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Concurrently, remediation of persistent per- and polyfluoroalkyl substances (PFAS) remains challenging. Although natural DOM can both photosensitize and scavenge reactive species, how BDOM modulates PFAS transformation in waters is unclear. Here, we show that low-level BDOM (1 mgC L\u20131) unexpectedly promotes PFAS defluorination in the UV\/sulfite (UV\/S) system by simultaneously boosting hydrated electron (eaq\u2013) production and generating oxidizing radicals via triplet states (3BDOM*). The hydrophilic, moderately condensed aromatic, fulvic\/humic-like fraction of BDOM is most effective across all tested feedstocks and pyrolysis temperatures. BDOM derived at 500 \u00b0C raises eaq\u2013 yield 2.6-fold over UV\/S alone while co-producing \u2022OH. Crucially, BDOM appears to reroute the eaq\u2013-mediated decarboxylation\u2013hydroxylation\u2013elimination\u2013hydrolysis pathway: instead of water addition, \u2022OH may directly attack perfluorinated radical, making key steps more thermodynamically favorable and accelerating C\u2013F cleavage. Leveraging naturally derived BDOM in waters, this eaq\u2013\/\u2022OH-mediated reduction-oxidation coupling may reduce reliance on externally added chemicals while achieving complete degradation of perfluorocarboxylic acids and GenX within 1 h and \u223c80% defluorination within 6 h. The findings establish BDOM as an intrinsic photosensitizer and electron ejector that reshapes radical chemistry and PFAS reaction pathways, supporting more efficient and sustainable UV\/S-based remediation.<\/jats:p>","DOI":"10.1021\/acs.est.6c06874","type":"journal-article","created":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T21:02:14Z","timestamp":1788555734000},"page":"26801-26815","source":"Crossref","is-referenced-by-count":0,"title":["Pyrolysis-Tuned\nDual-Function Biochar-Derived Dissolved\nOrganic Matter Drives Redox Coupling for Deep PFAS Defluorination\nin UV\/Sulfite Systems"],"prefix":"10.1021","volume":"60","author":[{"given":"Fang","family":"Jiang","sequence":"first","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinrong","family":"Liao","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haonan","family":"Dong","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziyao","family":"Zhu","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li","family":"Guo","sequence":"additional","affiliation":[{"name":"Hubei Eco-Environment Monitoring Center Station , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huaxin","family":"Li","sequence":"additional","affiliation":[{"name":"Hubei Eco-Environment Monitoring Center Station , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0780-6504","authenticated-orcid":true,"given":"Li","family":"Rao","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8236-3643","authenticated-orcid":true,"given":"Zhihui","family":"Ai","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. China, 430079"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1622-7560","authenticated-orcid":true,"given":"Jingming","family":"Gong","sequence":"additional","affiliation":[{"name":"Central China Normal University , , ,","place":["Wuhan, P. R. 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Mater."},{"key":"2026092210093383400_cit40","doi-asserted-by":"publisher","DOI":"10.1016\/j.watres.2024.121892","article-title":"Novel insights into\nthe relationship between the functional groups and photoactivity of\nbiochar-derived dissolved organic matter","volume":"260","author":"Zuo","year":"2024","journal-title":"Water\nRes."},{"key":"2026092210093383400_cit41","doi-asserted-by":"publisher","DOI":"10.1016\/j.envres.2023.116174","article-title":"Photochemical\nbehaviors of dissolved organic matter in aquatic environment: Generation,\ncharacterization, influencing factors and practical application","volume":"231","author":"Cai","year":"2023","journal-title":"Environ. Res."},{"key":"2026092210093383400_cit42","doi-asserted-by":"publisher","first-page":"1101","DOI":"10.1016\/j.cej.2018.10.204","article-title":"Synergistic impact of humic acid on the photo-reductive\ndecomposition of perfluorooctanoic acid","volume":"360","author":"Guo","year":"2019","journal-title":"Chem.\nEng. 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Hazard. Mater."},{"key":"2026092210093383400_cit50","doi-asserted-by":"publisher","DOI":"10.1016\/j.watres.2025.124049","article-title":"Self-sustaining\nreduction-oxidation coupling driven by hydrated electrons and reactive\nbromine species for synergistic PFAS defluorination and bromate detoxification\nin bromide-rich water under UV\/sulfite","volume":"284","author":"Jiang","year":"2025","journal-title":"Water\nRes."},{"issue":"31","key":"2026092210093383400_cit51","doi-asserted-by":"publisher","first-page":"16709","DOI":"10.1021\/acs.est.5c03024","article-title":"Triplet-excited benzoates\nsignificantly enhance HO\u2022 formation\nand free chlorine decay in a UV222\/chlorine advanced oxidation\nprocess","volume":"59","author":"Guo","year":"2025","journal-title":"Environ. Sci. 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