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:

Spatial pattern of marine oxygenation set by tectonic and ecological drivers over the Phanerozoic

Abstract

Marine redox conditions (that is, oxygen levels) impact a wide array of biogeochemical cycles, but the main controls of marine redox since the start of the Phanerozoic about 538 million years ago are not well established. Here we combine supervised machine learning with shale-hosted trace metal concentrations to reconstruct a near-continuous record of redox conditions in major marine depositional settings. We find synchronously opposite redox changes in upper ocean versus deep shelf and (semi-)restricted basin settings ('redox anticouples', nomen novum) in several multi-million-year intervals, which can be used to track the positions of oxygen-minimum zones and the primary locations of organic burial through time. These changes coincided with biological innovations that altered large-scale oxidant-reductant fluxes (mid-Palaeozoic spread of land plants; Mesozoic plankton revolution) and tectonic upheavals that regulated sea-level elevation (Pangaea amalgamation and break-up). We find that the pre-Devonian deep shelf was buffered at a largely anoxic state probably by dissolved organic matter, switched to a transitional state during the Devonian–Carboniferous interval characterized by the inception of persistent oxygen-minimum zones and subsequently shifted to a redox regime featuring thin oxygen-minimum zones ballasted probably by particulate organic matter. Deep shelf redox changes are correlated with background extinction rates of marine animals, and mass extinctions during major redox transitions generally were more severe.

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: A schematic diagram of shale depositional settings defined in this study.
Fig. 2: Frequencies of depositional settings compared with paleobiotic and I/Ca records.
Fig. 3: Intensity of deep shelf reducing conditions compared with tectonic, sea-level and atmospheric variables.
Fig. 4: Relationship between deep shelf reducing conditions and GERMA.

Similar content being viewed by others

Data availability

All data needed to evaluate the conclusions of the manuscript are archived as Supplementary Data Files associated with the online version of this article and also available at figshare (https://doi.org/10.6084/m9.figshare.24139617).

Code availability

Python code for machine learning is archived as supplementary code files associated with the online version of this article and is also available at figshare (https://doi.org/10.6084/m9.figshare.24139617).

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  Google Scholar 

  2. Kopp, R. E., Kirschvink, J. L., Hilburn, I. A. & Nash, C. Z. The Paleoproterozoic snowball Earth: a climate disaster triggered by the evolution of oxygenic photosynthesis. Proc. Natl Acad. Sci. USA 102, 11131–11136 (2005).

    Article  Google Scholar 

  3. Sperling, E. A. et al. A long-term record of early to mid-Paleozoic marine redox change. Sci. Adv. 7, eabf4382 (2021).

    Article  Google Scholar 

  4. Sperling, E. A. et al. Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation. Nature 523, 451–454 (2015).

    Article  Google Scholar 

  5. Emmings, J. F. et al. Pyrite mega-analysis reveals modes of anoxia through geological time. Sci. Adv. 8, eabj5687 (2022).

    Article  Google Scholar 

  6. Pohl, A. et al. Continental configuration controls ocean oxygenation during the Phanerozoic. Nature 608, 523–527 (2022).

    Article  Google Scholar 

  7. Meyer, K. M. & Kump, L. R. Oceanic euxinia in Earth history: causes and consequences. Annu. Rev. Earth Planet. Sci. 36, 251–288 (2008).

    Article  Google Scholar 

  8. Poulton, S. W. & Canfield, D. E. Development of a sequential extraction procedure for iron: implications for iron partitioning in continentally derived particulates. Chem. Geol. 214, 209–221 (2005).

    Article  Google Scholar 

  9. Little, S. H., Vance, D., Lyons, T. W. & McManus, J. Controls on trace metal authigenic enrichment in reducing sediments: insights from modern oxygen-deficient settings. Am. J. Sci. 315, 77–119 (2015).

    Article  Google Scholar 

  10. Bennett, W. W. & Canfield, D. E. Redox-sensitive trace metals as paleoredox proxies: a review and analysis of data from modern sediments. Earth Sci. Rev. 204, 103175 (2020).

