Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Per- and polyfluoroalkyl ether acids in well water and blood serum from private well users residing by a fluorochemical facility near Fayetteville, North Carolina

Journal of Exposure Science & Environmental Epidemiology volume 34, pages 97–107 (2024)Cite this article

Abstract

Background

A fluorochemical facility near Fayetteville, North Carolina, emitted per- and polyfluoroalkyl ether acids (PFEAs), a subgroup of per- and polyfluoroalkyl substances (PFAS), to air.

Objective

Analyze PFAS in private wells near the facility and in blood from well users to assess relationships between PFEA levels in water and serum.

Methods

In 2019, we recruited private well users into the GenX Exposure Study and collected well water and blood samples. We targeted 26 PFAS (11 PFEAs) in water and 27 PFAS (9 PFEAs) in serum using liquid chromatography-mass spectrometry. We used regression modeling to explore relationships between water and serum PFAS. For the only PFEA detected frequently in water and serum, Nafion byproduct 2, we used generalized estimating equation (GEE) models to assess well water exposure metrics and then adjusted for covariates that may influence Nafion byproduct 2 serum concentrations.

Results

We enrolled 153 participants ages 6 and older (median = 56 years) using 84 private wells. Most wells (74%) had ≥6 detectable PFEAs; median ∑PFEAs was 842 ng/L (interquartile range = 197–1760 ng/L). Low molecular weight PFEAs (PMPA, HFPO-DA [GenX], PEPA, PFO2HxA) were frequently detected in well water, had the highest median concentrations, but were not detectable in serum. Nafion byproduct 2 was detected in 73% of wells (median = 14 ng/L) and 56% of serum samples (median = 0.2 ng/mL). Cumulative dose (well concentration × duration at address) was positively associated with Nafion byproduct 2 serum levels and explained the most variability (10%). In the adjusted model, cumulative dose was associated with higher Nafion byproduct 2 serum levels while time outside the home was associated with lower levels.

IMPACT

PFAS are a large class of synthetic, fluorinated chemicals. Fluorochemical facilities are important sources of environmental PFAS contamination globally. The fluorochemical industry is producing derivatives of perfluoroalkyl acids, including per- and polyfluoroalkyl ether acids (PFEAs). PFEAs have been detected in various environmental samples but information on PFEA-exposed populations is limited. While serum biomonitoring is often used for PFAS exposure assessment, serum biomarkers were not good measures of long-term exposure to low molecular weight PFEAs in a private well community. Environmental measurements and other approaches besides serum monitoring will be needed to better characterize PFEA exposure.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: PFAS detection frequency in well water and blood serum.
Fig. 2: GEE regression model results for serum Nafion byproduct 2 in private well users.

Similar content being viewed by others

Data availability

The datasets generated and analyzed during the current study are not publicly available due to human subjects protections of these data. Data may be made available from the corresponding author on reasonable request with IRB approval.

References

  1. US Environmental Protection Agency PFAS Master List of PFAS Substances. Accessed: 11 July 2023. Available from: https://comptox.epa.gov/dashboard/chemical-lists/PFASMASTER.

  2. Glüge J, Scheringer M, Cousins IT, DeWitt JC, Goldenman G, Herzke D. et al. An overview of the uses of per-and polyfluoroalkyl substances (PFAS). Environ Sci: Process Impacts. 2020;22:2345–73.

    PubMed  Google Scholar 

  3. United States Environmental Protection Agency Fact Sheet: 2010/2015 PFOA Stewardship Program. Available from: https://www.epa.gov/assessing-and-managing-chemicals-under-tsca/fact-sheet-20102015-pfoa-stewardship-program.

  4. National Academies of Sciences, Engineering, Medicine: Guidance on PFAS Exposure, Testing, and Clinical Follow-Up. Available from: https://www.nationalacademies.org/news/2022/07/new-report-calls-for-expanded-pfas-testing-for-people-with-history-of-elevated-exposure-offers-advice-for-clinical-treatment.

  5. Sunderland EM, Hu XC, Dassuncao C, Tokranov AK, Wagner CC, Allen JG. A review of the pathways of human exposure to poly-and perfluoroalkyl substances (PFASs) and present understanding of health effects. J Expo Sci Environ Epidemiol. 2019;29:131–47.

    Article  CAS  PubMed  Google Scholar 

  6. McCord J, Strynar M. Identification of per-and polyfluoroalkyl substances in the cape fear river by high resolution mass spectrometry and nontargeted screening. Environ Sci Technol. 2019;53:4717–27.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Hopkins ZR, Sun M, DeWitt JC, Knappe DR. Recently detected drinking water contaminants: genx and other per‐and polyfluoroalkyl ether acids. J‐Am Water Works Assoc. 2018;110:13–28.

