Identification of Novel Fluorinated Surfactants in Aqueous Film Forming Foams and Commercial Surfactant Concentrates
Abstract
Recent studies comparing the results of total organofluorine-combustion ion chromatography (TOF-CIC) to targeted analysis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) by liquid chromatography tandem mass spectrometry (LC-MS/MS) have shown that a significant yet variable portion of the total organofluorine in environmental and biological samples is in the form of unknown PFASs. A portion of this unknown organofluorine likely originates in proprietary fluorinated surfactants not included in LC-MS/MS analyses and not fully characterized by the environmental science community, which may enter the environment through use in aqueous film forming foams (AFFFs) for firefighting. Contamination of water, biota, and soils with various PFASs due to AFFF deployment has been documented. Ten fluorinated AFFF concentrates, 9 of which were obtained from fire sites in Ontario, Canada, and two commercial fluorinated surfactant concentrates were characterized in order to identify novel fluorinated surfactants. Mixed-mode ion exchange solid phase extraction (SPE) fractionated fluorinated surfactants based on ionic character. High resolution mass spectrometry assigned molecular formulas to fluorinated surfactant ions, while collision induced dissociation (CID) spectra assisted structural elucidation. LC-MS/MS detected isomers and low abundance fluorinated chain lengths. In total, 12 novel and 10 infrequently reported PFAS classes were identified in fluorinated chain lengths from C3 to C15 for a total of 103 compounds. Further research should examine the environmental fate and toxicology of these PFASs, especially their potential as perfluoroalkyl acid (PFAA) precursors.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
6:2 FTSA, 6:2 FTAB and FHxSA were developed as replacements and have been found in firefighting foams in high concentrations.
“For example, 6:2 fluorotelomer sulfonates (6:2 FTSA), 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB or 6:2 FTSA-PrB) and perfluorohexane sulfonamide (FHxSA) where developed as replacements and have been found in firefighting foams in high concentrations”
From Release of per- and polyfluoroalkyl substances (PFAS) from a waste management facility fire to an urban creek (2022) · cites this paper as D'Agostino et al., 2014
High concentrations of short chain PFAAs among the two campaigns might be due to degradation of perfluoroalkyl sulfonamide substances.
“High concentrations of short chain PFAAs among the two campaigns might be due to degradation of perfluoroalkyl sulfonamide substances”
From Release of per- and polyfluoroalkyl substances (PFAS) from a waste management facility fire to an urban creek (2022) · cites this paper as D'Agostino et al., 2014
6:2 FTAB and 6:2 FTSA are both fluorotelomers compounds that have replaced PFOS and PFOA phasing out from AFFFs.
“6:2 FTAB and 6:2 FTSA are both fluorotelomers compounds that have been replaced PFOS and PFOA phasing out from AFFFs”
From Release of per- and polyfluoroalkyl substances (PFAS) from a waste management facility fire to an urban creek (2022) · cites this paper as D'Agostino et al., 2014
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 [10]
TOF, Orbitrap, and FTICR are three HRMS technologies already proven as useful tools in PFAS discovery.
“TOF [29e32,35,39e41], Orbitrap [34,37,38,42] and Fouriertransform ion cyclotron resonance (FTICR) [30] are three HRMS technologies already proven as useful tools in PFAS discovery.”
Substantial direct evidence of unresolved structural isomers from electrochemical fluorination has been observed in some nontarget studies with chromatography, but other studies used infusion which masks isomers for each distinct homologue.
“Substantial direct evidence of such isomers has been observed in some nontarget studies with chromatography [30,31,42] (Table 2), but others used infusion which masks any isomers for each distinct homologue.”
Performing offline SPE fractionation before nontarget HRMS can assist in reducing interferences.
“Performing offline SPE fractionation before nontarget HRMS can also assist in reducing interferences [30], and the availability of versatile SPE cartridges grants researchers many choices in method development.”
