Methane bioattenuation and implications for explosion risk reduction along the groundwater to soil surface pathway above a plume of dissolved ethanol

Fuel ethanol releases can stimulate methanogenesis in impacted aquifers, which could pose an explosion risk if methane migrates into enclosed spaces where ignitable conditions exist. To assess this potential risk, a flux chamber was emplaced on a pilot-scale aquifer exposed to continuous release (21 months) of an ethanol solution (10% v:v) that was introduced 22.5 cm below the water table. Despite methane concentrations within the ethanol plume reaching saturated levels (20-23 mg/L), the maximum methane concentration reaching the chamber (21 ppm(v)) was far below the lower explosion limit in air (50,000 ppm(v)). The low concentrations of methane observed in the chamber are attributed to methanotrophic activity, which was highest in the capillary fringe. This was indicated by methane degradation assays in microcosms prepared with soil samples from different depths, as well as by PCR measurements of pmoA, which is a widely used functional gene biomarker for methanotrophs. Simulations with the analytical vapor intrusion model "Biovapor" corroborated the low explosion risk associated with ethanol fuel releases under more generic conditions. Model simulations also indicated that depending on site-specific conditions, methane oxidation in the unsaturated zone could deplete the available oxygen and hinder aerobic benzene biodegradation, thus increasing benzene vapor intrusion potential. Overall, this study shows the importance of methanotrophic activity near the water table to attenuate methane generated from dissolved ethanol plumes and reduce its potential to migrate and accumulate at the surface.