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We amended phenanthrene-spiked agricultural soil with wheat-straw biochar and three DOM types (citric acid, oxalic acid and humic acid) and linked biodegradation to bioavailable pools and microbial responses. Citric and oxalic acids increased bioavailable fractions and raised microbial removal from 43.98 \u00b1 0.72% (control) to 55.84 \u00b1 0.87% and 54.74 \u00b1 2.29%, whereas humic acid lowered effective bioavailability and reduced removal to 39.65 \u00b1 0.73%. Biochar alone increased removal (48.20 \u00b1 0.98%) despite decreasing initial bioavailability. Biochar-driven microhabitat improvement coupled with citric\/oxalic-acid-enhanced bioavailability enriched key degraders and nidA copies (initiating phenanthrene oxidation), yielding the highest removal (64.20 \u00b1 0.49% and 60.52 \u00b1 0.09%). In contrast, biochar plus humic acid promoted sequestration and showed the lowest removal (36.55 \u00b1 0.97%). DOM chemistry modulates whether biochar favors bioremediation or stabilization.<\/jats:p>","DOI":"10.1021\/acs.jafc.6c01921","type":"journal-article","created":{"date-parts":[[2026,6,4]],"date-time":"2026-06-04T16:51:55Z","timestamp":1780591915000},"page":"17820-17831","source":"Crossref","is-referenced-by-count":2,"title":["Dissolved Organic\nMatter Chemistry Modulates Biochar\nEffects on Phenanthrene Biodegradation in Agricultural Soil: Bioavailability\nand Microbial Responses"],"prefix":"10.1021","volume":"74","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6979-6455","authenticated-orcid":true,"given":"Meng","family":"Zhang","sequence":"first","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Ran","sequence":"additional","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jichao","family":"Song","sequence":"additional","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Muqin","family":"Jiang","sequence":"additional","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liyuan","family":"Chen","sequence":"additional","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5668-9703","authenticated-orcid":true,"given":"Xilong","family":"Wang","sequence":"additional","affiliation":[{"name":"Peking University , , ,","place":["Beijing, China, 100871"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8850-7556","authenticated-orcid":true,"given":"Eugenia","family":"Valsami-Jones","sequence":"additional","affiliation":[{"name":"University of Birmingham , , ,","place":["Birmingham, United Kingdom, B15 2TT"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,4]]},"reference":[{"key":"2026073021133515900_cit1","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.jes.2022.07.026","article-title":"Nationwide\ndistribution of polycyclic aromatic hydrocarbons in soil of China\nand the association with bacterial community","volume":"128","author":"Zhang","year":"2023","journal-title":"J. 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Total Environ."},{"key":"2026073021133515900_cit5","doi-asserted-by":"publisher","first-page":"70","DOI":"10.1016\/j.soilbio.2017.09.027","article-title":"Effect of\nexogenous carbonaceous materials on the bioavailability of organic\npollutants and their ecological risks","volume":"116","author":"Ren","year":"2018","journal-title":"Soil\nBiol. Biochem."},{"key":"2026073021133515900_cit6","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2020.141123","article-title":"Polycyclic\naromatic hydrocarbons (PAHs) persistence,\nbioavailability and toxicity in sewage sludge- or sewage sludge-derived\nbiochar-amended soil","volume":"747","author":"Tomczyk","year":"2020","journal-title":"Sci. Total Environ."},{"key":"2026073021133515900_cit7","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2023.132550","article-title":"Biochar inoculated\nwith Pseudomonas putida alleviates its inhibitory\neffect on biodegradation pathways in phenanthrene-contaminated soil","volume":"461","author":"Lu","year":"2024","journal-title":"J. Hazard. Mater."},{"key":"2026073021133515900_cit8","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2022.129557","article-title":"The effects\nof biochar and its applications\nin the microbial remediation of contaminated soil: a review","volume":"438","author":"Zheng","year":"2022","journal-title":"J. Hazard. Mater."},{"key":"2026073021133515900_cit9","doi-asserted-by":"publisher","DOI":"10.1016\/j.geoderma.2020.114497","article-title":"Mechanism of biochar\nas a biostimulation strategy to\nremove polycyclic aromatic hydrocarbons from heavily contaminated\nsoil in a coking plant","volume":"375","author":"Zhang","year":"2020","journal-title":"Geoderma"},{"key":"2026073021133515900_cit10","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2022.156076","article-title":"Biochar enhanced polycyclic\naromatic hydrocarbons degradation in\nsoil planted with ryegrass: bacterial community and degradation gene\nexpression mechanisms","volume":"838","author":"Zhao","year":"2022","journal-title":"Sci. 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Hazard. Mater."},{"key":"2026073021133515900_cit18","doi-asserted-by":"publisher","DOI":"10.1016\/j.apsoil.2021.104046","article-title":"Effects of\nsoil organic matter on biochar application in developing the biodegradation\npotentials of polycyclic aromatic hydrocarbons (PAHs)","volume":"167","author":"Kong","year":"2021","journal-title":"Appl. Soil. 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Pollut."