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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Challenges and opportunities for porous media research to address PFAS groundwater contamination
Per- and polyfluoroalkyl substances (PFAS) have become one of the most important contaminants due to their ubiquitous presence in the environment and potentially profound impacts on human health and the environment even at parts per trillion (ppt) concentration levels. A growing number of field investigations have revealed that soils act as PFAS reservoirs at many contaminated sites, with significant amounts of PFAS accumulating over several decades. Because PFAS accumulated in soils may migrate downward to contaminate groundwater resources, understanding the fate and transport of PFAS in soils is of paramount importance for characterizing, managing, and mitigating long-term groundwater contamination risks.Many PFAS are surfactants that adsorb at air–water and solid–water interfaces, which leads to complex transport behaviors of PFAS in soils. Concomitantly, PFAS present in porewater can modify surface tension and other interfacial properties, which in turn may impact variably saturated flow and PFAS transport. Furthermore, some PFAS are volatile (i.e., can migrate in the gas phase) and/or can transform under environmental conditions into persistent PFAS. These nonlinear and coupled processes are further complicated by complexities of the soil environment such as thin water films, spatial heterogeneity, and complex geochemical conditions.In this commentary, we present an overview of the current challenges in understanding the fate and transport of PFAS in the environment. Building upon that, we identify a few potential areas where porous media research may play an important role in addressing the problem of PFAS contamination in groundwater.
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- Award ID(s):
- 2237015
- PAR ID:
- 10587395
- Publisher / Repository:
- InterPore
- Date Published:
- Journal Name:
- InterPore Journal
- Volume:
- 1
- Issue:
- 2
- ISSN:
- 3007-410X
- Page Range / eLocation ID:
- ipj240824 to 2
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Per‐ and poly‐fluoroalkyl substances (PFAS) are interfacially‐active contaminants that adsorb at air‐water interfaces (AWIs). Water‐unsaturated soils have abundant AWIs, which generally consist of two types: one is associated with the pendular rings of water between soil grains (i.e., bulk AWI) and the other arises from the thin water films covering the soil grains. To date, the two types of AWIs have been treated the same when modeling PFAS retention in vadose zones. However, the presence of electrical double layers of soil grain surfaces and the subsequently modified chemical potential of PFAS at the AWI may significantly change the PFAS adsorption at the thin‐water‐film AWI relative to that at the bulk AWI. Given that thin water films contribute to over 90% of AWIs in the vadose zone under many field‐relevant wetting conditions, it is critical to quantify the potential anomalous adsorption of PFAS at the thin‐water‐film AWI. We develop a thermodynamic‐based mathematical model to quantify this anomalous adsorption. The model couples the chemical equilibrium of PFAS with the Poisson‐Boltzmann equation that governs the distribution of electrical potential in a thin water film. Our model analyses suggest that PFAS adsorption at thin‐water‐film AWI can deviate significantly (up to 82%) from that at bulk AWIs. The deviation increases for lower porewater ionic strength, thinner water film, and higher soil grain surface charge. These results highlight the importance of accounting for the anomalous adsorption of PFAS at the thin‐water‐film AWI when modeling PFAS fate and transport in the vadose zone.more » « less
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