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==PFAS Transport and Fate==
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==Lysimeters for Measuring PFAS Concentrations in the Vadose Zone==  
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The transport and fate of Per- and Polyfluoroalkyl Substances (PFAS) in the environment is controlled by the nature of the PFAS source, characteristics of the individual PFAS, and environmental conditions where the PFAS are present. Transport, partitioning, and transformation are the primary processes controlling PFAS fate in the environment. PFAS compounds can also be taken up by both plants and animals, and in some cases, bioaccumulate through the food chain.
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[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] are frequently introduced to the environment through soil surface applications which then transport through the vadose zone to reach underlying groundwater receptors. Due to their unique properties and resulting transport and retention behaviors, PFAS in the vadose zone can be a persistent contaminant source to underlying groundwater systems. Determining the fraction of PFAS present in the mobile porewater relative to the total concentrations in soils is critical to understanding the risk posed by PFAS in vadose zone source areas. Lysimeters are instruments that have been used by agronomists and vadose zone researchers for decades to determine water flux and solute concentrations in unsaturated porewater. Lysimeters have recently been developed as a critical tool for field investigations and characterizations of PFAS impacted source zones.  
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Understanding PFAS transport and fate is necessary for evaluating the potential risk from a PFAS release and for predictions about PFAS occurrence, migration, and persistence, and about the potential vectors for exposure. This knowledge is important for site characterization, identification of potential sources of PFAS to the site, development of an appropriate conceptual site model (CSM), and selection and predicted performance of remediation strategies.  
 
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<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
  
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'''Related Article(s): '''
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'''Related Article(s):'''
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* [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
 
  
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'''Contributor(s): '''
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*[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
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Dr. Hunter Anderson and Dr. Mark L. Brusseau
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*[[PFAS Transport and Fate]]
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*[[PFAS Toxicology and Risk Assessment]]
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*[[Mass Flux and Mass Discharge]]
  
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'''Key Resource(s): '''
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'''Contributors:''' Dr. John F. Stults, Dr. Charles Schaefer
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*[https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf  Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC 2020.]<ref name="ITRC2020">Interstate Technology and Regulatory Council (ITRC), 2020. Technical/Regulatory Guidance: Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC, PFAS Team, Washington DC. [https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf  Free Download from ITRC].&nbsp;&nbsp; [[Media: ITRC_PFAS-1.pdf | Report.pdf]]</ref>
 
  
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*[[Media: Brusseau2018manuscript.pdf | Assessing the Potential Contributions of Additional Retention Processes to PFAS Retardation in the Subsurface. Brusseau 2018 (manuscript).]]<ref name="Brusseau2018">Brusseau, M.L., 2018. Assessing the Potential Contributions of Additional Retention Processes to PFAS Retardation in the Subsurface. Science of the Total Environment, 613-614, pp. 176-185. [https://doi.org/10.1016/j.scitotenv.2017.09.065 DOI: 10.1016/j.scitotenv.2017.09.065]&nbsp;&nbsp; [[Media: Brusseau2018manuscript.pdf | Author’s Manuscript]]</ref>
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'''Key Resources:'''
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*Assessment of PFAS in Collocated Soil and Porewater Samples at an AFFF-Impacted Source Zone: Field-Scale Validation of Suction Lysimeters<ref name="AndersonEtAl2022"/>
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*PFAS Concentrations in Soil versus Soil Porewater: Mass Distributions and the Impact of Adsorption at Air-Water Interfaces<ref name="BrusseauGuo2022"/>
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*Using Suction Lysimeters for Determining the Potential of Per- and Polyfluoroalkyl Substances to Leach from Soil to Groundwater: A Review<ref name="CostanzaEtAl2025"/>
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*Use of Lysimeters for Monitoring Soil Water Balance Parameters and Nutrient Leaching<ref name="MeissnerEtAl2020"/>
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*PFAS Porewater Concentrations in Unsaturated Soil: Field and Laboratory Comparisons Inform on PFAS Accumulation at Air-Water Interfaces<ref name="SchaeferEtAl2024"/>
  
 
==Introduction==
 
==Introduction==
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The transport and fate of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] is a rapidly evolving field of science, with many questions that are not yet resolved.  Much of the currently available information is based on a few well-studied PFAS compounds.  However, there is a large number and variety of PFAS with a wide range of physical and chemical characteristics that affect their behavior in the environment. The transport and fate of some PFAS could differ significantly from the compounds studied to date. Nevertheless, information about the behavior of some PFAS in the environment can be ascertained from the results of currently available research.  
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Lysimeters are devices that are placed in the subsurface above the groundwater table to monitor the movement of water through the soil<ref name="GossEhlers2009">Goss, M.J., Ehlers, W., 2009. The Role of Lysimeters in the Development of Our Understanding of Soil Water and Nutrient Dynamics in Ecosystems. Soil Use and Management, 25(3), pp. 213–223. [https://doi.org/10.1111/j.1475-2743.2009.00230.x doi: 10.1111/j.1475-2743.2009.00230.x]</ref><ref>Pütz, T., Fank, J., Flury, M., 2018. Lysimeters in Vadose Zone Research. Vadose Zone Journal, 17 (1), pp. 1-4. [https://doi.org/10.2136/vzj2018.02.0035 doi: 10.2136/vzj2018.02.0035]&nbsp; [[Media: PutzEtAl2018.pdf | Open Access Article]]</ref><ref name="CostanzaEtAl2025">Costanza, J., Clabaugh, C.D., Leibli, C., Ferreira, J., Wilkin, R.T., 2025. Using Suction Lysimeters for Determining the Potential of Per- and Polyfluoroalkyl Substances to Leach from Soil to Groundwater: A Review. Environmental Science and Technology, 59(9), pp. 4215-4229. [https://doi.org/10.1021/acs.est.4c10246 doi: 10.1021/acs.est.4c10246]</ref>. Lysimeters have historically been used in agricultural sciences for monitoring nutrient or contaminant movement, soil moisture release curves, natural drainage patterns, and dynamics of plant-water interactions<ref name="GossEhlers2009"/><ref>Bergström, L., 1990. Use of Lysimeters to Estimate Leaching of Pesticides in Agricultural Soils. Environmental Pollution, 67 (4), 325–347. [https://doi.org/10.1016/0269-7491(90)90070-S doi: 10.1016/0269-7491(90)90070-S]</ref><ref>Dabrowska, D., Rykala, W., 2021. A Review of Lysimeter Experiments Carried Out on Municipal Landfill Waste. Toxics, 9(2), Article 26. [https://doi.org/10.3390/toxics9020026 doi: 10.3390/toxics9020026]&nbsp; [[Media: Dabrowska Rykala2021.pdf | Open Access Article]]</ref><ref>Fernando, S.U., Galagedara, L., Krishnapillai, M., Cuss, C.W., 2023. Lysimeter Sampling System for Optimal Determination of Trace Elements in Soil Solutions. Water, 15(18), Article 3277. [https://doi.org/10.3390/w15183277 doi: 10.3390/w15183277]&nbsp; [[Media: FernandoEtAl2023.pdf | Open Access Article]]</ref><ref name="MeissnerEtAl2020">Meissner, R., Rupp, H., Haselow, L., 2020. Use of Lysimeters for Monitoring Soil Water Balance Parameters and Nutrient Leaching. In: Climate Change and Soil Interactions. Elsevier, pp. 171-205. [https://doi.org/10.1016/B978-0-12-818032-7.00007-2 doi: 10.1016/B978-0-12-818032-7.00007-2]</ref><ref name="RogersMcConnell1993">Rogers, R.D., McConnell, J.W. Jr., 1993. Lysimeter Literature Review, Nuclear Regulatory Commission Report Numbers: NUREG/CR--6073, EGG--2706. [https://www.osti.gov/] ID: 10183270. [https://doi.org/10.2172/10183270 doi: 10.2172/10183270]&nbsp; [[Media: RogersMcConnell1993.pdf | Open  Access Article]]</ref><ref>Sołtysiak, M., Rakoczy, M., 2019. An Overview of the Experimental Research Use of Lysimeters. Environmental and Socio-Economic Studies, 7(2), pp. 49-56. [https://doi.org/10.2478/environ-2019-0012 doi: 10.2478/environ-2019-0012]&nbsp; [[Media: SołtysiakRakoczy2019.pdf | Open Access Article]]</ref><ref name="Stannard1992">Stannard, D.I., 1992. Tensiometers—Theory, Construction, and Use. Geotechnical Testing Journal, 15(1), pp. 48-58. [https://doi.org/10.1520/GTJ10224J doi: 10.1520/GTJ10224J]</ref><ref name="WintonWeber1996">Winton, K., Weber, J.B., 1996. A Review of Field Lysimeter Studies to Describe the Environmental Fate of Pesticides. Weed Technology, 10(1), pp. 202-209. [https://doi.org/10.1017/S0890037X00045929 doi: 10.1017/S0890037X00045929]</ref>. Recently, there has been strong interest in the use of lysimeters to measure and monitor movement of per- and polyfluoroalkyl substances (PFAS) through the vadose zone<ref name="Anderson2021">Anderson, R.H., 2021. The Case for Direct Measures of Soil-to-Groundwater Contaminant Mass Discharge at AFFF-Impacted Sites. Environmental Science and Technology, 55(10), pp. 6580-6583. [https://doi.org/10.1021/acs.est.1c01543 doi: 10.1021/acs.est.1c01543]</ref><ref name="AndersonEtAl2022">Anderson, R.H., Feild, J.B., Dieffenbach-Carle, H., Elsharnouby, O., Krebs, R.K., 2022. Assessment of PFAS in Collocated Soil and Porewater Samples at an AFFF-Impacted Source Zone: Field-Scale Validation of Suction Lysimeters. Chemosphere, 308(1), Article 136247. [https://doi.org/10.1016/j.chemosphere.2022.136247 doi: 10.1016/j.chemosphere.2022.136247]</ref><ref name="SchaeferEtAl2024">Schaefer, C.E., Nguyen, D., Fang, Y., Gonda, N., Zhang, C., Shea, S., Higgins, C.P., 2024. PFAS Porewater Concentrations in Unsaturated Soil: Field and Laboratory Comparisons Inform on PFAS Accumulation at Air-Water Interfaces. Journal of Contaminant Hydrology, 264, Article 104359. [https://doi.org/10.1016/j.jconhyd.2024.104359 doi: 10.1016/j.jconhyd.2024.104359]&nbsp; [[Media: SchaeferEtAl2024.pdf | Open Access Manuscript]]</ref><ref name="SchaeferEtAl2023">Schaefer, C.E., Lavorgna, G.M., Lippincott, D.R., Nguyen, D., Schaum, A., Higgins, C.P., Field, J., 2023. Leaching of Perfluoroalkyl Acids During Unsaturated Zone Flushing at a Field Site Impacted with Aqueous Film Forming Foam. Environmental Science and Technology, 57(5), pp. 1940-1948. [https://doi.org/10.1021/acs.est.2c06903 doi: 10.1021/acs.est.2c06903]</ref><ref name="SchaeferEtAl2022">Schaefer, C.E., Lavorgna, G.M., Lippincott, D.R., Nguyen, D., Christie, E., Shea, S., O’Hare, S., Lemes, M.C.S., Higgins, C.P., Field, J., 2022. A Field Study to Assess the Role of Air-Water Interfacial Sorption on PFAS Leaching in an AFFF Source Area. Journal of Contaminant Hydrology, 248, Article 104001. [https://doi.org/10.1016/j.jconhyd.2022.104001 doi: 10.1016/j.jconhyd.2022.104001]&nbsp; [[Media: SchaeferEtAl2022.pdf | Open Access Manuscript]]</ref><ref name="QuinnanEtAl2021">Quinnan, J., Rossi, M., Curry, P., Lupo, M., Miller, M., Korb, H., Orth, C., Hasbrouck, K., 2021. Application of PFAS-Mobile Lab to Support Adaptive Characterization and Flux-Based Conceptual Site Models at AFFF Releases. Remediation, 31(3), pp. 7-26. [https://doi.org/10.1002/rem.21680 doi: 10.1002/rem.21680]</ref>. PFAS are frequently introduced to the environment through land surface application and have been found to be strongly retained within the upper 5 feet of soil<ref name="BrusseauEtAl2020">Brusseau, M.L., Anderson, R.H., Guo, B., 2020. PFAS Concentrations in Soils: Background Levels versus Contaminated Sites. Science of The Total Environment, 740, Article 140017. [https://doi.org/10.1016/j.scitotenv.2020.140017 doi: 10.1016/j.scitotenv.2020.140017]</ref><ref name="BiglerEtAl2024">Bigler, M.C., Brusseau, M.L., Guo, B., Jones, S.L., Pritchard, J.C., Higgins, C.P., Hatton, J., 2024. High-Resolution Depth-Discrete Analysis of PFAS Distribution and Leaching for a Vadose-Zone Source at an AFFF-Impacted Site. Environmental Science and Technology, 58(22), pp. 9863-9874. [https://doi.org/10.1021/acs.est.4c01615 doi: 10.1021/acs.est.4c01615]</ref>. PFAS recalcitrance in the vadose zone means that environmental program managers and consultants need a cost-effective way of monitoring concentration conditions within the vadose zone. Repeated soil sampling and extraction processes are time consuming and only give a representative concentration of total PFAS in the matrix<ref name="NickersonEtAl2020">Nickerson, A., Maizel, A.C., Kulkarni, P.R., Adamson, D.T., Kornuc, J. J., Higgins, C.P., 2020. Enhanced Extraction of AFFF-Associated PFASs from Source Zone Soils. Environmental Science and Technology, 54(8), pp. 4952-4962. [https://doi.org/10.1021/acs.est.0c00792 doi: 10.1021/acs.est.0c00792]</ref>, not what is readily transportable in mobile porewater<ref name="SchaeferEtAl2023"/><ref name="StultsEtAl2024">Stults, J.F., Schaefer, C.E., Fang, Y., Devon, J., Nguyen, D., Real, I., Hao, S., Guelfo, J.L., 2024. Air-Water Interfacial Collapse and Rate-Limited Solid Desorption Control Perfluoroalkyl Acid Leaching from the Vadose Zone. Journal of Contaminant Hydrology, 265, Article 104382. [https://doi.org/10.1016/j.jconhyd.2024.104382 doi: 10.1016/j.jconhyd.2024.104382]&nbsp; [[Media: StultsEtAl2024.pdf | Open Access Manuscript]]</ref><ref name="StultsEtAl2023">Stults, J.F., Choi, Y.J., Rockwell, C., Schaefer, C.E., Nguyen, D.D., Knappe, D.R.U., Illangasekare, T.H., Higgins, C.P., 2023. Predicting Concentration- and Ionic-Strength-Dependent Air–Water Interfacial Partitioning Parameters of PFASs Using Quantitative Structure–Property Relationships (QSPRs). Environmental Science and Technology, 57(13), pp. 5203-5215. [https://doi.org/10.1021/acs.est.2c07316 doi: 10.1021/acs.est.2c07316]</ref><ref name="BrusseauGuo2022">Brusseau, M.L., Guo, B., 2022. PFAS Concentrations in Soil versus Soil Porewater: Mass Distributions and the Impact of Adsorption at Air-Water Interfaces. Chemosphere, 302, Article 134938. [https://doi.org/10.1016/j.chemosphere.2022.134938 doi: 10.1016/j.chemosphere.2022.134938]&nbsp; [[Media: BrusseauGuo2022.pdf | Open Access Manuscript]]</ref>. Fortunately, lysimeters have been found to be a viable option for monitoring the concentration of PFAS in the mobile porewater phase in the vadose zone<ref name="Anderson2021"/><ref name="AndersonEtAl2022"/>. Note that while some lysimeters, known as weighing lysimeters, can directly measure water flux, the most commonly utilized lysimeters in PFAS investigations only provide measurements of porewater concentrations.
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PFAS transport and fate in the environment is controlled by the nature of the PFAS source, characteristics of the individual PFAS, and environmental conditions where the PFAS are present. Perfluoroalkyl acids (PFAAs) (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] for nomenclature) are strong acids and are anionic in the environmentally-relevant pH range. They are extremely persistent in the environment and do not degrade or transform under typical environmental conditions. Polyfluoroalkyl substances (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] for nomenclature) include compounds that have the potential to degrade to PFAAs. These compounds are commonly referred to as PFAA precursors or just ‘precursors’. Because some polyfluoroalkyl substances can degrade into PFAA via biotic or abiotic degradation pathways, PFAAs are sometimes referred to as “terminal PFAS” or “terminal degradation products”.
 
