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Here, we show that transient manganese (Mn) addition during biological activated carbon (BAC) start-up imprints a persistent bio-carbon interface that sustains NOM removal and delays PFAS breakthrough without continuous Mn input. Replicated BAC columns were operated for 400 days, with Mn supplied only during the first 60 days. Mn-imprinted BAC maintained &amp;gt;80% retention of 100 ng\/L perfluorooctanoic acid (PFOA), whereas Mn-free BAC declined to \u223c30%. After replacing PFOA with 100 ng\/L perfluorooctanesulfonate (PFOS), Mn-imprinted BAC maintained 60\u201370% PFOS retention, compared with 30\u201340% in Mn-free BAC. Surface characterization and density functional theory indicated persistent Mn\u2013O surface environments, plausibly including C\u2013O\u2013Mn motifs, which redistributed interfacial charge and stabilized anionic PFAS headgroups. In parallel, metagenomic, functional gene, and metabolomic analyses showed that Mn imprinting promoted a more active, extracellular polymeric substances (EPS)-rich, and functionally redundant biofilm with enhanced NOM-processing and Mn-oxidation potential. Microbial inhibition eliminated much of the retention benefit, while fluorine mass balance showed no measurable defluorination. Thus, start-up Mn imprinting improves BAC resilience by enhancing PFAS retention and delaying breakthrough.<\/jats:p>","DOI":"10.1021\/acs.est.6c07959","type":"journal-article","created":{"date-parts":[[2026,9,19]],"date-time":"2026-09-19T15:02:00Z","timestamp":1789830120000},"page":"27931-27943","source":"Crossref","is-referenced-by-count":0,"title":["Start-Up\nManganese\nImprinting Delays Breakthrough\nof Representative PFAS in Biological Activated Carbon through Persistent\nBio-Carbon Interfacial Conditioning"],"prefix":"10.1021","volume":"60","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6572-4892","authenticated-orcid":true,"given":"Haibo","family":"Wang","sequence":"first","affiliation":[{"name":"Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences , , ,","place":["Beijing, China, 100085"]},{"name":"Shandong Jianzhu University , , ,","place":["Jinan, China, 250101"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chen","family":"Cui","sequence":"additional","affiliation":[{"name":"Shandong Jianzhu University , , ,","place":["Jinan, China, 250101"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shan","family":"Wang","sequence":"additional","affiliation":[{"name":"Shandong Jianzhu University , , ,","place":["Jinan, China, 250101"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2129-4717","authenticated-orcid":true,"given":"Baoyou","family":"Shi","sequence":"additional","affiliation":[{"name":"Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences , , ,","place":["Beijing, China, 100085"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,19]]},"reference":[{"key":"2026100609073020700_cit1","doi-asserted-by":"publisher","DOI":"10.1016\/j.watres.2019.115381","article-title":"Removal of Poly- and Perfluoroalkyl\nSubstances (PFAS)\nfrom Water by Adsorption: Role of PFAS Chain Length, Effect of Organic\nMatter and Challenges in Adsorbent Regeneration","volume":"171","author":"Gagliano","year":"2020","journal-title":"Water Res."},{"issue":"7","key":"2026100609073020700_cit2","doi-asserted-by":"publisher","first-page":"4340","DOI":"10.1021\/acs.est.7b05718","article-title":"Per- and Polyfluoroalkyl\nSubstances in Swedish Groundwater and Surface Water: Implications\nfor Environmental Quality Standards and Drinking Water Guidelines","volume":"52","author":"Gobelius","year":"2018","journal-title":"Environ. 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