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UV-driven •OH oxidation releases perfluorocarboxylic acids from surface-fluorinated high-density polyethylene microplastics.
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Lab tests found that fluorinated plastic bits called microplastics, found in some household and industrial products, release harmful fluorinated chemicals called PFCAs when exposed to UV light. Release increased with heat, smaller particle size, and certain water conditions, with industrial plastics releasing more than personal care ones. The study identifies this plastic type as a previously unrecognized source of these chemicals in water.
Surface-fluorinated high-density polyethylene (F-HDPE) is an overlooked source of perfluoroalkyl carboxylic acids (PFCAs), yet the mechanisms governing PFCA release remain unclear. Here, we quantify PFCA (C4-C8) release from F-HDPE microplastics (MPs) under UV365 irradiation and provide mechanistic evidence for •OH-driven release. Industrial F-HDPE MPs showed a 10.4-44.4% higher release rate than personal care MPs, consistent with greater defluorination of industrial MPs. The release rate of small MPs was 1.3-2.4 times as fast as that of large MPs. No PFCA release was observed at 25 and 35 °C, whereas concentrations reached 4.2 ± 0.03 μg·L⁻1 at 50 °C. Humic acid promoted PFCA release at 10 mg·L-1 via photosensitization but decreased release by a factor of 1.5-2.3 at 50 mg·L-1 due to light shielding and •OH scavenging. PFCA release also occurred in natural waters, likely caused by DOM-mediated photosensitization. Short-chain PFCAs dominated because of their preferential formation, faster diffusion and desorption. Mechanistically, photoexcitation of carbonyls promotes adjacent C-C bond cleavage, generating unstable radicals (•C(=O)-(CF2)y-CHF-CH2- and -CF2CF2CF2•) that further undergo H-abstraction and/or •OH oxidation, ultimately yielding PFCAs. These findings identify F-HDPE as an unrecognized PFCA source and highlight associated environmental risks.
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