    Article  Google Scholar 

  11. Lu, W. et al. Late inception of a resiliently oxygenated upper ocean. Science 361, 174–177 (2018).

    Google Scholar 

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

    Article  Google Scholar 

  13. Young, A. et al. Long-term Phanerozoic sea level change from solid Earth processes. Earth Planet. Sci. Lett. 584, 117451 (2022).

    Article  Google Scholar 

  14. Lenton, T. M. et al. First plants cooled the Ordovician. Nat. Geosci. 5, 86–89 (2012).

    Article  Google Scholar 

  15. Lenton, T. M., Daines, S. J. & Mills, B. J. COPSE reloaded: an improved model of biogeochemical cycling over Phanerozoic time. Earth Sci. Rev. 178, 1–28 (2018).

    Article  Google Scholar 

  16. Algeo, T. J. & Scheckler, S. E. Terrestrial-marine teleconnections in the Devonian: links between the evolution of land plants, weathering processes, and marine anoxic events. Philos. Trans. R. Soc. London B 353, 113–130 (1998).

    Article  Google Scholar 

  17. Lenton, T. M. et al. Earliest land plants created modern levels of atmospheric oxygen. Proc. Natl Acad. Sci. USA 113, 9704–9709 (2016).

    Article  Google Scholar 

  18. Liu, Y. et al. Elevated marine productivity triggered nitrogen limitation on the Yangtze Platform (South China) during the Ordovician–Silurian transition. Palaeogeogr. Palaeoclimatol. Palaeoecol. 554, 109833 (2020).

    Article  Google Scholar 

  19. Stramma, L., Schmidtko, S., Levin, L. A. & Johnson, G. C. Ocean oxygen minima expansions and their biological impacts. Deep-Sea Res. I 57, 587–595 (2010).

    Article  Google Scholar 

  20. Li, N. et al. Redox changes in the outer Yangtze Sea (South China) through the Hirnantian Glaciation and their implications for the end-Ordovician biocrisis. Earth Sci. Rev. 212, 103443 (2021).

    Article  Google Scholar 

  21. Zhang, L. et al. Persistent oxic deep ocean conditions and frequent volcanic activities during the Frasnian–Famennian transition recorded in South China. Glob. Planet. Change 195, 103350 (2020).

    Article  Google Scholar 

  22. Joachimski, M. M. & Buggisch, W. Anoxic events in the late Frasnian—causes of the Frasnian–Famennian faunal crisis? Geology 21, 675–678 (1993).

    Article  Google Scholar 

  23. Chen, B. et al. Was climatic cooling during the earliest Carboniferous driven by expansion of seed plants? Earth Planet. Sci. Lett. 565, 116953 (2021).

    Article  Google Scholar 

  24. Berner, R. A. & Canfield, D. E. A new model for atmospheric oxygen over Phanerozoic time. Am. J. Sci. 289, 333–361 (1989).

    Article  Google Scholar 

  25. Royer, D. L. in Treatise on Geochemistry 2nd edn (eds Holland, H. D. & Turekian, K. K.) 251–267 (Elsevier, 2014).

  26. Liu, J., Algeo, T. J., Qie, W. & Saltzman, M. R. Intensified oceanic circulation during Early Carboniferous cooling events: evidence from carbon and nitrogen isotopes. Palaeogeogr. Palaeoclimatol. Palaeoecol. 531, 108962 (2019).

    Article  Google Scholar 

  27. Hull, P. M. Emergence of modern marine ecosystems. Curr. Biol. 27, R466–R469 (2017).

    Article  Google Scholar 

  28. Falkowski, P. G. et al. The evolution of modern eukaryotic phytoplankton. Science 305, 354–360 (2004).

    Article  Google Scholar 

  29. Meyer, K. M., Ridgwell, A. & Payne, J. The influence of the biological pump on ocean chemistry: implications for long‐term trends in marine redox chemistry, the global carbon cycle, and marine animal ecosystems. Geobiology 14, 207–219 (2016).