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 [93]
Cites
Buck, R. C., Franklin, J., Berger, U., Conder, J. M., Cousins, I. T., de Voogt, P., Jensen, A. A., Kannan, K., Mabury, S. A., & van Leeuwen, S. P. (2011) · Integrated Environmental Assessment and Management · doi:10.1002/ieam.258 · Cited by 4,641 · see citing works
Self-citationGlobal Distribution of Perfluorooctane Sulfonate in Wildlife
Giesy, J. P., & Kannan, K. (2001) · Environmental Science & Technology · doi:10.1021/es001834k · Cited by 2,750 · see citing works
Sorption of Perfluorinated Surfactants on Sediments
Higgins, C. P., & Luthy, R. G. (2006) · Environmental Science & Technology · doi:10.1021/es061000n · Cited by 1,563 · see citing works
Backe, W. J., Day, T. C., & Field, J. A. (2013) · Environmental Science & Technology · doi:10.1021/es3034999 · Cited by 611 · see citing works
Quantitative determination of fluorotelomer sulfonates in groundwater by LC MS/MS
Schultz, M. M., Barofsky, D. F., & Field, J. A. (2004) · Environmental Science & Technology · doi:10.1021/es035031j · Cited by 373 · see citing works
Wang, N., Liu, J., Buck, R. C., Korzeniowski, S. H., Wolstenholme, B. W., Folsom, P. W., & Sulecki, L. M. (2011) · Chemosphere · doi:10.1016/j.chemosphere.2010.11.003 · Cited by 333 · see citing works
Benskin, J. P., Ikonomou, M. G., Gobas, F. A. P. C., Begley, T. H., Woudneh, M. B., & Cosgrove, J. R. (2013) · Environmental Science & Technology · doi:10.1021/es304336r · Cited by 169 · see citing works
Rand, A. A., & Mabury, S. A. (2012) · Environmental Science & Technology · doi:10.1021/es3008485 · Cited by 30 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Barzen-Hanson, K. A., Roberts, S. C., Choyke, S., Oetjen, K., McAlees, A., Riddell, N., McCrindle, R., Ferguson, P. L., Higgins, C. P., & Field, J. A. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.6b05843 · Cited by 873 · see citing works
Worldwide trends in tracing poly- and perfluoroalkyl substances (PFAS) in the environment
Nakayama, S. F., Yoshikane, M., Onoda, Y., Nishihama, Y., Iwai-Shimada, M., Takagi, M., Kobayashi, Y., & Isobe, T. (2019) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.02.011 · Cited by 399 · see citing works
Anderson, R. H., Long, G. C., Porter, R. C., & Anderson, J. K. (2016) · Chemosphere · doi:10.1016/j.chemosphere.2016.01.014 · Cited by 394 · see citing works
Bioaccumulation of Perfluorinated Alkyl Acids: Observations and Models
Ng, C. A., & Hungerbühler, K. (2014) · Environmental Science & Technology · doi:10.1021/es404008g · Cited by 393 · see citing works
Xiao, X., Ulrich, B. A., Chen, B., & Higgins, C. P. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.7b00970 · Cited by 391 · see citing works
Brase, R. A., Mullin, E. J., & Spink, D. C. (2021) · International Journal of Molecular Sciences · doi:10.3390/ijms22030995 · Cited by 374 · see citing works
Liu, Y., D'Agostino, L. A., Qu, G., Jiang, G., & Martin, J. W. (2019) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.02.021 · Cited by 344 · see citing works
Self-citationPer- and polyfluorinated substances (PFASs): Environmental challenges
Krafft, M. P., & Riess, J. G. (2015) · Current Opinion in Colloid & Interface Science · doi:10.1016/j.cocis.2015.07.004 · Cited by 294 · see citing works
Harding-Marjanovic, K. C., Houtz, E. F., Yi, S., Field, J. A., Sedlak, D. L., & Alvarez-Cohen, L. (2015) · Environmental Science & Technology · doi:10.1021/acs.est.5b01219 · Cited by 295 · see citing works
What are the effects of PFAS exposure at environmentally relevant concentrations?
