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oai:figshare.com:article/34021602 2026-09-29T06:06:09Z category_1 category_4 category_8 category_14 category_24 category_272 category_873 category_39 category_502 category_734 category_69 category_128 category_132 portal_63 item_type_6 month_year_09_2026

Calcium Metal Mechanochemically Defluorinates PFAS to Environmentally Benign CaF₂ Luis Simbari (23654830) Moosa Wasim (24488088) Anže Zupanc (10452130) Shrestha Banerjee (14033273) Benjamin M. Gallant (14045803) Joshua Deakin (22833902) Francisco Alvarado Cesar (25051528) Roly J. Armstrong (3987503) Tomislav Friščić (1410901) Erli Lu (1973095) Dominik J. Kubicki (6386849) Biophysics Biochemistry Microbiology Molecular Biology Evolutionary Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Ecology Astronomical and Space Sciences not elsewhere classified Biological Sciences not elsewhere classified Inorganic Chemistry Hematology Infectious Diseases typically require incineration secondary environmental hazard safety constraints relevant remain environmentally problematic persistent anthropogenic materials partial (∼ 64 mg (< 1 lived fluorinated microplastics irreversibly sequestering fluorine frequently generate water existing destruction strategies environmentally benign caf edx reveal caf coupling efficient defluorination abrasion generate long soluble fluoride products metal fluoride waste free mechanochemical defluorination environmentally benign solid molecular pfas accumulate although bulk fluoropolymers 19 </ sup 2 </ sub quantitative solid mechanochemical strategy fluoride sequestration calcium fluoride work establishes polyfluoroalkyl substances perfluorooctanoic acid often regarded mobile contaminants f nmr chemically inert aggressive reagents 30 min Fluoropolymers and other per- and polyfluoroalkyl substances (PFAS) are among the most persistent anthropogenic materials. Although bulk fluoropolymers such as polytetrafluoroethylene (PTFE) are often regarded as chemically inert, weathering and abrasion generate long-lived fluorinated microplastics, while molecular PFAS accumulate in the environment as mobile contaminants. Existing destruction strategies can cleave C–F bonds, but typically require incineration or aggressive reagents and frequently generate water-soluble fluoride products that remain environmentally problematic. Here we show that calcium metal enables solvent-free mechanochemical defluorination of PTFE and perfluorooctanoic acid (PFOA) at ambient starting temperature without external heating, while irreversibly sequestering fluorine as calcium fluoride, a nontoxic, insoluble, and environmentally benign solid. Quantitative solid-state ¹⁹F NMR, with detection limits explicitly assessed, shows no resolvable PTFE after 30 min of milling with Ca and Mg (<1.0% residual PTFE); Sr gives near-complete conversion (<10% residual PTFE), whereas Ba gives only partial (∼64% residual PTFE) conversion after 30 min of milling. TEM and SEM-EDX reveal CaF₂-rich nanocrystalline domains intimately mixed with an oxygen-containing disordered carbonaceous material. By coupling efficient defluorination with fluoride sequestration, this work establishes a mechanochemical strategy for mineralization of persistent fluorinated materials without generating soluble alkali-metal fluoride waste as a secondary environmental hazard, while defining the analytical and process-safety constraints relevant to further development. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c11635.s001 https://figshare.com/articles/journal_contribution/Calcium_Metal_Mechanochemically_Defluorinates_PFAS_to_Environmentally_Benign_CaF_sub_2_sub_/34021602 CC BY-NC 4.0