Laboratory and Natural Constraints on the Temperature Limit for Preservation of the Dolomite Clumped Isotope Thermometer

Abstract:

Kinetic barriers generally inhibit intercrystalline equilibration of cations and isotopic compositions at temperatures below ~350˚C, greatly limiting the geothermometers available to study the upper 10-15 km of the crust. Calcite ‘clumped’ isotopes commonly appear to record homogeneous equilibrium during crystallization at surface temperatures, but kinetic models predict that reordering due to solid-state exchange among nearby carbonate groups modifies primary compositions at temperatures above ~115˚C on timescales of 10^6 - 10^8 years and fully re-equilibrates above 200˚C in most geological environments¹. Slowly cooled dolomitic marbles commonly preserve apparent temperatures of ~300˚C, indicating that dolomite may have slower reordering kinetics and thus greater preservation of primary crystallization temperatures. If so, dolomite clumped isotope thermometry may be a useful geothermometer in much of the the shallow crust.

We measured the kinetics of clumped isotope reordering in dolomite with heating experiments at 400-800˚C in a TZM cold seal apparatus pressurized with CO2. Results predict that no detectable reordering occurs in dolomite held at temperatures less than ~250˚C over timescales of up to 10^8 years, demonstrating the viability of the system as a shallow crustal geothermometer. The non-first order behavior observed in calcite^1,2,3is exhibited by dolomite as well, albeit at higher temperatures.

To test these predictions, we measured the clumped isotopic compositions of coexisting calcite and dolomite in marbles from the Notch Peak aureole, UT. Dolomite clumped isotope temperatures in the outer aureole match peak conditions predicted by thermal models up to ~275˚C, indicating that the system resisted reordering below this grade. Calcite clumped isotope temperatures are never greater than ~150˚C at all grades in the aureole; this is consistent with the ambient burial temperature in the section and indicates that all metamorphic calcite was fully reset in the >100 my subsequent to intrusion. Dolomite and calcite blocking temperatures in high-grade samples are consistent with those predicted by model sample T-t paths using experimentally-derived kinetic parameters.

References: 1. Henkes and Passey (2014), 2. Passey et al. (2012), 3. Stolper and Eiler (2014)

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