawater O2 and enhanced denitrification. This O2 deficit was followed by a second phase of increasing O2 levels as indicated by a gradual return to moderately positive δ15N values in the ~2.46 Ga Joffre Member and 2.45 Ga Weeli Wolli Iron Formation. These variations underscore a nonlinear history of marine oxygenation and reveal a previously unrecognized oscillation in seawater O2 levels preceding the Great Oxidation Event.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

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

Fig. 1: Simplified stratigraphy and isotopic profiles of sediments in the Hamersley Group.
The alternative text for this image may have been generated using AI.
Fig. 2: Modelling the degree of denitrification for sedimentary rocks in the Hamersley Basin.
The alternative text for this image may have been generated using AI.
Fig. 3: Depositional models (not to scale) for Hamersley BIFs.
The alternative text for this image may have been generated using AI.

Similar content being viewed by others

Data availability

All data supporting this study are provided in Extended Data Table 1 and are available via figshare at https://doi.org/10.6084/m9.figshare.26094001 (ref. 63). Source data are provided with this paper.

References

  1. Lyons, T. W., Reinhard, C. T. & Planavsky, N. J. The rise of oxygen in Earth’s early ocean and atmosphere. Nature 506, 307–315 (2014).

    Article  CAS  Google Scholar 

  2. Garvin, J., Buick, R., Anbar, A. D., Arnold, G. L. & Kaufman, A. J. Isotopic evidence for an aerobic nitrogen cycle in the latest Archean. Science 323, 1045–1048 (2009).

    Article  CAS  Google Scholar 

  3. Ostrander, C. M. et al. Fully oxygenated water columns over continental shelves before the Great Oxidation Event. Nat. Geosci. 12, 186–191 (2019).

    Article  CAS  Google Scholar 

  4. Kendall, B. et al. Pervasive oxygenation along late Archaean ocean margins. Nat. Geosci. 3, 647–652 (2010).

    Article  CAS  Google Scholar 

  5. Wang, C. et al. A craton-wide geochemical survey of late Archean banded iron formations in China. Earth Planet. Sci. Lett. 642, 118879 (2024).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  7. Planavsky, N. J. et al. Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event. Nat. Geosci. 7, 283–286 (2014).

    Article  CAS  Google Scholar 

  8. Rosing, M. T. & Frei, R. U-rich Archaean sea-floor sediments from Greenland—indications of >3700 Ma oxygenic photosynthesis. Earth Planet. Sci. Lett. 217, 237–244 (2004).

    Article  CAS  Google Scholar 

  9. Anbar, A. D. et al. A whiff of oxygen before the great oxidation event? Science 317, 1903–1906 (2007).

    Article  CAS  Google Scholar 

  10. Lalonde, S. V. & Konhauser, K. O. Benthic perspective on Earth’s oldest evidence for oxygenic photosynthesis. Proc. Natl Acad. Sci. USA 112, 995–1000 (2015).

    Article  CAS  Google Scholar 

  11. He, H. et al. An abiotic source of Archean hydrogen peroxide and oxygen that pre-dates oxygenic photosynthesis. Nat. Commun. 12, 6611 (2021).

    Article  CAS  Google Scholar 

  12. Busigny, V. & Bebout, G. E. Nitrogen in the silicate Earth: speciation and isotopic behavior during mineral-fluid interactions. Elements 9, 353–358 (2013).

    Article  CAS  Google Scholar 

  13. Stüeken, E. E., Kipp, M. A., Koehler, M. C. & Buick, R. The evolution of Earth’s biogeochemical nitrogen cycle. Earth Sci. Rev. 160, 220–239 (2016).

    Article  Google Scholar 

  14. Zhang, X., Sigman, D. M., Morel, F. M. & Kraepiel, A. M. Nitrogen isotope fractionation by alternative nitrogenases and past ocean anoxia. Proc. Natl Acad. Sci. USA 111, 4782–4787 (2014).

