Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse

Long Yang; Zijun Chen; Christopher A. Goult; Thomas Schlatzer; Robert Paton; Véronique Gouverneur

doi:10.1038/s41586-025-08698-5

journal article Open Access Mar 26, 2025

Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse

Long Yang

Zijun Chen Christopher A. Goult

Thomas Schlatzer

Robert Paton Véronique Gouverneur

Nature Vol. 640 No. 8057 pp. 100-106 · Springer Science and Business Media LLC

View at Publisher Save 10.1038/s41586-025-08698-5

Abstract

Abstract
Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are persistent, bioaccumulative and anthropogenic pollutants that have attracted the attention of the public and private sectors because of their adverse impact on human health1. Although various technologies have been deployed to degrade PFASs with a focus on non-polymeric functionalized compounds (perfluorooctanoic acid and perfluorooctanesulfonic acid)2–4, a general PFAS destruction method coupled with fluorine recovery for upcycling is highly desirable. Here we disclose a protocol that converts multiple classes of PFAS, including the fluoroplastics polytetrafluoroethylene and polyvinylidene fluoride, into high-value fluorochemicals. To achieve this, PFASs were reacted with potassium phosphate salts under solvent-free mechanochemical conditions, a mineralization process enabling fluorine recovery as KF and K2PO3F for fluorination chemistry. The phosphate salts can be recovered for reuse, implying no detrimental impact on the phosphorus cycle. Therefore, PFASs are not only destructible but can now contribute to a sustainable circular fluorine economy.

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References

50

[1]

Leung, S. C. E., Wanninayake, D., Chen, D., Nguyen, N.-T. & Li, Q. Physicochemical properties and interactions of perfluoroalkyl substances (PFAS)—challenges and opportunities in sensing and remediation. Sci. Total Environ. 905, 166764 (2023). 10.1016/j.scitotenv.2023.166764

[2]

Meegoda, J. N., Bezerra de Souza, B., Casarini, M. M. & Kewalramani, J. A. A review of PFAS destruction technologies. Int. J. Environ. Res. Public Health 19, 16397 (2022). 10.3390/ijerph192416397

[3]

Merino, N. et al. Degradation and removal methods for perfluoroalkyl and polyfluoroalkyl substances in water. Environ. Eng. Sci. 33, 615–649 (2016). 10.1089/ees.2016.0233

[4]

Recent advances on PFAS degradation via thermal and nonthermal methods

Sanny Verma, Tae Lee, Endalkachew Sahle-Demessie et al.

Chemical Engineering Journal Advances 2023 10.1016/j.ceja.2022.100421

[5]

An overview of the uses of per- and polyfluoroalkyl substances (PFAS)

Juliane Glüge, Martin Scheringer, Ian T. Cousins et al.

Environmental Science: Processes & Impacts 2020 10.1039/d0em00291g

[6]

Hoskins, T. D. et al. Chronic exposure to a PFAS mixture resembling AFFF-impacted surface water decreases body size in northern leopard frogs (Rana pipiens). Environ. Sci. Technol. 57, 14797–14806 (2023). 10.1021/acs.est.3c01118

[7]

Mikkonen, A. T. et al. Spatio-temporal trends in livestock exposure to per- and polyfluoroalkyl substances (PFAS) inform risk assessment and management measures. Environ. Res. 225, 115518 (2023). 10.1016/j.envres.2023.115518

[8]

Ateia, M., Alsbaiee, A., Karanfil, T. & Dichtel, W. Efficient PFAS removal by amine-functionalized sorbents: critical review of the current literature. Environ. Sci. Technol. Lett. 6, 688–695 (2019). 10.1021/acs.estlett.9b00659

[9]

Ilango, A. K. et al. Enhanced adsorption of mixtures of per- and polyfluoroalkyl substances in water by chemically modified activated carbon. ACS ES&T Water 3, 3708–3715 (2023). 10.1021/acsestwater.3c00483

[10]

Destruction of Per- and Polyfluoroalkyl Substances (PFAS) with Advanced Reduction Processes (ARPs): A Critical Review

Junkui Cui, Panpan Gao, Yang Deng

Environmental Science & Technology 2020 10.1021/acs.est.9b05565

[11]

Khan, Q. et al. Advanced oxidation/reduction processes (AO/RPs) for wastewater treatment, current challenges, and future perspectives: a review. Environ. Sci. Pollut. Res. 31, 1863–1889 (2024). 10.1007/s11356-023-31181-5

[12]

Photocatalytic low-temperature defluorination of PFASs

Hong Zhang, Jin-Xiang Chen, Jian-Ping Qu et al.