    Article  CAS  Google Scholar 

  8. Galloway JE, Moreno AV, Lindstrom AB, Strynar MJ, Newton S, May AA, et al. Evidence of air dispersion: HFPO–DA and PFOA in Ohio and West Virginia surface water and soil near a fluoropolymer production facility. Environ Sci Technol. 2020;54:7175–84.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. Washington JW, Rosal CG, McCord JP, Strynar MJ, Lindstrom AB, Bergman EL, et al. Nontargeted mass-spectral detection of chloroperfluoropolyether carboxylates in New Jersey soils. Science. 2020;368:1103–7.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Gebbink, W.A., Van Asseldonk, L., Van Leeuwen, S.P.J.E.S., and technology, Presence of emerging per-and polyfluoroalkyl substances (PFASs) in river and drinking water near a fluorochemical production plant in the Netherlands. 2017. 51: p. 11057-65.

  11. Yao J, Pan Y, Sheng N, Su Z, Guo Y, Wang J, et al. Novel perfluoroalkyl ether carboxylic acids (PFECAs) and sulfonic acids (PFESAs): occurrence and association with serum biochemical parameters in residents living near a fluorochemical plant in China. Environ Sci Technol. 2020;54:13389–98.

    Article  CAS  PubMed  Google Scholar 

  12. Pike KA, Edmiston PL, Morrison JJ, Faust JA. Correlation analysis of perfluoroalkyl substances in regional US precipitation events. Water Res. 2021;190:116685.

    Article  CAS  PubMed  Google Scholar 

  13. North Carolina Department of Environmental Quality GenX Information for Residents in Bladen, Cumberland, Robeson and Sampson Counties. Accessed: 25 Jan 2023. Available from: https://deq.nc.gov/news/key-issues/genx-investigation/genx-information-residents#DEQMaps-11849.

  14. Pan Y, Zhang H, Cui Q, Sheng N, Yeung LW, Sun Y, et al. Worldwide distribution of novel perfluoroether carboxylic and sulfonic acids in surface water. Environ Sci Technol. 2018;52:7621–9.

    Article  CAS  PubMed  Google Scholar 

  15. Strynar M, Dagnino S, McMahen R, Liang S, Lindstrom A, Andersen E, et al. Identification of novel perfluoroalkyl ether carboxylic acids (PFECAs) and sulfonic acids (PFESAs) in natural waters using accurate mass time-of-flight mass spectrometry (TOFMS). Environ Sci Technol. 2015;49:11622–30.

    Article  CAS  PubMed  Google Scholar 

  16. Sun M, Arevalo E, Strynar M, Lindstrom A, Richardson M, Kearns B, et al. Legacy and emerging perfluoroalkyl substances are important drinking water contaminants in the Cape Fear River Watershed of North Carolina. Environ Sci Technol Lett. 2016;3:415–9.

    Article  CAS  Google Scholar 

  17. Espartero LJL, Yamada M, Ford J, Owens G, Prow T, Juhasz A. Health-related toxicity of emerging per-and polyfluoroalkyl substances: Comparison to legacy PFOS and PFOA. Environ Res. 2022;212:113431.

    Article  Google Scholar 

  18. Yao J, Dong Z, Jiang L, Pan Y, Zhao M, Bai X, et al. Emerging and legacy perfluoroalkyl substances in breastfed Chinese infants: renal clearance, body burden, and implications. Environ Health Perspect. 2023;131:037003.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Kotlarz N, McCord J, Collier D, Lea CS, Strynar M, Lindstrom AB, et al. Measurement of novel, drinking water-associated PFAS in blood from adults and children in Wilmington, North Carolina. Environ Health Perspect. 2020;128:077005.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Hoffman K, Webster TF, Bartell SM, Weisskopf MG, Fletcher T, Vieira VM. Private drinking water wells as a source of exposure to perfluorooctanoic acid (PFOA) in communities surrounding a fluoropolymer production facility. Environ Health Perspect. 2011;119:92–97.

    Article  CAS  PubMed  Google Scholar 

  21. Hu XC, Tokranov AK, Liddie J, Zhang X, Grandjean P, Hart JE, et al. Tap water contributions to plasma concentrations of poly-and perfluoroalkyl substances (PFAS) in a nationwide prospective cohort of US women. Environ Health Perspect. 2019;127:067006.

