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Transient ocean oxygenation at end-Permian mass extinction onset shown by thallium isotopes

Abstract

The end-Permian mass extinction (EPME) represents the largest biocrisis in Earth’s history, a result of environmental perturbations following volatiles released during Siberian Traps magmatism. A leading hypothesis links the marine mass extinction to the expansion of oceanic anoxia, although uncertainties exist as to the timing and extent. Thallium isotopes, a novel palaeoredox proxy with a rapid global response due to its short residence time in seawater, track global rates of manganese oxide burial, one of the first redox half-reactions to occur under reduced oxygen conditions. For this study, we analysed thallium isotopes from three widely distributed sites in Panthalassa, the largest ocean basin at the time. Our results provide evidence for the onset of deoxygenation considerably before the EPME, earlier by ≥1 Myr than the onset implied by other proxy records. Notably, there is a transient negative thallium isotope excursion concurrent with the EPME, which requires substantial manganese oxide burial based on the thallium isotope mass balance. This feature suggests a brief oxygenation episode before a return to more anoxic conditions, implying a more complex redox scenario, with rapid changes in oceanic (de)oxygenation leading to spatially and temporally variable biotic stresses. This oxygenation event may have been related to a transient cooling episode, based on published oxygen isotope records. These findings show that the Earth system experienced a highly fluctuating response to forcings linked to volcanogenic volatiles during the EPME.

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Fig. 1: Site locations during the EPME.
Fig. 2: Thallium isotope stratigraphy of each section.
Fig. 3: Model of Permian–Triassic oceanic redox changes as related to thallium isotopes.
Fig. 4: Generalized chemostratigraphic records of the Permian–Triassic transition.

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Data availability

The datasets generated during the current study are available as supplementary files alongside the published manuscript. They are available through the Pangaea online data repository at https://doi.pangaea.de/10.1594/PANGAEA.933389.

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Acknowledgements

We thank C. Bowman, N. Kozik and A. Karl for assistance in sample processing and data collection. The FSU EOAS Winchester Fund helped fund work done by S.M.N. Grants to J.D.O. through the NASA Exobiology program (NNX16AJ60G and 80NSSC18K1532) and the Sloan Research Foundation (FG-2020–13552) funded this work. This work was performed at the National High Magnetic Field Laboratory in Tallahassee, Florida, which is supported by National Science Foundation Cooperative Agreement No. DMR-1644779 and by the State of Florida.

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S.M.N. processed the samples and performed Tl isotope analyses with contributions and direction from J.D.O. S.M.N. and J.D.O. developed the project idea and discussed and analysed the data. S.D.S. and T.J.A. provided samples. S.M.N. wrote the manuscript with direction from J.D.O. and contributions from all co-authors.

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Correspondence to Sean M. Newby.

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Peer review information Nature Geoscience thanks Matthew Clarkson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Full chemostratigraphy of all three sections.

Biostratigraphy, lithostratigraphy, and chemostratigraphy for Opal Creek (a), Gujo-Hachiman (b), and Ubara (c). Chemostratigraphy includes carbon isotopes (black line), manganese concentrations (red line), vanadium concentrations (purple line), molybdenum concentrations (green line), and thallium isotopes (blue line). Biostratigraphy, lithostratigraphy, and trace metal concentrations are from previous sources18,19,39,40, as well as carbon isotopes of Opal Creek40. For Opal Creek, biozones 1–4 represent Mesogondolella bitteri and M. rosenckrantzi (1), M. sheni (2), Clarkina hauschkei and C. meishanensis (3), and Hindeodus parvus (4). Lithostratigraphic columns are present on the left adjacent to height. Separate patterns are used to distinguish lithologies, including chert (rounded bricks), shale (dashed lines), and silty mudstones (dashed and dotted lines), with approximate colour of the rocks. All three trace metal concentration charts have upper continental crust concentrations marked with a dashed vertical line, with arrow pointing towards more reducing conditions. The Tl isotope plots have a dashed vertical line indicating modern seawater values, with more positive values representing greater extent of anoxia. All three sites are correlated with the EPME (red dashed line) and PTB (light blue dashed line) using both biostratigraphy and carbon isotope stratigraphy. Thallium plotted with error bars (2σ). Opal Creek features an Upper Permian19,40 unconformity near the base of the described section (wavy line), below the EPME. Opal Creek here features a more extensive section up to 43m as compared to Fig. 2. Trace metal concentrations generally indicate reducing conditions at all three sections, though each trace metal responds in a different manner for each locality due to fluctuating local redox18,19. Global similarity in thallium isotopes despite this indicates little local explanation for the excursion.

Extended Data Fig. 2 Modeled Tl isotopic values across the EPME.

Model showing how changes in Mn oxide burial can cause the negative isotope excursion exhibited during the EPME. Parameters can be found in Extended Data Table 1. The approximate duration of the oxygenation interval (~60 kyr;18 see Supplementary Discussion) is highlighted in blue, while the approximate duration of the extinction interval (~60 kyr53) is highlighted in red, with these slightly overlapping based on average position of the negative thallium isotope excursion compared to the negative carbon isotope excursion (see Fig. 4). Various runs were conducted under the premise of decreasing Mn oxide burial between 0.20 and 1.50 Myr, representing the upper Changhsingian data found in the lower part of the Gujo-Hachiman section. As there is relatively small change at a steady rate across this interval, a gap between 0.4 and 1.4 Myr was applied for convenience of space, though this trend continues at a constant rate across this interval (represented as a dashed line in the gap). Following this, a short-term major increase in Mn oxide burial is recreated. The duration and flux of Mn oxide burial is modulated so that the minimum value of the excursion is consistent, all values near ε205Tl = ~6.0, with included table within the figure to distinguish the different runs and how the duration of the excursion compares. This can be compared to a scenario with no major isotope excursion (thick black line).

Supplementary information

Supplementary Information

Supplementary Methods, Discussion and Table 1.

Supplementary Data

Geochemical data from sections and geochemical model results.

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Newby, S.M., Owens, J.D., Schoepfer, S.D. et al. Transient ocean oxygenation at end-Permian mass extinction onset shown by thallium isotopes. Nat. Geosci. 14, 678–683 (2021). https://doi.org/10.1038/s41561-021-00802-4

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