Effects of Water on Carbonate Clumped Isotope Bond Reordering Kinetics

Abstract:

Carbonate clumped isotope geothermometry is a powerful tool for reconstructing past temperatures, both in surface environments and in the shallow crust. The method is based on heavy isotope "clumps" within single carbonate groups (e.g., ¹³C¹⁸O¹⁶O₂^-2), whose overabundance beyond levels predicted by chance is determined by mineralization temperature. The degree of clumped isotope overabundance can change at elevated temperatures (ca. >100ºC) owing to solid-state diffusion of C and O through the mineral lattice. Understanding the kinetics of this clumped isotope reordering process is a prerequisite for application to geological questions involving samples that have been heated in the subsurface. Thus far, the effect of water on reordering kinetics has not been explored. The presence of water dramatically increases rates of oxygen self-diffusion in calcite, but whether this water-enhanced diffusion is limited to the mineral surface or extends into the bulk crystal lattice is not clear. Here we present experimentally determined Arrhenius parameters for reordering rates in optical calcite heated under aqueous high pressure (100 MPa) conditions. We observe only marginal increases in reordering rates under these wet, high pressure conditions relative to rates observed for the same material reacted under dry, low pressure conditions. The near identical clumped isotope reordering rates for wet and dry conditions contrasts with the orders of magnitude increase in oxygen diffusivity at the mineral surface when water is present. This suggests the latter effect arises from surface reactions that have minimal influence on the diffusivity of C or O in the bulk mineral. Our results also imply that previously published reordering kinetics determined under dry, low pressure experimental conditions are applicable to geological samples that have been heated in the presence of water.