Most Earth-surface calcites precipitate out of isotopic equilibrium
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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.
| 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 |
| 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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