Abstract Per‐ and polyfluoroalkyl substances (PFAS) are surface‐active contaminants experiencing strong retention in vadose zones due to adsorption at air–water and solid–water interfaces. Leaching of PFAS through vadose zones poses great risks of groundwater contamination. Prior PFAS transport studies have focused on homogenous or layered vadose zones that significantly underrepresented the impact of preferential flow caused by soil heterogeneities—a primary factor known to dominantly control the subsurface transport of many contaminants. We conduct numerical simulations to investigate the impact of preferential flow on PFAS leaching in stochastically generated heterogeneous vadose zones. The simulations show that while shorter‐chain PFAS experience accelerated leaching similar to non‐surfactant solutes, the accelerated leaching of more surface‐active longer‐chain PFAS is uniquely amplified by 1.1–4.5 times due to reduced accessible air–water interfacial areas along preferential flow pathways. Our study highlights the criticality of characterizing soil heterogeneities for accurately predicting the leaching of long‐chain PFAS in vadose zones. 
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                            Sensitivity Analysis and Uncertainty Quantification of PFAS Fate and Transport in Heterogeneous Riparian Sediments
                        
                    
    
            Per- and polyfluoroalkyl substances (PFAS) are surface-active contaminants, which are detected in groundwater globally, presenting serious health concerns. The vadose zone and surface water are recognized as primary sources of PFAS contamination. Previous studies have explored PFAS transport and retention mechanisms in the vadose zone, revealing that adsorption at interfaces and soil/sediment heterogeneity significantly influences PFAS retention. However, our understanding of how surface water−groundwater interactions along river corridors impact PFAS transport remains limited. To analyze PFAS transport during surface water−groundwater interactions, we performed saturated−unsaturated flow and reactive transport simulations in heterogeneous riparian sediments. Incorporating uncertainty quantification and sensitivity analysis, we identified key physical and geochemical sediment properties influencing PFAS transport. Our models considered aqueous-phase transport and adsorption both at the air−water interface (AWI) and the solid-phase surface. We tested different cases of heterogeneous sediments with varying volume proportions of higher permeability sediments, conducting 2000 simulations for each case, followed by global sensitivity and response surface analyses. Results indicate that sediment porosities, which are correlated to permeabilities, are crucial for PFAS transport in riparian sediments during river stage fluctuations. High-permeable sediment (e.g., sandy gravel, sand) is the preferential path for the PFAS transport, and low-permeable sediment (e.g., silt, clay) is where PFAS is retained. Additionally, the results show that adsorption at interfaces (AWI and solid phase) has a small impact on PFAS retention in riparian environments. This study offers insights into factors influencing PFAS transport in riparian sediments, potentially aiding the development of strategies to reduce the risk of PFAS contamination in groundwater from surface water. 
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                            - Award ID(s):
- 2048452
- PAR ID:
- 10548348
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- ACS Earth and Space Chemistry
- Volume:
- 8
- Issue:
- 8
- ISSN:
- 2472-3452
- Page Range / eLocation ID:
- 1560 to 1573
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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