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.

Microbial community response to a release of neat ethanol onto residual hydrocarbons in a pilot-scale aquifer tank.

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.

Fuel-grade ethanol transport and impacts to groundwater in a pilot-scale aquifer tank.

Fuel-grade ethanol (76L of E95, 95%v/v ethanol, 5%v/v hydrocarbon mixture as a denaturant) was released at the water table in an 8150-L continuous-flow tank packed with fine-grain masonry sand. Ethanol, which is buoyant and hygroscopic, quickly migrated upwards and spread laterally in the capillary zone. Horizontal migration of ethanol occurred through a shallow thin layer with minimal vertical dispersion, and was one order of magnitude slower than the preceding bromide tracer. Dyes, one hydrophobic (Sudan-IV) and one hydrophilic (Fluorescein) provided evidence that the fuel hydrocarbons phase separated from the E95 mixture as ethanol was diluted by pore water and its cosolvent effect was diminished. Most of the added ethanol (98%) was recovered in the effluent wells that captured the flow through the high water content regions above the water table. Complementary bench-scale 2-D visualization experiments with E95 confirmed hydrocarbon phase separation, residual NAPL formation and migration within the capillary fringe. These results corroborate previous bench-scale studies showing that ethanol has high affinity for vadose-zone pore water and can migrate through the capillary zone. The pilot-scale tank experiment provides the first hydrocarbon and ethanol concentration measurements (and thus, quantification of impacts to groundwater quality) from a subsurface spill of E95 in a well-characterized system with a well-defined source. It also provides the first quantitative near-field-scale evidence that capillarity can significantly retard the vertical dispersion and horizontal advection of ethanol. Such effects could be important determinants of the extent of ethanol migration and longevity as well as groundwater impacts.