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.

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Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous‐flow, sand‐packed aquifer tank (8.2 m3) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench‐scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench‐ and pilot‐scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near‐source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre‐existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.

The microbial community response to a neat ethanol release (E100, 76 l) onto residual hydrocarbons in sandy soil was evaluated in a continuous-flow 8 m(3) pilot-scale aquifer tank, simulating a release at a bulk fuel terminal. Microbial genotypic shifts were assessed using quantitative real-time PCR analysis. High ethanol concentrations in the capillary fringe at potentially toxic levels, exceeding 100,000 mg l(-1), were tolerated by the microbial community. The high biochemical oxygen demand exerted by ethanol rapidly induced anaerobic conditions, and both methane production (up to 1.2 mg l(-1)) and growth of putative methanogenic Archaea (up to 10(6) gene copies per g of soil) were observed in shallow groundwater and soil samples 75 cm down gradient from the source. Aerobic conditions returned after ethanol was flushed out of the system, approximately 45 days after the spill (less than 7.5 pore volumes flushed). Total Bacteria growth coincided with ethanol migration and availability, which was restricted to a relatively thin layer at the capillary fringe and water table interface. The concentrations of bacteria harbouring the aerobic catabolic genes dmpN (coding for phenol hydroxylase) and to dC1 (coding for toluene dioxygenase) increased (up to 100x) down gradient from the source, likely as a result of both fortuitous growth on ethanol and on aromatic hydrocarbons mobilized by ethanol. Growth of hydrocarbon degraders was corroborated by denaturing gradient gel electrophoresis analysis showing proliferation of Azospirillum and Brevundimonas spp., which are bacteria commonly associated with microaerophilic hydrocarbon degradation. Nevertheless, the relative abundance of hydrocarbon-specific degraders (as a fraction of total Bacteria) decreased as other bacteria grew to a higher extent. Overall, the observed growth of hydrocarbon degraders suggests a potential enhancement in aerobic natural attenuation in shallow aquifers after ethanol and its degradation by-products are degraded or flushed from sites impacted by ethanol-blended fuels.