Low-temperature mineralization of perfluorocarboxylic acids
Abstract
Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative pollutants found in water resources at concentrations harmful to human health. Whereas current PFAS destruction strategies use nonselective destruction mechanisms, we found that perfluoroalkyl carboxylic acids (PFCAs) could be mineralized through a sodium hydroxide-mediated defluorination pathway. PFCA decarboxylation in polar aprotic solvents produced reactive perfluoroalkyl ion intermediates that degraded to fluoride ions (78 to ~100%) within 24 hours. The carbon-containing intermediates and products were inconsistent with oft-proposed one-carbon-chain shortening mechanisms, and we instead computationally identified pathways consistent with many experiments. Degradation was also observed for branched perfluoroalkyl ether carboxylic acids and might be extended to degrade other PFAS classes as methods to activate their polar headgroups are identified.
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?
The carboxy terminal tail of PFCAs can facilitate a sodium hydroxide-mediated defluorination mechanism, leading to highly reactive perfluoroalkyl intermediates and ultimately fluoride ions.
“A recent study has shown that the carboxy terminal tail of PFCAs can facilitate a sodium hydroxide-mediated defluorination mechanism. This chemical degradation process occurs in the presence of the solvent dimethylsulfoxide and leads to highly reactive perfluoroalkyl intermediates that undergo further degradation, culminating in the final generation of fluoride ions [27].”
From The EU’s Per- and Polyfluoroalkyl Substances (PFAS) Ban: A Case of Policy over Science (2023) · cites this paper as [27]
A recent laboratory study showed that exposure of PFCAs to sodium hydroxide in a polar aprotic solvent resulted in degradation to fluoride ions in yields between 78 and 100% in 24 h.
“A recent laboratory study of degradation of PFCAs [240], has shown that exposure of PFCAs (see Table 2) to sodium hydroxide in a polar aprotic solvent (e.g., dimethyl sulfoxide) resulted in degradation to fluoride ions in yields between 78 and 100% in 24 h.”
From Changes in tropospheric air quality related to the protection of stratospheric ozone in a changing climate (2023) · cites this paper as [240]
TFA was formed in amounts of 19-39 mol% for PFCAs with 5-9 carbon chains.
“TFA was formed in amounts of 19–39 mol% for PFCAs with 5–9 carbon chains.”
From Changes in tropospheric air quality related to the protection of stratospheric ozone in a changing climate (2023) · cites this paper as [240]
Cites
Zhao, Y., & Truhlar, D. G. (2007) · Theoretical Chemistry Accounts · doi:10.1007/s00214-007-0310-x · Cited by 30,407 · see citing works
Marenich, A. V., Cramer, C. J., & Truhlar, D. G. (2009) · The Journal of Physical Chemistry B · doi:10.1021/jp810292n · Cited by 17,971 · see citing works
Direct And Mediated Anodic Oxidation of Organic Pollutants
Panizza, M., & Cerisola, G. (2009) · Chemical Reviews · doi:10.1021/cr9001319 · Cited by 2,351 · see citing works
Supramolecular Binding Thermodynamics by Dispersion‐Corrected Density Functional Theory
Grimme, S. (2012) · Chemistry - A European Journal · doi:10.1002/chem.201200497 · Cited by 2,132 · see citing works
Calafat, A. M., Wong, L.-Y., Kuklenyik, Z., Reidy, J. A., & Needham, L. L. (2007) · Environmental Health Perspectives · doi:10.1289/ehp.10598 · Cited by 1,247 · see citing works
Hori, H., Yamamoto, A., Hayakawa, E., Taniyasu, S., Yamashita, N., Kutsuna, S., Kiatagawa, H., & Arakawa, R. (2005) · Environmental Science & Technology · doi:10.1021/es0484754 · Cited by 596 · see citing works