    Article  Google Scholar 

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

    Article  Google Scholar 

  31. Li, C. et al. The redox structure of Ediacaran and early Cambrian oceans and its controls. Sci. Bull. 65, 2141–2149 (2020).

    Article  Google Scholar 

  32. Leavitt, W. D., Halevy, I., Bradley, A. S. & Johnston, D. T. Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record. Proc. Natl Acad. Sci. USA 110, 11244–11249 (2013).

    Article  Google Scholar 

  33. Reinhard, C. T. et al. Earth’s oxygen cycle and the evolution of animal life. Proc. Natl Acad. Sci. USA 113, 8933–8938 (2016).

    Article  Google Scholar 

  34. Li, C., Cheng, M., Zhu, M. & Lyons, T. W. Heterogeneous and dynamic marine shelf oxygenation and coupled early animal evolution. Emerg. Top. Life Sci. 2, 279–288 (2018).

    Article  Google Scholar 

  35. Bopp, L. et al. Potential impact of climate change on marine export production. Glob. Biogeochem. Cycles 15, 81–99 (2001).

    Article  Google Scholar 

  36. Spiridonov, A. & Lovejoy, S. Life rather than climate influences diversity at scales greater than 40 million years. Nature 607, 307–312 (2022).

    Article  Google Scholar 

  37. Finnegan, S., Payne, J. L. & Wang, S. C. The Red Queen revisited: reevaluating the age selectivity of Phanerozoic marine genus extinctions. Paleobiology 34, 318–341 (2008).

    Article  Google Scholar 

  38. Peters, S. E. Environmental determinants of extinction selectivity in the fossil record. Nature 454, 626–629 (2008).

    Article  Google Scholar 

  39. Stockey, R. G. et al. Decreasing Phanerozoic extinction intensity as a consequence of Earth surface oxygenation and metazoan ecophysiology. Proc. Natl Acad. Sci. USA 118, e2101900118 (2021).

    Article  Google Scholar 

  40. Shi, W. et al. Decoupled oxygenation of the Ediacaran ocean and atmosphere during the rise of early animals. Earth Planet. Sci. Lett. 591, 117619 (2022).

    Article  Google Scholar 

  41. MacKenzie, F. T. & Andersson, A. J. The marine carbon system and ocean acidification during Phanerozoic time. Geochem. Perspect. 2, 1–3 (2013).

    Article  Google Scholar 

  42. Song, H. et al. Thresholds of temperature change for mass extinctions. Nat. Comm. 12, 4694 (2021).

    Article  Google Scholar 

  43. Ronov, A. B. Phanerozoic transgressions and regressions on the continents; a quantitative approach based on areas flooded by the sea and areas of marine and continental deposition. Am. J. Sci. 294, 777–801 (1994).

    Article  Google Scholar 

  44. Hallam, A. & Wignall, P. Mass extinctions and sea-level changes. Earth Sci. Rev. 48, 217–250 (1999).

    Article  Google Scholar 

  45. Bond, D. P. & Wignall, P. B. in Volcanism, Impacts and Mass Extinctions: Causes and Effects (eds Keller, G. & Kerr, A. C.) 29–55 (Geological Society of America, 2014).

  46. Raup, D. M. & Sepkoski, J. J. Jr Mass extinctions in the marine fossil record. Science 215, 1501–1503 (1982).

    Article  Google Scholar 

  47. Foote, M. Origination and extinction components of taxonomic diversity: general problems. Paleobiology 26, 74–102 (2000).

    Article  Google Scholar 

  48. Alroy, J. Dynamics of origination and extinction in the marine fossil record. Proc. Natl Acad. Sci. USA 105, 11536–11542 (2008).

    Article  Google Scholar 

  49. D’Antonio, M. P., Ibarra, D. E. & Boyce, C. K. Land plant evolution decreased, rather than increased, weathering rates. Geology 48, 29–33 (2020).

    Article  Google Scholar 

  50. Martin, R. E. Cyclic and secular variation in microfossil biomineralization: clues to the biogeochemical evolution of Phanerozoic oceans. Glob. Planet. Change 11, 1–23 (1995).

