Reconstructing the Composition of Per- and Polyfluoroalkyl Substances in Contemporary Aqueous Film-Forming Foams
Open accessAbstract
Hundreds of public water systems across the United States have been contaminated by the use of aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS) during firefighting and training activities. Prior work shows AFFF contain hundreds of polyfluoroalkyl precursors missed by standard methods. However, the most abundant precursors in AFFF remain uncertain, and mixture contents are confidential business information, hindering proactive management of PFAS exposure risks. Here, we develop and apply a novel method (Bayesian inference) for reconstructing the fluorinated chain lengths, manufacturing origin, and concentrations of oxidizable precursors obtained from the total oxidizable precursor (TOP) assay that is generally applicable to all aqueous samples. Results show virtually all (median 104 ± 19%) extractable organofluorine (EOF) in contemporary and legacy AFFF consists of targeted compounds and oxidizable precursors, 90% of which are 6:2 fluorotelomers in contemporary products. Using high-resolution mass spectrometry, we further resolved the 6:2 fluorotelomers to assign the identity of 14 major compounds, yielding a priority list that accounts for almost all detectable PFAS in contemporary AFFF. This combination of methods can accurately assign the total PFAS mass attributable to AFFF in any aqueous sample with differentiation of gross precursor classes and identification of major precursor species.
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Much of the PFAS at AFFF-contaminated sites consists of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods.
“Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods.”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
3M AFFF manufactured prior to 2001 contained hundreds of precursors that accounted for >50% of the total PFAS.
“For example, AFFF manufactured by 3M prior to 2001 (3M AFFF) contained hundreds of precursors that accounted for >50% of the total PFAS.5−7”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
6:2 fluorotelomer compounds comprise >90% of PFAS in contemporary non-3M AFFF.
“This class of precursors comprises >90% of PFAS in contemporary non-3M AFFF.6”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
Past work showed that EOF concentrations provide a good proxy for total PFAS in AFFF and range between (850-900) ×10^6 nM F in the 3M product.
“Past work showed that EOF concentrations provide a good proxy for total PFAS in AFFF and range between (850–900) ×106 nM F in the 3M product.6”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
PFOA is present in 3M AFFF but is not a major biotransformation endpoint for sulfonamido precursors.
“The other major terminal PFAS in groundwater was PFOA (C7 PFCA; 17 ± 8% of total PFAS), which is present in 3M AFFF but is not a major biotransformation endpoint for sulfonamido precursors.5,6,24”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
TOP+BI can reproduce EOF measurements in AFFF, confirming that it quantitatively captures all PFAS derived from AFFF use.
“TOP+BI can reproduce extractable organofluorine measurements (EOF) in AFFF, thereby confirming that it quantitatively captures all PFAS derived from AFFF use.6”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
PFOS is absent from contemporary foams and its production was phased out by 3M around 2002, indicating residual contamination is a legacy problem.
“PFOS is absent from contemporary foams and its production was phased out by 3M (the main global manufacturer) around 2002, indicating residual contamination is a legacy problem.5,6,8”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [6]
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- Authors
- Ruyle, B. J., Thackray, C. P., McCord, J. P., Strynar, M. J., Mauge-Lewis, K. A., Fenton, S. E., & Sunderland, E. M.
- Affiliations
- Harvard University (US)
- Environmental Protection Agency (US)
- National Institutes of Health (US)
- Corresponding author
- Ruyle, Bridger J.
- ORCID
- Venue
- Environmental Science & Technology Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-11-04
- Volume
- 8
- Issue
- 1
- Pages
- 59-65
- ISSN
- 2328-8930 (ISSN-L)
- PMC
- PMC7898139
- OpenAlex
- W3097197566
- Cited by
- 131
- References
- 29
- Citations by year
- 2026: 36 · 2025: 24 · 2024: 23 · 2023: 18 · 2022: 18 · 2021: 11 · 2020: 1
- FWCI
- 4.45
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Licence
- Locations
- Environmental Science & Technology Letters (publishedVersion)
- PubMed (publishedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institute of Environmental Health Sciences (P42ES027706, Z0ES102785)
- U.S. Department of Defense (SERDP ER18-1280)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Toxic Organic Pollutants Impact
- Physical Sciences › Materials Science › Polymers and Plastics › Synthesis and properties of polymers
- Keywords
- aqueous film-forming foam, per- and polyfluoroalkyl substances, fluorotelomers, Bayesian inference, total oxidizable precursor assay
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