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Biogeosciences An interactive open-access journal of the European Geosciences Union
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Volume 12, issue 7
Biogeosciences, 12, 2131–2151, 2015
https://doi.org/10.5194/bg-12-2131-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
Biogeosciences, 12, 2131–2151, 2015
https://doi.org/10.5194/bg-12-2131-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 10 Apr 2015

Research article | 10 Apr 2015

Reconstruction of secular variation in seawater sulfate concentrations

T. J. Algeo3,2,1, G. M. Luo1, H. Y. Song2, T. W. Lyons4, and D. E. Canfield5 T. J. Algeo et al.
  • 1State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan, 430074, China
  • 2State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan, 430074, China
  • 3Department of Geology, University of Cincinnati, Cincinnati, Ohio 45221-0013, USA
  • 4Department of Earth Sciences, University of California, Riverside, California 92521-0423, USA
  • 5Nordic Center for Earth Evolution (NordCEE) and Institute of Biology, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark

Abstract. Long-term secular variation in seawater sulfate concentrations ([SO42−]SW) is of interest owing to its relationship to the oxygenation history of Earth's surface environment. In this study, we develop two complementary approaches for quantification of sulfate concentrations in ancient seawater and test their application to late Neoproterozoic (635 Ma) to Recent marine units. The "rate method" is based on two measurable parameters of paleomarine systems: (1) the S-isotope fractionation associated with microbial sulfate reduction (MSR), as proxied by Δ34SCAS-PY, and (2) the maximum rate of change in seawater sulfate, as proxied by &partial; δ 34SCAS/∂ t(max). The "MSR-trend method" is based on the empirical relationship of Δ34SCAS-PY to aqueous sulfate concentrations in 81 modern depositional systems. For a given paleomarine system, the rate method yields an estimate of maximum possible [SO42−]SW (although results are dependent on assumptions regarding the pyrite burial flux, FPY), and the MSR-trend method yields an estimate of mean [SO42−]SW. An analysis of seawater sulfate concentrations since 635 Ma suggests that [SO42−]SW was low during the late Neoproterozoic (<5 mM), rose sharply across the Ediacaran–Cambrian boundary (~5–10 mM), and rose again during the Permian (~10–30 mM) to levels that have varied only slightly since 250 Ma. However, Phanerozoic seawater sulfate concentrations may have been drawn down to much lower levels (~1–4 mM) during short (<~2 Myr) intervals of the Cambrian, Early Triassic, Early Jurassic, and Cretaceous as a consequence of widespread ocean anoxia, intense MSR, and pyrite burial. The procedures developed in this study offer potential for future high-resolution quantitative analyses of paleo-seawater sulfate concentrations.

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Seawater sulfate concentrations are closely related to the oxygenation history of Earth's surface environment. We develop two approaches for quantification of ancient seawater sulfate concentrations based on the sulfur isotopic composition of pyrite and carbonate-associated sulfur (CAS). Our analysis indicates low seawater sulfate (<5mM) at 635 million years ago, rising in a stepwise manner to near-modern levels (~20-30mM) by about 250 million years ago.
Seawater sulfate concentrations are closely related to the oxygenation history of Earth's...
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