Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration

We measure the clumped isotopic signature of carbonatites to assess the integrity of the clumped isotope paleothermometer over long timescales (10⁷-10⁹ years) and the susceptibility of the proxy to closed system re-equilibration of isotopes during burial diagenesis. We find pristine carbonatites that have primary oxygen isotope signatures, along with a Carrara marble standard, do not record clumped isotope signatures lighter than 0.31‰ suggesting atoms of carbon and oxygen freely exchange within the carbonate lattice at temperatures above 250-300 °C. There is no systematic trend in the clumped isotope signature of pristine carbonatites with age, although partial re-equilibration to lower temperatures can occur if a carbonatite has been exposed to burial temperatures for long periods of time. We conclude that the solid-state re-ordering of carbon and oxygen atoms is sufficiently slow to enable the use of clumped isotope paleothermometry on timescales of 10⁸ years, but that diagenetic resetting can still occur, even without bulk recrystallization. In addition to the carbonatite data, an inorganic calibration of the clumped isotope paleothermometer for low temperature carbonates (7.5-77 °C) is presented and highlights the need for further inter-lab standardization.