Limitations of Current Approaches for Predicting Groundwater Vulnerability from PFAS Contamination in the Vadose Zone
Matt Rovero
Search for more papers by this authorDiana Cutt
Search for more papers by this authorRachel Griffiths
Search for more papers by this authorUrszula Filipowicz
Search for more papers by this authorKatherine Mishkin
Search for more papers by this authorBrad White
Search for more papers by this authorSandra Goodrow
Search for more papers by this authorMatt Rovero
Search for more papers by this authorDiana Cutt
Search for more papers by this authorRachel Griffiths
Search for more papers by this authorUrszula Filipowicz
Search for more papers by this authorKatherine Mishkin
Search for more papers by this authorBrad White
Search for more papers by this authorSandra Goodrow
Search for more papers by this authorArticle impact statement: Sorption coefficients for eight anionic PFAS spanned three to five log units indicating limited value for estimating impacts to groundwater.
Abstract
Published literature for reported sorption coefficients (Kd) of eight anionic per- and polyfluoroalkyl substances (PFAS) in soil was reviewed. Kd values spanned three to five log units indicating that no single value would be appropriate for use in estimating PFAS impacts to groundwater using existing soil-water partition equations. Regression analysis was used to determine if the soil or solution parameters might be used to predict Kd values. None of the 15 experimental parameters collected could individually explain variability in reported Kd values. Significant associations between Kd and soil calcium and sodium content were found for many of the selected PFAS, suggesting that soil cation content may be critical to PFAS sorption, as previously noted in sources like Higgins and Luthy (2006), while organic carbon content was significant only at elevated levels (>5%). Unexplained discrepancies between the results from studies where PFAS were introduced to soil and desorbed in the laboratory and those that used material from PFAS-impacted sites suggest that laboratory experiments may be overlooking some aspects critical to PFAS sorption. Future studies would benefit from the development and use of standardized analytical methods to improve data quality and the establishment of soil parameters appropriate for collection to produce more complete data sets for predictive analysis.
Supporting Information
Filename | Description |
---|---|
gwmr12485-sup-0001-Supinfo.pdfPDF document, 2.8 MB | Table S1. PFAS vapor pressure and Henry's Law constants. Table S2. Range of Kd values from included studies. Table S3. Methods for PFAS extraction and quantitation, by study. Table S4. Results from simple linear regression of variables versus log Kd by chemical. Table S5. Summary of ANOVA results—laboratory vs. field measurements. Table S6. Summary of ANOVA results—adsorption vs. desorption measurements. Table S7. Results from multiple linear regression of three models for PFOA. Table S8. Results from multiple linear regression of three models for PFOS. Table S9. Results from multiple linear regression of three models for PFBS. Table S10. Results from multiple linear regression of three models for PFBA. Table S11. Results from multiple linear regression of three models for PFNA. Table S12. Results from multiple linear regression of three models for PFDA. Table S13. Results from multiple linear regression of three models for PFHxS. Figure S1. Linear regression of log Kd vs. percent sand content of soil. Figure S2. Linear regression of log Kd vs. percent clay content of soil. Figure S3. Linear regression of log Kd vs. percent silt content of soil. Figure S4. Linear regression of log Kd vs. soil pH. Figure S5. Linear regression of log Kd vs. aqueous pH. Figure S6. Linear regression of log Kd vs. calcium concentration of soil (mg/kg). Figure S7. Linear regression of log Kd vs. potassium concentration of soil (mg/kg). Figure S8. Linear regression of log Kd vs. sodium concentration of soil (mg/kg). Figure S9. Linear regression of log Kd vs. iron concentration of soil (g/kg). Figure S10. Linear regression of log Kd vs. aluminum concentration of soil (g/kg). Figure S11. Linear regression of log Kd vs. magnesium concentration of soil (mg/kg). Figure S12. Linear regression of log Kd vs. cation exchange capacity of soil (mmol/kg). Figure S13. Linear regression of log Kd vs. anion exchange capacity of soil (mmol/kg). Figure S14. Linear regression of log Kd vs. aqueous concentration of PFAS (μg/L) over entire data range. Two additional figures (S15 and S16) are provided at different scales. Figure S15. Linear regression of log Kd vs. aqueous concentration of PFAS (μg/L) up to a concentration of 600 μg/L. Figure S16. Linear regression of log Kd vs. aqueous concentration of PFAS (μg/L) up to a concentration of 25 μg/L. |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- Ahrens, L., L.W.Y. Yeung, S. Taniyasu, P.K.S. Lam, and N. Yamashita. 2011. Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment. Chemosphere 85, no. 5: 731–737. https://doi.org/10.1016/j.chemosphere.2011.06.046
- Al-Ghouti, M.A., and D.A. Da'ana. 2020. Guidelines for the use and interpretation of adsorption isotherm models: A review. Journal of Hazardous Materials 393: 122383. https://doi.org/10.1016/j.jhazmat.2020.122383
- Allen-King, R.M., L.D. McKay, and M.R. Trudell. 1997. Organic carbon dominated trichloroethene sorption in a clay-rich glacial deposit. Ground Water 35, no. 1: 124.
