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.
more »
« less
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.
more »
« less
- 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
More Like this
-
-
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.more » « less
-
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
-
In order to understand the extent to which airborne PFAS emission can impact soil and groundwater, we conducted a sampling campaign in areas of conserved forest lands near Bennington, VT/Hoosick Falls, NY. This has been home to sources of PFAS air-emissions from Teflon-coating operations for over 50 years. Since 2015, the Vermont and New York Departments of Environmental Conservation have documented ∼1200 residential wells and two municipal water systems across a 200 km 2 area contaminated with perfluorooctanoic acid (PFOA). Given the large areal extent of the plume, and the fact that much of the contaminated area lies up-gradient and across rivers from manufactures, we seek to determine if groundwater contamination could have resulted primarily from air-emission, land deposition, and subsequent leaching to infiltrating groundwater. Sampling of soils and groundwater in the Green Mountain National Forest (GMNF) downwind of factories shows that both soil and groundwater PFOA contamination extend uninterrupted from inhabited areas into conserved forest lands. Groundwater springs and seeps in the GMNF located 8 km downwind, but >300 meters vertically above factories, contain up to 100 ppt PFOA. Our results indicate that air-emitted PFAS can contaminate groundwater and soil in areas outside of those normally considered down-gradient of a source with respect to regional groundwater flow.more » « less
-
Per- and polyfluoroalkyl substances (PFAS) are a large group of man-made fluorinated organic chemicals that can accumulate in the environment. In water resource recovery facilities (WRRFs), some commonly detected PFAS tend to partition to and concentrate in biosolids where they can act as a source to ecological receptors and may leach to groundwater when land-applied. Although biosolids undergo some stabilization to reduce pathogens before land application, they still contain many microorganisms, contributing to the eventual decomposition of different components of the biosolids. This work demonstrates ways in which microbial weathering can influence biosolids decomposition, degrade PFAS, and impact PFAS partitioning in small-scale, controlled laboratory experiments. In the microbial weathering experiments, compound-specific PFAS biosolids–water partitioning coefficients ( K d ) were demonstrated to decrease, on average, 0.4 logs over the course of the 91 day study, with the most rapid changes occurring during the first 10 days. Additionally, the highest rates of lipid, protein, and organic matter removal occurred during the same time. Among the evaluated independent variables, statistical analyses demonstrated that the most significant solids characteristics that impacted PFAS partitioning were organic matter, proteins, lipids, and molecular weight of organics. A multiple linear regression model was built to predict PFAS partitioning behavior in biosolids based on solid characteristics of the biosolids and PFAS characteristics with a R 2 value of 0.7391 when plotting predicted and measured log K d . The findings from this work reveal that microbial weathering can play a significant role in the eventual fate and transport of PFAS and their precursors from biosolids.more » « less
An official website of the United States government

