Abstract
Mass extinctions in the early Palaeozoic have been attributed to global climate change and ocean anoxia with elevated phosphorus (P) proposed as a key driver. However, this hypothesis has lacked geochemical support due to the absence of proxies that can reconstruct changes in marine P availability. Focusing on the Late Ordovician Mass Extinction (LOME) and the Late Devonian Mass Extinction (LDME), we present carbonate-associated phosphate (CAP) data from seven globally distributed sections, providing a proxy record for seawater P variation across these events. Our data reveal short-lived, globally coherent P pulses that coincided with both events. These transient P surges align with biodiversity loss, widespread anoxia, and seawater temperature declines, suggesting a link between P flux, ocean anoxia, and global climate shifts, as supported by biogeochemical model results. These findings provide an empirical connection between brief marine P pulses and ecological crises during the LOME and LDME.
Similar content being viewed by others
Data availability
The CAP, C and O isotope data generated in this study have been deposited in the Figshare database under accession code ZZ https://doi.org/10.6084/m9.figshare.30271312. Canning Basin phosphate oxygen isotope data are held in the UWA Repository https://research-repository.uwa.edu.au/en/persons/annette-george/datasets/.
Materials availability
All samples were collected and exported in a responsible manner and in accordance with relevant permits and local laws. Global coordinates and/ or location information and drill core names are given for all samples collected in the Supplementary Information files. Requests for materials should be addressed to C.L., A.D., O.H., D.Y., X.Y., A.G., M.E., Q.W., C.B.
References
Harper, D. A. T., Hammarlund, E. U. & Rasmussen, C. M. Ø. End Ordovician extinctions: a coincidence of causes. Gondwana Res. 25, 1294–1307 (2014).
Hallam, A. & Wignall, P. B. Mass extinctions and their aftermath. (Oxford University Press, UK, 1997).
Algeo, T. J. & Shen, J. Theory and classification of mass extinction causation. National Science Review, nwad237 https://doi.org/10.1093/nsr/nwad237 (2023).
Bond, D. P. G. & Grasby, S. E. On the causes of mass extinctions. Palaeogeogr. Palaeoclimatol. Palaeoecol. 478, 3–29 (2017).
Joachimski, M. M. & Buggisch, W. Conodont apatite δ18O signatures indicate climatic cooling as a trigger of the Late Devonian mass extinction. Geology 30, 711–714 (2002).
Finnegan, S. et al. The magnitude and duration of late ordovician–early silurian glaciation. Science 331 (2011).
Bartlett, R. et al. Abrupt global-ocean anoxia during the Late Ordovician–early Silurian detected using uranium isotopes of marine carbonates. Proc. Natl. Acad. Sci. USA 115, 5896–5901 (2018).
White, D. A., Elrick, M., Romaniello, S. & Zhang, F. Global seawater redox trends during the Late Devonian mass extinction detected using U isotopes of marine limestones. Earth Planet. Sci. Lett. 503, 68–77 (2018).
Bond, D. P. G. & Wignall, P. B. in Volcanism, Impacts, and Mass Extinctions: Causes and Effects (eds Gerta Keller & Andrew C. Kerr) 0 (Geological Society of America, 2014).
Algeo, T. J., Berner, R., Maynard, J. & Scheckler, S. Late Devonian oceanic anoxic events and biotic crises: “Rooted” in the evolution of vascular plants. GSA Today 5, 64–66 (1995).
Lenton, T. M., Crouch, M., Johnson, M., Pires, N. & Dolan, L. First plants cooled the Ordovician. Nat. Geosci. 5, 86–89 (2012).
Longman, J., Mills, B. J. W., Manners, H. R., Gernon, T. M. & Palmer, M. R. Late Ordovician climate change and extinctions driven by elevated volcanic nutrient supply. Nat. Geosci. 14, 924–929 (2021).
Jones, D. S., Martini, A. M., Fike, D. A. & Kaiho, K. A volcanic trigger for the Late Ordovician mass extinction? Mercury data from south China and Laurentia. Geology 45, 631–634 (2017).