    Article  PubMed  PubMed Central  Google Scholar 

  22. Seals R, Bartell SM, Steenland K. Accumulation and clearance of perfluorooctanoic acid (PFOA) in current and former residents of an exposed community. Environ Health Perspect. 2011;119:119–24.

    Article  CAS  PubMed  Google Scholar 

  23. Emmett EA, Shofer FS, Zhang H, Freeman D, Desai C, Shaw LM. Community exposure to perfluorooctanoate: relationships between serum concentrations and exposure sources. J Occup Environ Med. 2006;48:759.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Zhou J, Baumann K, Surratt JD, Turpin BJ. Legacy and emerging airborne per-and polyfluoroalkyl substances (PFAS) collected on PM 2.5 filters in close proximity to a fluoropolymer manufacturing facility. Environ Sci Process Impacts. 2022;24:2272–83.

    Article  CAS  PubMed  Google Scholar 

  25. North Carolina Department of Environmental Quality (NC DEQ) GenX Investigation: Groundwater. Accessed: 11 July 2022. Available from: https://deq.nc.gov/news/key-issues/genx-investigation/groundwater.

  26. United States Environmental Protection Agency (US EPA) Drinking Water Health Advisory: Hexafluoropropylene Oxide (HFPO) Dimer Acid (CASRN 13252-13-6) and HFPO Dimer Acid Ammonium Salt (CASRN 62037-80-3), Also Known as “GenX Chemicals”. Available from: https://www.epa.gov/system/files/documents/2022-06/drinking-water-genx-2022.pdf.

  27. United States Environmental Protection Agency. Per- and Polyfluoroalkyl Substances (PFAS): Proposed PFAS National Primary Drinking Water Regulation. Accessed: Oct 4, 2023. Available from: https://www.epa.gov/sdwa/and-polyfluoroalkyl-substances-pfas.

  28. U.S. EPA, 2011 U.S. EPA, 2011 Exposure Factors Handbook 2011 Edition (Final Report). U.S. Environmental Protection Agency, Washington, DC, EPA/600/R-09/052F. Accessed: Jan 9, 2023. Available from: https://www.epa.gov/expobox/about-exposure-factors-handbook.

  29. Pétré M-A, Genereux DP, Koropeckyj-Cox L, Knappe DR, Duboscq S, Gilmore TE, et al. Per-and polyfluoroalkyl substance (PFAS) transport from groundwater to streams near a PFAS manufacturing facility in North Carolina, USA. Environ Sci Technol. 2021;55:5848–56. https://doi.org/10.1021/acs.est.0c07978.

    Article  CAS  PubMed  Google Scholar 

  30. OECD Synthesis paper on per and polyfluorinated chemicals. Accessed: 11 July 2023. Available from: https://www.oecd.org/chemicalsafety/risk-management/synthesis-paper-on-per-and-polyfluorinated-chemicals.htm.

  31. Barton KE, Starling AP, Higgins CP, McDonough CA, Calafat AM, Adgate JL. Sociodemographic and behavioral determinants of serum concentrations of per-and polyfluoroalkyl substances in a community highly exposed to aqueous film-forming foam contaminants in drinking water. Int J Hyg Environ Health. 2020;223:256–66.

    Article  CAS  PubMed  Google Scholar 

  32. Park SK, Peng Q, Ding N, Mukherjee B, Harlow SD. Determinants of per-and polyfluoroalkyl substances (PFAS) in midlife women: evidence of racial/ethnic and geographic differences in PFAS exposure. Environ Res. 2019;175:186–99.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Roostaei J, Colley S, Mulhern R, May AA, Gibson JM. Predicting the risk of GenX contamination in private well water using a machine-learned Bayesian network model. J Hazard Mater. 2021;411:125075.

    Article  CAS  PubMed  Google Scholar 

  34. European Chemicals Agency Exposure related observations in humans: other data for Ammonium 2,3,3,3-tetrauoro-2-(heptauoropropoxy)propanoate.

  35. Pritchett JR, Rinsky JL, Dittman B, Christensen A, Langley R, Moore Z, et al. Notes from the field: targeted biomonitoring for GenX and other per-and polyfluoroalkyl substances following detection of drinking water contamination—North Carolina, 2018. Morbidity Mortal Wkly Rep. 2019;68:647.

    Article  Google Scholar 

  36. C8 Science Panel. Accessed: Oct 11, 2023. Available from: http://www.c8sciencepanel.org/index.html.

  37. Johanson G, Gyllenhammar I, Ekstrand C, Pyko A, Xu Y, Li Y, et al. Quantitative relationships of perfluoroalkyl acids in drinking water associated with serum concentrations above background in adults living near contamination hotspots in Sweden. Environ Res. 2023;219:115024.

