Fate and transport of per- and polyfluoroalkyl substances (PFASs) in the vadose zone

Per- and polyfluoroalkyl substances (PFASs) are a heterogeneous group of persistent organic pollutants that have been detected in various environmental compartments around the globe. Emerging research has revealed the preferential accumulation of PFASs in shallow soil horizons, particularly at sites impacted by firefighting activities, agricultural applications, and atmospheric deposition. Once in the vadose zone, PFASs can sorb to soil, accumulate at interfaces, become volatilized, be taken up in biota, or leach to the underlying aquifer. At the same time, polyfluorinated precursor species may transform into highly recalcitrant perfluoroalkyl acids, changing their chemical identity and thus transport behavior along the way. In this review, we critically discuss the current state of the knowledge and aim to interconnect the complex processes that control the fate and transport of PFASs in the vadose zone. Furthermore, we identify key challenges and future research needs. Consequently, this review may serve as an interdisciplinary guide for the risk assessment and management of PFAS-contaminated sites.