- Anderson, R.H., D.T. Adamson, and H.F. Stroo. 2019. Partitioning of poly- and perfluoroalkyl substances from soil to groundwater within aqueous film-forming foam source zones. Journal of Contaminant Hydrology 220: 59–65. https://doi.org/10.1016/j.jconhyd.2018.11.011
- Baduel, C., C.J. Paxman, and J.F. Mueller. 2015. Perfluoroalkyl substances in a firefighting training ground (FTG), distribution and potential future release. Journal of Hazardous Materials 296: 46–53. https://doi.org/10.1016/j.jhazmat.2015.03.007
- Barzen-Hanson, K.A., S.E. Davis, M. Kleber, and J.A. Field. 2017. Sorption of fluorotelomer sulfonates, fluorotelomer sulfonamido betaines, and a fluorotelomer sulfonamido amine in national foam aqueous film-forming foam to soil. Environmental Science & Technology 51, no. 21: 12394–12404. https://doi.org/10.1021/acs.est.7b03452
- Bloxham, P.A. 2008. Estimation of the adsorption coefficient (KOC) of HFPO dimer acid ammonium salt on soil and sludge. DuPont de Nemours, Inc. Study Number DuPont-17568-1675.
- Bräunig, J., C. Baduel, C.M. Barnes, and J.F. Mueller. 2019. Leaching and bioavailability of selected perfluoroalkyl acids (PFAAs) from soil contaminated by firefighting activities. Science of the Total Environment 646: 471–479. https://doi.org/10.1016/j.scitotenv.2018.07.231
- 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 254: 113102. https://doi.org/10.1016/j.envpol.2019.113102
- Brusseau, M.L., N. Yan, S. Van Glubt, Y. Wang, W. Chen, Y. Lyu, B. Dungan, K.C. Carroll, and F. Omar Holguin. 2019. Comprehensive retention model for PFAS transport in subsurface systems. Water Research 148: 41–50. https://doi.org/10.1016/j.watres.2018.10.035
- Campos Pereira, H., M.U. Hugo, D.B. Kleja, J.P. Gustafsson, and L. Ahrens. 2018. Sorption of Perfluoroalkyl substances (PFASs) to an organic soil horizon – Effect of cation composition and PH. Chemosphere 207: 183–191. https://doi.org/10.1016/j.chemosphere.2018.05.012
- Chen, H., M. Reinhard, V.T. Nguyen, and K.Y.-H. Gin. 2016. Reversible and irreversible sorption of perfluorinated compounds (PFCs) by sediments of an urban reservoir. Chemosphere 144: 1747–1753. https://doi.org/10.1016/j.chemosphere.2015.10.055
- Dalahmeh, S., S. Tirgani, A.J. Komakech, C.B. Niwagaba, and L. Ahrens. 2018. Per- and polyfluoroalkyl substances (PFASs) in water, soil and plants in wetlands and agricultural areas in Kampala, Uganda. Science of the Total Environment 631–632: 660–667. https://doi.org/10.1016/j.scitotenv.2018.03.024
- Du, Z., S. Deng, Y. Bei, Q. Huang, B. Wang, J. Huang, and Y. Gang. 2014. Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents—A review. Journal of Hazardous Materials 274: 443–454. https://doi.org/10.1016/j.jhazmat.2014.04.038
- Enevoldsen, R., and R.K. Juhler. 2010. Perfluorinated compounds (PFCs) in groundwater and aqueous soil extracts: Using inline SPE-LC-MS/MS for screening and sorption characterisation of perfluorooctane sulphonate and related compounds. Analytical and Bioanalytical Chemistry 398, no. 3: 1161–1172. https://doi.org/10.1007/s00216-010-4066-0
- Ferrey, M.L., J.T. Wilson, C. Adair, S. Chunming, D.D. Fine, X. Liu, and J.W. Washington. 2012. Behavior and fate of PFOA and PFOS in Sandy aquifer sediment. Groundwater Monitoring & Remediation 32, no. 4: 63–71. https://doi.org/10.1111/j.1745-6592.2012.01395.x
- Galloway, J.E., A.V.P. Moreno, A.B. Lindstrom, M.J. Strynar, S. Newton, A.A. May, and L.K. Weavers. 2020. Evidence of air dispersion: HFPO–DA and PFOA in Ohio and West Virginia surface water and soil near a fluoropolymer production facility. Environmental Science & Technology 54, no. 12: 7175–7184. https://doi.org/10.1021/acs.est.9b07384
