Clumped isotope and Δ¹⁷O measurements of carbonates in CM carbonaceous chondrites: New insights into parent body thermal and fluid evolution

The CM carbonaceous chondrites are key archives for understanding the earliest history of the solar system. Their C-complex asteroid parent body(ies) underwent aqueous alteration, among the products of which are carbonate minerals that can faithfully record the conditions of their formation. In this study we report carbon, triple oxygen and clumped isotope compositions of carbonates in six CM chondrites which span a range in degrees of aqueous alteration (Allan Hills 83100, Cold Bokkeveld, LaPaz Icefield 031166, Lonewolf Nunataks 94101, Murchison, Scott Glacier 06043). Δ¹⁷O values range from −2.6 to −1.0 ‰ (±0.1), and where calcite and dolomite co-exist their Δ¹⁷O differ by 0.6 permil, suggesting precipitation from distinct fluids. Calculated crystallization temperatures range from 5 to 51 °C for calcite (typically ± 10 °C) and 75 to 101(±15) °C for dolomite. The δ¹⁸O_VSMOW of the aqueous fluids from which they formed ranges from −6.6 to 2.3 ‰, with no relationship to the δ¹³C of carbonates. As the population of carbonates in any one CM chondrite can include multiple generations of grains that formed at different conditions, these values represent the mode of the temperature of carbonate formation for each meteorite. We observe that in the more altered meteorites carbonate Δ¹⁷O values are lower and formation temperatures are higher. These correlations are consistent with aqueous alteration of the CM chondrites being a prograde reaction whereby the hotter fluids had undergone greater isotope exchange with the anhydrous matrix. Our data are broadly consistent with the closed system model for water/rock interaction, but carbonate mineral formation in the latter stages of aqueous alteration may be linked to fluid movement via fractures.