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Dolomite clumped isotope compositions are indispensable for determining the temperatures and fluid sources of dolomitizing environments, but can be misleading if they have modified since formation. Carbonate Δ_(47) values are susceptible to resetting by recrystallization during diagenesis, and, even in the absence of dissolution and reprecipitation reactions, alteration by solid-state reordering during prolonged residences at elevated temperatures. In order to understand the potential of dolomite Δ_(47) values to preserve the conditions of dolomitizationin ancient sections, the kinetic parameters of solid-state reordering in this phase must be determined. We heated mm-sized crystals of near-stoichiometric dolomite in a Rene-type cold seal apparatus at temperatures between 409 and 717 °C for 0.1–450 h. In order to prevent the decarbonation of dolomite to calcite, periclase, and CO_2 at these conditions, the system was pressurized with CO_2 to 0.45–0.8 kbar. Over the course of 31 temperature-time points and 128 individual Δ_(47) measurements of powdered dolomite crystals from these points, we observed the evolution of dolomite Δ_(47) values from the initial (unheated) composition of the crystals (0.452 ± 0.004‰, corresponding to a formation temperature of ∼145 °C) towards high-temperature equilibrium distributions. Complete re-equilibration occurred in the 563–717 °C experiments. As with previous heating experiments using calcite and apatite, dolomite Δ_(47) exhibited complex reordering behavior inadequately described by first-order Arrhenian-style models. Instead, we fit the data using two published models for clumped isotope reordering: the transient defect/equilibrium defect model of Henkes et al. (2014), and the exchange-diffusion model of Stolper and Eiler (2015). For both models, we found optimal reordering parameters by using global least-squares minimization algorithms and estimated uncertainties on these fits with a Monte Carlo scheme that resampled individual Δ_(47) measurements and re-fit the dataset of these new mean values. Because the exact Δ_(47)–T relationship between 250 and 800 °C is uncertain, we repeated these fitting exercises using three published high-temperature Δ_(47)–T calibrations. Regardless of calibration choice, dolomite Δ_(47) rate constants determined using both models are resolvably slower than those of calcite and apatite, and predict that high-grade dolomite crystals should preserve apparent equilibrium blocking temperatures of between ∼210 and 300 °C during cooling on geologic timescales. Best agreement between model predictions and natural dolomite marbles was found when using the exchange-diffusion model and the ab initio Δ_(63)–T calibration of Schauble et al. (2006), projected into the Δ_(47) reference frame by Bonifacie et al. (2017). Therefore, we recommend modeling dolomite Δ_(47) reordering using the exchange-diffusion model and this parameter set. In simple heating scenarios, the two models disagree. The transient defect/equilibrium defect model suggests that dolomite fabrics resist detectable reordering at ambient temperatures as high as 180 °C for tens of millions of years, while the exchange-diffusion model predicts incipient partial reordering perhaps as low as 150 °C. In either case, barring later recrystallization, dolomite Δ_(47) values should be faithful recorders of the conditions of dolomitization in sedimentary sections buried no hotter than ∼150 °C for tens of millions of years.

Clumped isotope compositions of slowly-cooled calcite and dolomite marbles record apparent equilibrium temperatures of roughly 150-200 °C and 300-350 °C, respectively. Because clumped isotope compositions are sensitive to the details of T-t path within these intervals, measurements of the Δ_(47) values of coexisting calcite and dolomite can place new constraints on thermal history of low-grade metamorphic rocks over a large portion of the upper crust (from ∼5 to ∼15 km depth). We studied the clumped isotope geochemistry of coexisting calcite and dolomite in marbles from the Notch Peak contact metamorphic aureole, Utah. Here, flat-lying limestones were intruded by a pluton, producing a regular, zoned metamorphic aureole. Calcite Δ_(47) temperatures are uniform, 156 ± 12 ˚C (2σ s.e.), across rocks varying from high-grade marbles that exceeded 500 °C to nominally unmetamorphosed limestones >5 km from the intrusion. This result appears to require that the temperature far from the pluton was close to this value; an ambient temperature just 20 ˚C lower would not have permitted substantial re-equilibration, and should have preserved depositional or early diagenetic Δ_(47) values several km from the pluton. Combining this result with depth constraints from overlying strata suggests the country rock here had an average regional geotherm of 22.3–27.4 ˚C/km from the late Jurassic Period until at least the middle Paleogene Period. Dolomite Δ_(47) in all samples above the talc+tremolite-in isograd record apparent equilibrium temperatures of 328^(+13)_(-12) °C (1σ s.e.), consistent with the apparent equilibrium blocking temperature we expect for cooling from peak metamorphic conditions. At greater distances, dolomite Δ_(47) records temperatures of peak (anchi)metamorphism or pre-metamorphic diagenetic conditions. The interface between these domains is the location of the 330 ˚C isotherm associated with intrusion. Multiple-phase clumped isotope measurements are complemented by bulk δ^(13)C and δ^(18)O dolomite-calcite thermometry. These isotopic exchange thermometers are largely consistent with peak temperatures in all samples within 4 km of the contact, indicating that metamorphic recrystallization can occur even in samples too low-grade to produce growth of conventional metamorphic index minerals (i.e., talc and tremolite). Altogether, this work demonstrates the potential of these methods to quantify the conditions of metamorphism at sub-greenschist facies.