- Guelfo, J.L., and C.P. Higgins. 2013. Subsurface transport potential of perfluoroalkyl acids at aqueous film-forming foam (AFFF)-impacted sites. Environmental Science & Technology 47, no. 9: 4164–4171. https://doi.org/10.1021/es3048043
- Guo, B., J. Zeng, and M.L. Brusseau. 2020. A mathematical model for the release, transport, and retention of per- and polyfluoroalkyl substances (PFAS) in the Vadose zone. Water Resources Research 56, no. 2: e2019WR026667. https://doi.org/10.1029/2019WR026667
- Hale, S.E., H.P.H. Arp, G.A. Slinde, E.J. Wade, K. Bjørseth, G.D. Breedveld, B.F. Straith, K.G. Moe, M. Jartun, and Å. Høisæter. 2017. Sorbent amendment as a remediation strategy to reduce PFAS mobility and leaching in a contaminated sandy soil from a Norwegian firefighting training facility. Chemosphere 171: 9–18. https://doi.org/10.1016/j.chemosphere.2016.12.057
- Hellsing, M.S., S. Josefsson, A.V. Hughes, and L. Ahrens. 2016. Sorption of perfluoroalkyl substances to two types of minerals. Chemosphere 159: 385–391. https://doi.org/10.1016/j.chemosphere.2016.06.016
- Heydebreck, F., J. Tang, Z. Xie, and R. Ebinghaus. 2015. Alternative and legacy perfluoroalkyl substances: Differences between European and Chinese river/estuary systems. Environmental Science & Technology 49, no. 14: 8386–8395. https://doi.org/10.1021/acs.est.5b01648
- Higgins, C.P., and R.G. Luthy. 2007. Modeling sorption of anionic surfactants onto sediment materials: An a priori approach for perfluoroalkyl surfactants and linear alkylbenzene sulfonates. Environmental Science & Technology 41, no. 9: 3254–3261. https://doi.org/10.1021/es062449j
- Higgins, C.P., and R.G. Luthy. 2006. Sorption of perfluorinated surfactants on sediments. Environmental Science & Technology 40, no. 23: 7251–7256. https://doi.org/10.1021/es061000n
- Høisæter, Å., A. Pfaff, and G.D. Breedveld. 2019. Leaching and transport of PFAS from aqueous film-forming foam (AFFF) in the unsaturated soil at a firefighting training facility under cold climatic conditions. Journal of Contaminant Hydrology 222: 112–122. https://doi.org/10.1016/j.jconhyd.2019.02.010
- Jeon, J., K. Kannan, B.J. Lim, K.G. An, and S.D. Kim. 2011. Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles. Journal of Environmental Monitoring 13, no. 6: 1803. https://doi.org/10.1039/c0em00791a
- Joerss, H., C. Apel, and R. Ebinghaus. 2019. Emerging per- and polyfluoroalkyl substances (PFASs) in surface water and sediment of the north and Baltic seas. Science of the Total Environment 686: 360–369. https://doi.org/10.1016/j.scitotenv.2019.05.363
- Johnson, R.L., A.J. Anschutz, J.M. Smolen, M.F. Simcik, and R.L. Penn. 2007. The adsorption of perfluorooctane sulfonate onto sand, clay, and iron oxide surfaces. Journal of Chemical & Engineering Data 52, no. 4: 1165–1170. https://doi.org/10.1021/je060285g
- Knight, E.R., L.J. Janik, D.A. Navarro, R.S. Kookana, and M.J. McLaughlin. 2019. Predicting partitioning of radiolabelled 14C-PFOA in a range of soils using diffuse reflectance infrared spectroscopy. Science of the Total Environment 686: 505–513. https://doi.org/10.1016/j.scitotenv.2019.05.339
- Li, F., X. Fang, Z. Zhou, X. Liao, J. Zou, B. Yuan, and W. Sun. 2019. Adsorption of perfluorinated acids onto soils: Kinetics, isotherms, and influences of soil properties. Science of the Total Environment 649: 504–514. https://doi.org/10.1016/j.scitotenv.2018.08.209
- Li, Y., D.P. Oliver, and R.S. Kookana. 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 628–629: 110–120. https://doi.org/10.1016/j.scitotenv.2018.01.167
