Observations of mass fractionation of noble gases in synthetic methane hydrate

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings are presently dissociating and releasing methane and other gases to the oceanatmosphere system. A key challenge in assessing the susceptibility of gas hydrates to warming climate is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sublake and subseafloor sediments, coalbeds, and other sources. Carbon and deuterium stable isotopic data provide only a first-order characterization of methane sources, while gas hydrate can sequester any type of methane. Here, we investigate the possibility of exploiting the pattern of noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under careful laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.