Clumped isotope thermometry and catagenesis

Abstract:

Clumped- and site-specific isotopic compositions of organic compounds can constrain their formation temperatures, sources, and chemical reaction histories. The large number of isotopologues of organic molecules may allow for the isotopic composition of a single compound to illuminate many processes. For example, it is possible that clumping or site specific effects in different parts of the same molecule will differ in blocking temperature, such that a molecule’s full isotopic structure could simultaneously constrain conditions of biosynthesis, catagenic ‘cracking’, and storage in the crust.

Recent innovations in high-resolution mass spectrometry and methods of IR and NMR spectroscopy make it possible to explore these questions. Methane is the first organic molecule to have its clumped isotope geochemistry analyzed in a variety of natural environments and controlled experiments. Methane generated through catagenic cracking of kerogen and other organic matter forms in equilibrium with respect to isotopic clumping, and preserves that state through later storage or migration, up to temperatures of ~250 ˚C. This kinetic behavior permits a variety of useful geological applications. But it is unexpected because the bulk stable isotope composition of thermogenic methane is thought to reflect kinetic isotope effects on irreversible reactions. Our observations imply a new interpretation of the chemical physics of catagenic methane formation.

Additional instrument and methods developments are currently extending the measurement of isotopic clumping and position specific effects to larger alkanes, other hydrocarbon compounds, and amino acids. These measurements will ultimately expand our capacity to understand the formational conditions and fates of organic molecules in high- and low-temperature environments through geological time.