Most Earth-surface calcites precipitate out of isotopic equilibrium

Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18 O/ 16 O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. Howe...

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Published in:	Nature communications Vol. 10; no. 1; p. 429
Main Authors:	Daëron, M., Drysdale, R. N., Peral, M., Huyghe, D., Blamart, D., Coplen, T. B., Lartaud, F., Zanchetta, G.
Format:	Journal Article
Language:	English
Published:	London Nature Publishing Group UK 25-01-2019 Nature Publishing Group Nature Portfolio
Subjects:	140/58 704/106/2738 704/106/413 704/172/169/209 Calcite Earth Sciences Earth surface Equilibrium Fractionation Geochemistry Humanities and Social Sciences Isotope fractionation Isotopes Minerals multidisciplinary Oxygen Science Science (multidisciplinary) Sciences of the Universe Thermodynamic equilibrium Geochemistry Palaeoceanography Palaeoclimate
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Abstract	Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18 O/ 16 O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium 18 O/ 16 O fractionation between calcite and water ( 18 α cc/w ). Here, we constrain the equilibrium relations linking temperature, 18 α cc/w , and clumped isotopes ( Δ 47 ) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium 18 α cc/w values are systematically ~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ 47 in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations. Isotopic thermometry of carbonate minerals postulates that their composition reflects thermodynamic equilibrium constants. Here the authors constrain equilibrium relationships between temperature, 18 O/ 16 O and clumped isotopes and find that most natural calcites form out of isotopic equilibrium.
AbstractList	Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18 O/ 16 O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium 18 O/ 16 O fractionation between calcite and water (18 α cc/w). Here, we constrain the equilibrium relations linking temperature, 18 α cc/w , and clumped isotopes (Δ 47) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium 18 α cc/w values are systematically~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ 47 in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations. Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18 O/ 16 O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium 18 O/ 16 O fractionation between calcite and water ( 18 α cc/w ). Here, we constrain the equilibrium relations linking temperature, 18 α cc/w , and clumped isotopes ( Δ 47 ) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium 18 α cc/w values are systematically ~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ 47 in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations. Isotopic thermometry of carbonate minerals postulates that their composition reflects thermodynamic equilibrium constants. Here the authors constrain equilibrium relationships between temperature, 18 O/ 16 O and clumped isotopes and find that most natural calcites form out of isotopic equilibrium. Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that O/ O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium O/ O fractionation between calcite and water ( α ). Here, we constrain the equilibrium relations linking temperature, α , and clumped isotopes (Δ ) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium α values are systematically ~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations. Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18O/16O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium 18O/16O fractionation between calcite and water (18αcc/w). Here, we constrain the equilibrium relations linking temperature, 18αcc/w, and clumped isotopes (Δ47) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium 18αcc/w values are systematically ~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ47 in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations.Isotopic thermometry of carbonate minerals postulates that their composition reflects thermodynamic equilibrium constants. Here the authors constrain equilibrium relationships between temperature, 18O/16O and clumped isotopes and find that most natural calcites form out of isotopic equilibrium. Isotopic thermometry of carbonate minerals postulates that their composition reflects thermodynamic equilibrium constants. Here the authors constrain equilibrium relationships between temperature, 18O/16O and clumped isotopes and find that most natural calcites form out of isotopic equilibrium. Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical foundations rest on the assumption that 18 O/ 16 O partitioning among water and carbonate minerals primarily reflects thermodynamic equilibrium. However, after decades of research, there is no consensus on the true equilibrium 18 O/ 16 O fractionation between calcite and water ( 18 α cc/w ). Here, we constrain the equilibrium relations linking temperature, 18 α cc/w , and clumped isotopes ( Δ 47 ) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium 18 α cc/w values are systematically ~1.5‰ greater than those in biogenic and synthetic calcite traditionally considered to approach oxygen-isotope equilibrium. We further demonstrate that subtle disequilibria also affect Δ 47 in biogenic calcite. These observations provide evidence that most Earth-surface calcites fail to achieve isotopic equilibrium, highlighting the need to improve our quantitative understanding of non-equilibrium isotope fractionation effects instead of relying on phenomenological calibrations.
ArticleNumber	429
Author	Daëron, M. Peral, M. Coplen, T. B. Lartaud, F. Blamart, D. Huyghe, D. Zanchetta, G. Drysdale, R. N.
Author_xml	– sequence: 1 givenname: M. surname: Daëron fullname: Daëron, M. email: daeron@lsce.ipsl.fr organization: Laboratoire des Sciences du Climat et de l’Environnement, LSCE/IPSL, CEA-CNRS-UVSQ, Université Paris-Saclay – sequence: 2 givenname: R. N. surname: Drysdale fullname: Drysdale, R. N. organization: School of Geography, The University of Melbourne, EDYTEM UMR CNRS 5204, Bâtiment “Pôle Montagne”, Université Savoie Mont Blanc – sequence: 3 givenname: M. surname: Peral fullname: Peral, M. organization: Laboratoire des Sciences du Climat et de l’Environnement, LSCE/IPSL, CEA-CNRS-UVSQ, Université Paris-Saclay – sequence: 4 givenname: D. surname: Huyghe fullname: Huyghe, D. organization: Laboratoire d’Ecogéochimie des Environnements Benthiques, LECOB, Sorbonne Université, CNRS, Géosciences Environnement Toulouse, UMR 5563 CNRS, UR 234 IRD, UM 97 UPS, Observatoire Midi-Pyrénées, CNES, Centre de Géosciences, MINES ParisTech, PSL University – sequence: 5 givenname: D. surname: Blamart fullname: Blamart, D. organization: Laboratoire des Sciences du Climat et de l’Environnement, LSCE/IPSL, CEA-CNRS-UVSQ, Université Paris-Saclay – sequence: 6 givenname: T. B. surname: Coplen fullname: Coplen, T. B. organization: U.S. Geological Survey – sequence: 7 givenname: F. surname: Lartaud fullname: Lartaud, F. organization: Laboratoire d’Ecogéochimie des Environnements Benthiques, LECOB, Sorbonne Université, CNRS – sequence: 8 givenname: G. surname: Zanchetta fullname: Zanchetta, G. organization: Dipartimento di Scienze della Terra, Università di Pisa
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Keywords	Geochemistry Palaeoceanography Palaeoclimate
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Snippet	Oxygen-isotope thermometry played a critical role in the rise of modern geochemistry and remains extensively used in (bio-)geoscience. Its theoretical... Isotopic thermometry of carbonate minerals postulates that their composition reflects thermodynamic equilibrium constants. Here the authors constrain...
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SubjectTerms	140/58 704/106/2738 704/106/413 704/172/169/209 Calcite Earth Sciences Earth surface Equilibrium Fractionation Geochemistry Humanities and Social Sciences Isotope fractionation Isotopes Minerals multidisciplinary Oxygen Science Science (multidisciplinary) Sciences of the Universe Thermodynamic equilibrium
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Title	Most Earth-surface calcites precipitate out of isotopic equilibrium
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