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The most important molecular properties controlling PFAA transport are the carbon chain length and functional moieties of the headgroups (e.g., sulfonate, carboxylate). The molecular properties of PFAA precursors are more varied, with different carbon chain lengths, headgroups and ionic states<ref name="Buck2011">Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., de Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A., and van Leeuwen, S.P.J., 2011. Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins. Integrated Environmental Assessment and Management, 7(4): pp. 513-541. [ https://doi.org/10.1002/ieam.258  DOI: 10.1002/ieam.258]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/epdf/10.1002/ieam.258 Open Access Article]</ref><ref name="Wang2017">Wang, Z., DeWitt, J.C., Higgins, C.P., and Cousins, I.T., 2017. A Never-Ending Story of Per- and Polyfluoroalkyl Substances (PFASs)? Environmental Science and Technology, 51(5), pp. 2508-2518. American Chemical Society. [https://doi.org/10.1021/acs.est.6b04806 DOI: 10.1021/acs.est.6b04806]&nbsp;&nbsp; [https://pubs.acs.org/doi/pdf/10.1021/acs.est.6b04806 Free Download from ACS]</ref> (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]]). All of these properties can influence transport and fate of PFAA precursors in the environment.  
 
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Important environmental characteristics include the nature of the source (mode of input into the environment), the length of time that the source was active, and the magnitude of the input, as well as precipitation and infiltration rates, depth to groundwater, surface water and groundwater flow rates and interactions, prevailing atmospheric conditions, the properties of the porous-media (e.g., soil and sediment) and aqueous solution, microbiological factors, and the presence of additional fluid phases such as air and non-aqueous phase liquids [[Wikipedia: Non-aqueous phase liquid | (NAPLs)]] in the vadose zone and water-saturated source. In the subsurface, soil characteristics (texture, organic carbon content, clay mineralogy, metal-oxide content, solid surface area, surface charge, and exchange capacity) and solution characteristics (pH, redox potential, major ion chemistry, and co-contaminants) can influence PFAS transport and fate.  
 
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==PFAS Transport and Fate Processes==
 
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[[File:AndersonBrusseau1w2Fig1.png | thumb | 400px | Figure 1. Illustration of PFAS partitioning and transformation processes. Source: D. Adamson, GSI, used with permission.]]
 
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Transport, partitioning, and transformation are the primary processes controlling PFAS fate in the environment (Figure 1). PFAS compounds can also be taken up by both plants and animals, and in some cases, bioaccumulate through the food chain. However, PFAS uptake and bioaccumulation is not discussed in this article (see “Environmental Concern” section of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]).
 
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* '''Transport:''' PFAS can be transported substantial distances in the atmosphere<ref name="Ahrens2012">Ahrens, L., Harner, T., Shoeib, M., Lane, D.A. and Murphy, J.G., 2012. Improved Characterization of Gas–Particle Partitioning for Per- and Polyfluoroalkyl Substances in the Atmosphere Using Annular Diffusion Denuder Samplers. Environmental Science and Technology, 46(13), pp. 7199-7206. [https://doi.org/10.1021/es300898s DOI: 10.1021/es300898s]&nbsp;&nbsp; Free download available from [https://www.researchgate.net/profile/Tom_Harner/publication/225046057_Improved_Characterization_of_Gas-Particle_Partitioning_for_Per-_and_Polyfluoroalkyl_Substances_in_the_Atmosphere_Using_Annular_Diffusion_Denuder_Samplers/links/5cc730c4299bf12097893fdc/Improved-Characterization-of-Gas-Particle-Partitioning-for-Per-and-Polyfluoroalkyl-Substances-in-the-Atmosphere-Using-Annular-Diffusion-Denuder-Samplers.pdf ResearchGate].</ref>, surface water<ref name="Taniyasu2013">Taniyasu, S., Yamashita, N., Moon, H.B., Kwok, K.Y., Lam, P.K., Horii, Y., Petrick, G. and Kannan, K., 2013.  Does wet precipitation represent local and regional atmospheric transportation by perfluorinated alkyl substances? Environment International, 55, pp. 25-32. [https://doi.org/10.1016/j.envint.2013.02.005 DOI: 10.1016/j.envint.2013.02.005]</ref>, soil<ref name="Braunig2017">Bräunig, J., Baduel, C., Heffernan, A., Rotander, A., Donaldson, E. and Mueller, J.F., 2017. Fate and redistribution of perfluoroalkyl acids through AFFF-impacted groundwater. Science of the Total Environment, 596, pp. 360-368. [https://doi.org/10.1016/j.scitotenv.2017.04.095 DOI: 10.1016/j.scitotenv.2017.04.095]</ref>, and groundwater<ref name="Weber2017">Weber, A.K., Barber, L.B., LeBlanc, D.R., Sunderland, E.M. and Vecitis, C.D., 2017. Geochemical and Hydrologic Factors Controlling Subsurface Transport of Poly- and Perfluoroalkyl Substances, Cape Cod, Massachusetts. Environmental Science and Technology, 51(8), pp. 4269-4279. [https://doi.org/10.1021/acs.est.6b05573 DOI: 10.1021/acs.est.6b05573]&nbsp;&nbsp; [https://bgc.seas.harvard.edu/assets/weber2017_final.pdf Free Download]</ref>. The primary mechanisms controlling PFAS transport are [[Wikipedia:Advection | advection]] and [[Wikipedia:Dispersive_mass_transfer | dispersion]], similar to other dissolved compounds. For additional information on transport in groundwater, see [[Advection and Groundwater Flow]] and [[Dispersion and Diffusion]].
 