Bond, D. P. G. & Grasby, S. E. Late Ordovician mass extinction caused by volcanism, warming, and anoxia, not cooling and glaciation. Geology 48, 777–781 (2020).
Smolarek-Lach, J., Marynowski, L., Trela, W. & Wignall, P. B. Mercury spikes indicate a volcanic trigger for the late ordovician mass extinction event: an example from a deep shelf of the Peri-Baltic Region. Sci. Rep. 9, 3139 (2019).
Müller, J., Joachimski, M. M., Lehnert, O., Männik, P. & Sun, Y. Phosphorus cycling during the Hirnantian glaciation. Palaeogeogr. Palaeoclimatol. Palaeoecol. 634, 111906 (2024).
Qiu, Z. et al. A nutrient control on expanded anoxia and global cooling during the Late Ordovician mass extinction. Commun. Earth Environ. 3, 82 (2022).
Zou, C. et al. Ocean euxinia and climate change “double whammy” drove the Late Ordovician mass extinction. Geology 46, 535–538 (2018).
Paytan, A. & McLaughlin, K. The oceanic phosphorus cycle. Chem. Rev. 107, 563–576 (2007).
Ingall, E. D., Bustin, R. M. & Van Cappellen, P. Influence of water column anoxia on the burial and preservation of carbon and phosphorus in marine shales. Geochimica et. Cosmochimica Acta 57, 303–316 (1993).
Ruttenberg, K. C. in Treatise on Geochemistry (eds Heinrich D. Holland & Karl K. Turekian) 585−643 (Pergamon, 2003).
Slomp, C. P. & Van Cappellen, P. The global marine phosphorus cycle: sensitivity to oceanic circulation. Biogeosciences 4, 155–171 (2007).
Ahm, A.-S. C., Bjerrum, C. J. & Hammarlund, E. U. Disentangling the record of diagenesis, local redox conditions, and global seawater chemistry during the latest Ordovician glaciation. Earth Planet. Sci. Lett. 459, 145–156 (2017).
Melchin, M. J. & Holmden, C. Carbon isotope chemostratigraphy in Arctic Canada: Sea-level forcing of carbonate platform weathering and implications for Hirnantian global correlation. Palaeogeogr. Palaeoclimatol. Palaeoecol. 234, 186–200 (2006).
LaPorte, D. F. et al. Local and global perspectives on carbon and nitrogen cycling during the Hirnantian glaciation. Palaeogeogr. Palaeoclimatol. Palaeoecol. 276, 182–195 (2009).
Jones, D. S. et al. Sea level, carbonate mineralogy, and early diagenesis controlled δ13C records in Upper Ordovician carbonates. Geology 48, 194–199 (2019).
Meidla, T., Ainsaar, L., Hints, O. & Radzevičius, S. Ordovician of the Eastern Baltic palaeobasin and the Tornquist Sea margin of Baltica. Geol. Soc. Lond. Spec. Publ. 532, 317–343 (2023).
Zhang, J. et al. Linking carbon cycle perturbations to the Late Ordovician glaciation and mass extinction: a modeling approach. Earth Planet. Sci. Lett. 631, 118635 (2024).
Dodd, M. S. et al. Development of carbonate-associated phosphate (CAP) as a proxy for reconstructing ancient ocean phosphate levels. Geochimica et. Cosmochimica Acta 301, 48–69 (2021).
Ingalls, M. et al. P/Ca in carbonates as a proxy for alkalinity and phosphate levels. Geophys. Res. Lett. 47, e2020GL088804 (2020).
Montagna, P., McCulloch, M., Taviani, M., Mazzoli, C. & Vendrell, B. Phosphorus in cold-water corals as a proxy for seawater nutrient chemistry. Science 312, 1788–1791 (2006).
Dodd, M. S. et al. Uncovering the Ediacaran phosphorus cycle. Nature 618, 974–980 (2023).
Barkan, Y., Paris, G., Webb, S. M., Adkins, J. F. & Halevy, I. Sulfur isotope fractionation between aqueous and carbonate-associated sulfate in abiotic calcite and aragonite. Geochimica et. Cosmochimica Acta 280, 317–339 (2020).