- Liu, Y., Y. Zhang, J. Li, N. Wu, W. Li, and Z. Niu. 2019. Distribution, partitioning behavior and positive matrix factorization-based source analysis of legacy and emerging polyfluorinated alkyl substances in the dissolved phase, surface sediment and suspended particulate matter around coastal areas of Bohai Bay, China. Environmental Pollution 246: 34–44. https://doi.org/10.1016/j.envpol.2018.11.113
- Løland, B. 2014. Fate and transport of PFCs in a peat bog environment. Master thesis, University of Oslo, Oslo, Norway.
- Lu, C., P.L. Bjerg, F. Zhang, and M.M. Broholm. 2011. Sorption of chlorinated solvents and degradation products on natural clayey tills. Chemosphere 83, no. 11: 1467–1474. https://doi.org/10.1016/j.chemosphere.2011.03.007
- Lyu, Y., and M.L. Brusseau. 2020. The influence of solution chemistry on air-water interfacial adsorption and transport of PFOA in unsaturated porous media. Science of the Total Environment 713: 136744. https://doi.org/10.1016/j.scitotenv.2020.136744
- Mejia-Avendaño, S., Y. Zhi, B. Yan, and J. Liu. 2020. Sorption of polyfluoroalkyl surfactants on surface soils: Effect of molecular structures, soil properties, and solution chemistry. Environmental Science & Technology 54, no. 3: 1513–1521. https://doi.org/10.1021/acs.est.9b04989
- Milinovic, J., S. Lacorte, M. Vidal, and A. Rigol. 2015. Sorption behaviour of perfluoroalkyl substances in soils. Science of the Total Environment 511: 63–71. https://doi.org/10.1016/j.scitotenv.2014.12.017
- Montagnolli, R.N., P.R.M. Lopes, J.M. Cruz, M.T. Claro, G.M. Quiterio, and E.D. Bidoia. 2017. Metabolical shifts towards alternative BTEX biodegradation intermediates induced by perfluorinated compounds in firefighting foams. Chemosphere 173: 49–60. https://doi.org/10.1016/j.chemosphere.2016.12.144
- Moody, C.A., and J.A. Field. 2000. Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams. Environmental Science & Technology 34, no. 18: 3864–3870. https://doi.org/10.1021/es991359u
- Nguyen, T.M.H., J. Bräunig, K. Thompson, J. Thompson, S. Kabiri, D.A. Navarro, R.S. Kookana, C. Grimison, C.M. Barnes, C.P. Higgins, M.J. McLaughlin, and J.F. Mueller. 2020. Influences of chemical properties, soil properties, and solution PH on soil-water partitioning coefficients of per- and polyfluoroalkyl substances (PFASs). Environmental Science & Technology 54, no. 24: 15883–15892. https://doi.org/10.1021/acs.est.0c05705
- Nguyen, T.V., M. Reinhard, H. Chen, and K.Y.-H. Gin. 2016. Fate and transport of perfluoro- and polyfluoroalkyl substances including perfluorooctane sulfonamides in a managed urban water body. Environmental Science and Pollution Research 23, no. 11: 10382–10392. https://doi.org/10.1007/s11356-016-6788-9
- Oliver, D.P., Y. Li, R. Orr, P. Nelson, M. Barnes, M.J. McLaughlin, and R.S. Kookana. 2020. Sorption behaviour of per- and polyfluoroalkyl substances (PFASs) in tropical soils. Environmental Pollution 258: 113726. https://doi.org/10.1016/j.envpol.2019.113726
- Prevedouros, K., I.T. Cousins, R.C. Buck, and S.H. Korzeniowski. 2006. Sources, fate and transport of perfluorocarboxylates. Environmental Science & Technology 40, no. 1: 32–44. https://doi.org/10.1021/es0512475
- Schaefer, C.E., V. Culina, D. Nguyen, and J. Field. 2019. Uptake of poly- and perfluoroalkyl substances at the air–water interface. Environmental Science & Technology 53, no. 21: 12442–12448. https://doi.org/10.1021/acs.est.9b04008
- Shoemaker, J., and D. Tettenhorst. 2018. Method 537.1: Determination of selected per- and polyfluorinated alkyl substances in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS). U.S. Environmental Protection Agency, Office of Research and Development, National Center for Environmental Assessment, Washington, DC.
