[1] A mathematical model was developed to evaluate the effect of the common fuel additive ethanol on benzene fate and transport in fuel-contaminated groundwater and to discern the most influential benzene plume elongation mechanisms. The model, developed as a module for the Reactive Transport in 3 Dimensions (RT3D) model, includes commonly considered fate and transport processes (advection, dispersion, adsorption, biodegradation, and depletion of molecular oxygen during biodegradation) and substrate interactions previously not considered (e.g., a decrease in the specific benzene utilization rate due to metabolic flux dilution and/or catabolite repression) as well as microbial population shifts. Benzene plume elongation predictions, based on literature model parameters, were on the order of 40% for a constant source of E10 gasoline (10% vol/vol ethanol), which compares favorably to field observations. For low benzene concentrations (<1 mg/L), oxygen depletion during ethanol degradation was the principal mechanism hindering benzene natural attenuation. For higher benzene concentrations (exerting an oxygen demand higher than the available dissolved oxygen), metabolic flux dilution was the dominant plume elongation process. If oxygen were not limiting, as might be the case in zones undergoing aerobic biostimulation, model simulations showed that microbial growth on ethanol could offset negative substrate interactions and enhance benzene degradation, resulting in shorter plumes than baseline conditions without ethanol.Citation: Gomez, D. E., P. C. de Blanc, W. G. Rixey, P. B. Bedient, and P. J. J. Alvarez (2008), Modeling benzene plume elongation mechanisms exerted by ethanol using RT3D with a general substrate interaction module, Water Resour. Res., 44, W05405,

US EPA and many state regulatory agency guidance documents recommend belowfoundation vapor sampling as a key element of site investigations to determine if vapor migration from underlying soil into buildings is a completed exposure pathway (USEPA, 2002; WIDHFS, 2003; San Diego County, 2004; PADEP, 2004). If volatile organic compounds (VOCs) are detected below the building foundation, then VOC migration from the subsurface is assumed to be occurring, and further investigation is needed to determine the extent of the VOC impact. These guidance documents are predicated on the assumption that VOCs detected in below-foundation samples have originated from deeper within the subsurface. However, detection of VOCs in below-foundation vapor samples alone is not sufficient to conclude that the VOCs are migrating from the subsurface upward towards a building. VOCs detected in below-foundation vapor samples can originate from indoor sources, migrating down through the slab by diffusion or advection. Commonly referenced conceptual models for vapor intrusion address VOC migration from the subsurface into buildings but do not consider the potential for VOC migration from buildings into the subsurface (USEPA, 2002;Johnson and Ettinger, 1991;Parker, 2003). The advective and diffusive forces that lead to the migration of VOCs from the subsurface into buildings are equally likely to result in the migration of VOCs from buildings into the subsurface when pressure or concentration gradients support such migration. In this paper we present: i) pressure gradient measurements indicating bidirectional advective flow across building foundations, ii) simple modeling indicating that indoor sources of VOCs may cause subsurface impacts through advection across the building foundation, and iii) field data from a site where indoor sources rather than subsurface contamination were the source of VOCs detected in below-foundation vapor samples.

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