Parvez, Zeeshan A., El-Shenawy, Mohammed I., Lucarelli, Jamie K., Kim, Sang-Tae, Johnson, Kathleen R., Wright, Kevin, Gebregiorgis, Daniel, Montanez, Isabel P., Wortham, Barbara, Asrat, Asfawossen, Reinhardt, Eduard, Christensen, John N., Matamoros, Irvin W., Rubi, Joshua, Miguel, Kevin, Elliott, Ben M., Flores, Randy, Kovacs, Shawn, Eagle, Robert A., and Tripati, Aradhna
Cave carbonate minerals are an important terrestrial paleoclimate archive. A few studies have explored the potential for applying carbonate clumped isotope thermometry to speleothems as a tool for constraining past temperatures. To date, most papers utilizing this method have focused on mass-47 clumped isotope values (Δ 47) at a single location and reported that cave carbonate minerals rarely achieve isotopic equilibrium, with kinetic isotope effects (KIEs) attributed to CO 2 degassing. More recently, studies have shown that mass-47 and mass-48 CO 2 from acid digested carbonate minerals (Δ 47 and Δ 48) can be used together to assess equilibrium and probe KIEs. Here, we examined 44 natural and synthetic modern cave carbonate mineral samples from 13 localities with varying environmental conditions (ventilation, water level, pCO 2 , temperature) for (dis)equilibrium using Δ 47 -Δ 48 values, in concert with traditional stable carbon (δ13C) and oxygen (δ18O) isotope ratios. Data showed that 19 of 44 samples exhibited Δ 47 -Δ 48 values indistinguishable from isotopic equilibrium, and 18 (95 %) of these samples yield Δ 47 -predicted temperatures within error of measured modern temperatures. Conversely, 25 samples exhibited isotopic disequilibria, 13 of which yield erroneous temperature estimates. Within some speleothem samples, we find Δ 47 -Δ 48 values consistent with CO 2 degassing effects, however, the majority of samples with KIEs are consistent with other processes being dominant. We hypothesize that these values reflect isotopic buffering effects on clumped isotopes that can be considerable and cannot be overlooked. Using a Raleigh Distillation Model, we examined carbon and oxygen isotope exchange trajectories and their relationships with dual clumped isotope disequilibria. Carbon isotope exchange is associated with depletion of both Δ 47 and Δ 48 relative to equilibrium, while oxygen isotope exchange is associated with enrichment of both Δ 47 and Δ 48 relative to equilibrium. Cave rafts collected from proximate locations in Mexico exhibit the largest average departures from equilibrium ( Δ Δ 47 ¯ = −0.032 ± 0.007, Δ Δ 48 ¯ = −0.104 ± 0.035, where ΔΔ i is the measured value – the equilibrium value). This study shows how the Δ 47 -Δ 48 dual carbonate clumped isotope framework can be applied to a variety of tcave carbonate mineral samples, enabling identification of isotopic equilibria and therefore quantitative application of clumped isotope thermometry for paleoclimate reconstruction, or alternatively, constraining the mechanisms of kinetic effects. [ABSTRACT FROM AUTHOR]