Clumped isotopes of paired dolomite and calcite constraining alteration histories of ancient carbonate successions

Clumped isotope thermometry is an effective tool which allows to understand the post-depositional alteration, including recrystallization and solid-state reordering, of carbonate rocks. However, as both processes are controlled by elevated temperatures, it is frequently a challenge to distinguish between the relative importance of these two processes in deeply buried carbonate successions (depth > 5000 m or formation temperature > 150°C). In this paper, we have established a clumped isotopic framework of paired dolomite and calcite in order to decipher the relative influence of solid-state reordering versus recrystallization and consequently offer an improved understanding of the mechanisms involved. The material studied was derived from two deeply buried successions (Jurassic-Ediacaran) drilled in the central Sichuan Basin of South China. The calcite and dolomite minerals from these cores were separated using buffered acetic acid, and based on a two-component mixing model, the carbon, oxygen and clumped isotopic (Δ47) compositions of the two endmembers were determined. Based on an evaluation of solid-state reordering models, we conclude that micritic carbonates (dolomite and calcite) from the Jurassic to the Cambrian have been altered during burial by the geothermal gradient as determined by vitrinite reflectance. The Ediacaran micritic dolomite records a hydrothermal event in the transition between the Ediacaran and Cambrian. In contrast, the clumped isotopic temperature of Ediacaran saddle dolomites reflects subsequent hydrothermal activity during the Silurian and Devonian and shows compositional variations controlled by cooling rates. This study highlights the utility of the theoretical framework based on paired dolomite and calcite records to untangle overprinted signals of clumped isotopes in ancient carbonate rocks and gives insight to better understand the complexity of alteration processes in deeply burial carbonate successions.