Fluid-mediated exchange reaction induces clumped isotope resetting: Insights from aragonite dolomitization experiments

Carbon and oxygen isotopic exchange between external and internal fluids of carbonate minerals can reset the clumped isotope composition (Δ47) of paleotemperature archives. Understanding the nature of this exchange during carbonate diagenetic alterations is essential for correctly interpreting the paleoenvironmental significance of Δ47-derived temperatures. Through batch hydrothermal experiments on aragonitic coral carbonates, we examine the kinetic signatures of clumped isotope fractionation from the initial disequilibrium to final equilibrium states during the dolomitization of the aragonite. By analyzing oxygen isotope fractionation and Sr partitioning between carbonate and fluid, we simulate the effect of exchange reactions on the Δ47 values. As the resetting feature of Δ47 values in our aragonite samples disagrees with the fractionation pattern observed in previous aragonite solid-state reordering experiment, we rule out the effect of the solid-state reordering. Our findings demonstrate that isotope exchanges with internal or external fluids coexist, particularly during the early stage of aragonite self-recrystallization. The results of this study indicate that the Δ47 value of coral aragonite is susceptible to internal exchange reactions in Mg-bearing solutions at 160–220 °C. Additionally, by modeling the bulk recrystallization and internal fluid-mineral exchange and evaluating their relative importance, we determine that the internal exchange reaction results in a nonlinear correlation between δ18O and Δ47 values. Importantly, we highlight the previously unrecognized diagenetic scenario in which the internal fluid-mineral exchange effect on the Δ47 value can outweigh the bulk recrystallization effect with external fluid coexisting. Consequently, our findings emphasize the need for a comprehensive assessment on the reaction kinetics for different types of recrystallization effects, to support the application of clumped isotope proxies for altered carbonate samples in diagenetic environments.