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* '''Partitioning:''' Partitioning of PFAS between the mobile and immobile phases is one of the most important processes controlling the rate of migration in the environment. The primary mobile phases are typically air and water. Relatively immobile phases include stream sediments, soils, aquifer material, NAPLs, and interfaces between different phases (air-water, NAPL-water). Partitioning of a significant portion of the PFAS mass into an immobile phase increases the amount of material stored in the system and slows the apparent rate of migration in the mobile phase – a phenomenon that has been observed in field metadata<ref name="Anderson2019">Anderson, R.H., Adamson, D.T. and Stroo, H.F., 2019. Partitioning of poly-and perfluoroalkyl substances from soil to groundwater within aqueous film-forming foam source zones. Journal of Contaminant Hydrology, 220, pp. 59-65. [https://doi.org/10.1016/j.jconhyd.2018.11.011 DOI: 10.1016/j.jconhyd.2018.11.011]&nbsp;&nbsp; Manuscript available from [https://www.researchgate.net/profile/Hans_Stroo3/publication/329227107_Partitioning_of_poly-_and_perfluoroalkyl_substances_from_soil_to_groundwater_WITHIN_aqueous_film-forming_foam_source_zones/links/5e56996b299bf1bdb83e2f69/Partitioning-of-poly-and-perfluoroalkyl-substances-from-soil-to-groundwater-WITHIN-aqueous-film-forming-foam-source-zones.pdf ResearchGate]</ref>.
 
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* '''Transformation:''' Transformation of PFAS is controlled by the molecular structure of the individual compounds. Perfluorinated compounds, including PFAAs, are resistant to abiotic and biotic transformation reactions under typical conditions and highly persistent in the environment. In contrast, precursors can be transformed by both abiotic and biotic processes, often resulting in the production of so-called “terminal” PFAA daughter products.
 
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==Transport and Partitioning in the Atmosphere==
 
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Air serves as a transport media for PFAS, particularly for uncharged polyfluorinated PFAS. Airborne PFAS transport contributes to global distribution and can lead to localized deposition to soils and surface water in the vicinity of emission sources<ref name="Simcik2005">Simcik, M.F. and Dorweiler, K.J., 2005. Ratio of Perfluorochemical Concentrations as a Tracer of Atmospheric Deposition to Surface Waters. Environmental Science and Technology, 39(22), pp. 8678-8683. [https://doi.org/10.1021/es0511218 DOI: 10.1021/es0511218]&nbsp;&nbsp; Free download available from [https://www.researchgate.net/profile/Matt_Simcik/publication/7444956_Ratio_of_Perfluorochemical_Concentrations_as_a_Tracer_of_Atmospheric_Deposition_to_Surface_Waters/links/5f035861299bf1881603c3be/Ratio-of-Perfluorochemical-Concentrations-as-a-Tracer-of-Atmospheric-Deposition-to-Surface-Waters.pdf ResearchGate]</ref><ref name="Prevedouros2006">Prevedouros, K., Cousins, I.T., Buck, R.C. and Korzeniowski, S.H., 2006. Sources, Fate and Transport of Perfluorocarboxylates. Environmental Science and Technology, 40(1), pp. 32-44. [https://doi.org/10.1021/es0512475 DOI: 10.1021/es0512475]&nbsp;&nbsp; Free download available from [https://d1wqtxts1xzle7.cloudfront.net/39945519/Sources_Fate_and_Transport_of_Perfluoroc20151112-1647-19vcvbf.pdf?1447365456=&response-content-disposition=inline%3B+filename%3DSources_Fate_and_Transport_of_Perfluoroc.pdf&Expires=1605023809&Signature=Z6KqgaDN6lKdAazoe6qoASoCtVystG5i~5EnrTcb~qMg3xZPz4O49Kghh62WmMzqEKE788~6EwrnlBVo9o6cM0hjf2vymFYxg4mx-eSIOEonfFjk6RonSaWp5gRbA6m~SNjwsjaKXID3OQyWIlLVpUd2LzAdI5rLGFA~gIXXtNPyCArLuGn-kbPYUIcBUg5TIkTZ6TDLXF~ujmzK9tNv~55UYabsJL4pmwIGC2sNGkEyJrYMfU577fbactdrmQXTJH7XbgpfDSfd4-xWkDZTdvVf~TypDDqUCZdtCkY8wINdpqtfe1KEzLrAj7rxxALAHUYxlVbPB45XTkLAGe5qww__&Key-Pair-Id=APKAJLOHF5GGSLRBV4ZA  Academia]</ref><ref name="Ahrens2011">Ahrens, L., Shoeib, M., Harner, T., Lane, D.A., Guo, R. and Reiner, E.J., 2011. Comparison of Annular Diffusion Denuder and High Volume Air Samplers for Measuring Per- and Polyfluoroalkyl Substances in the Atmosphere." Analytical Chemistry, 83(24), pp. 9622-9628. [https://doi.org/10.1021/ac202414w DOI: 10.1021/ac202414w]&nbsp;&nbsp; Free download available from [https://www.informea.org/sites/default/files/imported-documents/UNEP-POPS-POPRC11FU-SUBM-PFOA-Canada-2-20151211.En.pdf Informea].</ref><ref name="Rauert2018">Rauert, C., Shoieb, M., Schuster, J.K., Eng, A. and Harner, T., 2018. Atmospheric concentrations and trends of poly-and perfluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) over 7 years of sampling in the Global Atmospheric Passive Sampling (GAPS) network. Environmental Pollution, 238, pp. 94-102. [https://doi.org/10.1016/j.envpol.2018.03.017 DOI: 10.1016/j.envpol.2018.03.017]&nbsp;&nbsp; Open access article available from [https://reader.elsevier.com/reader/sd/pii/S0269749117352521?token=4C770E6E8AEDB0B3BA6A1D5B2C20ED5385F81823612551FA3380AAA1DA7A978F9CB36834AF6B7F91F35FF57E32013252 ScienceDirect]&nbsp;&nbsp; [[Media:Rauert2018.pdf | Report.pdf]]</ref>.
 
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PFAAs, which are ionic and possess a negative charge under ambient environmental conditions, are far less volatile than many other groundwater contaminants.  An online database of vapor pressures and Henry’s Law constants for different PFAS, including PFAAs, is maintained by the Interstate Technology Regulatory Council<ref name="ITRC2020"/>. In general, vapor pressures of PFAS are low and water solubilities are high, limiting partitioning from water to air<ref name="ITRC2020"/>. However, under certain conditions, particularly within industrial stack emissions, PFAS can be transported through the atmosphere in both the gas phase and associated with fugitive particulates. In particular, volatile compounds including fluorotelomer alcohols (FTOHs) may be present in the gas phase, whereas, PFAAs can aerosolize and be transported as particulates<ref name="Ahrens2012"/>. In addition, precursors can be transformed to PFAAs in the atmosphere, which can result in PFAA deposition.
 
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Short-range atmospheric transport and deposition can result in PFAS contamination in terrestrial and aquatic systems near points of significant emissions, impacting soil, groundwater, and other media of concern<ref name="Fang2018">Fang, X., Wang, Q., Zhao, Z., Tang, J., Tian, C., Yao, Y., Yu, J. and Sun, H., 2018. Distribution and dry deposition of alternative and legacy perfluoroalkyl and polyfluoroalkyl substances in the air above the Bohai and Yellow Seas, China. Atmospheric Environment, 192, pp. 128-135. [https://doi.org/10.1016/j.atmosenv.2018.08.052 DOI: 10.1016/j.atmosenv.2018.08.052]</ref><ref name="Brandsma2019">Brandsma, S.H., Koekkoek, J.C., van Velzen, M.J.M. and de Boer, J., 2019. The PFOA substitute GenX detected in the environment near a fluoropolymer manufacturing plant in the Netherlands. Chemosphere, 220, pp. 493-500. [https://doi.org/10.1016/j.chemosphere.2018.12.135 DOI: 10.1016/j.chemosphere.2018.12.135]&nbsp;&nbsp; Open access article available from [https://reader.elsevier.com/reader/sd/pii/S0045653518324706?token=E541D5C4B200C8626A86F41049FE9DCA92652BC9A8BA7D9E47832C08070AB5AF256F4872474C50B5C4908F5CA4C24947 ScienceDirect].&nbsp;&nbsp; [[Media: Brandsma2019.pdf | Report.pdf]]</ref>.  Releases of ionic PFAS from factories are likely tied to particulate matter, which settle to the ground in dry weather and are also wet-scavenged by precipitation<ref name="Barton2006">Barton, C.A., Butler, L.E., Zarzecki, C.J., Flaherty, J. and Kaiser, M., 2006. Characterizing Perfluorooctanoate in Ambient Air near the Fence Line of a Manufacturing Facility: Comparing Modeled and Monitored Values. Journal of the Air and Waste Management Association, 56(1), pp. 48-55. [https://doi.org/10.1080/10473289.2006.10464429 DOI: 10.1080/10473289.2006.10464429]&nbsp;&nbsp; Free access article available from [https://www.tandfonline.com/doi/pdf/10.1080/10473289.2006.10464429?needAccess=true Taylor and Francis Online]&nbsp;&nbsp; [[Media: Barton2006.pdf | Report.pdf]]</ref>. The impact of other potential sources, such as combustion emissions or wind-blown fire-fighting foam from fire training and fire response sites, on the fate and transport of PFAS in air may need to be assessed.
 