Sinclair, G. M., Long, S. M., & Jones, O. A. H. (2020) · Chemosphere · doi:10.1016/j.chemosphere.2020.127340 · Cited by 285 · see citing works
McGuire, M. E., Schaefer, C., Richards, T., Backe, W. J., Field, J. A., Houtz, E., Sedlak, D. L., Guelfo, J. L., Wunsch, A., & Higgins, C. P. (2014) · Environmental Science & Technology · doi:10.1021/es5006187 · Cited by 269 · see citing works
Gao, K., Zhuang, T., Liu, X., Fu, J., Zhang, J., Fu, J., Wang, L., Zhang, A., Liang, Y., Song, M., et al. (2019) · Environmental Science & Technology · doi:10.1021/acs.est.9b00715 · Cited by 231 · see citing works
Shaw, D. M. J., Munoz, G., Bottos, E. M., Duy, S. V., Sauvé, S., Liu, J., & Van Hamme, J. D. (2019) · Science of The Total Environment · doi:10.1016/j.scitotenv.2018.08.012 · Cited by 232 · see citing works
Eriksson, U., Haglund, P., & Kärrman, A. (2017) · Journal of Environmental Sciences · doi:10.1016/j.jes.2017.05.004 · Cited by 225 · see citing works
Newton, S., McMahen, R., Stoeckel, J. A., Chislock, M., Lindstrom, A., & Strynar, M. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.6b05330 · Cited by 217 · see citing works
Yu, N., Guo, H., Yang, J., Jin, L., Wang, X., Shi, W., Zhang, X., Yu, H., & Wei, S. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b02492 · Cited by 200 · see citing works
Dauchy, X., Boiteux, V., Bach, C., Rosin, C., & Munoz, J.-F. (2017) · Chemosphere · doi:10.1016/j.chemosphere.2017.05.056 · Cited by 198 · see citing works
Gobelius, L., Hedlund, J., Dürig, W., Tröger, R., Lilja, K., Wiberg, K., & Ahrens, L. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.7b05718 · Cited by 198 · see citing works
Xiao, F., Jin, B., Golovko, S. A., Golovko, M. Y., & Xing, B. (2019) · Environmental Science & Technology · doi:10.1021/acs.est.9b05379 · Cited by 197 · see citing works
Martin, D., Munoz, G., Mejia-Avendaño, S., Duy, S. V., Yao, Y., Volchek, K., Brown, C. E., Liu, J., & Sauvé, S. (2019) · Talanta · doi:10.1016/j.talanta.2018.11.093 · Cited by 191 · see citing works
Fate and transport of per- and polyfluoroalkyl substances (PFASs) in the vadose zone
Sharifan, H., Bagheri, M., Wang, D., Burken, J. G., Higgins, C. P., Liang, Y., Liu, J., Schaefer, C. E., & Blotevogel, J. (2021) · Science of The Total Environment · doi:10.1016/j.scitotenv.2021.145427 · Cited by 180 · see citing works
Rotander, A., Kärrman, A., Toms, L.-M. L., Kay, M., Mueller, J. F., & Gómez Ramos, M. J. (2015) · Environmental Science & Technology · doi:10.1021/es503653n · Cited by 172 · see citing works
Mejia-Avendaño, S., Vo Duy, S., Sauvé, S., & Liu, J. (2016) · Environmental Science & Technology · doi:10.1021/acs.est.6b00140 · Cited by 168 · see citing works
Munoz, G., Mercier, L., Duy, S. V., Liu, J., Sauvé, S., & Houde, M. (2022) · Environmental Pollution · doi:10.1016/j.envpol.2022.119739 · Cited by 160 · see citing works
Discovery of a Novel Polyfluoroalkyl Benzenesulfonic Acid around Oilfields in Northern China
Xu, L., Shi, Y., Li, C., Song, X., Qin, Z., Cao, D., & Cai, Y. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.7b04332 · Cited by 148 · see citing works
Cheng, W., & Ng, C. A. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b01268 · Cited by 141 · see citing works
Houtz, E., Wang, M., & Park, J.-S. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b04028 · Cited by 145 · see citing works
Centurial Persistence of Forever Chemicals at Military Fire Training Sites
Ruyle, B. J., Thackray, C. P., Butt, C. M., LeBlanc, D. R., Tokranov, A. K., Vecitis, C. D., & Sunderland, E. M. (2023) · Environmental Science & Technology · doi:10.1021/acs.est.3c00675 · Cited by 142 · see citing works
Brown, J. B., Conder, J. M., Arblaster, J. A., & Higgins, C. P. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.0c03411 · Cited by 135 · see citing works
Analysis of emerging per- and polyfluoroalkyl substances: Progress and current issues
Pan, Y., Wang, J., Yeung, L. W. Y., Wei, S., & Dai, J. (2020) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.04.013 · Cited by 133 · see citing works
Ruyle, B. J., Thackray, C. P., McCord, J. P., Strynar, M. J., Mauge-Lewis, K. A., Fenton, S. E., & Sunderland, E. M. (2021) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.0c00798 · Cited by 131 · see citing works
Charbonnet, J. A., Rodowa, A. E., Joseph, N. T., Guelfo, J. L., Field, J. A., Jones, G. D., Higgins, C. P., Helbling, D. E., & Houtz, E. F. (2021) · Environmental Science & Technology · doi:10.1021/acs.est.0c08506 · Cited by 121 · see citing works
