The triple oxygen isotope composition of marine sulfate and 130 million years of microbial control

Proc Natl Acad Sci U S A. 2022 Aug 2;119(31):e2202018119. doi: 10.1073/pnas.2202018119. Epub 2022 Jul 26.

Abstract

The triple oxygen isotope composition (Δ'17O) of sulfate minerals is widely used to constrain ancient atmospheric pO2/pCO2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the [Formula: see text]O and Δ'17O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ'17O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably.

Keywords: Cenozoic; Cretaceous; barite; marine sulfate; triple oxygen isotopes.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Oxygen Isotopes* / analysis
  • Seawater* / chemistry
  • Seawater* / microbiology
  • Sulfates* / chemistry
  • Sulfur Oxides

Substances

  • Oxygen Isotopes
  • Sulfates
  • Sulfur Oxides