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Low marine sulphate and protracted oxygenation of the Proterozoic biosphere
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Progressive oxygenation of the Earth's early biosphere is thought to have resulted in increased sulphide oxidation during continental weathering, leading to a corresponding increase in marine sulphate concentration. Accurate reconstruction of marine sulphate reservoir size is therefore important for interpreting the oxygenation history of early Earth environments. Few data, however, specifically constrain how sulphate concentrations may have changed during the Proterozoic era (2.5-0.54 Gyr ago). Prior to 2.2 Gyr ago, when oxygen began to accumulate in the Earth's atmosphere, sulphate concentrations are inferred to have been <1 mM and possibly <200 microM, on the basis of limited isotopic variability preserved in sedimentary sulphides and experimental data showing suppressed isotopic fractionation at extremely low sulphate concentrations. By 0.8 Gyr ago, oxygen and thus sulphate levels may have risen significantly. Here we report large stratigraphic variations in the sulphur isotope composition of marine carbonate-associated sulphate, and use a rate-dependent model for sulphur isotope change that allows us to track changes in marine sulphate concentrations throughout the Proterozoic. Our calculations indicate sulphate levels between 1.5 and 4.5 mM, or 5-15 per cent of modern values, for more than 1 Gyr after initial oxygenation of the Earth's biosphere. Persistence of low oceanic sulphate demonstrates the protracted nature of Earth's oxygenation. It links biospheric evolution to temporal patterns in the depositional behaviour of marine iron- and sulphur-bearing minerals, biological cycling of redox-sensitive elements and availability of trace metals essential to eukaryotic development.
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“The rate of change of seawater sulphate sulphur isotope ratios allows us to estimate marine sulphate concentrations through this interval.”
From Possible links between extreme oxygen perturbations and the Cambrian radiation of animals (2019) · cites this paper as [26]
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“Maximum seawater sulphate concentrations are calculated using the modified 'rate method' 25,26 .”
From Possible links between extreme oxygen perturbations and the Cambrian radiation of animals (2019) · cites this paper as [26]
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“We can imagine oceans during the boring billion with appreciable levels of dissolved sulfate (e.g., Kah et al., 2004; Fakhraee et al., 2019; Blättler et al., 2020).”
From Oxygenation, Life, and the Planetary System during Earth's Middle History: An Overview (2021) · cites this paper as Kah et al., 2004
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Self-citation
Metadata
- Authors
- Kah, L. C., Lyons, T. W., & Frank, T. D.
- Affiliations
- University of Tennessee at Knoxville (US)
- University of Missouri (US)
- University of Nebraska–Lincoln (US)
- Corresponding author
- Kah, Linda C.
- Venue
- Nature
- Published
- 2004-10
- Volume
- 431
- Issue
- 7010
- Pages
- 834-838
- ISSN
- 0028-0836 (ISSN-L)
- 1476-4687
- OpenAlex
- W2097417202
- Cited by
- 482
- References
- 31
- Citations by year
- 2026: 11 · 2025: 23 · 2024: 23 · 2023: 23 · 2022: 18 · 2021: 22 · 2020: 26 · 2019: 37 · 2018: 31 · 2017: 20 · 2016: 17 · 2015: 24 · 2014: 16 · 2013: 31 · 2012: 30
- FWCI
- 14.27
- Type
- journal article
- Language
- en
- Open access
- Licence
- www.springer.com/tdm (tdm)
- Locations
- Nature (publishedVersion)
- PubMed (publishedVersion)
- Lincoln (University of Nebraska) (submittedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
- Keywords
- sulfur isotopes, sulfide oxidation, continental weathering, early Earth atmosphere, eukaryotic evolution, trace metal availability, redox-sensitive elements
- MeSH terms
- Atmosphere, Calcium Sulfate, Carbonates, Environment, Eukaryotic Cells, Biological Evolution, Oxygen, Seawater, Sulfates, Time Factors, Geologic Sediments
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