Abstract
Per- and polyfluoroalkyl substances (PFAS) are highly recalcitrant pollutants in the water environment worldwide. Aqueous film-foaming foam (AFFF) for fire-fighting is a major source of PFAS pollution. However, complete defluorination (i.e., cleaving all C−F bonds into F− ions) of PFAS by a non-thermal technology is rare. The destruction of the PFAS mixture in the complex organic matrix of AFFF is even more challenging. In this study, we designed and demonstrated a UV/sulfite−electrochemical oxidation (UV/S−EO) process. The tandem UV/S−EO leverages the complementary advantages of UV/S and EO modules in (i) PFAS transformation mechanism and (ii) engineering process design (e.g., foaming control, chemical dosage, and energy consumption). At ambient temperature and pressure, The UV/S−EO realized near-complete defluorination and mineralization of most PFAS and organics in AFFF (50−500x diluted, containing up to 200 mg L−1 organic fluorine and >4000 mg L−1 organic carbon). This work highlights the integration of molecular-level insight and engineering design toward solving major challenges of AFFF water pollution and stockpile disposal.



![Author ORCID: We display the ORCID iD icon alongside authors names on our website to acknowledge that the ORCiD has been authenticated when entered by the user. To view the users ORCiD record click the icon. [opens in a new tab]](https://www.cambridge.org/engage/assets/public/coe/logo/orcid.png)