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.
CITATION STYLE
Daëron, M., Drysdale, R. N., Peral, M., Huyghe, D., Blamart, D., Coplen, T. B., … Zanchetta, G. (2019). Most Earth-surface calcites precipitate out of isotopic equilibrium. Nature Communications, 10(1). https://doi.org/10.1038/s41467-019-08336-5
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