    Article  Google Scholar 

  51. Cooper, R. A., Sadler, P. M., Munnecke, A. & Crampton, J. S. Graptoloid evolutionary rates track Ordovician–Silurian global climate change. Geol. Mag. 151, 349–364 (2014).

    Article  Google Scholar 

  52. Vérard, C. & Veizer, J. On plate tectonics and ocean temperatures. Geology 47, 881–885 (2019).

    Article  Google Scholar 

  53. Foster, G. L., Royer, D. L. & Lunt, D. J. Future climate forcing potentially without precedent in the last 420 million years. Nat. Comm. 8, 14845 (2017).

    Article  Google Scholar 

  54. Grossman, E. L. & Joachimski, M. M. Ocean temperatures through the Phanerozoic reassessed. Sci. Rep. 12, 8938 (2022).

    Article  Google Scholar 

  55. Farrell, Ú. C. et al. The sedimentary geochemistry and paleoenvironments project. Geobiology 19, 545–556 (2021).

    Article  Google Scholar 

  56. Algeo, T. J. & Liu, J. A re-assessment of elemental proxies for paleoredox analysis. Chem. Geol. 540, 119549 (2020).

    Article  Google Scholar 

  57. Van der Weijden, C. H. Pitfalls of normalization of marine geochemical data using a common divisor. Mar. Geol. 184, 167–187 (2002).

    Article  Google Scholar 

  58. Aitchison, J. The statistical analysis of compositional data. J. R. Stat. Soc. Ser. B 44, 139–160 (1982).

    Google Scholar 

  59. Sadler, P. M. Sediment accumulation rates and the completeness of stratigraphic sections. J. Geol. 89, 569–584 (1981).

    Article  Google Scholar 

  60. Crombez, V. et al. Trace metal elements as paleoenvironmental proxies: why should we account for sedimentation rate variations? Geology 48, 839–843 (2020).

    Article  Google Scholar 

  61. Algeo, T. J. Can marine anoxic events draw down the trace element inventory of seawater? Geology 32, 1057–1060 (2004).

    Article  Google Scholar 

  62. McArthur, J. M., Howarth, R. & Bailey, T. Strontium isotope stratigraphy: LOWESS version 3: best fit to the marine Sr-isotope curve for 0–509 Ma and accompanying look-up table for deriving numerical age. J. Geol. 109, 155–170 (2001).

    Article  Google Scholar 

  63. Condie, K. C. Chemical composition and evolution of the upper continental crust: contrasting results from surface samples and shales. Chem. Geol. 104, 1–37 (1993).

    Article  Google Scholar 

  64. Kump, L. R., Bralower, T. J. & Ridgwell, A. Ocean acidification in deep time. Oceanography 22, 94–107 (2009).

    Article  Google Scholar 

  65. Li, C. et al. Coupled oceanic oxygenation and metazoan diversification during the Early–Middle Cambrian? Geology 45, 743–746 (2017).

    Google Scholar 

  66. Edwards, C. T., Saltzman, M. R., Royer, D. L. & Fike, D. A. Oxygenation as a driver of the Great Ordovician Biodiversification Event. Nat. Geosci. 10, 925–929 (2017).

    Article  Google Scholar 

  67. Zheng, Y., Anderson, R. F., van Geen, A. & Fleisher, M. Q. Preservation of particulate non-lithogenic uranium in marine sediments. Geochim. Cosmochim. Acta 66, 3085–3092 (2002).

    Article  Google Scholar 

  68. 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 

  69. Puttiwongrak, A., Giao, P. H. & Vann, S. An easily used mathematical model of porosity change with depth and geologic time in deep shale compaction. GEOMATE J. 19, 108–115 (2020).

    Google Scholar 

  70. Shipboard Scientific Party in Deep Sea Drilling Project: Initial report Vol. 15 (eds Edgar, N. T. et al.) 169–215 (Deep Sea Drilling Project, 1973).

