A comprehensive compartment model is presented for PFAS retention that incorporates all potential processes relevant for transport in source zones. Miscible-displacement experiments were conducted to investigate separately the impact of adsorption at the air-water and decane- water interfaces on PFAS retention and transport. Two porous media were used, a quartz sand and a soil, and perfluorooctanesulfonic acid (PFOS) was used as the model PFAS. The breakthrough curves for transport under water-unsaturated conditions were shifted noticeably rightward (delayed arrival) compared to the breakthrough curves for saturated conditions, indicating greater retardation due to adsorption at the air-water or decane-water interface. The retardation factor was 7 for PFOS transport in the sand for the air-water system, compared to 1.8 for saturated conditions. PFOS retardation factors for transport in the soil were 7.3 and 3.6 for unsaturated (air-water) vs saturated conditions. Air-water interfacial adsorption is a significant source of retention for PFOS in these two systems, contributing more than 80% of total retention for the sand and 32% for the soil. For the experiments conducted with decane residual emplaced within the sand, adsorption at the decane-water interface contributed more than 70% to total retention for PFOS transport. Methods to determine or estimate key distribution variables are presented for parameterization of the model. Predicted retardation factors were similar to the measured values, indicating that the conceptual model provided adequate representation of the relevant retention processes and that the parameter estimation methods produced reasonable values. The results of this work indicate that adsorption by fluid-fluid interfaces in variably saturated porous media can be a significant retention process for PFAS that should be considered when characterizing their transport and fate behavior in source zones.

The objective of this research was to examine the influence of nonideal sorption/desorption on the transport of polyfluorinated alkyl substances (PFASs) in soil, with a specific focus on characterizing and quantifying potential extended, mass-transfer-limited elution behavior. Perfluorooctane sulfonic acid (PFOS) was used as a representative PFAS, and miscible-displacement experiments were conducted with two soils comprising contrasting geochemical properties. The influence of nonlinear, rate-limited, hysteretic, and irreversible sorption/desorption on transport was investigated through experiments and model simulations. The breakthrough curves measured for PFOS transport in the two soils were asymmetrical and exhibited extensive elution tailing, indicating that sorption/desorption was significantly nonideal. The widely used two-domain sorption kinetics model could not fully simulate the observed transport behavior, whereas a multirate model employing a continuous distribution of sorption domains was successful. The overall results indicated that sorption/desorption was significantly rate-limited and that nonlinear, hysteretic, and irreversible sorption/desorption had minimal impact on PFOS transport. Comparison of PFOS transport data to data reported for two hydrophobic organic contaminants (HOCs) showed that the HOCs exhibited much more extensive elution tailing, likely reflecting differences in sorption/desorption mechanisms. The projected influence of rate-limited sorption/desorption on PFOS transport at the field scale was investigated through simulation. The results of the study suggest that rate-limited sorption/desorption may affect the field-scale transport of PFOS and other PFAS for systems influenced by transient or short-residence-time conditions and in some cases could possibly increase the amount of flushing required to reduce PFOS concentrations to levels below those associated with human-health concerns.

This textbook integrates classic principles of flow through porous media with recently developed stochastic analyses to provide new insight on subsurface hydrology. Importantly, each of the authors has extensive experience in both academia and the world of applied groundwater hydrology. The book not only presents theories but also emphasizes their underlying assumptions, their limitations, and the potential pitfalls that may occur as a result of blind application of the theories as "cookiecutter" solutions. The book has been developed for advanced-level courses on groundwater fluid flow, hydraulics, and hydrogeology, in either civil/environmental engineering or geoscience departments. It is also a valuable reference text for researchers and professionals in civil/environmental engineering, geology, soil science, environmental science, and petroleum and mining engineering.

A series of flow-cell experiments was conducted to investigate the impact of organic-liquid distribution and flow-field heterogeneity on the relationship between source-zone mass removal and reductions in contaminant mass flux from the source zone. Changes in source-zone architecture were quantified using image analysis, allowing explicit examination of their impact on the mass-fluxreduction/mass-removal behavior. The results showed that there was minimal reduction in mass flux until a large fraction of mass was removed for systems wherein organic liquid was present solely as residual saturation in regions that were hydraulically accessible. Conversely, significant reductions in mass flux occurred with relatively minimal mass removal for systems wherein organic liquid was present at both residual and higher saturations. The latter systems exhibited multi-step mass-fluxreduction/mass-removal behavior, and characterization of the organic-liquid saturation distribution throughout flushing allowed identification of the cause of the nonideal behavior. The age of the source zone (time from initial emplacement to time of initial characterization) significantly influenced the observed mass-flux-reduction/mass-removal behavior. The results of this study illustrate the impact of both organic-liquid distribution and flow-field heterogeneity on mass-removal and mass-flux processes.

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