Most Earth-surface calcites precipitate out of isotopic equilibrium

Nature Communications
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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 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.

Suggested Citation

Daeron, M., Drysdale, R.N., Peral, M., Huyghe, D., Blamart, D., Coplen, T.B., Lartaud, F., Zanchetta, G., 2019, Most Earth-surface calcites precipitate out of isotopic equilibrium: Nature Communications, v. 10, no. 1, p. 1-7, https://doi.org/10.1038/s41467-019-08336-5.

Publication type Article
Publication Subtype Journal Article
Title Most Earth-surface calcites precipitate out of isotopic equilibrium
Series title Nature Communications
DOI 10.1038/s41467-019-08336-5
Volume 10
Issue 1
Publication Date January 25, 2019
Year Published 2019
Language English
Publisher Nature
Contributing office(s) WMA - Earth System Processes Division
Description Article number: 429; 7 p.
First page 1
Last page 7
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