The geochemistry of methane isotopologues

Abstract

This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of ¹²CH₄, ¹³CH₄, ¹²CH₃D, and ¹³CH₃D record the formation, transport, and breakdown of methane in selected settings. Chapter 2 reports precise determinations of ¹³CH₃D, a "clumped" isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of ¹³CH₃D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped- and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H₂ and the reversibility of microbially-mediated methanogenesis in the environment. Determination of ¹³CH₃D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C-H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow- and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300 °C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O₂ by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of ¹³C/¹²C and D/H isotope fractionation factors alone.