PNNL

Abstract

Volcanism and post-magmatism contribute both significant annual CH4 fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit methane in addition to other greenhouse gases (e.g. carbon dioxide) but the ultimate source of this methane flux has not been elucidated. Here we use dual stable isotope analysis (2H and 13C) of CH4(g) sampled from ten high-temperature geothermal pools in Yellowstone National Park to show that the predominant flux of CH4(g) is abiotic. The average 13C and 2H values of CH4(g) emitted from hot springs (-26.7 (±2.4) and -236.9 (±12.0) ‰, respectively) are not consistent with biotic (microbial or thermogenic) methane sources, but are within previously reported ranges for abiotic methane production. Correlation between 13C-CH4 and 13C-dissolved inorganic C (DIC) also suggests that CO2 is a parent C source for the observed CH4(g). Moreover, CH4-CO2 isotopic geothermometry was used to estimate CH4(g) formation temperatures ranging from ~ 250 - 350 °C, which is just below the temperature estimated for the hydrothermal reservoir and consistent with the hypothesis that subsurface, rock-water interactions are responsible for large methane fluxes from this volcanic system. An understanding of conditions leading to the abiotic production of methane and associated isotopic signatures are central to understanding the evolutionary history of deep carbon sources on Earth.