Per- and polyfluorinated alkyl substances (PFAS) are an environmentally persistent group of chemicals that can pose an imminent threat to human health through groundwater and surface water contamination. In this review, we evaluate the subsurface behavior of a variety of PFAS chemicals with a focus on aqueous film forming foam (AFFF) discharge sites. AFFF is the primary PFAS contamination risk at sites such as airports and military bases due to use as a fire extinguisher. Understanding the fate and transport of PFAS in the subsurface environment is a multifaceted issue. This review focuses on the role of adsorbent, adsorbate, and aqueous solution in the fate and transport of PFAS chemicals. Additionally, other hydrogeological, geochemical, ecological factors such as accumulation at air–water interfaces, subsurface heterogeneity, polyfluorinated PFAS degradation pathways, and plant interactions are discussed. This review also examines several case studies at AFFF discharge sites in order to examine if the findings are consistent with the broader PFAS literature. We present the most crucial future research directions and trends regarding PFAS and provide valuable insights into understanding PFAS fate and transport at AFFF discharge sites. We suggest a more comprehensive approach to PFAS research endeavors that accounts for the wide variety of environmental variables that have been shown to impact PFAS fate and transport.

Groundwater-surface water interaction (hyporheic exchange) is critical in numerous hydrogeochemical processes; however, hyporheic exchange is difficult to characterize due to the various spatial (e.g., sedimentary architecture) and temporal (e.g., stage fluctuations) variables that influence it. This interdisciplinary study brings forth novel insights by integrating various methodologies including geophysical surveys, physical and chemical sediment characterization, and water chemistry analysis to explore the interplay of the numerous facets governing hyporheic zone processes within a compound bar deposit. The findings reveal distinct sedimentary facies and geochemical zones within the compound bar, driven by the sedimentary architecture. Cross-bar channel fills are identified as critical structures influencing hydrogeochemical dynamics, acting as baffles to groundwater flow and modulating nutrient transformations. Geophysical imaging and hydrogeochemical analyses highlight the complex interplay between sediment characteristics and subsurface hydraulic connectivity, emphasizing the role of sediment heterogeneity in controlling hyporheic exchange and solute mixing. The study concludes that sediment heterogeneity, particularly the presence of cross-bar channel fills, plays a pivotal role in the hydrogeochemical dynamics of the hyporheic zone. These structures significantly influence hyporheic flow paths, solute residence times, and nutrient cycling, underscoring the necessity to consider the fine-scale sedimentary architecture in models of hyporheic exchange. The findings contribute to a deeper understanding of riverine ecosystem processes, offering insights that can inform management strategies for water quality and ecological integrity.