Shimura, T. et al. In-situ analyses of phosphorus contents of carbonate minerals: Reconstruction of phosphorus contents of seawater from the Ediacaran to early Cambrian. Gondwana Res. 25, 1090–1107 (2014).
Swart & Kennedy, P. K. M. J. Does the global stratigraphic reproducibility of δ 13 C in Neoproterozoic carbonates require a marine origin? A Pliocene–Pleistocene comparison. Geology 40, 87–90 (2012).
Bergmann, K. D. et al. A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition. Geochimica et. Cosmochimica Acta 224, 18–41 (2018).
Thiagarajan, N. et al. Reconstruction of Phanerozoic climate using carbonate clumped isotopes and implications for the oxygen isotopic composition of seawater. Proc. Natl. Acad. Sci. 121, e2400434121 (2024).
Yang, X. et al. Spatiotemporal variations of sedimentary carbon and nitrogen isotopic compositions in the Yangtze Shelf Sea across the Ordovician-Silurian boundary. Palaeogeogr. Palaeoclimatol. Palaeoecol. 567, 110257 (2021).
Liu, M. et al. Oceanic anoxia and extinction in the latest Ordovician. Earth Planet. Sci. Lett. 588, 117553 (2022).
George, A. D., Chow, N. & Trinajstic, K. M. Oxic facies and the Late Devonian mass extinction, Canning Basin, Australia. Geology 42, 327–330 (2014).
Hagen-Peter, G., Wang, Y., Hints, O., Prave, A. R. & Lepland, A. Late diagenetic evolution of Ordovician limestones in the Baltoscandian basin revealed through trace-element mapping and in situ U–Pb dating of calcite. Chem. Geol. 585, 120563 (2021).
Evans, D. et al. Trace and major element incorporation into amorphous calcium carbonate (ACC) precipitated from seawater. Geochimica et. Cosmochimica Acta 290, 293–311 (2020).
Sandberg, P. A. An oscillating trend in Phanerozoic non-skeletal carbonate mineralogy. Nature 305, 19–22 (1983).
Martiny, A. dam et al. Biogeochemical controls of surface ocean phosphate. Sci. Adv. 5, eaax0341 (2019).
Mills, B. J. W., Donnadieu, Y. & Goddéris, Y. Spatial continuous integration of Phanerozoic global biogeochemistry and climate. Gondwana Res. 100, 73–86 (2021).
Merdith, A. S. et al. Phanerozoic icehouse climates as the result of multiple solid-Earth cooling mechanisms. Sci. Adv. 11, eadm9798 (2025).
Zhou, L. et al. Changes in marine productivity and redox conditions during the Late Ordovician Hirnantian glaciation. Palaeogeogr. Palaeoclimatol. Palaeoecol. 420, 223–234 (2015).
Lv, Y. et al. Enhanced organic carbon burial intensified the end-Ordovician glaciation. Geochem. Perspect. Lett. 21, 13–17 (2022).
Hammarlund, E. U. et al. A sulfidic driver for the end-Ordovician mass extinction. Earth Planet. Sci. Lett. 331–332, 128–139 (2012).
Zhang, T., Shen, Y., Zhan, R., Shen, S. & Chen, X. Large perturbations of the carbon and sulfur cycle associated with the Late Ordovician mass extinction in South China. Geology 37, 299–302 (2009).
Hints, O. et al. New data on Ordovician stable isotope record and conodont biostratigraphy from the Viki reference drill core, Saaremaa Island, western Estonia. GFF 136, 100–104 (2014).
Melchin, M. J., Mitchell, C. E. & Holmden, C. & Štorch, P. Environmental changes in the Late Ordovician–early Silurian: Review and new insights from black shales and nitrogen isotopes. GSA Bull. 125, 1635–1670 (2013).
Jaffrés, J. B. D., Shields, G. A. & Wallmann, K. The oxygen isotope evolution of seawater: A critical review of a long-standing controversy and an improved geological water cycle model for the past 3.4 billion years. Earth-Sci. Rev. 83, 83–122 (2007).
Stockey, R. G. et al. Persistent global marine euxinia in the early Silurian. Nat. Commun. 11, 1804 (2020).
