Dual clumped isotopes (Δ47 and Δ48) reveal non-equilibrium formation of freshwater cements

Abstract

Low-Mg calcite, precipitating from meteoric fluids, is a common mineral that forms in a variety of near-surface diagenetic environments. However, recent studies, based on a combination of analyses of δ18O and Δ47 values, have suggested that this mineral might form in disequilibrium and consequently yield kinetic bias in Δ47-derived temperatures and fluid δ18O values. Here, we use dual clumped isotope proxies (Δ47 and Δ48) to investigate the influence of kinetic isotope effects within different meteoric diagenetic zones of Holocene and Pleistocene carbonates from the southern Florida and the Dominican Republic. In the Miami Oolite, the primary aragonite ooids and secondary low-Mg calcite cements in the bulk sample were separated from each other and their isotopic compositions (δ13C, δ18O, Δ47 and Δ48 values) were measured. The Δ47 and Δ48 values of the separated aragonite are consistent with the modern ooid sediments and in approximate equilibrium with the surface seawater. In contrast, the low-Mg calcite cement shows the higher Δ48 and lower Δ47 values, than expected, with the disequilibrium arising as a result of CO2 degassing in the vadose zone. Such deviations of Δ47 and Δ48 values are also observed in low-Mg calcite vadose cements in the Dominican Republic. While low-Mg calcites formed in the lower freshwater phreatic zone in the Dominican Republic have the Δ47- and Δ48-derived temperatures close to expected, the same mineral forming near the water-table and upper phreatic zone shows much higher Δ48-derived temperatures (up to ∼ 90 °C). The possible origin of such elevated temperatures can be attributed to non-equilibrium processes caused by changes in pH and pCO2, mediated by microbial sulfate reduction. Such differential kinetic behavior of Δ48 values between vadose and phreatic zones could be used as a proxy marker for the presence and the location of a water-table. This study demonstrates the great potential of dual clumped isotopes in the investigation of meteoric diagenesis and will help understand the alteration of ancient sequences and the interpretation of stable C isotope trends that they contain.