The Influence of Temperature, pH, and Growth Rate on the Stable Isotope Composition of Calcite

The oxygen isotope composition of carbonate minerals varies with temperature as well as other environmental variables. For carbonates that precipitate slowly, under conditions that approach thermodynamic equilibrium, the temperature-dependence of ¹⁸O uptake is the dominant signal and the measured ¹⁸O content can be used as a paleotemperature proxy. In the more common case where carbonate minerals grow in a regime where they are not in isotopic equilibrium with their host solution, their stable isotope compositions are a convolution of the effects of multiple environmental variables.

We present results from inorganic calcite growth experiments demonstrating the occurrence of non-equilibrium oxygen isotope effects that vary systematically with pH and crystal growth rate. We have developed an isotopic ion-by-ion crystal growth model that quantifies the competing roles of temperature, pH, and growth rate, and provides a general description of calcite-water oxygen isotope fractionation under non-equilibrium conditions. The model predicts that (1) there are both equilibrium and kinetic contributions to calcite oxygen isotopes at biogenic growth rates, (2) calcite does not inherit the stable isotopic composition of dissolved inorganic carbon (DIC), (3) for oxygen isotopes there is a kinetically controlled variation of about 1‰ per pH unit between pH=7.7 and 9.3 at constant growth rate for inorganic calcite as well as the foraminifera Orbulina universa, and (4) extreme light isotope enrichments in calcite in alkaline environments are likely due to disequilibrium among DIC species in aqueous solution.

The experimental and modeling approaches can be extended to carbon isotope as well as clumped isotope uptake into calcite but additional data are needed to constrain the kinetic fractionation factors for carbon isotopes and doubly-substituted isotopologues. The results will be discussed in the context of separating the relative influence of inorganic and biologic processes on isotopic fractionation.