Bentel, M. J., Yu, Y., Xu, L., Li, Z., Wong, B. M., Men, Y.-J., & Liu, J. (2019) · Environmental Science and Technology · doi:10.1021/acs.est.8b06648 · Cited by 558 · see citing works
Mardirossian, N., & Head‐Gordon, M. (2016) · Journal of Chemical Theory and Computation · doi:10.1021/acs.jctc.6b00637 · Cited by 482 · see citing works
Hori, H., Hayakawa, E., Einaga, H., Kutsuna, S., Koike, K., Ibusuki, T., Kiatagawa, H., & Arakawa, R. (2004) · Environmental Science & Technology · doi:10.1021/es049719n · Cited by 464 · see citing works
Singh, R. K., Fernando, S., Baygi, . F., Multari, N., Thagard, S. M., & Holsen, T. M. (2019) · Environmental Science & Technology · doi:10.1021/acs.est.8b07031 · Cited by 463 · see citing works
Bentel, M. J., Yu, Y., Xu, L., Kwon, H., Li, Z., Wong, B. M., Men, Y., & Liu, J. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.9b05869 · Cited by 384 · see citing works
Efficient Electrochemical Oxidation of Perfluorooctanoate Using a Ti/SnO2-Sb-Bi Anode
Zhuo, Q., Deng, S., Yang, B., Huang, J. G., & Yu, G. (2011) · Environmental Science & Technology · doi:10.1021/es1024542 · Cited by 377 · see citing works
Efficient PFAS Removal by Amine-Functionalized Sorbents: Critical Review of the Current Literature
Ateia, M., Alsbaiee, A., Karanfil, T., & Dichtel, W. R. (2019) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.9b00659 · Cited by 360 · see citing works
Self-citationPhysico-Chemical Processes for the Treatment of Per- And Polyfluoroalkyl Substances (PFAS): A review
Nzeribe, B. N., Crimi, M., Mededovic Thagard, S., & Holsen, T. M. (2019) · Critical Reviews in Environmental Science and Technology · doi:10.1080/10643389.2018.1542916 · Cited by 314 · see citing works
Thermal Stability and Decomposition of Perfluoroalkyl Substances on Spent Granular Activated Carbon
Xiao, F., Sasi, P. C., Yao, B., Kubátová, A., Golovko, S. A., Golovko, M. Y., & Soli, D. (2020) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.0c00114 · Cited by 308 · see citing works
Maimaiti, A., Deng, S., Meng, P., Wang, W., Wang, B., Huang, J., Wang, Y., & Yu, G. (2018) · Chemical Engineering Journal · doi:10.1016/j.cej.2018.05.006 · Cited by 305 · see citing works
Vecitis, C. D., Park, H., Cheng, J., Mader, B. T., & Hoffmann, M. R. (2008) · The Journal of Physical Chemistry A · doi:10.1021/jp801081y · Cited by 266 · see citing works
Electrochemical production of lactic acid from glycerol oxidation catalyzed by AuPt nanoparticles
Dai, C., Sun, L., Liao, H., Khezri, B., Webster, R. D., Fisher, A. C., & Xu, Z. J. (2017) · Journal of Catalysis · doi:10.1016/j.jcat.2017.10.010 · Cited by 255 · see citing works
Schaefer, C. E., Andaya, C., Urtiaga, A. M., McKenzie, E. R., & Higgins, C. P. (2015) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2015.04.024 · Cited by 238 · see citing works
Li, Y., Gomes, J., Sharada, S. M., et al. (2014) · The Journal of Physical Chemistry C · doi:10.1021/jp509921r · Cited by 210 · see citing works
Self-citationCheng, J., Vecitis, C. D., Park, H., Mader, B. T., & Hoffmann, M. R. (2009) · Environmental Science & Technology · doi:10.1021/es902651g · Cited by 203 · see citing works
Hao, S., Choi, Y. J., Wu, B., Higgins, C. P., Deeb, R. A., & Strathmann, T. J. (2021) · Environmental Science & Technology · doi:10.1021/acs.est.0c06906 · Cited by 197 · see citing works
Rapid Destruction and Defluorination of Perfluorooctanesulfonate by Alkaline Hydrothermal Reaction
Wu, B., Hao, S., Choi, Y. J., Higgins, C. P., Deeb, R. A., & Strathmann, T. J. (2019) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.9b00506 · Cited by 192 · see citing works
Liu, Z., Bentel, M. J., Yu, Y., Ren, C., Gao, J., Pulikkal, V. F., Sun, M., Men, Y., & Liu, J. (2021) · Environmental Science & Technology · doi:10.1021/acs.est.1c00353 · Cited by 192 · see citing works
