Equilibrium Ca isotope fractionation and the rates of isotope exchange in the calcite-fluid and aragonite-fluid systems at 25 degrees C

The Ca isotope composition of calcite and aragonite can provide insights into their formation conditions. The accurate interpretation of the Ca isotope composition of natural samples, however, requires precise knowledge of the equilibrium Ca isotope fractionation between the solid and fluid phases. In this study, the three-isotope method with 42Ca, 43Ca and 44Ca has been used to estimate the equilibrium isotope fractionation of Ca between the CaCO3 minerals calcite and aragonite and the Ca2+ aquo ion. Reactive fluids were enriched with 43Ca and equilibrated with synthetic calcite and aragonite of natural Ca isotope distribution up to 3745 h at 25 degrees C. The isotopic composition of solids and fluids was measured using MC-ICP-MS and the estimated equilibrium fractionation for calcite-Ca2+(aq) and aragonite-Ca2+(aq) was A44/42Casolid-fluid = -0.02 +/- 0.13%o and -0.80 +/- 0.10%o, respectively. Textural observations of the reacted solids suggest that isotope equilibration in aragonite experiments occurs via extensive Ostwald ripening, yielding large crystalline needles at the end of the experiments. In contrast, calcite did not exhibit an observable increase in size during the course of the experiments. Isotope exchange rates in the case of calcite are similar to those reported in previous studies and similar to 4 orders of magnitude lower than the far-from-equilibrium calcite dissolution rate. Calcium isotope exchange rates for aragonite are more rapid than calcite driven by a greater extent of Ostwald ripening occurring via dissolution/precipitation reactions. The results of this study suggest that the Ca isotope compositions of calcite and aragonite crystals in chemical equilibrium, but isotope disequilibrium, with natural fluids could be significantly altered without overt evidence of diagenesis, especially in the case of calcite. The extent to which Ca isotope compositions are altered, however, would depend strongly on the environmental conditions, such as fluid:solid ratio and permeability of the solid facilitating fluid transport. (c) 2022 Elsevier B.V. All rights reserved.