Dahl, T. W., Hammarlund, E. U., Rasmussen, C. M. Ø, Bond, D. P. G. & Canfield, D. E. Sulfidic anoxia in the oceans during the Late Ordovician mass extinctions – insights from molybdenum and uranium isotopic global redox proxies. Earth-Sci. Rev. 220, 103748 (2021).
Van Cappellen, P. & Ingall, E. D. Benthic phosphorus regeneration, net primary production, and ocean anoxia: a model of the coupled marine biogeochemical cycles of carbon and phosphorus. Paleoceanography 9, 677–692 (1994).
Smart, M. S. et al. Enhanced terrestrial nutrient release during the Devonian emergence and expansion of forests: evidence from lacustrine phosphorus and geochemical records. GSA Bull. 135, 1879–1898 (2022).
Yao, L. et al. The longest delay: Re-emergence of coral reef ecosystems after the Late Devonian extinctions. Earth-Sci. Rev. 203, 103060 (2020).
McGhee, G. R. & Racki, G. in Encyclopedia of Life Sciences 1–8 (2021).
Murphy, A. E., Sageman, B. B. & Hollander, D. J. Eutrophication by decoupling of the marine biogeochemical cycles of C, N, and P: A mechanism for the Late Devonian mass extinction. Geology 28, 427–430 (2000).
Joachimski, M. M. et al. Water column anoxia, enhanced productivity and concomitant changes in δ13C and δ34S across the Frasnian–Famennian boundary (Kowala — Holy Cross Mountains/Poland). Chem. Geol. 175, 109–131 (2001).
Sheehan, P. M. The late ordovician mass extinction. Annu. Rev. Earth Planet. Sci. 29, 331–364 (2001).
Rasmussen, C. M. Ø & Harper, D. A. T. Interrogation of distributional data for the End Ordovician crisis interval: where did disaster strike? Geol. J. 46, 478–500 (2011).
Huang, B., Harper, D. A. T., Zhou, H. & Rong, J. From shallow to deep water: an ecological study of the Hirnantia brachiopod Fauna (Late Ordovician) and its global implications. Lethaia 53, 332–344 (2020).
Finnegan, S., Heim, N. A., Peters, S. E. & Fischer, W. W. Climate change and the selective signature of the late Ordovician mass extinction. Proc. Natl. Acad. Sci. USA 109, 6829–6834 (2012).
Jeon, J. et al. Nearshore warm-water biota development in the aftermath of the Late Ordovician Mass Extinction in South China. Palaeogeogr. Palaeoclimatol. Palaeoecol. 603, 111182 (2022).
Copper, P. Reef development at the Frasnian/Famennian mass extinction boundary. Palaeogeogr. Palaeoclimatol. Palaeoecol. 181, 27–65 (2002).
Christie, M., Holland, S. M. & Bush, A. M. Contrasting the ecological and taxonomic consequences of extinction. Paleobiology 39, 538–559 (2013).
Acknowledgements
C.L. acknowledges support from the NSFC (grants # 42425002) and the National Key Research and Development Program of China (grant numbers 2022YFF0800100). M.S.D. acknowledges support from the Forrest Research Foundation and UWA School of Earth and Oceans. B.J.W.M. is supported by UKRI grant EP/Y008790/1. A.D. acknowledges support from the research incubator of the Société du patrimoine Mondial Anticosti. O.H. was supported by the Estonian Research Council (grant PRG1701). A.S.M. is supported by ARC DECRA Fellowship DE230101642.
Author information
Authors and Affiliations
Contributions
M.S.D. and C.L. designed and organised the research. M.S.D., Z.Z., and A.Y.S. performed analyses. A.S.M. and B.J.W.M. performed modelling. C.L., A.D., O.H., D.Y., X.Y., A.G., M.E., D.W., Q.W., C.B. provided samples. The paper was written by M.S.D. with important inputs from all authors.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks the anonymous reviewers for their contribution to the peer review of this work. A peer review file is available.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Dodd, M.S., Li, C., Zhang, Z. et al. Recurring marine phosphorus spikes during major palaeozoic mass extinctions and climate change. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70701-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-70701-y