    Article  CAS  PubMed  Google Scholar 

  38. Calafat AM, Kato K, Hubbard K, Jia T, Botelho JC, Wong L-Y. Legacy and alternative per-and polyfluoroalkyl substances in the US general population: paired serum-urine data from the 2013-4 National Health and Nutrition Examination Survey. Environ Int. 2019;131:105048.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Calafat AM, Kuklenyik Z, Reidy JA, Caudill SP, Tully JS, Needham LL. Serum concentrations of 11 polyfluoroalkyl compounds in the US population: data from the National Health and Nutrition Examination Survey (NHANES) 1999− 2000. Environ Sci Technol. 2007;41:2237–42.

    Article  CAS  PubMed  Google Scholar 

  40. Calafat AM, Wong L-Y, Kuklenyik Z, Reidy JA, Needham LL. Polyfluoroalkyl chemicals in the US population: data from the National Health and Nutrition Examination Survey (NHANES) 2003-4 and comparisons with NHANES 1999–2000. Environ Health Perspect. 2007;115:1596–602.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  41. Chow SJ, Ojeda N, Jacangelo JG, Schwab KJ. Detection of ultrashort-chain and other per-and polyfluoroalkyl substances (PFAS) in US bottled water. Water Res. 2021;201:117292.

    Article  CAS  PubMed  Google Scholar 

  42. Neuwald IJ, Hübner D, Wiegand HL, Valkov V, Borchers U, Nödler K, et al. Ultra-short-chain PFASs in the sources of German drinking water: prevalent, overlooked, difficult to remove, and unregulated. Environ Sci Technol. 2022;56:6380–90.

    Article  CAS  PubMed  Google Scholar 

  43. Pelch KE, McKnight T, Reade A. 70 analyte PFAS test method highlights need for expanded testing of PFAS in drinking water. Sci Total Environ. 2023;876:162978.

    Article  CAS  PubMed  Google Scholar 

  44. Poothong S, Thomsen C, Padilla-Sanchez JA, Papadopoulou E, Haug LS.Distribution of novel and well-known poly-and perfluoroalkyl substances (PFASs) in human serum, plasma, and whole blood.Environ Sci Technol. 2017;51:13388–96.

    Article  CAS  PubMed  Google Scholar 

  45. Wallis D, Kotlarz N, Knappe D, Collier D, Lea CS, Reif D, et al. Estimation of the half-lives of recently detected per- and poly- fluorinated alkyl ethers in an exposed community. Environ Sci Technol. 2023;57:15348–55.

    Article  CAS  PubMed  Google Scholar 

  46. Kirkwood KI, Fleming J, Nguyen H, Reif DM, Baker ES, Belcher SM. Utilizing pine needles to temporally and spatially profile per-and polyfluoroalkyl substances (PFAS). Environ Sci Technol. 2022;56:3441–51.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  47. Mulhern R, Bynum N, Liyanapatirana C, DeStefano NJ, Knappe DR, MacDonald Gibson J. Longitudinal assessment of point‐of‐use carbon filters for removal of per‐and polyfluoroalkyl substances from private well water. AWWA Water Sci. 2021;3:e1262.

    Article  CAS  Google Scholar 

  48. Timeline: Tracking GenX contamination in NC. WRAL News. Posted on Aug 10, 2017. Available from: https://www.wral.com/story/timeline-tracking-the-route-of-genx-in-the-cape-fear-river/16869639/.

  49. Nakayama SF, Yoshikane M, Onoda Y, Nishihama Y, Iwai-Shimada M, Takagi M, et al. Worldwide trends in tracing poly-and perfluoroalkyl substances (PFAS) in the environment. TrAC Trends Anal Chem. 2019;121:115410.

  50. Hölzer J, Midasch O, Rauchfuss K, Kraft M, Reupert R, Angerer J, et al. Biomonitoring of perfluorinated compounds in children and adults exposed to perfluorooctanoate-contaminated drinking water. Environ Health Perspect. 2008;116:651–7.

    Article  PubMed  PubMed Central  Google Scholar 

  51. Daly ER, Chan BP, Talbot EA, Nassif J, Bean C, Cavallo SJ, et al. Per-and polyfluoroalkyl substance (PFAS) exposure assessment in a community exposed to contaminated drinking water, New Hampshire, 2015. Int J Hyg Environ Health. 2018;221:569–77.

