Equilibrated Gas and Carbonate Standard-Derived Dual (Delta(47) and Delta(48)) Clumped Isotope Values

Carbonate clumped isotope geochemistry has primarily focused on mass spectrometric determination of m/z 47 CO2 for geothermometry, but theoretical calculations and recent experiments indicate paired analysis of the m/z 47 ((COO)-C-13-O-18-O-16) and m/z 48 ((COO)-C-12-O-18-O-18) isotopologues (referred to as Delta(47) and Delta(48)) can be used to study non-equilibrium isotope fractionations and refine temperature estimates. We utilize 5,448 Delta(47) and 3,400 Delta(48) replicate measurements of carbonate samples and standards, and 183 Delta(47) and 195 Delta(48) replicate measurements of gas standards from 2015 to 2021 from a multi-year and multi-instrument data set to constrain Delta(47) and Delta(48) values for 27 samples and standards, including Devils Hole cave calcite, and study equilibrium Delta(47)-Delta(48), Delta(47)-temperature, and Delta(48)-temperature relationships. We compare results to previously published findings and calculate equilibrium regressions based on data from multiple laboratories. We report acid digestion fractionation factors, Delta*(63-47) and Delta*(64-48), and account for their dependence on the initial clumped isotope values of the mineral.