The Triple Oxygen Isotope Composition of Marine Sulfate and 130 Million Years of Microbial Control

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2022 Jul 26

PMID 35881806

Authors

Anna R Waldeck

Jordon D Hemingway

Weiqi Yao

Adina Paytan

David T Johnston

Affiliations

Soon will be listed here.

Abstract

The triple oxygen isotope composition (Δ'O) of sulfate minerals is widely used to constrain ancient atmospheric O/CO 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 O 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'O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ'O 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.

Citing Articles

Marine sulphate captures a Paleozoic transition to a modern terrestrial weathering environment.

Waldeck A, Olson H, Crockford P, Couture A, Cowie B, Hodgin E Nat Commun. 2025; 16(1):2087.

PMID: 40025066 PMC: 11873193. DOI: 10.1038/s41467-025-57282-y.

Sulfate triple-oxygen-isotope evidence confirming oceanic oxygenation 570 million years ago.

Wang H, Peng Y, Li C, Cao X, Cheng M, Bao H Nat Commun. 2023; 14(1):4315.

PMID: 37463883 PMC: 10354052. DOI: 10.1038/s41467-023-39962-9.

References

Paytan A, Kastner M, Campbell D, Thiemens M . Seawater sulfur isotope fluctuations in the Cretaceous. Science. 2004; 304(5677):1663-5. DOI: 10.1126/science.1095258. View

Brunner B, Einsiedl F, Arnold G, Muller I, Templer S, Bernasconi S . The reversibility of dissimilatory sulphate reduction and the cell-internal multi-step reduction of sulphite to sulphide: insights from the oxygen isotope composition of sulphate. Isotopes Environ Health Stud. 2011; 48(1):33-54. DOI: 10.1080/10256016.2011.608128. View

Bao H, Lyons J, Zhou C . Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation. Nature. 2008; 453(7194):504-6. DOI: 10.1038/nature06959. View

Paytan , Kastner , Campbell , Thiemens . Sulfur isotopic composition of cenozoic seawater sulfate . Science. 1998; 282(5393):1459-62. DOI: 10.1126/science.282.5393.1459. View

Paytan , Kastner , Chavez . Glacial to Interglacial Fluctuations in Productivity in the Equatorial Pacific as Indicated by Marine Barite. Science. 1996; 274(5291):1355-7. DOI: 10.1126/science.274.5291.1355. View

Wortmann U, Paytan A . Rapid variability of seawater chemistry over the past 130 million years. Science. 2012; 337(6092):334-6. DOI: 10.1126/science.1220656. View

Brand W, Coplen T, Aerts-Bijma A, Bohlke J, Gehre M, Geilmann H . Comprehensive inter-laboratory calibration of reference materials for delta18O versus VSMOW using various on-line high-temperature conversion techniques. Rapid Commun Mass Spectrom. 2009; 23(7):999-1019. DOI: 10.1002/rcm.3958. View

Turchyn A, Schrag D . Oxygen isotope constraints on the sulfur cycle over the past 10 million years. Science. 2004; 303(5666):2004-7. DOI: 10.1126/science.1092296. View

Halevy I, Peters S, W Fischer W . Sulfate burial constraints on the Phanerozoic sulfur cycle. Science. 2012; 337(6092):331-4. DOI: 10.1126/science.1220224. View

10.

Foster G, Royer D, Lunt D . Future climate forcing potentially without precedent in the last 420 million years. Nat Commun. 2017; 8:14845. PMC: 5382278. DOI: 10.1038/ncomms14845. View

11.

Cao X, Bao H . Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth. Proc Natl Acad Sci U S A. 2013; 110(36):14546-50. PMC: 3767505. DOI: 10.1073/pnas.1302972110. View

12.

Hemingway J, Olson H, Turchyn A, Tipper E, Bickle M, Johnston D . Triple oxygen isotope insight into terrestrial pyrite oxidation. Proc Natl Acad Sci U S A. 2020; 117(14):7650-7657. PMC: 7149429. DOI: 10.1073/pnas.1917518117. View

13.

Bertran E, Waldeck A, Wing B, Halevy I, Leavitt W, Bradley A . Oxygen isotope effects during microbial sulfate reduction: applications to sediment cell abundances. ISME J. 2020; 14(6):1508-1519. PMC: 7242377. DOI: 10.1038/s41396-020-0618-2. View

14.

Johnston D, Gill B, Masterson A, Beirne E, Casciotti K, Knapp A . Placing an upper limit on cryptic marine sulphur cycling. Nature. 2014; 513(7519):530-3. DOI: 10.1038/nature13698. View

15.

Galili N, Shemesh A, Yam R, Brailovsky I, Sela-Adler M, Schuster E . The geologic history of seawater oxygen isotopes from marine iron oxides. Science. 2019; 365(6452):469-473. DOI: 10.1126/science.aaw9247. View

16.

Hayes J, Waldbauer J . The carbon cycle and associated redox processes through time. Philos Trans R Soc Lond B Biol Sci. 2006; 361(1470):931-50. PMC: 1578725. DOI: 10.1098/rstb.2006.1840. View

17.

Laakso T, Waldeck A, Macdonald F, Johnston D . Volcanic controls on seawater sulfate over the past 120 million years. Proc Natl Acad Sci U S A. 2020; 117(35):21118-21124. PMC: 7474628. DOI: 10.1073/pnas.1921308117. View

18.

Torres M, West A, Li G . Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales. Nature. 2014; 507(7492):346-9. DOI: 10.1038/nature13030. View

19.

Killingsworth B, Bao H, Kohl I . Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data. Environ Sci Technol. 2018; 52(11):6126-6136. DOI: 10.1021/acs.est.7b05792. View