Juliana G. Freitas

Methane production and isotopic fingerprinting in ethanol fuel contaminated sites.

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = -11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from -20‰ to -30‰, while the methane from toluene (δ¹³C = -28.5‰) had a carbon isotopic signature of -55‰. The field samples had δ¹³C values varying over a wide range (-10‰ to -80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded.

Simulating the evolution of an ethanol and gasoline source zone within the capillary fringe.

Blending of ethanol into gasoline as a fuel oxygenate has created the scenario where inadvertent releases of E95 into soil previously contaminated by gasoline may remobilize these pre-existing NAPLs and lead to higher dissolved hydrocarbon (BTEX) concentrations in groundwater. We contribute to the development of a risk-based corrective action framework addressing this issue by conducting two laboratory experiments involving the release of ethanol into a gasoline source zone established in the capillary fringe. We then develop and apply the numerical model CompFlow Bio to replicate three specific experimental observations: (1) depression of the capillary fringe by the addition of the gasoline fuel mixture due to a reduction in the surface tension between the gas and liquid phases, (2) further depression of the capillary fringe by the addition of ethanol, and (3) remobilization of the gasoline fuel mixture LNAPL source zone due to the cosolvent behaviour of ethanol in the presence of an aqueous phase, as well as a reduction in the interfacial tension between the aqueous/non-aqueous phases due to ethanol. While the simulated collapse of the capillary fringe was not as extensive as that which was observed, the simulated and observed remobilized non-aqueous phase distributions were in agreement following ethanol injection. Specifically, injection of ethanol caused the non-aqueous phase to advect downwards toward the water table as the capillary fringe continued to collapse, finally collecting on top of the water table in a significantly reduced area exhibiting higher saturations than observed prior to ethanol injection. Surprisingly, the simulated ethanol and gasoline aqueous phase plumes were uniform despite the redistribution of the source zone. Dissolution of gasoline into the aqueous phase was dramatically increased due to the cosolvency effect of ethanol on the non-aqueous phase source zone. We advocate further experimental studies focusing on eliminating data gaps identified here, as well as field-scale experiments to address issues associated with ethanol-BTEX biodegradation and sorption within the development of a risk-based corrective action framework.

Migration and fate of ethanol-enhanced gasoline in groundwater: A modelling analysis of a field experiment

Ethanol use as a gasoline additive is increasing, as are the chances of groundwater contamination caused by gasoline releases involving ethanol. To evaluate the impact of ethanol on dissolved hydrocarbon plumes, a field test was performed in which three gasoline residual sources with different ethanol fractions (E0: no ethanol, E10: 10% ethanol and E95: 95% ethanol) were emplaced below the water table. Using the numerical model BIONAPL/3D, the mass discharge rates of benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene were simulated and results compared to those obtained from sampling transects of multilevel samplers. It was shown that ethanol dissolved rapidly and migrated downgradient as a short slug. Mass discharge of the hydrocarbons from the E0 and E10 sources suggested similar first-order hydrocarbon decay rates, indicating that ethanol from E10 had no impact on hydrocarbon degradation. In contrast, the estimated hydrocarbon decay rates were significantly lower when the source was E95. For the E0 and E10 cases, the aquifer did not have enough oxygen to support complete mineralization of the hydrocarbon compounds to the extent suggested by the field-based mass discharge. Introducing a heterogeneous distribution of hydraulic conductivity did little to overcome this discrepancy. A better match between the numerical model and the field data was obtained assuming partial degradation of the hydrocarbons to intermediate compounds. Besides depending on the ethanol concentration, the impact of ethanol on hydrocarbon degradation appears to be highly dependent on the availability of electron acceptors.

Oxygenated gasoline release in the unsaturated zone — Part 1: Source zone behavior

Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone.

Oxygenated gasoline release in the unsaturated zone, Part 2: Downgradient transport of ethanol and hydrocarbons.

In the event of a gasoline spill containing oxygenated compounds such as ethanol and MTBE, it is important to consider the impacts these compounds might have on subsurface contamination. One of the main concerns commonly associated with ethanol is that it might decrease the biodegradation of aromatic hydrocarbon compounds, leading to an increase in the hydrocarbon dissolved plume lengths. The first part of this study (Part 1) showed that when gasoline containing ethanol infiltrates the unsaturated zone, ethanol is likely to partition to and be retained in the unsaturated zone pore water. In this study (Part 2), a controlled field test is combined with a two-dimensional laboratory test and three-dimensional numerical modelling to investigate how ethanol retention in the unsaturated zone affects the downgradient behaviour of ethanol and aromatic hydrocarbon compounds. Ethanol transport downgradient was extremely limited. The appearance of ethanol in downgradient wells was delayed and the concentrations were lower than would be expected based on equilibrium dissolution. Oscillations in the water table resulted in minor flushing of ethanol, but its effect could still be perceived as an increase in the groundwater concentrations downgradient from the source zone. Ethanol partitioning to the unsaturated zone pore water reduced its mass fraction within the NAPL thus reducing its anticipated impact on the fate of the hydrocarbon compounds. A conceptual numerical simulation indicated that the potential ethanol-induced increase in benzene plume length after 20 years could decrease from 136% to 40% when ethanol retention in the unsaturated zone is considered.

Monitoring of sequential gasoline-ethanol releases using high frequency ground penetrating radar

Our hydrogeophysical field experiment evaluated the ability of high frequency (450 & 900 MHz) ground penetrating radar (GPR) to monitor sequential releases of gasoline followed by ethanol. The initial GPR images of the gasoline release zone reveal the development of shallow (i.e., above 10 ns) high reflectivity events and a significant velocity pull-up of an underlying stratigraphic reflection. Temporal evolution of the impacted zone reflectivity and the velocity pull-up indicate a progressive redistribution of gasoline in the impacted zone. GPR profiles obtained during frozen soil conditions clearly show that the presence of gasoline affects the freezing process. Preliminary analysis of the sequential ethanol release GPR data indicates an significant expansion of the impacted zone following this release.