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

Fuel-grade ethanol (76 L 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.