  
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Long-range transport processes are responsible for the wide distribution of neutral and ionic PFAS across the Earth as evidenced by their occurrence in biota, surface snow, ice cores, seawater, and other environmental media in regions as remote as the Arctic and Antarctic<ref name="Bossi2016">Bossi, R., Vorkamp, K. and Skov, H., 2016. Concentrations of organochlorine pesticides, polybrominated diphenyl ethers and perfluorinated compounds in the atmosphere of North Greenland. Environmental Pollution, 217, pp. 4-10. [https://doi.org/10.1016/j.envpol.2015.12.026 DOI: 10.1016/j.envpol.2015.12.026]</ref><ref name="Ahrens2010">Ahrens, L., Gerwinski, W., Theobald, N. and Ebinghaus, R., 2010. Sources of polyfluoroalkyl compounds in the North Sea, Baltic Sea and Norwegian Sea: Evidence from their spatial distribution in surface water. Marine Pollution Bulletin, 60(2), pp. 255-260. [https://doi.org/10.1016/j.marpolbul.2009.09.013 DOI: 10.1016/j.marpolbul.2009.09.013]</ref>.
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==PFAS Background==
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Distribution of PFAS to remote regions far removed from direct industrial input is believed to occur from both: a) long-range atmospheric transport and subsequent degradation of volatile precursors; and b) transport via ocean currents and release into the air as marine aerosols (sea spray)<ref name="DeSilva2009">De Silva, A.O., Muir, D.C. and Mabury, S.A., 2009. Distribution of perfluorocarboxylate isomers in select samples from the North American environment. Environmental Toxicology and Chemistry: An International Journal 28(9), pp. 1801-1814. [https://doi.org/10.1897/08-500.1 DOI: 10.1897/08-500.1]</ref><ref name="Armitage2009">Armitage, J.M., 2009. Modeling the global fate and transport of perfluoroalkylated substances (PFAS). Doctoral Dissertation, Institutionen för tillämpad miljövetenskap (ITM), Stockholm University. [[Media: Armitage2009.pdf | Report.pdf]]</ref>.
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PFAS are a broad class of chemicals with highly variable chemical structures<ref>Moody, C.A., Field, J.A., 1999. Determination of Perfluorocarboxylates in Groundwater Impacted by Fire-Fighting Activity. Environmental Science and Technology, 33(16), pp. 2800-2806. [https://doi.org/10.1021/es981355+ doi: 10.1021/es981355+]</ref><ref name="MoodyField2000">Moody, C.A., Field, J.A., 2000. Perfluorinated Surfactants and the Environmental Implications of Their Use in Fire-Fighting Foams. Environmental Science and Technology, 34(18), pp. 3864-3870. [https://doi.org/10.1021/es991359u doi: 10.1021/es991359u]</ref><ref name="GlügeEtAl2020">Glüge, J., Scheringer, M., Cousins, I.T., DeWitt, J.C., Goldenman, G., Herzke, D., Lohmann, R., Ng, C.A., Trier, X., Wang, Z., 2020. An Overview of the Uses of Per- and Polyfluoroalkyl Substances (PFAS). Environmental Science: Processes and Impacts, 22(12), pp. 2345-2373. [https://doi.org/10.1039/D0EM00291G doi: 10.1039/D0EM00291G]&nbsp; [[Media: GlügeEtAl2020.pdf | Open Access Article]]</ref>. One characteristic feature of PFAS is that they are fluorosurfactants, distinct from more traditional hydrocarbon surfactants<ref name="MoodyField2000"/><ref name="Brusseau2018">Brusseau, M.L., 2018. Assessing the Potential Contributions of Additional Retention Processes to PFAS Retardation in the Subsurface. Science of The Total Environment, 613-614, pp. 176-185. [https://doi.org/10.1016/j.scitotenv.2017.09.065 doi: 10.1016/j.scitotenv.2017.09.065]&nbsp; [[Media: Brusseau2018.pdf | Open Access Manuscript]]</ref><ref>Dave, N., Joshi, T., 2017. A Concise Review on Surfactants and Its Significance. International Journal of Applied Chemistry, 13(3), pp. 663-672. [https://doi.org/10.37622/IJAC/13.3.2017.663-672 doi: 10.37622/IJAC/13.3.2017.663-672]&nbsp; [[Media: DaveJoshi2017.pdf  | Open Access Article]]</ref><ref>García, R.A., Chiaia-Hernández, A.C., Lara-Martin, P.A., Loos, M., Hollender, J., Oetjen, K., Higgins, C.P., Field, J.A., 2019. Suspect Screening of Hydrocarbon Surfactants in Afffs and Afff-Contaminated Groundwater by High-Resolution Mass Spectrometry. Environmental Science and Technology, 53(14), pp. 8068-8077. [https://doi.org/10.1021/acs.est.9b01895 doi: 10.1021/acs.est.9b01895]</ref>. Fluorosurfactants typically have a fully or partially fluorinated, hydrophobic tail with ionic (cationic, zwitterionic, or anionic) head group that is hydrophilic<ref name="MoodyField2000"/><ref name="GlügeEtAl2020"/>. The hydrophobic tail and ionic head group mean PFAS are very stable at hydrophobic adsorption interfaces when present in the aqueous phase<ref>Krafft, M.P., Riess, J.G., 2015. Per- and Polyfluorinated Substances (PFASs): Environmental Challenges. Current Opinion in Colloid and Interface Science, 20(3), pp. 192-212. [https://doi.org/10.1016/j.cocis.2015.07.004 doi: 10.1016/j.cocis.2015.07.004]</ref>. Examples of these interfaces include naturally occurring organic matter in soils and the air-water interface in the vadose zone<ref>Schaefer, C.E., Culina, V., Nguyen, D., Field, J., 2019. Uptake of Poly- and Perfluoroalkyl Substances at the Air–Water Interface. Environmental Science and Technology, 53(21), pp. 12442-12448. [https://doi.org/10.1021/acs.est.9b04008 doi: 10.1021/acs.est.9b04008]</ref><ref>Lyu, Y., Brusseau, M.L., Chen, W., Yan, N., Fu, X., Lin, X., 2018. Adsorption of PFOA at the Air–Water Interface during Transport in Unsaturated Porous Media. Environmental Science and Technology, 52(14), pp. 7745-7753. [https://doi.org/10.1021/acs.est.8b02348 doi: 10.1021/acs.est.8b02348]</ref><ref>Costanza, J., Arshadi, M., Abriola, L.M., Pennell, K.D., 2019. Accumulation of PFOA and PFOS at the Air-Water Interface. Environmental Science and Technology Letters, 6(8), pp. 487-491. [https://doi.org/10.1021/acs.estlett.9b00355 doi: 10.1021/acs.estlett.9b00355]</ref><ref>Li, F., Fang, X., Zhou, Z., Liao, X., Zou, J., Yuan, B., Sun, W., 2019. Adsorption of Perfluorinated Acids onto Soils: Kinetics, Isotherms, and Influences of Soil Properties. Science of The Total Environment, 649, pp. 504-514. [https://doi.org/10.1016/j.scitotenv.2018.08.209 doi: 10.1016/j.scitotenv.2018.08.209]</ref><ref>Nguyen, T.M.H., Bräunig, J., Thompson, K., Thompson, J., Kabiri, S., Navarro, D.A., Kookana, R.S., Grimison, C., Barnes, C.M., Higgins, C.P., McLaughlin, M.J., Mueller, J.F., 2020. Influences of Chemical Properties, Soil Properties, and Solution pH on Soil–Water Partitioning Coefficients of Per- and Polyfluoroalkyl Substances (PFASs). Environmental Science and Technology, 54(24), pp. 15883-15892. [https://doi.org/10.1021/acs.est.0c05705 doi: 10.1021/acs.est.0c05705]&nbsp; [[Media: NguyenEtAl2020.pdf  | Open Access Article]]</ref>. Their strong adsorption to both soil organic matter and the air-water interface is a major contributor to elevated concentrations of PFAS observed in the upper 5 feet of the soil column<ref name="BrusseauEtAl2020"/><ref name="BiglerEtAl2024"/>. While several other PFAS partitioning processes exist<ref name="Brusseau2018"/>, adsorption to solid phase soils and air-water interfaces are the two primary processes present at nearly all PFAS sites<ref>Brusseau, M.L., Yan, N., Van Glubt, S., Wang, Y., Chen, W., Lyu, Y., Dungan, B., Carroll, K.C., Holguin, F.O., 2019. Comprehensive Retention Model for PFAS Transport in Subsurface Systems. Water Research, 148, pp. 41-50. [https://doi.org/10.1016/j.watres.2018.10.035 doi: 10.1016/j.watres.2018.10.035]</ref>. The total PFAS mass obtained from a vadose zone soil sample contains the solid phase, air-water interfacial, and aqueous phase PFAS mass, which can be converted to porewater concentrations using Equation 1<ref name="BrusseauGuo2022"/>.</br>
 +
:: <big>'''Equation 1:'''</big>&nbsp;&nbsp; [[File: StultsEq1.png | 400 px]]</br>
 +
Where ''C<sub>p</sub>'' is the porewater concentration, ''C<sub>t</sub>'' is the total PFAS concentration, ''ρ<sub>b</sub>'' is the bulk density of the soil, ''θ<sub>w</sub>'' is the volumetric water content, ''R<sub>d</sub>'' is the PFAS retardation factor, ''K<sub>d</sub>'' is the solid phase adsorption coefficient, ''K<sub>ia</sub>'' is the air-water interfacial adsorption coefficient, and ''A<sub>aw</sub>'' is the air-water interfacial area. The air-water interfacial area of the soil is primarily a function of both the soil properties and the degree of volumetric water saturation in the soil. There are several methods of estimating air-water interfacial areas including thermodynamic functions based on the soil moisture retention curve. However, the thermodynamic function has been shown to underestimate air-water interfacial area<ref name="Brusseau2023">Brusseau, M.L., 2023. Determining Air-Water Interfacial Areas for the Retention and Transport of PFAS and Other Interfacially Active Solutes in Unsaturated Porous Media. Science of The Total Environment, 884, Article 163730. [https://doi.org/10.1016/j.scitotenv.2023.163730 doi: 10.1016/j.scitotenv.2023.163730]&nbsp; [[Media: Brusseau2023.pdf | Open Access Article]]</ref>, and must typically be scaled using empirical scaling factors. An empirical method recently developed to estimate air-water interfacial area is presented in Equation 2<ref name="Brusseau2023"/>.</br>
 +
:: <big>'''Equation 2:'''</big>&nbsp;&nbsp; [[File: StultsEq2.png | 400 px]]</br>
 +
Where ''S<sub>w</sub>'' is the water phase saturation as a ratio of the water content over the volumetric soil porosity, and ''d<sub>50</sub>'' is the median grain diameter.
  
