Identification of Novel Fluorochemicals in Aqueous Film-Forming Foams Used by the US Military
Open accessAbstract
Aqueous film-forming foams (AFFFs) are a vital tool to fight large hydrocarbon fires and can be used by public, commercial, and military firefighting organizations. In order to possess these superior firefighting capabilities, AFFFs contain fluorochemical surfactants, of which many of the chemical identities are listed as proprietary. Large-scale controlled (e.g., training activities) and uncontrolled releases of AFFF have resulted in contamination of groundwater. Information on the composition of AFFF formulations is needed to fully define the extent of groundwater contamination, and the first step is to fully define the fluorochemical composition of AFFFs used by the US military. Fast atom bombardment mass spectrometry (FAB-MS) and high resolution quadrupole-time-of-flight mass spectrometry (QTOF-MS) were combined to elucidate chemical formulas for the fluorochemicals in AFFF mixtures, and, along with patent-based information, structures were assigned. Sample collection and analysis was focused on AFFFs that have been designated as certified for US military use. Ten different fluorochemical classes were identified in the seven military-certified AFFF formulations and include anionic, cationic, and zwitterionic surfactants with perfluoroalkyl chain lengths ranging from 4 to 12. The environmental implications are discussed, and research needs are identified.
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A study identifying PFAS components in 3M AFFF indicated only perfluorosulfonates were in surfactants produced between 1988 and 2001.
“A study identifying PFAS components in 3M AFFF indicated only perfluorosulfonates were in surfactants produced between 1988 and 2001 (Place & Field, 2012).”
From Perfluoroalkyl acids in sediment and water surrounding historical fire training areas at Barksdale Air Force Base (2022) · cites this paper as Place & Field, 2012
In Results and Discussion, the paper identifies perfluoroalkyl sulfonates in the analyzed 3M AFFF samples dated 1988–2001 and reports no detectable perfluoroalkyl carboxylates. But it also identifies zwitterionic perfluoroalkyl sulfonamides in samples from 1993, 1998, and 2001. The claim that only perfluorosulfonates were present therefore overstates the findings; the method could also miss minor components. (LLM, conf=0.88)
Experimental — accuracy not yet measuredElectrochemical fluorination produces fully fluorinated compounds, such as PFOS.
“Electrochemical fluorination is a process that produces fully fluorinated compounds, such as PFOS (Place & Field, 2012).”
From Perfluoroalkyl acids in sediment and water surrounding historical fire training areas at Barksdale Air Force Base (2022) · cites this paper as Place & Field, 2012
Place and Field (2012) identified 10 subclasses of PFASs in multiple aqueous film forming foam (AFFF) formulations.
“Place and Field (2012)5 identified 10 subclasses of PFASs in multiple aqueous film forming foam (AFFF) formulations”
From A Never-Ending Story of Per- and Polyfluoroalkyl Substances (PFASs)? (2017) · cites this paper as Place and Field (2012)5
Commercial standards are available for <10 out of the hundreds of precursors previously detected in AFFF.
“Commercial standards are available for <10 out of the hundreds of precursors previously detected in AFFF.7−10”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [8]
Almost all (14/15) identified precursors were perfluoroalkyl sulfonamido compounds previously identified in 3M AFFF or suspected metabolites.
“Almost all (14/15) were perfluoroalkyl sulfonamido compounds previously identified in 3M AFFF or suspected metabolites.7,8”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [8]
3M AFFF does not contain substantial precursors for the C7 PFCA.
“Eqs 1 and 3 and the term for kbio were not included in the model for PFOA (2-box model) because 3M AFFF does not contain substantial precursors for the C7 PFCA7,8”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [8]
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 [8]
A pioneer study on novel PFAS identification in AFFF formulations used fast atom bombardment (FAB)-MS and quadrupole TOF-MS.
“A pioneer study on novel PFAS identification in AFFF formulations used fast atom bombardment (FAB)-MS and quadrupole TOF-MS [92].”
From Worldwide trends in tracing poly- and perfluoroalkyl substances (PFAS) in the environment (2019) · cites this paper as [92]
Diverse novel PFAS including anions, zwitterions, cations and neutral species were identified in AFFF samples, Fluorad surfactants, water, airborne particulate matter, fish and circulating blood.
“diverse novel PFAS including anions, zwitterions, cations and neutral species were identified in AFFF samples [92,93], Fluorad surfactants [94], water [17], airborne particulate matter [16], fish [18] and circulating blood [19].”
From Worldwide trends in tracing poly- and perfluoroalkyl substances (PFAS) in the environment (2019) · cites this paper as [92]
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- Authors
- Place, B. J., & Field, J. A.
- Affiliations
- Oregon State University (US)
- Corresponding author
- Field, Jennifer A.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-06-15
- Volume
- 46
- Issue
- 13
- Pages
- 7120-7127
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- PMC
- PMC3390017
- OpenAlex
- W2054550313
- Cited by
- 543
- References
- 11
- Citations by year
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- FWCI
- 10.49
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institute of Environmental Health Sciences (P30ES000210, #P30-ES00210)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Toxic Organic Pollutants Impact
- Keywords
- aqueous film-forming foam, fluorochemicals, groundwater contamination, perfluorinated compounds, surfactant composition, compound identification, environmental implications
- MeSH terms
- Flame Retardants, Fluorocarbons, Mass Spectrometry, Surface-Active Agents, Water Pollutants, Chemical, Spectrometry, Mass, Fast Atom Bombardment, Military Facilities, Groundwater
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
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