- USEPA. 2020a. Regional screening levels (RSLs).” Environmental Protection Agency. https://www.epa.gov/risk/regional-screening-levels-rsls (accessed October 1, 2020).
- USEPA. 2020b. Status of EPA Research and Development on PFAS. Environmental Protection Agency. www.epa.gov/chemical-research/status-epa-research-and-development-pfas (accessed October 1, 2020).
- USEPA. 1999. Understanding variation in partition coefficient, Kd, values. Washington, DC: Office of Air and Radiation.
- USEPA. 1996. Soil screening guidance: Technical background document. Washington, DC. Office of Solid Waste and Emergency Response. https://www.epa.gov/superfund/superfund-soil-screening-guidance (accessed October 1, 2020)
- USEPA. 1994. Method 1312, Revision 0. Final update II to the third edition of the test methods for evaluating solid waste, physical/chemical methods, EPA Publication SW-846.
- Vo, P., H. Nhat, H.H. Ngo, W. Guo, T.M.H. Nguyen, J. Li, H. Liang, L. Deng, Z. Chen, and T.A.H. Nguyen. 2020. Poly-and perfluoroalkyl substances in water and wastewater: A comprehensive review from sources to remediation. Journal of Water Process Engineering 36: 101393. https://doi.org/10.1016/j.jwpe.2020.101393
- Wang, Q., M.M.P. Tsui, Y. Ruan, H. Lin, Z. Zhao, J.P.H. Ku, H. Sun, and P.K.S. Lam. 2019. Occurrence and distribution of per- and polyfluoroalkyl substances (PFASs) in the seawater and sediment of the South China Sea coastal region. Chemosphere 231: 468–477. https://doi.org/10.1016/j.chemosphere.2019.05.162
- Wang, F., K. Shih, R. Ma, and X.-y. Li. 2015. Influence of cations on the partition behavior of perfluoroheptanoate (PFHpA) and perfluorohexanesulfonate (PFHxS) on wastewater sludge. Chemosphere 131: 178–183. https://doi.org/10.1016/j.chemosphere.2015.03.024
- Weber, A.K., L.B. Barber, D.R. LeBlanc, E.M. Sunderland, and C.D. Vecitis. 2017. Geochemical and hydrologic factors controlling subsurface transport of poly- and perfluoroalkyl substances, Cape Cod, Massachusetts. Environmental Science & Technology 51, no. 8: 4269–4279. https://doi.org/10.1021/acs.est.6b05573
- Xiao, F., B. Jin, S.A. Golovko, M.Y. Golovko, and B. Xing. 2019. Sorption and desorption mechanisms of cationic and zwitterionic per- and polyfluoroalkyl substances in natural soils: Thermodynamics and hysteresis. Environmental Science & Technology 53, no. 20: 11818–11827. https://doi.org/10.1021/acs.est.9b05379
- Zareitalabad, P., J. Siemens, M. Hamer, and W. Amelung. 2013. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in surface waters, sediments, soils and wastewater – A review on concentrations and distribution coefficients. Chemosphere 91, no. 6: 725–732. https://doi.org/10.1016/j.chemosphere.2013.02.024
- Zhang, D.Q., W.L. Zhang, and Y.N. Liang. 2019. Adsorption of perfluoroalkyl and polyfluoroalkyl substances (PFASs) from aqueous solution – A review. Science of The Total Environment 694: 133606. https://doi.org/10.1016/j.scitotenv.2019.133606