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==Transport and Partitioning in Aqueous Systems==
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==Lysimeters Background==
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PFAS adsorb from water to a variety of solid materials including organic materials, clay minerals, metal oxides, and granular activated carbon<ref name="Du2014">Du, Z., Deng, S., Bei, Y., Huang, Q., Wang, B., Huang, J. and Yu, G., 2014. Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents – A review. Journal of Hazardous Materials, 274, pp. 443-454. [https://doi.org/10.1016/j.jhazmat.2014.04.038 DOI: 10.1016/j.jhazmat.2014.04.038]</ref>. This process is thought to occur through two primary mechanisms: 1) sorption to organic-carbon components of the solids; and 2) electrostatic (and other) interactions with inorganic constituents of the solids, including clay minerals and metal-oxides<ref name="Guelfo2013">Guelfo, J.L. and Higgins, C.P., 2013. Subsurface Transport Potential of Perfluoroalkyl Acids at Aqueous Film-Forming Foam (AFFF)-Impacted Sites. Environmental Science and Technology, 47(9), pp. 4164-4171. [https://doi.org/10.1021/es3048043 DOI: 10.1021/es3048043]&nbsp;&nbsp; [https://mountainscholar.org/bitstream/handle/11124/80055/Guelfo_mines_0052E_10298.pdf?sequence=1#page=64 Doctoral Dissertation]</ref><ref name="Zhao2014">Zhao, L., Bian, J., Zhang, Y., Zhu, L. and Liu, Z., 2014. Comparison of the sorption behaviors and mechanisms of perfluorosulfonates and perfluorocarboxylic acids on three kinds of clay minerals. Chemosphere, 114, pp. 51-58. [https://doi.org/10.1016/j.chemosphere.2014.03.098 DOI: 10.1016/j.chemosphere.2014.03.098]&nbsp;&nbsp; Free download available from [https://www.researchgate.net/profile/Lixia_Zhao8/publication/262148355_Comparison_of_the_sorption_behaviors_and_mechanisms_of_perfluorosulfonates_and_perfluorocarboxylic_acids_on_three_kinds_of_clay_minerals/links/5b1be5dca6fdcca67b681a4f/Comparison-of-the-sorption-behaviors-and-mechanisms-of-perfluorosulfonates-and-perfluorocarboxylic-acids-on-three-kinds-of-clay-minerals.pdf ResearchGate].</ref>. The relative contribution of each mechanism varies depending on surface chemistry and other geochemical factors, as well as the molecular properties of the PFAS.  In general, the impact of electrostatic interactions with charged soil constituents is more important for PFAS than non-polar, hydrophobic organic contaminants (e.g. hydrocarbons, chlorinated solvents).  Adsorption of PFAS by solids is often nonlinear, with greater sorption at lower solute concentrations. The impacts of adsorption kinetics and their potential reversibility on PFAS transport have not yet been examined for most PFAS compounds.
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[[File: StultsFig1.png |thumb|600 px|Figure 1. (a) A field suction lysimeter with labeled parts typically used in field settings – Credit: Bibek Acharya and Dr. Vivek Sharma, UF/IFAS, https://edis.ifas.ufl.edu/publication/AE581. (b) Laboratory suction lysimeters used in Schaefer ''et al.'' 2024<ref name="SchaeferEtAl2024"/>, which employed the use of micro-sampling suction lysimeters. (c) A field lysimeter used in Schaefer ''et al.'' 2023<ref name="SchaeferEtAl2023"/>. (d) Diagram of a drainage wicking lysimeter – Credit: Edaphic Scientific, https://edaphic.com.au/products/water/lysimeter-wick-for-drainage/]]
 +
Lysimeters,&nbsp;generally&nbsp;speaking, refer to instruments which collect water from unsaturated soils<ref name="MeissnerEtAl2020"/><ref name="RogersMcConnell1993"/>. However, there are multiple types of lysimeters which can be employed in field or laboratory settings. There are three primary types of lysimeters relevant to PFAS listed here and shown in Figure 1a-d.
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# <u>Suction Lysimeters (Figure 1a,b):</u> These lysimeters are the most relevant for PFAS sampling and are the majority of discussion in this article. These lysimeters operate by extracting liquid from the unsaturated vadose zone by applying negative suction pressure at the sampling head<ref name="CostanzaEtAl2025"/><ref name="SchaeferEtAl2024"/><ref name="QuinnanEtAl2021"/>. The sampling head is typically constructed of porous ceramic or stainless steel. A PVC case or stainless-steel case is attached to the sampling head and extends upward above the ground surface. Suction lysimeters are typically installed between 1 and 9 feet below ground surface, but can extend as deep as 40-60 feet in some cases<ref name="CostanzaEtAl2025"/>. Shallow lysimeters (< 10 feet) are typically installed using a hand auger. For ceramic lysimeters, a silica flour slurry should be placed at the base of the bore hole and allowed to cover the ceramic head before backfilling the hole partially with natural soil. Once the hole is partially backfilled with soil to cover the sampling head, the remainder of the casing should be sealed with hydrated bentonite chips. When sampling events occur, suction is applied at the ground surface using a rubber gasket seal and a hand pump or electric pump. After sufficient porewater is collected (the time for which can vary greatly based on the soil permeability and moisture content), the seal can be removed and a peristaltic pump used to extract liquid from the lysimeter.
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# <u>Field Lysimeters (Figure 1c):</u> These large lysimeters can be constructed from plastic or metal sidings. They can range from approximately 2 feet in diameter to as large as several meters in diameter<ref name="MeissnerEtAl2020"/>. Instrumentation such as soil moisture probes and tensiometers, or even multiple suction lysimeters, are typically placed throughout the lysimeter to measure the movement of water and determine characteristic soil moisture release curves<ref name="Stannard1992"/><ref name="WintonWeber1996"/><ref name="SchaeferEtAl2023"/><ref name="SchaeferEtAl2022"/><ref>van Genuchten, M.Th. , 1980. A Closed‐form Equation for Predicting the Hydraulic Conductivity of Unsaturated Soils. Soil Science Society of America Journal, 44(5), pp. 892-898. [https://doi.org/10.2136/sssaj1980.03615995004400050002x doi: 10.2136/sssaj1980.03615995004400050002x]</ref>. Water is typically collected at the base of the field lysimeter to determine net recharge through the system. These field lysimeters are intended to represent more realistic, intermediate scale conditions of field systems.
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# <u>Drainage Lysimeters (Figure 1d):</u>  Also known as a “wick” lysimeter, these lysimeters typically consist of a hollow cup attached to a spout which protrudes above ground to relieve air pressure from the system and act as a sampling port. The hollow cup typically has filters and wicking devices at the base to collect water from the soil. The cup is filled with natural soil and collects water as it percolates through the vadose zone. These lysimeters are used to directly monitor net recharge from the vadose zone to the groundwater table and could be useful in determining PFAS mass flux.
  
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Sorption of hydrocarbons, chlorinated solvents and other hydrophobic organics is often controlled the by organic-carbon components of the solid phase (see [[Sorption of Organic Contaminants]]). However, studies of PFAS sorption to solid phase organic carbon have reported conflicting results.  In a study of field sites with aqueous film-forming foam (AFFF, a type of fire-fighting foam) releases, solid phase organic carbon content was found to significantly influence PFAS soil-to-groundwater concentration ratios.  Statistical modeling was then used to derive apparent organic carbon partition coefficients for 18 different PFAS<ref name="Anderson2019"/>.  A recent compilation of published organic carbon partition coefficients found a good correspondence to PFAS molecular structure<ref name="Brusseau2019a">Brusseau, M.L., 2019. Estimating the relative magnitudes of adsorption to solid-water and air/oil-water interfaces for per-and poly-fluoroalkyl substances. Environmental Pollution, 254B, p. 113102. [https://doi.org/10.1016/j.envpol.2019.113102 DOI: 10.1016/j.envpol.2019.113102]</ref>. However, other studies have shown a general lack of correlation between solid phase partition coefficients and organic carbon<ref name="Li2018">Li, Y., Oliver, D.P. and Kookana, R.S., 2018. A critical analysis of published data to discern the role of soil and sediment properties in determining sorption of per and polyfluoroalkyl substances (PFASs). Science of the Total Environment, 628, pp. 110-120. [https://doi.org/10.1016/j.scitotenv.2018.01.167 DOI: 10.1016/j.scitotenv.2018.01.167]</ref>. It is possible that greater variability may be observed for broader data sets that incorporate different ranges of PFAS concentrations, different solution conditions, different measurement methods, and field-based data which often have less well-defined conditions and may also be influenced by other retention processes<ref name="Anderson2019"/><ref name="Brusseau2019a"/>.
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==Analysis of PFAS Concentrations in Soil and Porewater==
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{| class="wikitable mw-collapsible" style="float:left; margin-right:20px; text-align:center;"
 +
|+Table 1. Measured and Predicted PFAS Concentrations in Porewater for Select PFAS in Three Different Soils
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|-
 +
!Site
 +
!PFAS
 +
!Field</br>Porewater</br>Concentration</br>(&mu;g/L)
 +
!Lab Core</br>Porewater</br>Concentration</br>(&mu;g/L)
 +
!Predicted</br>Porewater</br>Concentration</br>(&mu;g/L)
 +
|-
 +
|Site A||PFOS||6.2 ± 3.4||3.0 ± 0.37||6.6 ± 3.3
 +
|-
 +
|Site B||PFOS||2.2 ± 2.0||0.78 ± 0.38||2.8
 +
|-
 +
|rowspan="3"|Site C||PFOS||13 ± 4.1||680 ± 460||164 ± 75
 +
|-
 +
|8:2 FTS||1.2 ± 0.46||52 ± 13||16 ± 6.0
 +
|-
 +
|PFHpS||0.36 ± 0.051||2.9 ± 2.0||5.9 ± 3.4
 +
|}
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[[File: StultsFig2.png | thumb | 600 px | Figure 2. Field Measured PFAS concentration Data (Orange) and Lab Core Measured Concentration Data (Blue) for four PFAS impacted sites<ref name="AndersonEtAl2022"/>]]
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[[File: StultsFig3.png | thumb | 400 px | Figure 3. Measured and predicted data for PFAS concentrations from a single site field lysimeter study. Model predictions both with and without PFAS sorption to the air-water interface were considered<ref name="SchaeferEtAl2023"/>.]]
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Schaefer&nbsp;''et&nbsp;al.''<ref name="SchaeferEtAl2024"/>&nbsp;measured&nbsp;PFAS porewater concentrations with field and laboratory suction lysimeters across several sites. Intact cores from the site were collected for soil water extraction using laboratory lysimeters. The lysimeters were used to directly compare field derived measurements of PFAS concentration in the mobile porewater phase. Results from measurements are for four sites presented in Figure 2.
  
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[[File:AndersonBrusseau1w2Fig2.png | thumb | 400px | Figure 2. Example of expected orientation and accumulation of PFAS at air-water interface. Source: D. Adamson, GSI, used with permission.]]
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Data from sites A and B showed reasonably good agreement (within ½ order of magnitude) for most PFAS measured in the systems. At site C, more hydrophobic constituents (> C6 PFAS) tended to have higher concentrations in the lab core than the field site while less hydrophobic constituents (< C6) had higher concentrations in the field than lab cores. Site D showed substantially greater (1 order of magnitude or more) PFAS concentrations measured in the laboratory-collected porewater sample compared to what was measured in the field lysimeters. This discrepancy for the Site D soil can likely be attributed to soil heterogeneity (as indicated by ground penetrating radar) and the fact that the soil consisted of back-filled materials rather than undisturbed native soils.  
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Most solids present in the environment contain both fixed-charged (negative) and variably charged surfaces. At neutral to high pH, variably charged clay minerals have a net-negative charge. As a result, negatively charged PFAAs do not strongly interact electrostatically in most soils, although as the soil pH decreases electrostatic sorption would be expected to increase in soils with variably charged clay minerals.  Cationic and zwitterionic precursors are expected to be more strongly sorbed than anionic PFAAs in most environments due to well-established cation exchange reactions. Other factors, including ionic strength, composition, and the presence of co-solutes, can affect adsorption of PFAS<ref name="Higgins2006">Higgins, C.P. and Luthy, R.G., 2006. Sorption of Perfluorinated Surfactants on Sediments. Environmental Science and Technology, 40(23), pp. 7251-7256. [https://doi.org/10.1021/es061000n DOI: 10.1021/es061000n]</ref><ref name="Chen2009">Chen, H., Chen, S., Quan, X., Zhao, Y. and Zhao, H., 2009. Sorption of perfluorooctane sulfonate (PFOS) on oil and oil-derived black carbon: Influence of solution pH and [Ca2+]. Chemosphere, 77(10), pp. 1406-1411. [https://doi.org/10.1016/j.chemosphere.2009.09.008 DOI: 10.1016/j.chemosphere.2009.09.008]</ref><ref name="Pan2009">Pan, G., Jia, C., Zhao, D., You, C., Chen, H. and Jiang, G., 2009. Effect of cationic and anionic surfactants on the sorption and desorption of perfluorooctane sulfonate (PFOS) on natural sediments. Environmental Pollution, 157(1), pp.325-330. [https://doi.org/10.1016/j.envpol.2008.06.035 DOI: 10.1016/j.envpol.2008.06.035]&nbsp;&nbsp; Free download available from [https://www.researchgate.net/profile/Gang_Pan2/publication/23189567_Effect_of_cationic_and_anionic_surfactants_on_the_sorption_and_desorption_of_perfluorooctane_sulfonate_PFOS_on_natural_sediments/links/5be19d23a6fdcc3a8dc2550d/Effect-of-cationic-and-anionic-surfactants-on-the-sorption-and-desorption-of-perfluorooctane-sulfonate-PFOS-on-natural-sediments.pdf ResearchGate]</ref><ref name="Guelfo2013"/><ref name="Zhao2014"/>.
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Site&nbsp;C&nbsp;showed&nbsp;elevated PFAS concentrations in the laboratory collected porewater for the more surface-active compounds. This increase was attributed to the soil wetting that occurred at the bench scale, which was reasonably described by the model shown in Equations 1 and 2 (see Table 1<ref name="AndersonEtAl2022"/>). Equations 1 and 2 were also used to predict PFAS porewater concentrations (using porous cup lysimeters) in a highly instrumented test cell<ref name="SchaeferEtAl2023"/>(Figure 3). The ability to predict soil concentrations from recurring porewater samples is critical to the practical application of lysimeters in field settings<ref name="AndersonEtAl2022"/>.
  
