Novel approaches for quantifying source zone natural attenuation of fossil and alternative fuels

Natural attenuation represents an environmentally and economically sustainable means to manage contaminants in situ. To assess potential human and environmental risks associated with this strategy, there is a need to characterize the extent of contaminant containing source zones. Moreover, to obtain public and regulatory support, there is a need to demonstrate that mass losses are occurring. However, quantifying the extent and rate of natural attenuation under field conditions remain challenging. Here a novel approach for assessing and monitoring sites impacted by hydrocarbon and ethanol-blended fuels using surficial gas effluxes is developed. The approach is tested at several sites including those impacted by a crude oil pipeline rupture, ethanol-blended fuel train car derailments, and historic refinery operations. The approach was refined through inclusion of isotopic measurements, comparison to other approaches for monitoring microbial activity, and evaluation of seasonal dynamics and microbial communities. Process-based reactive transport modeling was used to integrate and interpret field data and develop and illustrate a more robust conceptual model of the processes occurring at the different field sites. Results demonstrate that surficial gas effluxes are able to both delineate contaminant containing source zones, and distinguish between the rates of natural soil respiration and contaminant mineralization. In scenarios where methane oxidation goes to completion, carbon dioxide fluxes are sufficient for evaluating natural attenuation rates; when methane escapes oxidation, measurements of methane fluxes are also needed. Results also demonstrated that measurement of radiocarbon is particularly useful for determining the contribution of contaminant degradation to the measured efflux. Comparison of seasonal dynamics showed that both biological and physical parameters must be considered when quantifying average annual contaminant degradation rates while comparison to other approaches for measuring microbial activity showed good correlations with gas effluxes. Comparison across the field sites investigated, showed degradation rates were relatively high at ethanol-blended fuel release sites. In-depth microbiological evaluation of microbial communities at one ethanol-blended fuel release site showed a substantial change in the microbial community associated with the release. Overall, the novel methods provide a useful approach for assessing the extent and rate of natural attenuation at hydrocarbon contaminated field sites.Science, Faculty ofEarth, Ocean and Atmospheric Sciences, Department ofGraduat