Biodiesel presence in the source zone hinders aromatic hydrocarbons attenuation in a B20-contaminated groundwater.

The behavior of biodiesel blend spills have received limited attention in spite of the increasing and widespread introduction of biodiesel to the transportation fuel matrix. In this work, a controlled field release of biodiesel B20 (100L of 20:80 v/v soybean biodiesel and diesel) was monitored over 6.2years to assess the behavior and natural attenuation of constituents of major concern (e.g., BTEX (benzene, toluene, ethyl-benzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons)) in a sandy aquifer material. Biodiesel was preferentially biodegraded compared to diesel aromatic compounds with a concomitant increase in acetate, methane (near saturation limit (≈22mgL-1)) and dissolved BTEX and PAH concentrations in the source zone during the first 1.5 to 2.0years after the release. Benzene and benzo(a)pyrene concentrations remained above regulatory limits in the source zone until the end of the experiment (6.2years after the release). Compared to a previous adjacent 100-L release of ethanol-amended gasoline, biodiesel/diesel blend release resulted in a shorter BTEX plume, but with higher residual dissolved hydrocarbon concentrations near the source zone. This was attributed to greater persistence of viscous (and less mobile) biodiesel than the highly-soluble and mobile ethanol in the source zone. This persistence of biodiesel/diesel NAPL at the source zone slowed BTEX and PAH biodegradation (by the establishment of an anaerobic zone) but reduced the plume length by reducing mobility. This is the first field study to assess biodiesel/diesel blend (B20) behavior in groundwater and its effects on the biodegradation and plume length of priority groundwater pollutants.

BTEX plume dynamics following an ethanol blend release: geochemical footprint and thermodynamic constraints on natural attenuation.

In this 10 year study, Brazilian gasoline (100 L, containing 24% ethanol by volume) was released to a sandy aquifer to evaluate the natural attenuation of benzene, toluene, ethylbenzene, and total xylenes (BTEX) in the presence of ethanol. Groundwater concentrations of BTEX, ethanol, and degradation products (e.g., acetate and methane) were measured over the entire plume using an array of monitoring well clusters, to quantify changes in plume mass and region of influence. Ethanol biodegradation coincided with the development of methanogenic conditions while acetate (a common anaerobic metabolite) accumulated. The benzene plume expanded beyond the 30 m long monitored area and began to recede after 2.7 years, when ethanol had disappeared. Theoretical calculations suggest that the transient accumulation of acetate (up to 166 mg L(-1)) may have hindered the thermodynamic feasibility of benzene degradation under methanogenic conditions. Yet, benzene removal proceeded relatively fast compared to literature values (and faster than the alkylbenzenes present at this site) after acetate concentrations had decreased below inhibitory levels. Thus, site investigations of ethanol blend releases should consider monitoring acetate concentrations. Overall, this study shows that inhibitory effects of ethanol and acetate are relatively short-lived, and demonstrates that monitored natural attenuation can be a viable option to deal with ethanol blend releases.