Bentel, M. J., Liu, Z., Yu, Y., Gao, J., Men, Y., & Liu, J. (2020) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.0c00236 · Cited by 183 · see citing works
Electrochemical degradation of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in groundwater
Trautmann, A.-L., Schell, H., Schmidt, K. R., Mangold, K.-M., & Tiehm, A. (2015) · Water Science & Technology · doi:10.2166/wst.2015.143 · Cited by 154 · see citing works
Watanabe, N., Takata, M., Takemine, S., & Yamamoto, K. (2015) · Environmental Science and Pollution Research · doi:10.1007/s11356-015-5353-2 · Cited by 151 · see citing works
Garcia‐Segura, S., Nienhauser, A. B., Fajardo, A. S., Bansal, R., Conrad, C. L., Fortner, J. D., Marcos−Hernández, M., Rogers, T. K., Villagrán, D., Wong, M. S., et al. (2020) · Current Opinion in Electrochemistry · doi:10.1016/j.coelec.2020.03.001 · Cited by 142 · see citing works
Direct reversible decarboxylation from stable organic acids in dimethylformamide solution
Kong, D., Moon, P. J., Lui, E. K. J., et al. (2020) · Science · doi:10.1126/science.abb4129 · Cited by 142 · see citing works
Supercritical Water Oxidation as an Innovative Technology for PFAS Destruction
Krause, M. J., Thoma, E. D., Sahle-Damesessie, E., Crone, B. C., Whitehill, A., Shields, E. P., & Gullett, B. K. (2021) · Journal of Environmental Engineering · doi:10.1061/(asce)ee.1943-7870.0001957 · Cited by 119 · see citing works
Pyrolyses of the Salts of the Perfluoro Carboxylic Acids1
LaZerte, J. D., Hals, L. J., Reid, T. S., & Smith, G. H. (1953) · Journal of the American Chemical Society · doi:10.1021/ja01114a040 · Cited by 118 · see citing works
Watanabe, N., Takemine, S., Yamamoto, K., Haga, Y., & Takata, M. (2016) · Journal of Material Cycles and Waste Management · doi:10.1007/s10163-016-0532-x · Cited by 107 · see citing works
Leeson, A., Thompson, T., Stroo, H. F., Anderson, R. H., Speicher, J., Mills, M. A., Willey, J., Coyle, C., Ghosh, R., Lebrón, C., et al. (2020) · Environmental Toxicology and Chemistry · doi:10.1002/etc.4894 · Cited by 106 · see citing works
Chatterjee, T., Boutin, E., & Robert, M. (2020) · Dalton Transactions · doi:10.1039/c9dt04749b · Cited by 100 · see citing works
Structures and stabilities of fluorinated carbanions. Evidence for anionic hyperconjugation
Dixon, D. A., Fukunaga, T., & Smart, B. E. (1986) · Journal of the American Chemical Society · doi:10.1021/ja00274a029 · Cited by 94 · see citing works
Liang, X., Cheng, J., Yang, C., & Yang, S. (2016) · Chemical Engineering Journal · doi:10.1016/j.cej.2016.03.150 · Cited by 87 · see citing works
Haszeldine, R. N. (1952) · Journal of the Chemical Society (Resumed) · doi:10.1039/jr9520004259 · Cited by 86 · see citing works
Solvent Suitability for HFPO-DA (“GenX” Parent Acid) in Toxicological Studies
Liberatore, H. K., Jackson, S. R., Strynar, M. J., & McCord, J. P. (2020) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.0c00323 · Cited by 84 · see citing works
Zhang, C., McElroy, A. C., Liberatore, H. K., Alexander, N. L. M., & Knappe, D. R. U. (2022) · Environmental Science & Technology · doi:10.1021/acs.est.1c03979 · Cited by 78 · see citing works
19F and 1H NMR spectra of halocarbons
Foris, A. (2004) · Magnetic Resonance in Chemistry · doi:10.1002/mrc.1368 · Cited by 62 · see citing works
Butch, C., Cope, E. D., Pollet, P., Gelbaum, L., Krishnamurthy, R., & Liotta, C. L. (2013) · Journal of the American Chemical Society · doi:10.1021/ja405103r · Cited by 46 · see citing works
Fluorocarbonate, [FCO2]−: Preparation and Structure
Zhang, X., Groß, U., & Seppelt, K. (1995) · Angewandte Chemie International Edition in English · doi:10.1002/anie.199518581 · Cited by 40 · see citing works