    Article  CAS  Google Scholar 

  15. Zerkle, A. L., Junium, C. K., Canfield, D. E. & House, C. H. Production of 15N‐depleted biomass during cyanobacterial N2‐fixation at high Fe concentrations. J. Geophys. Res. Biogeosci. https://doi.org/10.1029/2007JG000651 (2008).

  16. Casciotti, K. L. Inverse kinetic isotope fractionation during bacterial nitrite oxidation. Geochim. Cosmochim. Acta 73, 2061–2076 (2009).

    Article  CAS  Google Scholar 

  17. Thunell, R. C., Sigman, D. M., Muller‐Karger, F., Astor, Y. & Varela, R. Nitrogen isotope dynamics of the Cariaco Basin, Venezuela. Glob. Biogeochem. Cycles https://doi.org/10.1029/2003GB002185 (2004).

  18. Brunner, B. et al. Nitrogen isotope effects induced by anammox bacteria. Proc. Natl Acad. Sci. USA 110, 18994–18999 (2013).

    Article  CAS  Google Scholar 

  19. McCready, R. G. L., Gould, W. D. & Barendregt, R. W. Nitrogen isotope fractionation during the reduction of NO3− to NH4+ by Desulfovibrio sp. Can. J. Microbiol. 29, 231–234 (1983).

    Article  CAS  Google Scholar 

  20. Godfrey, L. V. & Falkowski, P. G. The cycling and redox state of nitrogen in the Archaean ocean. Nat. Geosci. 2, 725–729 (2009).

    Article  CAS  Google Scholar 

  21. Koehler, M. C., Buick, R., Kipp, M. A., Stueken, E. E. & Zaloumis, J. Transient surface ocean oxygenation recorded in the approximately 2.66 Ga Jeerinah Formation, Australia. Proc. Natl Acad. Sci. USA 115, 7711–7716 (2018).

    Article  CAS  Google Scholar 

  22. Busigny, V., Lebeau, O., Ader, M., Krapež, B. & Bekker, A. Nitrogen cycle in the late Archean ferruginous ocean. Chem. Geol. 362, 115–130 (2013).

    Article  CAS  Google Scholar 

  23. Luo, G. et al. Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event. Nat. Commun. 9, 978 (2018).

    Article  Google Scholar 

  24. Kipp, M. A., Stüeken, E. E., Yun, M., Bekker, A. & Buick, R. Pervasive aerobic nitrogen cycling in the surface ocean across the Paleoproterozoic Era. Earth Planet. Sci. Lett. 500, 117–126 (2018).

    Article  CAS  Google Scholar 

  25. Cheng, C. et al. Nitrogen isotope evidence for stepwise oxygenation of the ocean during the Great Oxidation Event. Geochim. Cosmochim. Acta 261, 224–247 (2019).

    Article  CAS  Google Scholar 

  26. Yamaguchi, K. Geochemistry of Archean–Paleoproterozoic Black Shales: The Early Evolution of the Atmosphere, Oceans, and Biosphere. Pennsylvania State University, PhD dissertation (2002).

  27. Lantink, M. L., Davies, J., Ovtcharova, M. & Hilgen, F. J. Milankovitch cycles in banded iron formations constrain the Earth–Moon system 2.46 billion years ago. Proc. Natl Acad. Sci. USA 119, e2117146119 (2022).

    Article  CAS  Google Scholar 

  28. Lantink, M. L. et al. Towards an astrochronological framework for the lower Paleoproterozoic Kuruman and Brockman Iron formations. S. Afr. J. Geol. 127, 325–358 (2024).

    Article  CAS  Google Scholar 

  29. Poulton, S. W. et al. A 200-million-year delay in permanent atmospheric oxygenation. Nature 592, 232–236 (2021).

    Article  CAS  Google Scholar 

  30. Thomazo, C., Couradeau, E. & Garcia-Pichel, F. Possible nitrogen fertilization of the early Earth Ocean by microbial continental ecosystems. Nat. Commun. 9, 2530 (2018).

    Article  Google Scholar 

  31. Klein, C. & Beukes, N. J. Geochemistry and sedimentology of a facies transition from limestone to iron-formation deposition in the early Proterozoic Transvaal Supergroup, South Africa. Econ. Geol. 84, 1733–1774 (1989).