  71. Shipboard Scientific Party in Proceedings of the Ocean Drilling Program, Initial Report Vol. 165 (eds Sigurdsson H. et al.) 359–373 (Ocean Drilling Program, 1997).

Download references

Acknowledgements

This research was supported by the National Natural Science Foundation of China (41888101 to X.W., C.L. and M.Z.; 42293293 to X.W.; 41921002 to M.Z.; 41821001, 41825019, 42130208 to C.L.), the National Key Research and Development Program of China (2022YFF0800100 to M.Z.; 2020YFA0607700 to X.W.) and the 111 Project of China (BP0820004 to C.L.). We gratefully acknowledge J. F. Emmings for constructive comments during review.

Author information

Authors and Affiliations

Authors

Contributions

Research design: X.W, C.L. Methodology: X.W. Validation: X.W., T.J.A. Investigation: X.W., T.J.A., C.L., M.Z. Data curation: X.W., T.J.A. Visualization: X.W. Supervision: X.W. Writing, original draft: X.W. Writing, review and editing: X.W., T.J.A., C.L., M.Z.

Corresponding authors

Correspondence to Xiangli Wang or Chao Li.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Geoscience thanks Joseph Emmings and Frantz Ossa Ossa for their contribution to the peer review of this work. Primary Handling Editor(s): James Super, 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 Map of sample locations.

Sample locations.

Extended Data Fig. 2 Paleo-map of reconstructed F′CPOMZ.

Paleogeographic distribution of FCPOMZ (value represented by the color bar). See definition and calculation of FCPOMZ in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates PALEOMAP PaleoAtlas35.

Extended Data Fig. 3 Paleo-map of reconstructed F′P-Euxinic.

Paleogeographic distribution of FP-Euxinic (value represented by the color bar). See definition and calculation of FP-Euxinic in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates PALEOMAP PaleoAtlas35.

Extended Data Fig. 4 Paleo-map of reconstructed FCPOMZ.

Paleogeographic distribution of FCPOMZ (value represented by the color bar). See definition and calculation of FCPOMZ in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates PALEOMAP PaleoAtlas35.

Extended Data Fig. 5 Paleo-map of reconstructed FP-Euxinic.

Paleogeographic distribution of FP-Euxinic (value represented by the color bar). See definition and calculation of FP-Euxinic in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates.

Extended Data Fig. 6 Paleo-map of reconstructed FBPOMZ.

Paleogeographic distribution of FBPOMZ (value represented by the color bar). See definition and calculation of FBPOMZ in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates PALEOMAP PaleoAtlas35.

Extended Data Fig. 7 Paleo-map of reconstructed FS-Euxinic.

Paleogeographic distribution of FS-Euxinic (value represented by the color bar). See definition and calculation of FS-Euxinic in the main text. Reconstruction of tectonic configuration and conversion of coordinates were performed using GPlates PALEOMAP PaleoAtlas35.

Extended Data Fig. 8 Secular evolution of Fe/Al, Mo/Al, U/Al and V/Al in Phanerozoic shales.

Secular evolution of Fe/Al (wt%/wt%), Mo/Al (ppm/wt%), U/Al (ppm/wt%) and V/Al (ppm/wt%) in Phanerozoic shales. Markers and error bars represent medians and 2SDs of 10,000 bootstrap resampling from spatiotemporally reweighted database (see Materials and Methods). Curves and bands are LOWESS fittings (smoothing factors optimized by 10-fold cross-validation) and prediction intervals (2σ). Raw data are represented by gray dots. Note that y-axes are cropped and thus some raw data fall outside of the graphs.

Supplementary information

Supplementary Information

Supplementary Data

Data used in this article.

Supplementary Code

Python code used for data analysis in this article.

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

Wang, X., Algeo, T.J., Li, C. et al. Spatial pattern of marine oxygenation set by tectonic and ecological drivers over the Phanerozoic. Nat. Geosci. 16, 1020–1026 (2023). https://doi.org/10.1038/s41561-023-01296-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41561-023-01296-y

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