Hogan, T. E., & Sen, A. (1997) · Journal of the American Chemical Society · doi:10.1021/ja964068j · Cited by 36 · see citing works
Zhou, S., Nguyen, B. T., Richard, J. P., et al. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c12414 · Cited by 28 · see citing works
Pellerite, M. J. (1990) · Journal of Fluorine Chemistry · doi:10.1016/s0022-1139(00)80362-0 · Cited by 22 · see citing works
Hydro-2 oxo-3 perfluoroesters. Synthese et properties remarquables: hydrate, equilibre ceto-enolique
Iznaden, M., & Portella, C. (1989) · Journal of Fluorine Chemistry · doi:10.1016/s0022-1139(00)81639-5 · Cited by 14 · see citing works
Rangarajan, T. M., Sathyamoorthi, S., Velayutham, D., et al. (2010) · Journal of Fluorine Chemistry · doi:10.1016/j.jfluchem.2010.12.004 · Cited by 12 · see citing works
Saloutina, L. V., Zapevalov, A. Y., Салоутин, В. И., et al. (2005) · Journal of Fluorine Chemistry · doi:10.1016/j.jfluchem.2005.05.001 · Cited by 10 · see citing works
Ge, Y., Liu, Z.-Z., Liu, H., et al. (2013) · Computational and Theoretical Chemistry · doi:10.1016/j.comptc.2013.12.013 · Cited by 9 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Recent Advances on PFAS Degradation via Thermal and Nonthermal Methods
Verma, S., Lee, T., Sahle-Demessie, E., Ateia, M., & Nadagouda, M. N. (2023) · Chemical Engineering Journal Advances · doi:10.1016/j.ceja.2022.100421 · Cited by 187 · see citing works
Self-citationThe EU’s Per- and Polyfluoroalkyl Substances (PFAS) Ban: A Case of Policy over Science
Spyrakis, F., & Dragani, T. A. (2023) · Toxics · doi:10.3390/toxics11090721 · Cited by 78 · see citing works
Madronich, S., Sulzberger, B., Longstreth, J. D., Schikowski, T., Andersen, M. P. S., Solomon, K. R., & Wilson, S. R. (2023) · Photochemical & Photobiological Sciences · doi:10.1007/s43630-023-00369-6 · Cited by 64 · see citing works
Electrothermal mineralization of per- and polyfluoroalkyl substances for soil remediation
Cheng, Y., Deng, B., Scotland, P., Eddy, L., Hassan, A., Wang, B., Silva, K. J., Li, B., Wyss, K. M., Ucak-Astarlioglu, M. G., et al. (2024) · Nature Communications · doi:10.1038/s41467-024-49809-6 · Cited by 64 · see citing works
Ameduri, B. (2023) · Journal of Fluorine Chemistry · doi:10.1016/j.jfluchem.2023.110117 · Cited by 43 · see citing works
Röhrig, A., Grasse, N., Krauss, M., Bücher, D., Brack, W., Kamjunke, N., Matousu, A., Sanders, T., Bussmann, I., Achterberg, E. P., et al. (2026) · ACS Environmental Au · doi:10.1021/acsenvironau.5c00219 · Cited by 7 · see citing works
- Authors
- Trang, B., Li, Y., Xue, X.-S., Ateia, M., Houk, K. N., & Dichtel, W. R.
- Affiliations
- Northwestern University (US)
- University of California, Los Angeles (US)
- Shanghai Institute of Organic Chemistry (CN)
- Corresponding author
- Houk, K. N.
- Dichtel, William R.
- Venue
- Science
- Published
- 2022-08-19
- Volume
- 377
- Issue
- 6608
- Pages
- 839-845
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W4292680108
- Cited by
- 425
- References
- 49
- Citations by year
- 2026: 126 · 2025: 102 · 2024: 109 · 2023: 71 · 2022: 17
- FWCI
- 26.48
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Science (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institutes of Health (1s10od012016-01)
- National Center for Research Resources (S10RR019071)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Physical Sciences › Environmental Science › Water Science and Technology › Advanced oxidation water treatment
- Keywords
- per- and polyfluoroalkyl substances, perfluorinated carboxylic acids, defluorination, decarboxylation, fluoride release, dipolar aprotic solvents, water pollution
- MeSH terms
- Carboxylic Acids, Fluorocarbons, Humans, Temperature, Water Pollutants, Chemical
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