    Article  CAS  PubMed  Google Scholar 

  52. Bartell SM, Calafat AM, Lyu C, Kato K, Ryan PB, Steenland KJEHP. Rate of decline in serum PFOA concentrations after granular activated carbon filtration at two public water systems in Ohio and West Virginia. Environ Health Perspect. 2010;118:222–8.

    Article  CAS  PubMed  Google Scholar 

  53. Guillette T, McCord J, Guillette M, Polera M, Rachels KT, Morgeson C, et al. Elevated levels of per-and polyfluoroalkyl substances in Cape Fear River Striped Bass (Morone saxatilis) are associated with biomarkers of altered immune and liver function. Environ Int. 2020;136:105358.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Acknowledgements

We thank our Fayetteville community science advisory board (T. Duncan, J. Green, V. Guidry, C Harrelson, A. Jones, J. Kimbrough, Z. Moore, J. Parsons, D. Sargent, W. Smith, T. Walters, M. Watters) for helpful discussions. We thank Stacie Reckling for creating the map in Fig. S2.

Funding

The GenX Exposure Study is supported by research funding from the National Institute of Environmental Health Sciences (1R21ES029353), Center for Human Health and the Environment (CHHE) at NC State University (P30 ES025128), the Center for Environmental and Health Effects of PFAS (P42 ES0310095), and the NC Policy Collaboratory. The research presented was not performed or funded by EPA and was not subject to EPA’s quality system requirements. The views expressed in this manuscript are those of the authors and do not necessarily represent the views or policies of the U.S. Environmental Protection Agency or the National Institutes of Health. Any mention of trade names or commercial products does not constitute EPA endorsement or recommendation for use.

Author information

Authors and Affiliations

  1. Center for Human Health and the Environment, North Carolina State University (NC State), Raleigh, NC, USA

    Nadine Kotlarz, David Collier, C. Suzanne Lea, Detlef R. U. Knappe & Jane A. Hoppin

  2. Department of Biological Sciences, NC State, Raleigh, NC, USA

    Nadine Kotlarz, Claire Critchley, Michael Cuffney & Jane A. Hoppin

  3. Oak Ridge Institute for Science and Education Research Participation Program, Oak Ridge, TN, USA

    Theresa Guillette

  4. Department of Pediatrics, Brody School of Medicine, East Carolina University (ECU), Greenville, NC, USA

    David Collier

  5. Department of Public Health, Brody School of Medicine, ECU, Greenville, NC, USA

    C. Suzanne Lea

  6. Center for Environmental Measurement and Modeling, U.S. Environmental Protection Agency, Research Triangle Park, Durham, NC, USA

    James McCord & Mark Strynar

  7. Department of Civil, Construction, and Environmental Engineering, NC State, Raleigh, NC, USA

    Zachary R. Hopkins & Detlef R. U. Knappe

Authors
  1. Nadine Kotlarz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Theresa Guillette
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Claire Critchley
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. David Collier
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. C. Suzanne Lea
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. James McCord
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Mark Strynar
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Michael Cuffney
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Zachary R. Hopkins
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Detlef R. U. Knappe
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jane A. Hoppin
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

NK: Study conceptualization, sample analysis, data acquisition and interpretation, led writing of original draft and revisions. CC: Data acquisition, contributed to original draft, review of final version. DC: Data acquisition, contributed to original draft, review of final version. CSL: Data acquisition, contributed to original draft, review of final version. TG, JM, MS, ZRH: Analytical methodology, sample analysis, contributed to original draft, review of final version. MC: Data acquisition, statistical analysis, review & editing. DRUK: Methodology, data interpretation, contributed to original draft, review & editing. JAH: Study conceptualization, methodology, data interpretation, review & editing, funding acquisition.

Corresponding author

Correspondence to Nadine Kotlarz.

Ethics declarations

Competing interests

The authors declare no competing interests.

Ethical approval

The GenX Exposure Study protocol and informed consent documents are approved by the Institutional Review Board of NC State University. Participants in the GenX Exposure Study gave informed consent to their information being used for research prior to participation this study.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kotlarz, N., Guillette, T., Critchley, C. et al. Per- and polyfluoroalkyl ether acids in well water and blood serum from private well users residing by a fluorochemical facility near Fayetteville, North Carolina. J Expo Sci Environ Epidemiol 34, 97–107 (2024). https://doi.org/10.1038/s41370-023-00626-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41370-023-00626-x

Keywords

This article is cited by

Search

Advanced search

Quick links