    Article  CAS  Google Scholar 

  32. Bekker, A. et al. Iron formation: the sedimentary product of a complex interplay among mantle, tectonic, oceanic, and biospheric processes. Econ. Geol. 105, 467–508 (2010).

    Article  CAS  Google Scholar 

  33. Konhauser, K. O. et al. Iron formations: a global record of Neoarchaean to Palaeoproterozoic environmental history. Earth Sci. Rev. 172, 140–177 (2017).

    Article  CAS  Google Scholar 

  34. Konhauser, K. O., Newman, D. K. & Kappler, A. The potential significance of microbial Fe(III) reduction during deposition of Precambrian banded iron formations. Geobiology 3, 167–177 (2005).

    Article  CAS  Google Scholar 

  35. Li, Y., Li, L. & Wu, Z. First-principles calculations of equilibrium nitrogen isotope fractionations among aqueous ammonium, silicate minerals and salts. Geochim. Cosmochim. Acta 297, 220–232 (2021).

    Article  CAS  Google Scholar 

  36. Bebout, G. E. & Fogel, M. L. Nitrogen-isotope compositions of metasedimentary rocks in the Catalina Schist, California: implications for metamorphic devolatilization history. Geochim. Cosmochim. Acta 56, 2839–2849 (1992).

    Article  CAS  Google Scholar 

  37. Hayes, J. in Early Life on Earth (ed. Bengston, S.) 220–236 (Columbia Univ. Press, 1994).

  38. Boetius, A. et al. A marine microbial consortium apparently mediating anaerobic oxidation of methane. Nature 407, 623–626 (2000).

    Article  CAS  Google Scholar 

  39. Beal, E. J., House, C. H. & Orphan, V. J. Manganese- and iron-dependent marine methane oxidation. Science 325, 184–187 (2009).

    Article  CAS  Google Scholar 

  40. Haroon, M. F. et al. Anaerobic oxidation of methane coupled to nitrate reduction in a novel archaeal lineage. Nature 500, 567–570 (2013).

    Article  CAS  Google Scholar 

  41. Konhauser, K. O. et al. Decoupling photochemical Fe(II) oxidation from shallow-water BIF deposition. Earth Planet. Sci. Lett. 258, 87–100 (2007).

    Article  CAS  Google Scholar 

  42. Pellerin, A. et al. Iron-mediated anaerobic ammonium oxidation recorded in the early Archean ferruginous ocean. Geobiology 21, 277–289 (2023).

    Article  CAS  Google Scholar 

  43. 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  CAS  Google Scholar 

  44. Li, Y. et al. Nitrogen isotopes as a robust tracer of fluid activities and mineral reactions in regional metamorphism. Geochim. Cosmochim. Acta 375, 76–89 (2024).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  46. Lantink, M. L. et al. Precessional pacing of early Proterozoic redox cycles. Earth Planet. Sci. Lett. 610, 118117 (2023).

    Article  CAS  Google Scholar 

  47. Philippot, P. et al. Globally asynchronous sulphur isotope signals require re-definition of the Great Oxidation Event. Nat. Commun. 9, 2245 (2018).

    Article  Google Scholar 

  48. Eigenbrode, J. L. & Freeman, K. H. Late Archean rise of aerobic microbial ecosystems. Proc. Natl Acad. Sci. USA 103, 15759–15764 (2006).

    Article  CAS  Google Scholar 

  49. Gregory, D. D. et al. The chemical conditions of the late Archean Hamersley basin inferred from whole rock and pyrite geochemistry with Δ33S and δ34S isotope analyses. Geochim. Cosmochim. Acta 149, 223–250 (2015).

    Article  CAS  Google Scholar 

  50. Wu, S., Zhao, Y.-H., Feng, X. & Wittmeier, A. Application of inductively coupled plasma mass spectrometry for total metal determination in silicon-containing solid samples using the microwave-assisted nitric acid–hydrofluoric acid–hydrogen peroxide–boric acid digestion system. J. Anal. At. Spectrom. 11, 287–296 (1996).