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Most PFAS compounds act as surface-active agents (or [[Wikipedia:Surfactant | surfactants]]) due to the presence of a hydrophilic headgroup and a hydrophobic tail. The hydrophilic headgroup will preferentially partition to the aqueous phase and the hydrophobic tail will preferentially partition to the non-aqueous phase (air or organic material).  As a result, PFAS tend to accumulate at interfaces (air-water, water-NAPL, water-solid) (Figure 2). This tendency to accumulate at interfaces can influence transport in the atmosphere (on water droplets and hydrated aerosols), in the vadose or unsaturated zone at air-water interfaces, in the presence of NAPLs, and in wastewater treatment systems<ref name="Brusseau2018"/><ref name="Brusseau2019b">Brusseau, M.L., 2019. The Influence of Molecular Structure on the Adsorption of PFAS to Fluid-Fluid Interfaces: Using QSPR to Predict Interfacial Adsorption Coefficients. Water Research, 152, pp. 148-158. [https://doi.org/10.1016/j.watres.2018.12.057 DOI: 10.1016/j.watres.2018.12.057]&nbsp;&nbsp; [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6374777/ Author’s Manuscript]</ref>.
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Results from suction lysimeters studies and field lysimeter studies show that PFAS concentrations in porewater predicted from soil concentrations using Equations 1 and 2 generally have reasonable agreement with measured ''in situ'' porewater data when air-water interfacial partitioning is considered. Results show that for less hydrophobic components like PFOA, the impact of air-water interfacial adsorption is less significant than for highly hydrophobic components like PFOS. The soil for the field lysimeter in Figure 3 was a sandy soil with a relatively low air-water interfacial area. The effect of air-water interfacial partitioning is expected to be much more significant for a greater range of PFAS in soils with high capillary pressure (i.e. silts/clays) with higher associated air-water interfacial areas<ref name="Brusseau2023"/><ref>Peng, S., Brusseau, M.L., 2012. Air-Water Interfacial Area and Capillary Pressure: Porous-Medium Texture Effects and an Empirical Function. Journal of Hydrologic Engineering, 17(7), pp. 829-832. [https://doi.org/10.1061/(asce)he.1943-5584.0000515 doi: 10.1061/(asce)he.1943-5584.0000515]</ref><ref>Brusseau, M.L., Peng, S., Schnaar, G., Costanza-Robinson, M.S., 2006. Relationships among Air-Water Interfacial Area, Capillary Pressure, and Water Saturation for a Sandy Porous Medium. Water Resources Research, 42(3), Article W03501, 5 pages. [https://doi.org/10.1029/2005WR004058 doi: 10.1029/2005WR004058]&nbsp; [[Media: BrusseauEtAl2006.pdf | Free Access Article]]</ref>.
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In theoretical and experimental studies of transport in unsaturated porous media, adsorption at the air-water interface increased PFOS and PFOA retention<ref name="Brusseau2018"/><ref name="Lyu2018">Lyu, Y., Brusseau, M.L., Chen, W., Yan, N., Fu, X., and Lin, X., 2018.  Adsorption of PFOA at the Air-Water Interface during Transport in Unsaturated Porous Media. Environmental Science and Technology, 52(14), pp. 7745-7753. [https://doi.org/10.1021/acs.est.8b02348 DOI: 10.1021/acs.est.8b02348]&nbsp;&nbsp; [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6312111/ Author’s Manuscript]</ref><ref name="BrusseauEtAl2019">Brusseau, M.L., Yan, N., Van Glubt, S., Wang, Y., Chen, W., Lyu, Y., Dungan, B., Carroll, K.C., and Holguin, F.O., 2019. Comprehensive Retention Model for PFAS Transport in Subsurface Systems. Water Research, 148, pp. 41-50. [https://doi.org/10.1016/j.watres.2018.10.035 DOI: 10.1016/j.watres.2018.10.035]&nbsp;&nbsp; [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6294326/ Author’s Manuscript]</ref>, contributing approximately 20% to 80% of total retention in sands and soil. The impact of oil-water interfacial adsorption on PFAS transport was also quantitatively characterized in recent studies and shown to contribute to total retention on a similar scale as air-water interfacial adsorption<ref name="Brusseau2018"/><ref name="BrusseauEtAl2019"/>.  These processes may result in increased PFAS mass retained in NAPL source zones, increased PFAS sorption with the resulting retardation of transport, and greater persistence of dissolved PFAS in the environment.  
 
  
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==Transformation==
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==Summary and Recommendations==
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[[File:AndersonBrusseau1w2Fig3.png | thumb | 400px | Figure 3. Conceptual model of precursor transformation resulting in the formation of PFAAs. Source L. Trozzolo, TRC and C. Higgins, Colorado School of Mines, used with permission.]]
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The majority of research with lysimeters for PFAS site investigations has been done using porous cup suction lysimeters<ref name="CostanzaEtAl2025"/><ref name="AndersonEtAl2022"/><ref name="SchaeferEtAl2024"/><ref name="QuinnanEtAl2021"/>. Porous cup suction lysimeters are advantageous because they can be routinely sampled or sampled after specific wetting or drying events much like groundwater wells. This sampling is easier and more efficient than routinely collecting soil samples from the same locations. Co-locating lysimeters with soil samples is important for establishing the baseline soil concentration levels at the lysimeter location and developing correlations between the soil concentrations and the mobile porewater concentration<ref name="CostanzaEtAl2025"/>. Appropriate standard operation procedures for lysimeter installation and operation have been established and have been reviewed in recent literature<ref name="CostanzaEtAl2025"/><ref name="SchaeferEtAl2024"/>. Lysimeters should typically be installed near the source area and just above the maximum groundwater level elevation to obtain accurate results of porewater concentrations year round. Depending upon the geology and vertical PFAS distribution in the soil, multilevel lysimeter installations should also be considered.
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Certain polyfluorinated substances have the potential to transform to other PFAS, with PFAAs as the typical terminal daughter products. These polyfluorinated substances are often referred to as “precursors”. The transformation potential of polyfluorinated precursors is influenced by the presence, location, and number of carbon-hydrogen (C-H) bonds and potentially carbon-oxygen (C-O) bonds throughout the carbon chain. Specifically, PFAS with C-H bonds are subject to a variety of biotic and abiotic reactions that ultimately result in the formation of PFAAs with perfluorinated carbon chains of the same length or shorter than the initial polyfluorinated precursor<ref name="Houtz2013">Houtz, E.F., Higgins, C.P., Field, J.A. and Sedlak, D.L., 2013. Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil. Environmental Science and Technology, 47(15), pp.  8187-8195.  [https://doi.org/10.1021/es4018877 DOI: 10.1021/es4018877]&nbsp;&nbsp; Free download from [https://www.researchgate.net/profile/Erika_Houtz/publication/252323955_Persistence_of_Perfluoroalkyl_Acid_Precursors_in_AFFF-Impacted_Groundwater_and_Soil/links/59dbddeeaca2728e2018336d/Persistence-of-Perfluoroalkyl-Acid-Precursors-in-AFFF-Impacted-Groundwater-and-Soil.pdf ReseqarchGate]</ref><ref name="McGuire2014">McGuire, M.E., Schaefer, C., Richards, T., Backe, W.J., Field, J.A., Houtz, E., Sedlak, D.L., Guelfo, J.L., Wunsch, A., and Higgins, C.P., 2014. Evidence of Remediation-Induced Alteration of Subsurface Poly- and Perfluoroalkyl Substance Distribution at a Former Firefighter Training Area. Environmental Science and Technology, 48(12) pp. 6644-6652.  [https://doi.org/10.1021/es5006187 DOI: 10.1021/es5006187]&nbsp;&nbsp; Manuscript available from [https://ir.library.oregonstate.edu/downloads/td96k706f Oregon State University]</ref><ref name="Anderson2016">Anderson, R.H., Long, G.C., Porter, R.C. and Anderson, J.K., 2016. Occurrence of select perfluoroalkyl substances at US Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties. Chemosphere, 150, pp. 678-685.  [https://doi.org/10.1016/j.chemosphere.2016.01.014 DOI: 10.1016/j.chemosphere.2016.01.014]</ref><ref name="Weber2017"/>.
 
  
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Transformation studies published to date have tested only a small subsample of possible precursors and, therefore, much uncertainty exists regarding 1) the extent to which precursor transformation occurs on a global scale, 2) which environmental compartments represent the majority of transformation, 3) relevant environmental conditions that affect transformation processes, and 4) transformation rates and pathways. Nevertheless, a portion of the precursors are expected to transform to PFAAs over time as shown in Figure 3.
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Results from several lysimeters studies across multiple field sites and modelling analysis has shown that lysimeters can produce reasonable results between field and laboratory studies<ref name="SchaeferEtAl2024"/><ref name="SchaeferEtAl2023"/><ref name="SchaeferEtAl2022"/>. Transient effects of wetting and drying as well as media heterogeneity affects appear to be responsible for some variability and uncertainty in lysimeter based PFAS measurements in the vadose zone. These mobile porewater concentrations can be coupled with effective recharge estimates and simplified modelling approaches to determine mass flux from the vadose zone to the underlying groundwater<ref name="Anderson2021"/><ref name="StultsEtAl2024"/><ref name="BrusseauGuo2022"/><ref>Stults, J.F., Schaefer, C.E., MacBeth, T., Fang, Y., Devon, J., Real, I., Liu, F., Kosson, D., Guelfo, J.L., 2025. Laboratory Validation of a Simplified Model for Estimating Equilibrium PFAS Mass Leaching from Unsaturated Soils. Science of The Total Environment, 970, Article 179036. [https://doi.org/10.1016/j.scitotenv.2025.179036 doi: 10.1016/j.scitotenv.2025.179036]</ref><ref>Smith, J. Brusseau, M.L., Guo, B., 2024. An Integrated Analytical Modeling Framework for Determining Site-Specific Soil Screening Levels for PFAS. Water Research, 252, Article121236. [https://doi.org/10.1016/j.watres.2024.121236 doi: 10.1016/j.watres.2024.121236]</ref>.
  
