Isolating the AFFF Signature in Coastal Watersheds Using Oxidizable PFAS Precursors and Unexplained Organofluorine
Open accessAbstract
Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary and legacy use of aqueous film forming foams (AFFF) is a major contamination source. However, diverse PFAS sources are present within watersheds, making it difficult to isolate their predominant origins. Here we examine PFAS source signatures among six adjacent coastal watersheds on Cape Cod, MA, U.S.A. using multivariate clustering techniques. A distinct signature of AFFF contamination enriched in precursors with six perfluorinated carbons (C6) was identified in watersheds with an AFFF source, while others were enriched in C4 precursors. Principal component analysis of PFAS composition in impacted watersheds showed a decline in precursor composition relative to AFFF stocks and a corresponding increase in terminal perfluoroalkyl sulfonates with < C6 but not those with ≥ C6. Prior work shows that in AFFF stocks, all extractable organofluorine (EOF) can be explained by targeted PFAS and precursors inferred using Bayesian inference on the total oxidizable precursor assay. Using the same techniques for the first time in impacted watersheds, we find that only 24%-63% of the EOF can be explained by targeted PFAS and oxidizable precursors. Our work thus indicates the presence of large non-AFFF organofluorine sources in these coastal watersheds.
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Multivariate analyses have been used to establish PFAS source signatures and distinguish PFAS source inputs in surface water.
“Multivariate analyses have been used to establish PFAS source signatures and distinguish PFAS source inputs in surface water.”
Perfluoroalkyl sulfonamido compounds (C4, C6, and C8) are the predominant precursors in 3M AFFF (46 ± 1% of total PFAS) and are biotransformed in the subsurface into PFSA of the same number of perfluorinated carbons.
“Perfluoroalkyl sulfonamido compounds (C4, C6, and C8) are the predominant precursors in 3M AFFF (46 ± 1% of total PFAS) and are biotransformed in the subsurface into PFSA of the same number of perfluorinated carbons.11,24”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [11]
Together with their terminal PFSA, the C4, C6, and C8 precursor groups make up 88 ± 1% of total PFAS in 3M AFFF and 40 ± 8% of total PFAS in groundwater beneath the JBCC fire training area.
“Together with their terminal PFSA, these three precursor groups make up 88 ± 1% of total PFAS in 3M AFFF and 40 ± 8% of total PFAS in groundwater beneath the JBCC fire training area.11”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [11]
For C6 compounds, the ratio of precursors to terminal PFSA was 0.7 ± 0.4 in groundwater compared to 6.7 ± 1.4 in 3M AFFF.
“For the C4 and C6 compounds, the ratios of precursors to their terminal PFSA were 4.9 ± 1.6 in groundwater compared to 11 ± 4.7 in 3M AFFF (C4 compounds), and 0.7 ± 0.4 in groundwater compared to 6.7 ± 1.4 in 3M AFFF (C6 compounds).5,11”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [11]
For C4 compounds, the ratio of precursors to terminal PFSA was 4.9 ± 1.6 in groundwater compared to 11 ± 4.7 in 3M AFFF.
“For the C4 and C6 compounds, the ratios of precursors to their terminal PFSA were 4.9 ± 1.6 in groundwater compared to 11 ± 4.7 in 3M AFFF (C4 compounds), and 0.7 ± 0.4 in groundwater compared to 6.7 ± 1.4 in 3M AFFF (C6 compounds).5,11”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [11]
The release of PFAS into the environment occurs through two major sources: point sources and nonpoint sources.
“The release of PFAS into the environment occurs through two major sources.”
From Per- and polyfluoroalkyl substances in water and wastewater: A critical review of their global occurrence and distribution (2022) · cites this paper as Ruyle et al., 2021
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- Authors
- Ruyle, B. J., Pickard, H. M., LeBlanc, D. R., Tokranov, A. K., Thackray, C. P., Hu, X. C., Vecitis, C. D., & Sunderland, E. M.
- Affiliations
- Harvard University (US)
- New England Water Science Center (US)
- Corresponding author
- Ruyle, Bridger J.
- ORCID
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2021-03-05
- Volume
- 55
- Issue
- 6
- Pages
- 3686-3695
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- PMC
- PMC11082878
- OpenAlex
- W3133663268
- Cited by
- 136
- References
- 45
- Citations by year
- 2026: 23 · 2025: 26 · 2024: 28 · 2023: 24 · 2022: 28 · 2021: 7
- FWCI
- 8.24
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Licence
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- PubMed Central (acceptedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- Funders
- National Institute of Environmental Health Sciences (P42ES027706)
- U.S. Department of Defense (SERDP ER18-1280)
- U.S. Geological Survey
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Chemical Analysis and Environmental Impact
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Keywords
- aqueous film-forming foam, perfluoroalkyl sulfonates, coastal watersheds, Cape Cod, PFAS contamination, multivariate clustering
- MeSH terms
- Alkanesulfonates, Bayes Theorem, Fluorocarbons, Humans, Water, Water Pollutants, Chemical
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