Most Earth-surface calcites precipitate out of isotopic equilibrium.

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 (¹⁸α_cc/w). Here, we constrain the equilibrium relations linking temperature, ¹⁸α_cc/w, and clumped isotopes (Δ₄₇) based on the composition of extremely slow-growing calcites from Devils Hole and Laghetto Basso (Corchia Cave). Equilibrium ¹⁸α_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 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.