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Precursors can be transformed by a variety of abiotic processes including hydrolysis, photolysis, and oxidation. Hydrolysis of some precursors, followed by subsequent biotransformation, can produce perfluoroalkyl sulfonates (PFSAs).  An important example is the production of PFOS from perfluorooctane sulfonyl fluoride (POSF)<ref name="Martin2010">Martin, J.W., Asher, B.J., Beesoon, S., Benskin, J.P. and Ross, M.S., 2010. PFOS or PreFOS? Are perfluorooctane sulfonate precursors (PreFOS) important determinants of human and environmental perfluorooctane sulfonate (PFOS) exposure? Journal of Environmental Monitoring, 12(11), pp.1979-2004.  [https://doi.org/10.1039/C0EM00295J DOI: 10.1039/C0EM00295J]&nbsp;&nbsp; Free download from [https://www.researchgate.net/profile/Matthew_Ross3/publication/47415684_PFOS_or_PreFOS_Are_perfluorooctane_sulfonate_precursors_PreFOS_important_determinants_of_human_and_environmental_perfluorooctane_sulfonate_PFOS_exposure/links/00b7d520a6132da945000000.pdf ResearchGate]</ref>.  Other hydrolysis reactions produce perfluoroalkyl carboxylates (PFCAs). At neutral pH, the hydrolysis of fluorotelomer-derived polymeric precursors results in the formation of monomeric precursors of PFOA and other PFAAs with half-lives of 50 to 90 years)<ref name="Washington2010">Washington, J.W., Ellington, J.J., Jenkins, T.M. and Yoo, H., 2010. Response to Comments on “Degradability of an Acrylate-Linked, Fluorotelomer Polymer in Soil”. Environmental Science and Technology, 44(2), pp. 849-850.  [https://doi.org/10.1021/es902672q DOI: 10.1021/es902672q]&nbsp;&nbsp;  [https://pubs.acs.org/doi/pdf/10.1021/es902672q Free Download from ACS].</ref>.  Oxidation of precursors by hydroxyl radicals can occur in natural waters, with the fluorotelomer-derived precursors being oxidized relatively rapidly<ref name="Gauthier2005">Gauthier, S.A. and Mabury, S.A., 2005. Aqueous photolysis of 8: 2 fluorotelomer alcohol. Environmental Toxicology and Chemistry, 24(8), pp.1837-1846.  [https://doi.org/10.1897/04-591R.1 DOI: 10.1897/04-591R.1]&nbsp;&nbsp; Free download from [https://www.researchgate.net/profile/Suzanne_Gauthier/publication/7609648_Aqueous_photolysis_of_8_2_fluorotelomer_alcohol/links/5ec16c4792851c11a86d9438/Aqueous-photolysis-of-8-2-fluorotelomer-alcohol.pdf ResearchGate].</ref><ref name="Plumlee2009">Plumlee, M.H., McNeill, K. and Reinhard, M., 2009. Indirect Photolysis of Perfluorochemicals: Hydroxyl Radical-Initiated Oxidation of N-Ethyl Perfluorooctane Sulfonamido Acetate (N-EtFOSAA) and Other Perfluoroalkanesulfonamides. Environmental Science and Technology, 43(10), pp.3662-3668.  [https://doi.org/10.1021/es803411w DOI: 10.1021/es803411w]&nbsp;&nbsp; Free download from [https://www.researchgate.net/profile/Megan_Plumlee/publication/26309488_Indirect_Photolysis_of_Perfluorochemicals_Hydroxyl_Radical-Initiated_Oxidation_of_N-Ethyl_Perfluorooctane_Sulfonamido_Acetate_N-EtFOSAA_and_Other_Perfluoroalkanesulfonamides/links/5aac0437a6fdcc1bc0b8d002/Indirect-Photolysis-of-Perfluorochemicals-Hydroxyl-Radical-Initiated-Oxidation-of-N-Ethyl-Perfluorooctane-Sulfonamido-Acetate-N-EtFOSAA-and-Other-Perfluoroalkanesulfonamides.pdf ResearchGate].</ref>.
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Future research opportunities should address the current key uncertainties related to the use of lysimeters for PFAS investigations, including:
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Evidence of aerobic biotransformation is provided from studies of PFAS composition throughout the continuum of wastewater treatments<ref name="Arvaniti2015">Arvaniti, O.S. and Stasinakis, A.S., 2015. Review on the occurrence, fate and removal of perfluorinated compounds during wastewater treatment. Science of the Total Environment, 524, pp. 81-92.  [https://doi.org/10.1016/j.scitotenv.2015.04.023 DOI: 10.1016/j.scitotenv.2015.04.023]</ref>, from field studies at AFFF-impacted sites<ref name="Houtz2013"/><ref name="McGuire2014"/><ref name="Anderson2016"/><ref name="Weber2017"/>, and from microcosm experiments. In general, the literature on aerobic biotransformation collectively demonstrates or indirectly supports the following conclusions as summarized in ITRC 2020<ref name="ITRC2020"/>:
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#<u>Collect larger datasets of PFAS concentrations</u> to determine how transient wetting or drying periods and media type affect PFAS concentrations in the mobile porewater. Some research has shown that non-equilibrium processes can occur in the vadose zone, which can affect grab sample concentration in the porewater at specific time periods.
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* Numerous aerobic biotransformation pathways exist with relatively rapid kinetics
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#<u>More work should be done with flux averaging lysimeters</u> like the drainage cup or wicking lysimeter. These lysimeters can directly measure net recharge and provide time averaged concentrations of PFAS in water over the sampling period. However, there is little work detailing their potential applications in PFAS research, or operational considerations for their use in remedial investigations for PFAS.
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* All polyfluorinated precursors studied to date have the potential to aerobically biotransform to PFAAs
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#<u>Lysimeters should be coupled with monitoring of wetting and drying</u> in the vadose zone using ''in situ'' soil moisture sensors or tensiometers and groundwater levels. Direct measurements of soil saturation at field sites are vital to directly correlate porewater concentrations with soil concentrations. Similarly, groundwater level fluctuations can inform net recharge estimates. By collecting these data we can continue to improve partitioning and leaching models which can relate porewater concentrations to total PFAS mass in soils and PFAS leaching at field sites.
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* Aerobic biotransformation of various fluorotelomer-derived precursors exclusively results in the formation of PFCAs, including PFOA, without necessarily the conservation of chain-length
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#<u>Comparisons of various bench-scale leaching or desorption tests to field-based lysimeter data</u> are recommended. The ability to correlate field measurements of PFAS concentrations with estimates of leaching from laboratory studies would provide a powerful method to empirically estimate PFAS leaching from field sites.
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* Aerobic biotransformation of various electrochemical fluorination-derived precursors primarily results in the formation of PFAAs, including PFOS, with the conservation of chain-length
 
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Precursor transformation can complicate CSMs (and risk assessments) and should be considered during comprehensive site investigations. For example, atmospheric emissions of volatile precursors can result in long-range transport where subsequent transformation and deposition can result in detectable levels of PFAAs in environmental media independent of obvious point-sources<ref name="Vedagiri2018">Vedagiri, U.K., Anderson, R.H., Loso, H.M. and Schwach, C.M., 2018. Ambient levels of PFOS and PFOA in multiple environmental media. Remediation Journal, 28(2), pp. 9-51.  [https://doi.org/10.1002/rem.21548 DOI: 10.1002/rem.21548]</ref>. With respect to site-related precursors, transformation of otherwise unmeasured PFAS into detectable PFAAs is obviously relevant to site investigations to the extent transformation occurs after initial site characterization efforts or if past remedial efforts have accelerated ''in situ'' transformation rates<ref name="McGuire2014"/>.  Additionally, differential transport rates between precursor PFAS and the corresponding terminal PFAA could also confound CSMs if transformation rates are slower than transport rates as has been suggested<ref name="Weber2017"/>. 
 
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To account for otherwise unmeasurable precursors, several surrogate analytical methods have been developed. See [[PFAS Sampling and Analytical Methods]] for additional detail.
 
  
 
==References==
 
==References==
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<references/>
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<references />
  
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==See Also:==
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==See Also==

Latest revision as of 15:50, 15 January 2026

Lysimeters for Measuring PFAS Concentrations in the Vadose Zone

PFAS are frequently introduced to the environment through soil surface applications which then transport through the vadose zone to reach underlying groundwater receptors. Due to their unique properties and resulting transport and retention behaviors, PFAS in the vadose zone can be a persistent contaminant source to underlying groundwater systems. Determining the fraction of PFAS present in the mobile porewater relative to the total concentrations in soils is critical to understanding the risk posed by PFAS in vadose zone source areas. Lysimeters are instruments that have been used by agronomists and vadose zone researchers for decades to determine water flux and solute concentrations in unsaturated porewater. Lysimeters have recently been developed as a critical tool for field investigations and characterizations of PFAS impacted source zones.

Related Article(s):

Contributors: Dr. John F. Stults, Dr. Charles Schaefer

Key Resources:

  • Assessment of PFAS in Collocated Soil and Porewater Samples at an AFFF-Impacted Source Zone: Field-Scale Validation of Suction Lysimeters[1]
  • PFAS Concentrations in Soil versus Soil Porewater: Mass Distributions and the Impact of Adsorption at Air-Water Interfaces[2]
  • Using Suction Lysimeters for Determining the Potential of Per- and Polyfluoroalkyl Substances to Leach from Soil to Groundwater: A Review[3]
  • Use of Lysimeters for Monitoring Soil Water Balance Parameters and Nutrient Leaching[4]
  • PFAS Porewater Concentrations in Unsaturated Soil: Field and Laboratory Comparisons Inform on PFAS Accumulation at Air-Water Interfaces[5]

Introduction

Lysimeters are devices that are placed in the subsurface above the groundwater table to monitor the movement of water through the soil[6][7][3]. Lysimeters have historically been used in agricultural sciences for monitoring nutrient or contaminant movement, soil moisture release curves, natural drainage patterns, and dynamics of plant-water interactions[6][8][9][10][4][11][12][13][14]. Recently, there has been strong interest in the use of lysimeters to measure and monitor movement of per- and polyfluoroalkyl substances (PFAS) through the vadose zone[15][1][5][16][17][18]. PFAS are frequently introduced to the environment through land surface application and have been found to be strongly retained within the upper 5 feet of soil[19][20]. PFAS recalcitrance in the vadose zone means that environmental program managers and consultants need a cost-effective way of monitoring concentration conditions within the vadose zone. Repeated soil sampling and extraction processes are time consuming and only give a representative concentration of total PFAS in the matrix[21], not what is readily transportable in mobile porewater[16][22][23][2]. Fortunately, lysimeters have been found to be a viable option for monitoring the concentration of PFAS in the mobile porewater phase in the vadose zone[15][1]. Note that while some lysimeters, known as weighing lysimeters, can directly measure water flux, the most commonly utilized lysimeters in PFAS investigations only provide measurements of porewater concentrations.