    Article  CAS  Google Scholar 

  51. Li, L. et al. Recommendations for offline combustion-based nitrogen isotopic analysis of silicate minerals and rocks. Rapid Commun. Mass Spectrom. 35, e9075 (2021).

    Article  CAS  Google Scholar 

  52. Li, L., He, Y., Zhang, Z. & Liu, Y. Nitrogen isotope fractionations among gaseous and aqueous NH4+, NH3, N2, and metal-ammine complexes: theoretical calculations and applications. Geochim. Cosmochim. Acta 295, 80–97 (2021).

    Article  CAS  Google Scholar 

  53. Devol, A. H. Denitrification, anammox, and N2 production in marine sediments. Ann. Rev. Mar. Sci. 7, 403–423 (2015).

    Article  Google Scholar 

  54. Tyrrell, T. The relative influences of nitrogen and phosphorus on oceanic primary production. Nature 400, 525–531 (1999).

    Article  CAS  Google Scholar 

  55. Jones, C., Nomosatryo, S., Crowe, S. A., Bjerrum, C. J. & Canfield, D. E. Iron oxides, divalent cations, silica, and the early Earth phosphorus crisis. Geology 43, 135–138 (2015).

    Article  CAS  Google Scholar 

  56. Anbar, A. D. & Knoll, A. H. Proterozoic ocean chemistry and evolution: a bioinorganic bridge? Science 297, 1137–1142 (2002).

    Article  CAS  Google Scholar 

  57. Cleveland, W. S. Robust locally weighted regression and smoothing scatterplots. J. Am. Stat. Assoc. 74, 829–836 (1979).

    Article  Google Scholar 

  58. Barley, M. E., Pickard, A. L. & Sylvester, P. J. Emplacement of a large igneous province as a possible cause of banded iron formation 2.45 billion years ago. Nature 385, 55–58 (1997).

    Article  CAS  Google Scholar 

  59. Trendall, A. F., Nelson, D. R., De Laeter, J. R. & Hassler, S. W. Precise zircon U–Pb ages from the Marra Mamba Iron Formation and Wittenoom Formation, Hamersley Group, Western Australia. Aust. J. Earth Sci. 45, 137–142 (1998).

    Article  CAS  Google Scholar 

  60. Pickard, A. L. SHRIMP U–Pb zircon ages of tuffaceous mudrocks in the Brockman Iron Formation of the Hamersley Range, Western Australia. Aust. J. Earth Sci. 49, 491–507 (2002).

    Article  Google Scholar 

  61. Trendall, A. F., Compston, W., Nelson, D. R., De Laeter, J. R. & Bennett, V. C. SHRIMP zircon ages constraining the depositional chronology of the Hamersley Group, Western Australia. Aust. J. Earth Sci. 51, 621–644 (2004).

    Article  CAS  Google Scholar 

  62. Arndt, N. T., Nelson, D. R., Compston, W., Trendall, A. F. & Thorne, A. M. The age of the Fortescue Group, Hamersley Basin, Western Australia, from ion microprobe zircon U–Pb results. Aust. J. Earth Sci. 38, 261–281 (2007).

    Article  Google Scholar 

  63. Liang, X., Stüeken, E. E., Alessi, D. S., Konhauser, K. O. & Li, L. Data for ’A seawater oxygen oscillation recorded by iron formations prior to the Great Oxidation Event’. Figshare https://doi.org/10.6084/m9.figshare.26094001 (2025).

  64. Rasmussen, B. & Muhling, J. R. Development of a greenalite–silica shuttle during incursions of hydrothermal vent plumes onto Neoarchean shelf, Hamersley region, Australia. Precambrian Res. 353, 106003 (2021).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Sciences and Engineering Research Council of Canada (NSERC) under grant no. RGPIN-2019-06003 (for L.L.) and RGPIN-165831 (for K.O.K.). E.E.S. acknowledges funding from a NERC Frontiers grant (NE/V010824/1). Samples used in this study were made available by the Geological Survey of Western Australia (GSWA). We thank GSWA for the drill core information. K.O.K. also acknowledges support from the Royal Society and the Wolfson Foundation, provided through the Royal Society Wolfson Visiting Fellowship.

