Stable carbon and oxygen isotopes (δ18O and δ13C values) and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years. As valuable as these insights have been, many problems regarding the interpretation of geochemical signals within mature rocks remain. For example, while the δ18O values of carbonate rocks are dependent both upon the temperature and the δ18O value of the fluid, and additional information including trace element composition aids in interpreting such signals, direct evidence of either the temperature or the composition of the fluids is required. Such information can be obtained by analysing the δ18O value of any fluid inclusions or by measuring the temperature using a method such as the ‘clumped’ isotope technique. Such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well-known tendency for δ18O values of carbonate rocks to decrease with increasing age. Unlike the δ18O, δ13C values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time. However, many studies have not sufficiently emphasized the effects of diagenesis and other post-depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored. Finally, many additional proxies are poised to contribute to the interpretation of carbonate diagenesis. Although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods, care should be taken to understand both old and new proxies before applying them to the ancient record.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/sed.12205

The geochemistry of carbonate diagenesis: The past, present and future

As the search for Earth-like exoplanets gathers pace, in order to understand them, we need comprehensive theories for how planetary atmospheres form and evolve. Written by two well-known planetary scientists, this text explains the physical and chemical principles of atmospheric evolution and planetary atmospheres, in the context of how atmospheric composition and climate determine a planet's habitability. The authors survey our current understanding of the atmospheric evolution and climate on Earth, on other rocky planets within our Solar System, and on planets far beyond. Incorporating a rigorous mathematical treatment, they cover the concepts and equations governing a range of topics, including atmospheric chemistry, thermodynamics, radiative transfer, and atmospheric dynamics, and provide an integrated view of planetary atmospheres and their evolution. This interdisciplinary text is an invaluable one-stop resource for graduate-level students and researchers working across the fields of atmospheric science, geochemistry, planetary science, astrobiology, and astronomy.

Atmospheric Evolution on Inhabited and Lifeless Worlds

Temperatures and oxygen isotopic composition of Phanerozoic oceans

Elemental proxies for paleosalinity analysis of ancient shales and mudrocks

Phanerozoic Paleotemperatures: The Earth’s Changing Climate during the Last 540 million years

Temperature limits for preservation of primary calcite clumped isotope paleotemperatures

Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

We utilize carbonate clumped isotope thermometry to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Permian Palmarito Formation, Venezuela, and the Carboniferous Bird Spring Formation, Nevada, USA. Carbonate components in the Palmarito Formation, buried to ∼4 km depth, yield statistically indistinguishable clumped isotope temperatures [ T (Δ47)] ranging from 86 to 122 °C. Clumped isotope temperatures of components in the more deeply buried Bird Spring Formation (>5 km) range from ∼100 to 165 °C and differ by component type, with brachiopods and pore-filling cements yielding the highest T (Δ47) (mean = 153 and 141 °C, respectively) and crinoids and host rock yielding significantly cooler T (Δ47) (mean = 103 and 114 °C). New high-resolution thermal histories are coupled with kinetic models to predict the extent of solid-state C-O bond reordering during burial and exhumation for both sites. Application of these models, termed “THRMs” (thermal history reordering models), suggests that brachiopods in the Palmarito Formation experienced partial bond reordering without complete equilibration of clumped isotopes at maximum burial temperature. In contrast, clumped isotope bonds of brachiopods from the Bird Spring Formation completely equilibrated at maximum burial temperature, and now reflect blocking temperatures achieved during cooling. The 40–50-°C-cooler clumped isotope temperatures measured in Bird Spring Formation crinoids and host rock can be explained by recrystallization and cementation during shallow burial combined with a greater inherent resistance to solid-state reordering than brachiopods.

Clumped isotope thermometry in deeply buried sedimentary carbonates: The effects of bond reordering and recrystallization

Carbonates form ubiquitously throughout the history of deposition, burial, and uplift of basins. As such, they potentially record the environmental conditions at the time of formation. Carbonate clumped isotopes provide the temperature of precipitation but can be internally reordered if the host rock is exposed to elevated temperatures over geologic time scales. Here, we exploited this kinetic behavior by analyzing multiple generations of cements that capture the range of environments experienced by the El Abra Formation from eastern Mexico. From this, we developed a quantitative diagenetic history for these different phases of cementation. We observed a 70 °C range in clumped isotope temperatures from 64 °C to 134 °C for these cements, which is not compatible with their inferred precipitation environments. This suggests that bond reordering occurred during burial but did not fully reorder all cements to a common apparent temperature. We reconstructed original cement growth temperatures and the isotopic signature of the parent fluids to show that precipitation from a marine pore fluid began at 125 Ma, contemporaneous with deposition, and continued throughout burial to temperatures of at least 138 °C at 42 Ma. We show that precipitation of equant cements, which occluded 90% of the pore space, was coincident with Laramide-related burial to depths greater than 3800 m. A U-Pb age of diagenetic calcite of 77.1 ± 3.6 Ma provides independent support for our estimates of the absolute timing of precipitation of two distinct phases of the paragenesis. This is the first demonstration of the utility of integrating U-Pb age dating with reordered clumped isotope temperatures to provide quantitative constraints on the time-temperature history of cementation. Such information may ultimately lead to advances in our understanding of the formational environments and geological processes that drive diagenesis in carbonates for temperatures below the clumped isotope “blocking temperature.”

/pdf/deciphering-the-diagenetic-history-of-the-el-abra-formation-3jlesg2tjv.pdf

Brock J. Shenton

Papers

Temperature limits for preservation of primary calcite clumped isotope paleotemperatures

Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

Clumped isotope thermometry in deeply buried sedimentary carbonates: The effects of bond reordering and recrystallization

Deciphering the diagenetic history of the El Abra Formation of eastern Mexico using reordered clumped isotope temperatures and U-Pb dating