PFAS Background

PFAS are a broad class of chemicals with highly variable chemical structures[24][25][26]. One characteristic feature of PFAS is that they are fluorosurfactants, distinct from more traditional hydrocarbon surfactants[25][27][28][29]. Fluorosurfactants typically have a fully or partially fluorinated, hydrophobic tail with ionic (cationic, zwitterionic, or anionic) head group that is hydrophilic[25][26]. The hydrophobic tail and ionic head group mean PFAS are very stable at hydrophobic adsorption interfaces when present in the aqueous phase[30]. Examples of these interfaces include naturally occurring organic matter in soils and the air-water interface in the vadose zone[31][32][33][34][35]. Their strong adsorption to both soil organic matter and the air-water interface is a major contributor to elevated concentrations of PFAS observed in the upper 5 feet of the soil column[19][20]. While several other PFAS partitioning processes exist[27], adsorption to solid phase soils and air-water interfaces are the two primary processes present at nearly all PFAS sites[36]. The total PFAS mass obtained from a vadose zone soil sample contains the solid phase, air-water interfacial, and aqueous phase PFAS mass, which can be converted to porewater concentrations using Equation 1[2].

Equation 1:   StultsEq1.png

Where Cp is the porewater concentration, Ct is the total PFAS concentration, ρb is the bulk density of the soil, θw is the volumetric water content, Rd is the PFAS retardation factor, Kd is the solid phase adsorption coefficient, Kia is the air-water interfacial adsorption coefficient, and Aaw is the air-water interfacial area. The air-water interfacial area of the soil is primarily a function of both the soil properties and the degree of volumetric water saturation in the soil. There are several methods of estimating air-water interfacial areas including thermodynamic functions based on the soil moisture retention curve. However, the thermodynamic function has been shown to underestimate air-water interfacial area[37], and must typically be scaled using empirical scaling factors. An empirical method recently developed to estimate air-water interfacial area is presented in Equation 2[37].

Equation 2:   StultsEq2.png

Where Sw is the water phase saturation as a ratio of the water content over the volumetric soil porosity, and d50 is the median grain diameter.

Lysimeters Background

Figure 1. (a) A field suction lysimeter with labeled parts typically used in field settings – Credit: Bibek Acharya and Dr. Vivek Sharma, UF/IFAS, https://edis.ifas.ufl.edu/publication/AE581. (b) Laboratory suction lysimeters used in Schaefer et al. 2024[5], which employed the use of micro-sampling suction lysimeters. (c) A field lysimeter used in Schaefer et al. 2023[16]. (d) Diagram of a drainage wicking lysimeter – Credit: Edaphic Scientific, https://edaphic.com.au/products/water/lysimeter-wick-for-drainage/

Lysimeters, generally speaking, refer to instruments which collect water from unsaturated soils[4][11]. However, there are multiple types of lysimeters which can be employed in field or laboratory settings. There are three primary types of lysimeters relevant to PFAS listed here and shown in Figure 1a-d.

  1. Suction Lysimeters (Figure 1a,b): These lysimeters are the most relevant for PFAS sampling and are the majority of discussion in this article. These lysimeters operate by extracting liquid from the unsaturated vadose zone by applying negative suction pressure at the sampling head[3][5][18]. The sampling head is typically constructed of porous ceramic or stainless steel. A PVC case or stainless-steel case is attached to the sampling head and extends upward above the ground surface. Suction lysimeters are typically installed between 1 and 9 feet below ground surface, but can extend as deep as 40-60 feet in some cases[3]. Shallow lysimeters (< 10 feet) are typically installed using a hand auger. For ceramic lysimeters, a silica flour slurry should be placed at the base of the bore hole and allowed to cover the ceramic head before backfilling the hole partially with natural soil. Once the hole is partially backfilled with soil to cover the sampling head, the remainder of the casing should be sealed with hydrated bentonite chips. When sampling events occur, suction is applied at the ground surface using a rubber gasket seal and a hand pump or electric pump. After sufficient porewater is collected (the time for which can vary greatly based on the soil permeability and moisture content), the seal can be removed and a peristaltic pump used to extract liquid from the lysimeter.
  2. Field Lysimeters (Figure 1c): These large lysimeters can be constructed from plastic or metal sidings. They can range from approximately 2 feet in diameter to as large as several meters in diameter[4]. Instrumentation such as soil moisture probes and tensiometers, or even multiple suction lysimeters, are typically placed throughout the lysimeter to measure the movement of water and determine characteristic soil moisture release curves[13][14][16][17][38]. Water is typically collected at the base of the field lysimeter to determine net recharge through the system. These field lysimeters are intended to represent more realistic, intermediate scale conditions of field systems.
  3. Drainage Lysimeters (Figure 1d): Also known as a “wick” lysimeter, these lysimeters typically consist of a hollow cup attached to a spout which protrudes above ground to relieve air pressure from the system and act as a sampling port. The hollow cup typically has filters and wicking devices at the base to collect water from the soil. The cup is filled with natural soil and collects water as it percolates through the vadose zone. These lysimeters are used to directly monitor net recharge from the vadose zone to the groundwater table and could be useful in determining PFAS mass flux.

Analysis of PFAS Concentrations in Soil and Porewater

Table 1. Measured and Predicted PFAS Concentrations in Porewater for Select PFAS in Three Different Soils
Site PFAS Field
Porewater
Concentration
(μg/L) 		Lab Core
Porewater
Concentration
(μg/L) 		Predicted
Porewater
Concentration
(μg/L)
Site A PFOS 6.2 ± 3.4 3.0 ± 0.37 6.6 ± 3.3
Site B PFOS 2.2 ± 2.0 0.78 ± 0.38 2.8
Site C PFOS 13 ± 4.1 680 ± 460 164 ± 75
8:2 FTS 1.2 ± 0.46 52 ± 13 16 ± 6.0
PFHpS 0.36 ± 0.051 2.9 ± 2.0 5.9 ± 3.4
Figure 2. Field Measured PFAS concentration Data (Orange) and Lab Core Measured Concentration Data (Blue) for four PFAS impacted sites[1]
Figure 3. Measured and predicted data for PFAS concentrations from a single site field lysimeter study. Model predictions both with and without PFAS sorption to the air-water interface were considered[16].

Schaefer et al.[5] measured PFAS porewater concentrations with field and laboratory suction lysimeters across several sites. Intact cores from the site were collected for soil water extraction using laboratory lysimeters. The lysimeters were used to directly compare field derived measurements of PFAS concentration in the mobile porewater phase. Results from measurements are for four sites presented in Figure 2.

Data from sites A and B showed reasonably good agreement (within ½ order of magnitude) for most PFAS measured in the systems. At site C, more hydrophobic constituents (> C6 PFAS) tended to have higher concentrations in the lab core than the field site while less hydrophobic constituents (< C6) had higher concentrations in the field than lab cores. Site D showed substantially greater (1 order of magnitude or more) PFAS concentrations measured in the laboratory-collected porewater sample compared to what was measured in the field lysimeters. This discrepancy for the Site D soil can likely be attributed to soil heterogeneity (as indicated by ground penetrating radar) and the fact that the soil consisted of back-filled materials rather than undisturbed native soils.

Site C showed elevated PFAS concentrations in the laboratory collected porewater for the more surface-active compounds. This increase was attributed to the soil wetting that occurred at the bench scale, which was reasonably described by the model shown in Equations 1 and 2 (see Table 1[1]). Equations 1 and 2 were also used to predict PFAS porewater concentrations (using porous cup lysimeters) in a highly instrumented test cell[16](Figure 3). The ability to predict soil concentrations from recurring porewater samples is critical to the practical application of lysimeters in field settings[1].

Results from suction lysimeters studies and field lysimeter studies show that PFAS concentrations in porewater predicted from soil concentrations using Equations 1 and 2 generally have reasonable agreement with measured in situ porewater data when air-water interfacial partitioning is considered. Results show that for less hydrophobic components like PFOA, the impact of air-water interfacial adsorption is less significant than for highly hydrophobic components like PFOS. The soil for the field lysimeter in Figure 3 was a sandy soil with a relatively low air-water interfacial area. The effect of air-water interfacial partitioning is expected to be much more significant for a greater range of PFAS in soils with high capillary pressure (i.e. silts/clays) with higher associated air-water interfacial areas[37][39][40].

Summary and Recommendations

The majority of research with lysimeters for PFAS site investigations has been done using porous cup suction lysimeters[3][1][5][18]. Porous cup suction lysimeters are advantageous because they can be routinely sampled or sampled after specific wetting or drying events much like groundwater wells. This sampling is easier and more efficient than routinely collecting soil samples from the same locations. Co-locating lysimeters with soil samples is important for establishing the baseline soil concentration levels at the lysimeter location and developing correlations between the soil concentrations and the mobile porewater concentration[3]. Appropriate standard operation procedures for lysimeter installation and operation have been established and have been reviewed in recent literature[3][5]. Lysimeters should typically be installed near the source area and just above the maximum groundwater level elevation to obtain accurate results of porewater concentrations year round. Depending upon the geology and vertical PFAS distribution in the soil, multilevel lysimeter installations should also be considered.

Results from several lysimeters studies across multiple field sites and modelling analysis has shown that lysimeters can produce reasonable results between field and laboratory studies[5][16][17]. Transient effects of wetting and drying as well as media heterogeneity affects appear to be responsible for some variability and uncertainty in lysimeter based PFAS measurements in the vadose zone. These mobile porewater concentrations can be coupled with effective recharge estimates and simplified modelling approaches to determine mass flux from the vadose zone to the underlying groundwater[15][22][2][41][42].

Future research opportunities should address the current key uncertainties related to the use of lysimeters for PFAS investigations, including:

  1. Collect larger datasets of PFAS concentrations to determine how transient wetting or drying periods and media type affect PFAS concentrations in the mobile porewater. Some research has shown that non-equilibrium processes can occur in the vadose zone, which can affect grab sample concentration in the porewater at specific time periods.
  2. More work should be done with flux averaging lysimeters like the drainage cup or wicking lysimeter. These lysimeters can directly measure net recharge and provide time averaged concentrations of PFAS in water over the sampling period. However, there is little work detailing their potential applications in PFAS research, or operational considerations for their use in remedial investigations for PFAS.
  3. Lysimeters should be coupled with monitoring of wetting and drying in the vadose zone using in situ soil moisture sensors or tensiometers and groundwater levels. Direct measurements of soil saturation at field sites are vital to directly correlate porewater concentrations with soil concentrations. Similarly, groundwater level fluctuations can inform net recharge estimates. By collecting these data we can continue to improve partitioning and leaching models which can relate porewater concentrations to total PFAS mass in soils and PFAS leaching at field sites.
  4. Comparisons of various bench-scale leaching or desorption tests to field-based lysimeter data are recommended. The ability to correlate field measurements of PFAS concentrations with estimates of leaching from laboratory studies would provide a powerful method to empirically estimate PFAS leaching from field sites.

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