Aqueous film-forming foams (AFFFs) have been used since the 1970s to suppress liquid fuel fires; there are thousands of sites impacted by PFAS. Although the DoD’s legacy use of AFFF included various fluorotelomer-based formulations, the vast majority of DoD’s environmental liability likely results from the use of perfluorooctanesulfonic acid (PFOS)-based AFFF.
Due to their chemical structure, PFAS are very stable in the environment and are relatively resistant to biodegradation, photo-oxidation, direct photolysis, and hydrolysis. Any quantitative approach to analyzing the behavior of PFAS in treatment systems or in the environment requires knowledge of the distribution of the PFAS of interest in the multiple phases that comprise the system being considered. For example, a successful treatment system should be designed such that the PFAS of interest is primarily associated with the treatment phase and not sequestered in other phases in the system such as soil or other matrix materials. This requires that the speciation the PFAS be considered. All of this information is required to build a reliable model of PFAS fate and transport within any media. If PFAS is primarily associated with stationary phases, its mobility is much less than if it is in the vapor or aqueous phases. Evaluation of the bioaccumulation and toxicity of PFAS also require consideration of its phase distribution and speciation. PFAS bound to phases not exposed to the organism or distributed among multiple chemical species will accumulate differently in organisms depending on the bioavailability of each species and their toxic potential. This is not a new requirement for understanding the transport, transformations, and toxicity of environmental contaminants, but the challenges and unknowns are extreme for PFAS.
Investigations of DoD sites impacted by AFFF have indicated significant retention of PFAS in the vadose zone, particularly in unsaturated soil and deeper horizons. The longevity of PFAS in source zones is a critical component of assessing management and remediation approaches for AFFF-impacted sites; significant uncertainties remain with respect to the key processes impacting the distribution and fluxes of AFFF-derived PFAS during vertical migration (and lateral dispersion) to groundwater. Given the diversity of hydrogeologic and climatic conditions throughout AFFF-impacted sites, it is likely that migration and flux of water, and associated PFAS transport, are highly variable. If quantitative models of source zone longevity are to be developed, there is a need to assess and validate the fundamental processes and parameters impacting both water and PFAS fluxes through the vadose zone. To date, field-scale modeling of PFAS fate and transport in the vadose zone has been limited, in particular for multi-dimensional systems that are likely to be important due to the potential effects of PFAS and AFFF constituents on water flow and retention. There is also a lack of model simulations that directly link PFAS mass discharge from the vadose zone with groundwater flow and transport, making it difficult to simulate the effects of fluctuating water tables and potential impacts on downgradient receptors (e.g., residential wells, surface water bodies). Further, most of the model simulations conducted to date focus on single PFAS, and the effects of potential competitive or synergistic interactions between multiple PFAS are not considered.
Several recent studies have shown that PFAS release from soils is a rate-limited process, and equilibrium models may be inappropriate for describing PFAS transport under many relevant field conditions. These rate limitations can be due to mechanisms at the grain scale, and/or due to mass transfer between advective and non-advective domains. While these rate-limited processes are recognized, there are several fundamental issues that remain unresolved.