Modeling Dissolution of Soluble Compounds from Multicomponent NAPL Using a Desorption Approximation.

Groundwater professionals require methods to estimate the potential time required to achieve remedial goals, including locations within and downgradient of zones containing nonaqueous phase liquids (NAPLs). NAPLs have long been recognized as persistent contaminant sources to groundwater. Dissolution of multicomponent NAPLs is particularly complex, and numerical models that explicitly simulate it are not widely available. This study introduces an equilibrium partitioning approximation to simulate the dissolution of the most soluble chemical components from multicomponent NAPL containing a significant fraction of relatively insoluble mass. The effective distribution coefficient that describes depletion of a specific compound from NAPL is estimated based on the properties of the NAPL and the porous medium. This study also presents numerical modeling results that support the utility of the method, with verification using published empirical data collected during dissolution of residual coal tar in a controlled laboratory sand tank experiment. The numerical modeling method uses equilibrium partitioning as an approximation and matched the concentrations of the two most soluble NAPL components in and downgradient of the NAPL zone with reasonable accuracy. The results suggest that the method should be useful for screening-level assessments and can be adapted to compare relative groundwater restoration timeframes of select NAPL components for various remedial alternatives.

Modeling PFAS Fate and Transport in Groundwater, with and Without Precursor Transformation.

Groundwater professionals require tools to evaluate a variety of technical issues related to per- and polyfluoroalkyl substances (PFAS). These include the potential impact of PFAS precursors on groundwater plumes of perfluoroalkyl acids (PFAAs). Numerical modeling results show that, by adjusting the mass loading rate, source zones with or without a precursor can produce similar PFAA plumes. However, if a precursor is present, it can impact PFAA plume concentrations and extend PFAA plume durations by decades. Additional research regarding in situ precursor transformation rates-and improvements in source area characterization-will further advance the predictive value of modeling.

Matrix diffusion-derived plume attenuation in fractured bedrock.

Matrix diffusion can attenuate the rate of plume migration in fractured bedrock relative to the rate of ground water flow for both conservative and nonconservative solutes of interest. In a system of parallel, equally spaced constant aperture fractures subject to steady-state ground water flow and an infinite source width, the degree of plume attenuation increases with time and travel distance, eventually reaching an asymptotic level. The asymptotic degree of plume attenuation in the absence of degradation can be predicted by a plume attenuation factor, beta, which is readily estimated as R' (phi(m)/phi(f)), where R' is the retardation factor in the matrix, phi(m) is the matrix porosity, and phi(f) is the fracture porosity. This dual-porosity relationship can also be thought of as the ratio of primary to secondary porosity. Beta represents the rate of ground water flow in fractures relative to the rate of plume advance. For the conditions examined in this study, beta increases with greater matrix porosity, greater matrix fraction organic carbon, larger fracture spacing, and smaller fracture aperture. These concepts are illustrated using a case study where dense nonaqueous phase liquid in fractured sandstone produced a dissolved-phase trichloroethylene (TCE) plume approximately 300 m in length. Transport parameters such as matrix porosity, fracture porosity, hydraulic gradient, and the matrix retardation factor were characterized at the site through field investigations. In the fractured sandstone bedrock examined in this study, the asymptotic plume attenuation factors (beta values) for conservative and nonconservative solutes (i.e., chloride and TCE) were predicted to be approximately 800 and 12,210, respectively. Quantitative analyses demonstrate that a porous media (single-porosity) solute transport model is not appropriate for simulating contaminant transport in fractured sandstone where matrix diffusion occurs. Rather, simulations need to be conducted with either a discrete fracture model that explicitly incorporates matrix diffusion, or a dual-continuum model that accounts for mass transfer between mobile and immobile zones. Simulations also demonstrate that back diffusion from the matrix to fractures will likely be the time-limiting factor in reaching ground water cleanup goals in some fractured bedrock environments.