Nature 2024 10.1038/s41586-024-08179-1

[13]

Liu, X. et al. Photocatalytic C–F bond activation in small molecules and polyfluoroalkyl substances. Nature https://doi.org/10.1038/s41586-024-08327-7 (2024). 10.1038/s41586-024-08327-7

[14]

Zhang, K. et al. Destruction of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) by ball milling. Environ. Sci. Technol. 47, 6471–6477 (2013). 10.1021/es400346n

[15]

Zhang, Q., Lu, J., Saito, F. & Baron, M. Mechanochemical solid-phase reaction between polyvinylidene fluoride and sodium hydroxide. J. Appl. Polym. Sci. 81, 2249–2252 (2001). 10.1002/app.1663

[16]

Ateia, M., Skala, L. P., Yang, A. & Dichtel, W. R. Product analysis and insight into the mechanochemical destruction of anionic PFAS with potassium hydroxide. J. Hazard. Mater. Adv. 3, 100014 (2021).

[17]

Yang, N. et al. Solvent-free nonthermal destruction of PFAS chemicals and PFAS in sediment by piezoelectric ball milling. Environ. Sci. Technol. Lett. 10, 198–203 (2023). 10.1021/acs.estlett.2c00902

[18]

Cagnetta, G. et al. Mechanochemical destruction of perfluorinated pollutants and mechanosynthesis of lanthanum oxyfluoride: a waste-to-materials process. Chem. Eng. J. 316, 1078–1090 (2017). 10.1016/j.cej.2017.02.050

[19]

Turner, L. P. et al. Mechanochemical remediation of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) amended sand and aqueous film-forming foam (AFFF) impacted soil by planetary ball milling. Sci. Total Environ. 765, 142722 (2021). 10.1016/j.scitotenv.2020.142722

[20]

Battye, N. J. et al. Use of a horizontal ball mill to remediate per- and polyfluoroalkyl substances in soil. Sci. Total Environ. 835, 155506 (2022). 10.1016/j.scitotenv.2022.155506

[21]

Turner, L. P., Kueper, B. H., Patch, D. J. & Weber, K. P. Elucidating the relationship between PFOA and PFOS destruction, particle size and electron generation in amended media commonly found in soils. Sci. Total Environ. 888, 164188 (2023). 10.1016/j.scitotenv.2023.164188

[22]

Battye, N. et al. Mechanochemical degradation of per- and polyfluoroalkyl substances in soil using an industrial-scale horizontal ball mill with comparisons of key operational metrics. Sci. Total Environ. 928, 172274 (2024). 10.1016/j.scitotenv.2024.172274

[23]

Gobindlal, K., Shields, E., Whitehill, A., Weber, C. C. & Sperry, J. Mechanochemical destruction of per- and polyfluoroalkyl substances in aqueous film-forming foams and contaminated soil. Environ. Sci.: Adv. 2, 982–989 (2023).

[24]

Gobindlal, K., Zujovic, Z., Jaine, J., Weber, C. C. & Sperry, J. Solvent-free, ambient temperature and pressure destruction of perfluorosulfonic acids under mechanochemical conditions: degradation intermediates and fluorine fate. Environ. Sci. Technol. 57, 277–285 (2023). 10.1021/acs.est.2c06673

[25]

Trang, B. et al. Low-temperature mineralization of perfluorocarboxylic acids. Science 377, 839–845 (2022). 10.1126/science.abm8868

[26]

Monsky, R. J., Li, Y., Houk, K. N. & Dichtel, W. R. Low-temperature mineralization of fluorotelomers with diverse polar head groups. J. Am. Chem. Soc. 146, 17150–17157 (2024). 10.1021/jacs.4c03117

[27]

Per- and Polyfluoroalkyl Substances (PFAS): Incineration to Manage PFAS Waste Streams (US Environmental Protection Agency, 2020); www.epa.gov/sites/default/files/2019-09/documents/technical_brief_pfas_incineration_ioaa_approved_final_july_2019.pdf.

[28]

Fang, J. et al. Treatment of per- and polyfluoroalkyl substances (PFAS): a review of transformation technologies and mechanisms. J. Environ. Chem. Eng. 12, 111833 (2024). 10.1016/j.jece.2023.111833

[29]

A review of microbial degradation of per- and polyfluoroalkyl substances (PFAS): Biotransformation routes and enzymes

Ashenafi Berhanu, Ishmael Mutanda, Ji Taolin et al.

Science of The Total Environment 2023 10.1016/j.scitotenv.2022.160010

[30]

Harsanyi, A. & Sandford, G. Organofluorine chemistry: applications, sources and sustainability. Green Chem. 17, 2081–2086 (2015). 10.1039/c4gc02166e

[31]

Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

Calum Patel, Emy André-Joyaux, Jamie A. Leitch et al.