Author information

Authors and Affiliations

  1. Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta, Canada

    Xueqi Liang, Daniel S. Alessi, Kurt O. Konhauser & Long Li

  2. School of Earth and Environmental Sciences, University of St Andrews, St Andrews, UK

    Eva E. Stüeken

  3. Department of Earth and Environmental Sciences, University of Manchester, Manchester, UK

    Kurt O. Konhauser

Authors
  1. Xueqi Liang
    View author publications

    Search author on:PubMed Google Scholar

  2. Eva E. Stüeken
    View author publications

    Search author on:PubMed Google Scholar

  3. Daniel S. Alessi
    View author publications

    Search author on:PubMed Google Scholar

  4. Kurt O. Konhauser
    View author publications

    Search author on:PubMed Google Scholar

  5. Long Li
    View author publications

    Search author on:PubMed Google Scholar

Contributions

X.L., L.L. and K.O.K. conceptualized the study. X.L. performed the N isotopic analyses, major elements analyses and visualization. L.L., K.O.K., E.E.S. and D.S.A. contributed to the methodology of modelling and analyses. X.L., L.L., K.O.K. and E.E.S. prepared the manuscript. All co-authors reviewed and commented on the manuscript.

Corresponding author

Correspondence to Xueqi Liang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Geoscience thanks Vincent Busigny and Margriet L. Lantink for their contribution to the peer review of this work. Primary Handling Editor: Alison Hunt, in collaboration with the Nature Geoscience team.

Additional information

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

Extended data

Extended Data Fig. 1 Geological map of the Hamersley Province, northwestern Australia, showing the location of the sampled drill holes.

Figure reproduced with permission from ref. 64, Elsevier.

Extended Data Fig. 2 Stratigraphic column of drill cores DD98, WRL1, WW1 and DGM1.

Drill core data of (a) Joffre Member, (b) Marra Mamba Formation, (c) Weeli Wolli Formation and (d) Dales Gorge Member are from the Geological Survey of Western Australia.

Extended Data Fig. 3 Core photos of representative BIF samples.

Red boxes represent the sampling locations of samples (a) WRL 1-8, (b) DD98-21, (c) WW1-8 and (d) DGM1-5.

Extended Data Fig. 4 Comparison of N concentrations with K2O concentrations of the studied BIF samples.

Note that the two samples with exceptional high Al2O3 contents (>2 wt.%) are not included. 2σ error bars of the data are smaller than the symbols and thus not shown. WWF = Weeli Wolli Formation; JM = Joffre Member; DGM = Dales Gorge Member; MMF = Marra Mamba Formation.

Extended Data Fig. 5 Comparison of the δ15N values of BIFs (triangles) and theoretical curves of metamorphic N devolatilization calculated by Rayleigh fractionation modeling.

Temperature is set at 250 °C for Panel (a) and 400 °C for panel (b) (see Methods). 2σ error bars of the data are smaller than the symbols and thus not shown.

Extended Data Fig. 6 Schematic box model of the nitrogen cycle on Earth’s surface.

See ‘Box model’ section in the Methods for details.

Extended Data Fig. 7 Comparison of N concentrations with Al2O3 concentrations of the studied BIF samples.

2σ error bars of the data are smaller than the symbols and thus not shown. WWF = Weeli Wolli Formation; JM = Joffre Member; DGM = Dales Gorge Member; MMF = Marra Mamba Formation.

Extended Data Table 1 Geochemical data for Hamersley BIFs
Full size table

Supplementary information

Source data

Source Data Fig. 1 (download XLSX )

Nitrogen isotopic data and elemental data.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liang, X., Stüeken, E.E., Alessi, D.S. et al. A seawater oxygen oscillation recorded by iron formations prior to the Great Oxidation Event. Nat. Geosci. 18, 417–422 (2025). https://doi.org/10.1038/s41561-025-01683-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41561-025-01683-7

This article is cited by

Search

Advanced search

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