Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this “water effect” also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes (‘clumped’ isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385–450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures (“blocking temperatures”) for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150–200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external fluids. We explore the mechanism(s) by which clumped isotope reordering rates may be modestly increased under wet, high-pressure conditions, including changes in defect concentrations in the near surface environment due to reactions at the water–mineral interface, and lattice deformation resulting from pressurization of samples.

Carbonate clumped isotope thermometry has been applied to fossil mollusk shells from Tibet to reconstruct the paleoclimate and paleoelevation of the region. However, inferred paleoelevation and climatic conditions from this proxy are inconsistent with paleontological evidence. Here, we report new clumped isotope data from both modern and fossil (5–4 Ma) freshwater mollusk shells with the results of X-ray diffraction (XRD) analyses of fossil shells from the Himalayan-Tibetan Plateau. Although all of the fossil shells analyzed in this study appeared pristine based on visual inspection, XRD data reveal that more than half of these apparently “pristine” fossil shells contain trace amounts of calcite. Clumped isotope temperatures derived from the fossil shells display a large range of variation (>22 °C). Among the fossil shells analyzed, those containing traces of calcite have yielded temperatures that are on average ∼10 °C lower than those with no detectable calcite from the same strata. These observations suggest that clumped isotope alteration can occur in aragonite shells in low-temperature environments and even in shells with no visible signs of alteration that contain only traces of calcite. The temperatures derived from fossil shells with no detectable calcite are on average 4 °C higher than those derived from modern shells, indicating that southwest Tibet was warmer 4–5 Ma than today. After accounting for temperature change due to global cooling, the difference in clumped isotope temperatures between pristine fossil shells and modern shells suggests that the paleoelevation of the southwestern Tibetan Plateau in the Pliocene was similar to its present-day elevation.