Science 2023 10.1126/science.adi1557

[32]

Lee, J., Zhang, Q. & Saito, F. Synthesis of nano-sized lanthanum oxyfluoride powders by mechanochemical processing. J. Alloys Compd. 348, 214–219 (2003). 10.1016/s0925-8388(02)00837-x

[33]

Qu, J., He, X., Zhang, Q., Liu, X. & Saito, F. Decomposition pathways of polytetrafluoroethylene by co-grinding with strontium/calcium oxides. Environ. Technol. 38, 1421–1427 (2017). 10.1080/09593330.2016.1231224

[34]

Sheldon, D. J., Parr, J. M. & Crimmin, M. R. Room temperature defluorination of poly(tetrafluoroethylene) by a magnesium reagent. J. Am. Chem. Soc. 145, 10486–10490 (2023). 10.1021/jacs.3c02526

[35]

Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends

Bruno Ameduri, Hisao Hori

Chemical Society Reviews 2023 10.1039/d2cs00763k

[36]

Saravanan, M., Ganesan, M. & Ambalavanan, S. An in situ generated carbon as integrated conductive additive for hierarchical negative plate of lead-acid battery. J. Power Sources 251, 20–29 (2014). 10.1016/j.jpowsour.2013.10.143

[37]

Frisch, M. J. et al. Gaussian 16, Revision C.01 (Gaussian, Inc., 2016).

[38]

Domingo, L. R., Chamorro, E. & Pérez, P. Understanding the reactivity of captodative ethylenes in polar cycloaddition reactions. A theoretical study. J. Org. Chem. 73, 4615–4624 (2008). 10.1021/jo800572a

[39]

Domingo, L. R. & Pérez, P. The nucleophilicity N index in organic chemistry. Org. Biomol. Chem. 9, 7168–7175 (2011). 10.1039/c1ob05856h

[40]

Electrophilicity Index

Robert G. Parr, László v. Szentpály, Shubin Liu

Journal of the American Chemical Society 1999 10.1021/ja983494x

[41]

Chattaraj, P. K. & Maiti, B. Reactivity dynamics in atom−field interactions: a quantum fluid density functional study. J. Phys. Chem. A 105, 169–183 (2001). 10.1021/jp0019660

[42]

Dixon, D. A., Smart, B. E., Krusic, P. J. & Matsuzawa, N. Bond energies in organofluorine systems: applications to Teflon® and fullerenes. J. Fluorine Chem. 72, 209–214 (1995). 10.1016/0022-1139(94)00409-9

[43]

Giannetti, E. Thermal stability and bond dissociation energy of fluorinated polymers: a critical evaluation. J. Fluorine Chem. 126, 623–630 (2005). 10.1016/j.jfluchem.2005.01.008

[44]

Wu, E. C. & Rodgers, A. S. Kinetics of the gas phase reaction of pentafluoroethyl iodide with hydrogen iodide. Enthalpy of formation of the pentafluoroethyl radical and the π bond dissociation energy in tetrafluoroethylene. J. Am. Chem. Soc. 98, 6112–6115 (1976). 10.1021/ja00436a007

[45]

Iashin, V., Wirtanen, T. & Perea-Buceta, J. E. Tetramethylammonium fluoride: fundamental properties and applications in C-F bond-forming reactions and as a base. Catalysts 12, 233 (2022). 10.3390/catal12020233

[46]

Morales-Colón, M. T. et al. Tetramethylammonium fluoride alcohol adducts for SNAr fluorination. Org. Lett. 23, 4493–4498 (2021). 10.1021/acs.orglett.1c01490

[47]

Kim, D. W., Jeong, H.-J., Lim, S. T. & Sohn, M.-H. Tetrabutylammonium tetra(tert-butyl alcohol)-coordinated fluoride as a facile fluoride source. Angew. Chem. Int. Ed. 47, 8404–8406 (2008). 10.1002/anie.200803150

[48]

Ye, Y., Schimler, S. D., Hanley, P. S. & Sanford, M. S. Cu(OTf)2-mediated fluorination of aryltrifluoroborates with potassium fluoride. J. Am. Chem. Soc. 135, 16292–16295 (2013). 10.1021/ja408607r

[49]

Zarganes-Tzitzikas, T., Neochoritis, C. G. & Dömling, A. Atorvastatin (Lipitor) by MCR. ACS Med. Chem. Lett. 10, 389–392 (2019). 10.1021/acsmedchemlett.8b00579

[50]

Phosphorus recovery and recycling – closing the loop

Andrew R. Jupp, Steven Beijer, Ganesha C. Narain et al.

Chemical Society Reviews 2021 10.1039/d0cs01150a

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Details

Published: Mar 26, 2025
Vol/Issue: 640(8057)
Pages: 100-106
License: View

Authors

L

Long Yang

College of Plant Protection, Shandong Agricultural University, Tai’an 271002, China

Department of Chemistry, Chemistry Research Laboratory; University of Oxford

T

Thomas Schlatzer

Department of Chemistry, Chemistry Research Laboratory; University of Oxford

R

Robert Paton

Department of Chemistry, Colorado State University, Fort Collins, CO 80528, USA.

V

Véronique Gouverneur

Chemistry Research Laboratory; Department of Chemistry; Oxford University; OX1 3TA Oxford; UK

Cite This Article

Long Yang, Zijun Chen, Christopher A. Goult, et al. (2025). Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse. Nature, 640(8057), 100-106. https://doi.org/10.1038/s41586-025-08698-5

Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse

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