Munoz, G., Ray, P., Mejia-Avendaño, S., Vo Duy, S., Tien Do, D., Liu, J., & Sauvé, S. (2018) · Analytica Chimica Acta · doi:10.1016/j.aca.2018.06.046 · Cited by 103 · see citing works
Ruan, T., & Jiang, G. (2017) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2017.07.024 · Cited by 94 · see citing works
Borthakur, A., Wang, M., He, M., Ascencio, K., Blotevogel, J., Adamson, D. T., Mahendra, S., & Mohanty, S. K. (2021) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2021.126159 · Cited by 87 · see citing works
McKenzie, E. R., Siegrist, R. L., McCray, J. E., & Higgins, C. P. (2015) · Environmental Science & Technology · doi:10.1021/es503676p · Cited by 84 · see citing works
Microbial biotransformation of aqueous film-forming foam derived polyfluoroalkyl substances
Choi, Y. J., Helbling, D. E., Liu, J., Olivares, C. I., & Higgins, C. P. (2022) · Science of The Total Environment · doi:10.1016/j.scitotenv.2022.153711 · Cited by 79 · see citing works
Allendorf, F., Berger, U., Goss, K.-U., & Ulrich, N. (2019) · Environmental Science: Processes & Impacts · doi:10.1039/c9em00290a · Cited by 74 · see citing works
Willach, S., Brauch, H.-J., & Lange, F. T. (2016) · Chemosphere · doi:10.1016/j.chemosphere.2015.11.113 · Cited by 71 · see citing works
Jeong, Y., Da Silva, K. M., Iturrospe, E., Fuiji, Y., Boogaerts, T., van Nuijs, A. L. N., Koelmel, J., & Covaci, A. (2022) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2022.129378 · Cited by 76 · see citing works
McDonough, C. A., Choyke, S., Ferguson, P. L., DeWitt, J. C., & Higgins, C. P. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.0c00234 · Cited by 72 · see citing works
Boucher, J. M., Cousins, I. T., Scheringer, M., Hungerbühler, K., & Wang, Z. (2019) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.8b00531 · Cited by 60 · see citing works
Kali, S. E., Österlund, H., Viklander, M., & Blecken, G.-T. (2025) · Water Research · doi:10.1016/j.watres.2024.122973 · Cited by 62 · see citing works
“…include atmospheric deposition (Kim and Kannan, 2007; Xiao et al., 2012), building materials (Be ˇ canov ´ a et al., 2016; Liu et al., 2024), AFFFs (D ’ Agostino and Mabury, 2014), traffic-related sources (i.e. hydraulic fluids, lubricant oils) (Zhu and Kannan, 2020), as well as various consumer…”
InfluentialFinding Fluorine: Photoproduct Formation during the Photolysis of Fluorinated Pesticides
Bhat, A. P., Pomerantz, W. C. K., & Arnold, W. A. (2022) · Environmental Science & Technology · doi:10.1021/acs.est.2c04242 · Cited by 49 · see citing works
Mumtaz, M., Bao, Y., Li, W., Kong, L., Huang, J., & Yu, G. (2019) · Frontiers of Environmental Science & Engineering · doi:10.1007/s11783-019-1145-0 · Cited by 45 · see citing works
Liu, M., Glover, C. M., Munoz, G., Duy, S. V., Sauvé, S., & Liu, J. (2024) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2023.133006 · Cited by 43 · see citing works
Fitzgerald, N. J. M., Temme, H. R., Simcik, M. F., & Novak, P. J. (2019) · Environmental Science: Processes & Impacts · doi:10.1039/c9em00241c · Cited by 24 · see citing works
Alghamdi, W., Marchiandi, J., Szabo, D., Samandra, S., & Clarke, B. O. (2022) · Journal of Hazardous Materials Advances · doi:10.1016/j.hazadv.2022.100167 · Cited by 19 · see citing works
- Authors
- D’Agostino, L. A., & Mabury, S. A.
- Affiliations
- University of Toronto (CA)
- Corresponding author
- Mabury, Scott A.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-12-16
- Volume
- 48
- Issue
- 1
- Pages
- 121-129
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W1977074879
- Cited by
- 387
- References
- 8
- Citations by year
- 2026: 32 · 2025: 37 · 2024: 40 · 2023: 40 · 2022: 48 · 2021: 38 · 2020: 38 · 2019: 33 · 2018: 25 · 2017: 26 · 2016: 9 · 2015: 17 · 2014: 3 · 2013: 1
- FWCI
- 7.99
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Natural Sciences and Engineering Research Council of Canada
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Keywords
- fluorinated surfactants, aqueous film-forming foam, per- and polyfluoroalkyl substances, molecular formula assignment, structure elucidation
- MeSH terms
- Betaine, Chromatography, Liquid, Environment, Hydrocarbons, Fluorinated, Ontario, Surface-Active Agents, Water, Water Pollutants, Chemical, Molecular Structure, Spectroscopy, Fourier Transform Infrared, Fluorine Compounds, Solid Phase Extraction, Tandem Mass Spectrometry
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 ›
Are you an author, or do you see a problem with this page? Request a review
