The influence of submarine hydrothermal systems on seawater sulfate

Eleanor R. Hughes; Anna R. Waldeck; Sarah N. Moriarty; John W. Jamieson; Andrew J. Martin; Peter P. Scheuermann; Drew D. Syverson; William E. Seyfried; Eoghan P. Reeves; David T. Johnston

doi:10.1016/j.gca.2023.01.009

The influence of submarine hydrothermal systems on seawater sulfate

Eleanor R. Hughes, Anna R. Waldeck, Sarah N. Moriarty, John W. Jamieson, Andrew J. Martin, Peter P. Scheuermann, Drew D. Syverson, William E. Seyfried, Eoghan P. Reeves, David T. Johnston

Earth and Environmental Sciences-Twin Cities

Research output: Contribution to journal › Article › peer-review

Abstract

Seawater sulfate is a major carrier of oxidizing capacity and influences the redox budget of the Earth's surface on geologic timescales. Records of oxygen and sulfur isotopes in seawater sulfate are used to track changes in sulfate cycling through geologic time. Interpretations of these records are typically based on models that describe the seawater sulfate reservoir as a mass balance between microbial, riverine and sedimentary sulfate fluxes. Here, we investigate the influence of hydrothermal sulfate cycling, which remains an unconstrained but potentially significant additional flux in this mass balance. We find that anhydrite (CaSO₄) from eight submarine hydrothermal vent fields is consistently offset from seawater sulfate in δ¹⁸O but not Δ’17O or δ³⁴S. Experiments at hydrothermal pressure–temperature conditions indicate that this δ¹⁸O offset is driven by oxygen isotope exchange between sulfate and hydrothermal H₂O at high temperature. An updated isotope mass balance model shows that a flux of hydrothermal sulfate into seawater, derived from retrograde dissolution of hydrothermal anhydrite, could cause high-temperature oxygen isotope exchange to buffer seawater sulfate δ¹⁸O and Δ’17O by as much as 25%. Hydrothermal sulfate preserved in the Troodos Ophiolite (Cretaceous) also records a δ¹⁸O and Δ’17O signal of high-temperature oxygen isotope exchange, supporting the conclusion that geologic records of seawater sulfate oxygen isotopes may include a hydrothermal component.

Original language	English (US)
Pages (from-to)	73-89
Number of pages	17
Journal	Geochimica et Cosmochimica Acta
Volume	344
DOIs	https://doi.org/10.1016/j.gca.2023.01.009
State	Published - Mar 1 2023

Bibliographical note

Funding Information:
This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. We acknowledge the research cruise leaders and funding agencies that made it possible to collect the samples used in this study. See the Supplementary Materials for details. Members of the Johnston Lab are thanked for their helpful comments. B. Passey and N. Ellis are thanked for their help with triple-oxygen isotope analysis of the experimental H2O. J. Alt, B. Killingsworth and one anonymous reviewer are thanked for their thoughtful reviews which significantly improved this manuscript.

Publisher Copyright:
© 2023

Keywords

Hydrothermal
Isotope
Oxygen
Seawater
Sulfate

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10.1016/j.gca.2023.01.009

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title = "The influence of submarine hydrothermal systems on seawater sulfate",

abstract = "Seawater sulfate is a major carrier of oxidizing capacity and influences the redox budget of the Earth's surface on geologic timescales. Records of oxygen and sulfur isotopes in seawater sulfate are used to track changes in sulfate cycling through geologic time. Interpretations of these records are typically based on models that describe the seawater sulfate reservoir as a mass balance between microbial, riverine and sedimentary sulfate fluxes. Here, we investigate the influence of hydrothermal sulfate cycling, which remains an unconstrained but potentially significant additional flux in this mass balance. We find that anhydrite (CaSO4) from eight submarine hydrothermal vent fields is consistently offset from seawater sulfate in δ18O but not Δ{\textquoteright}17O or δ34S. Experiments at hydrothermal pressure–temperature conditions indicate that this δ18O offset is driven by oxygen isotope exchange between sulfate and hydrothermal H2O at high temperature. An updated isotope mass balance model shows that a flux of hydrothermal sulfate into seawater, derived from retrograde dissolution of hydrothermal anhydrite, could cause high-temperature oxygen isotope exchange to buffer seawater sulfate δ18O and Δ{\textquoteright}17O by as much as 25%. Hydrothermal sulfate preserved in the Troodos Ophiolite (Cretaceous) also records a δ18O and Δ{\textquoteright}17O signal of high-temperature oxygen isotope exchange, supporting the conclusion that geologic records of seawater sulfate oxygen isotopes may include a hydrothermal component.",

keywords = "Hydrothermal, Isotope, Oxygen, Seawater, Sulfate",

author = "Hughes, {Eleanor R.} and Waldeck, {Anna R.} and Moriarty, {Sarah N.} and Jamieson, {John W.} and Martin, {Andrew J.} and Scheuermann, {Peter P.} and Syverson, {Drew D.} and Seyfried, {William E.} and Reeves, {Eoghan P.} and Johnston, {David T.}",

note = "Funding Information: This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. We acknowledge the research cruise leaders and funding agencies that made it possible to collect the samples used in this study. See the Supplementary Materials for details. Members of the Johnston Lab are thanked for their helpful comments. B. Passey and N. Ellis are thanked for their help with triple-oxygen isotope analysis of the experimental H2O. J. Alt, B. Killingsworth and one anonymous reviewer are thanked for their thoughtful reviews which significantly improved this manuscript. Publisher Copyright: {\textcopyright} 2023",