The clumped isotope compositions of carbonate minerals are subject to alteration at elevated temperatures. Understanding the mechanism of solid-state reordering in carbonate minerals is important in our interpretations of past climates and the thermal history of rocks. The kinetics of solid-state isotope reordering has been previously studied through controlled heating experiments of calcite, dolomite and apatite. Here we further explore this issue through controlled heating experiments on aragonite. We find that Δ47 values generally decrease during heating of aragonite, but increase by 0.05–0.15‰ as aragonite starts to transform into calcite. We argue that this finding is consistent with the presence of an intermediate pool of immediately adjacent singly-substituted carbonate ion isotopologues (‘pairs’), which back-react to form clumped isotopologues during aragonite to calcite transformation, revealing the existence of kinetically preferred isotope exchange pathways. Our results reinforce the ‘reaction-diffusion’ model as the mechanism for solid-state clumped isotope reordering in carbonate minerals. Our experiments also reveal that the reordering kinetics in aragonite is faster than in calcite and dolomite, making its clumped isotope composition highly susceptible to alteration during early diagenesis, even before conversion to calcite. publishedVersion

Exhumation and accompanying retrograde metamorphism alter the compositions and textures of metamorphic rocks through deformation, mineral–mineral reactions, water–rock reactions, and diffusion-controlled intra- and inter-mineral atomic mobility. Here, we demonstrate that these processes are recorded in the clumped- and single-isotope (δ^(13)C and δ^(18)O) compositions of marbles, which can be used to constrain retrograde metamorphic histories. We collected 27 calcite and dolomite marbles along a transect from the rim to the center of the metamorphic core-complex of Naxos (Greece), and analyzed their carbonate single- and clumped-isotope compositions. The majority of Δ_(47) values of whole-rock samples are consistent with exhumation- controlled cooling of the metamorphic complex. However, the data also reveal that water–rock interaction, deformation driven recrystallization and thermal shock associated with hydrothermal alteration may considerably impact the overall distribution of Δ_(47) values. We analyzed specific carbonate fabrics influenced by deformation and fluid–rock reaction to study how these processes register in the carbonate clumped-isotope system. Δ_(47) values of domains drilled from a calcite marble show a bimodal distribution. Low Δ_(47_ values correspond to an apparent temperature of 260 °C and are common in static fabrics; high Δ_(47) values correspond to an apparent temperature of 200 °C and are common in dynamically recrystallized fabrics. We suggest that the low Δ_(47) values reflect diffusion-controlled isotopic reordering during cooling, whereas high Δ_(47) values reflect isotopic reordering driven by dynamic recrystallization. We further studied the mechanism by which dynamic recrystallization may alter Δ_(47) values by controlled heating experiments. Results show no significant difference between laboratory reactions rates in the static and dynamic fabrics, consistent with a mineral-extrinsic mechanism, in which slip along crystal planes was associated with atomic-scale isotopic reordering in the calcite lattice. An intrinsic mechanism (enhanced isotopic reordering rate in deformed minerals) is contraindicated by these experiments. We suggest that Δ_(47) values of dynamically recrystallized fabrics that form below the diffusion-controlled blocking-temperature for calcite constrain the temperature of deformation. We find that Δ_(47)-based temperatures of static fabrics from Naxos marbles are ∼60–80 °C higher than commonly observed in slowly cooled metamorphic rocks, and would suggest cooling rates of ∼10^5°C Myr^(−1). A similar thermal history is inferred for dolomite marbles from the core vicinity, which preserve apparent temperatures up to 200 °C higher than a typical blocking temperature (∼300 °C). This finding could be explained by a hydrothermal event driving a brief thermal pulse and locally resetting Δ_(47) values. Rapid cooling of the core-complex region is consistent with a compilation of published cooling ages and a new apatite U–Th/He age, associating the thermal event with the emplacement of a granodiorite pluton at ∼12 Ma.