Oxygen Isotope Fractionation between Carbonate Minerals and Carbonic Acid Systems and Constraints for Environmental Science and Geological Processes

The equilibrium oxygen isotope fractionation factor is widely used in geological thermometry. However, under most natural conditions, the oxygen isotope exchange is rare to reach equilibrium. Especially for the complex water-rock interaction process, the contribution of the H2CO3 solution, CO32- solution, Ca(HCO3)(2) solution, and CaCO3 solution to the equilibrium oxygen isotope fractionation factor of this process is poorly understood. In view of this predicament, these key parameters are obtained by ab initio calculations. The results showed that the contributions of different carbonate minerals and different aqueous solutions to the equilibrium oxygen isotope fractionation factor were different. Among all nine carbonate minerals (dolomite, calcite, aragonite, magnesite, siderite, otavite, smithsonite, ankerite, and strontianite), the minerals with the highest and lowest reduced partition function ratios (RPFR) were siderite and strontianite, respectively. At the same time, the RPFR of nitratine, which has the same structure as carbonate, was studied. The RPFRs of the three most widely distributed carbonates in nature (dolomite, calcite, and aragonite) were dolomite > calcite > aragonite. Among the H2CO3 solution, CO32- solution, Ca(HCO3)(2) solution, and CaCO3 solution, the H2CO3 solution had the strongest ability to enrich O-18. In addition, the equilibrium oxygen isotope fractionation factors between aqueous solutions and gas phase species (CO2(g), H2O(g), and O-2(g), etc.) were calculated systematically. The results showed that the oxygen isotope fractionation factors between solutions and gas phases were often inconsistent with the temperature change direction and that the kinetic effects played a key role. These theoretical parameters obtained in this study will provide key equilibrium oxygen isotope constraints for water-rock interaction processes.