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doi = "10.1016/j.gca.2023.01.009",

language = "English (US)",

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T1 - The influence of submarine hydrothermal systems on seawater sulfate

AU - Hughes, Eleanor R.

AU - Waldeck, Anna R.

AU - Moriarty, Sarah N.

AU - Jamieson, John W.

AU - Martin, Andrew J.

AU - Scheuermann, Peter P.

AU - Syverson, Drew D.

AU - Seyfried, William E.

AU - Reeves, Eoghan P.

AU - Johnston, David T.

N1 - Funding Information: This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. We acknowledge the research cruise leaders and funding agencies that made it possible to collect the samples used in this study. See the Supplementary Materials for details. Members of the Johnston Lab are thanked for their helpful comments. B. Passey and N. Ellis are thanked for their help with triple-oxygen isotope analysis of the experimental H2O. J. Alt, B. Killingsworth and one anonymous reviewer are thanked for their thoughtful reviews which significantly improved this manuscript. Publisher Copyright: © 2023

PY - 2023/3/1

Y1 - 2023/3/1

N2 - Seawater sulfate is a major carrier of oxidizing capacity and influences the redox budget of the Earth's surface on geologic timescales. Records of oxygen and sulfur isotopes in seawater sulfate are used to track changes in sulfate cycling through geologic time. Interpretations of these records are typically based on models that describe the seawater sulfate reservoir as a mass balance between microbial, riverine and sedimentary sulfate fluxes. Here, we investigate the influence of hydrothermal sulfate cycling, which remains an unconstrained but potentially significant additional flux in this mass balance. We find that anhydrite (CaSO4) from eight submarine hydrothermal vent fields is consistently offset from seawater sulfate in δ18O but not Δ’17O or δ34S. Experiments at hydrothermal pressure–temperature conditions indicate that this δ18O offset is driven by oxygen isotope exchange between sulfate and hydrothermal H2O at high temperature. An updated isotope mass balance model shows that a flux of hydrothermal sulfate into seawater, derived from retrograde dissolution of hydrothermal anhydrite, could cause high-temperature oxygen isotope exchange to buffer seawater sulfate δ18O and Δ’17O by as much as 25%. Hydrothermal sulfate preserved in the Troodos Ophiolite (Cretaceous) also records a δ18O and Δ’17O signal of high-temperature oxygen isotope exchange, supporting the conclusion that geologic records of seawater sulfate oxygen isotopes may include a hydrothermal component.

AB - Seawater sulfate is a major carrier of oxidizing capacity and influences the redox budget of the Earth's surface on geologic timescales. Records of oxygen and sulfur isotopes in seawater sulfate are used to track changes in sulfate cycling through geologic time. Interpretations of these records are typically based on models that describe the seawater sulfate reservoir as a mass balance between microbial, riverine and sedimentary sulfate fluxes. Here, we investigate the influence of hydrothermal sulfate cycling, which remains an unconstrained but potentially significant additional flux in this mass balance. We find that anhydrite (CaSO4) from eight submarine hydrothermal vent fields is consistently offset from seawater sulfate in δ18O but not Δ’17O or δ34S. Experiments at hydrothermal pressure–temperature conditions indicate that this δ18O offset is driven by oxygen isotope exchange between sulfate and hydrothermal H2O at high temperature. An updated isotope mass balance model shows that a flux of hydrothermal sulfate into seawater, derived from retrograde dissolution of hydrothermal anhydrite, could cause high-temperature oxygen isotope exchange to buffer seawater sulfate δ18O and Δ’17O by as much as 25%. Hydrothermal sulfate preserved in the Troodos Ophiolite (Cretaceous) also records a δ18O and Δ’17O signal of high-temperature oxygen isotope exchange, supporting the conclusion that geologic records of seawater sulfate oxygen isotopes may include a hydrothermal component.

KW - Hydrothermal

KW - Isotope

KW - Oxygen

KW - Seawater

KW - Sulfate

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JO - Geochmica et Cosmochimica Acta

JF - Geochmica et Cosmochimica Acta

ER -

The influence of submarine hydrothermal systems on seawater sulfate

Abstract

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Keywords

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