Rates of carbon and oxygen isotope exchange between calcite and fluid at chemical equilibrium

The isotopic composition of carbonate minerals provides a record of historical geochemical and environ-mental conditions, but the ability to interpret these compositions as paleo-proxies hinges on their preservation over thousand to million year timescales. At chemical equilibrium, alteration of initial isotopic compositions of calcite can occur in the presence of a fluid without visible changes in morphology at the submicron scale, complicating the interpretation of stable isotope compositions of carbonates. However, the rates and mechanisms of isotope exchange at chemical equilibrium are poorly understood. To evaluate the rates and processes by which C and O isotopes are exchanged between calcite and fluid, batch reactor experiments were conducted at chemical equilibrium between calcite and a fluid enriched in C-13 and O-18 relative to the solid at 25 degrees C. Both natural and synthetic calcite of different grain sizes were investigated to evaluate the impact of mineral surface area and size on C and O isotope exchange rates. Our experimental results indicate that rapid exchange of both C and O isotopes occurs within 72 h for all calcite grain sizes studied, likely indicative of exchange of surface species in combination with a back-ward reaction during dissolution and Ostwald ripening of high energy surface sites. After 72 h, C and O isotope exchange rates were slower but near constant for timescales of thousands of hours. Surface -area normalized C and O isotope exchange rates were similar for all calcite grain sizes studied, and O and C were exchanged in a-3:1 ratio consistent with exchange of CO32-. The rates of C and O exchange were-4 orders of magnitude lower than far-from-equilibrium calcite dissolution rates, suggesting exchange was controlled either by dissolution-precipitation of pre-existing reactive sites alone, or a combination of dissolution-precipitation and solid state/aqueous mediated diffusion. Overall, the results of this study suggest alteration of O and C isotope compositions of calcite at ambient temperatures can proceed readily over short time scales, though the extent to which this process continues to operate over geologic time scales is difficult to predict at present. The results of this study further highlight the importance of generating a mechanistic understanding of the process of isotope exchange at chemical equilibrium, and represent a step towards this understanding. (C) 2022 Elsevier Ltd. All rights reserved.