},{"key":"2026073021133515900_cit26","doi-asserted-by":"publisher","DOI":"10.1016\/j.jenvman.2021.112998","article-title":"Combined application\nof rhamnolipid and agricultural\nwastes enhances PAHs degradation via increasing their bioavailability\nand changing microbial community in contaminated soil","volume":"294","author":"Wang","year":"2021","journal-title":"J. Environ. Manage."},{"key":"2026073021133515900_cit27","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2019.133879","article-title":"Can biochar and oxalic\nacid alleviate the toxicity stress caused by polycyclic aromatic hydrocarbons\nin soil microbial communities?","volume":"695","author":"Li","year":"2019","journal-title":"Sci. Total Environ."},{"key":"2026073021133515900_cit28","doi-asserted-by":"publisher","first-page":"107","DOI":"10.1016\/j.jes.2019.05.013","article-title":"Combination of rhamnolipid\nand biochar in assisting phytoremediation\nof petroleum hydrocarbon contaminated soil using Spartina anglica","volume":"85","author":"Zhen","year":"2019","journal-title":"J. Environ. Sci."},{"key":"2026073021133515900_cit29","doi-asserted-by":"publisher","first-page":"1912","DOI":"10.1080\/10643389.2023.2190333","article-title":"Biochar-derived dissolved\norganic matter (BDOM) and its influence on soil microbial community\ncomposition, function, and activity: a review","volume":"53","author":"Azeem","year":"2023","journal-title":"Crit. Rev. Environ. Sci. Technol."},{"key":"2026073021133515900_cit30","doi-asserted-by":"publisher","first-page":"427","DOI":"10.1016\/j.scitotenv.2018.09.097","article-title":"Effect of\nTenax addition amount and desorption time on desorption behaviour\nfor bioavailability prediction of polycyclic aromatic hydrocarbons","volume":"651","author":"Wang","year":"2019","journal-title":"Sci. Total Environ."},{"key":"2026073021133515900_cit31","doi-asserted-by":"publisher","DOI":"10.1007\/s42773-023-00213-1","article-title":"Insights into the mechanisms underlying the biodegradation\nof phenanthrene in biochar-amended soil: from bioavailability to soil\nmicrobial communities","volume":"5","author":"Zhang","year":"2023","journal-title":"Biochar"},{"key":"2026073021133515900_cit32","doi-asserted-by":"publisher","first-page":"996","DOI":"10.1038\/nmeth.2604","article-title":"UPARSE:\nhighly accurate OTU sequences from microbial amplicon reads","volume":"10","author":"Edgar","year":"2013","journal-title":"Nat. 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Manage."},{"key":"2026073021133515900_cit38","doi-asserted-by":"publisher","first-page":"10869","DOI":"10.1021\/es5011253","article-title":"Role of desorption kinetics in the rhamnolipid-enhanced\nbiodegradation of polycyclic aromatic hydrocarbons","volume":"48","author":"Congiu","year":"2014","journal-title":"Environ. Sci. Technol."},{"key":"2026073021133515900_cit39","doi-asserted-by":"publisher","first-page":"935","DOI":"10.1016\/S1001-0742(13)60570-7","article-title":"A review of environmental characteristics and effects of low-molecular\nweight organic acids in the surface ecosystem","volume":"26","author":"Xiao","year":"2014","journal-title":"J. Environ. Sci."},{"key":"2026073021133515900_cit40","doi-asserted-by":"publisher","first-page":"339","DOI":"10.1111\/ejss.12227","article-title":"Low-molecular-weight\norganic acids enhance desorption of polycyclic aromatic hydrocarbons\nfrom soil","volume":"66","author":"Ling","year":"2015","journal-title":"Eur. J. Soil Sci."},{"key":"2026073021133515900_cit41","doi-asserted-by":"publisher","DOI":"10.3390\/molecules26082256","article-title":"Chemical structure\nand biological\nactivity of humic substances define their role as plant growth promoters","volume":"26","author":"Nardi","year":"2021","journal-title":"Molecules"},{"key":"2026073021133515900_cit42","doi-asserted-by":"publisher","DOI":"10.3390\/w13040446","article-title":"Using low\nmolecular weight organic acids to enhance microbial degradation of\npolycyclic aromatic hydrocarbons: current understanding and future\nperspectives","volume":"13","author":"Zhang","year":"2021","journal-title":"Water"},{"key":"2026073021133515900_cit43","doi-asserted-by":"publisher","DOI":"10.1016\/j.envres.2025.123611","article-title":"Mechanistic insights\ninto organic\nacid-enhanced polycyclic aromatic hydrocarbon release from soil: disruption\nof metal cation bridges and charge-assisted hydrogen bonds","volume":"291","author":"Wei","year":"2026","journal-title":"Environ. 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Mater."},{"key":"2026073021133515900_cit49","doi-asserted-by":"publisher","DOI":"10.3390\/molecules25040918","article-title":"Sorption of\norganic pollutants by humic acids: a review","volume":"25","author":"Chianese","year":"2020","journal-title":"Molecules"},{"key":"2026073021133515900_cit50","doi-asserted-by":"publisher","first-page":"516","DOI":"10.1016\/j.jhazmat.2016.11.020","article-title":"Effects of\ndissolved organic matter derived from forest leaf litter\non biodegradation of phenanthrene in aqueous phase","volume":"324","author":"Cai","year":"2017","journal-title":"J. Hazard. Mater."},{"key":"2026073021133515900_cit51","doi-asserted-by":"publisher","DOI":"10.1016\/j.envpol.2022.119591","article-title":"Promotion of the biodegradation of\nphenanthrene adsorbed\non microplastics by the functional bacterial consortium QY1 in the\npresence of humic acid: Bioavailability and toxicity evaluation","volume":"307","author":"Zhu","year":"2022","journal-title":"Environ. Pollut."},{"key":"2026073021133515900_cit52","doi-asserted-by":"publisher","first-page":"435","DOI":"10.1016\/j.envpol.2013.09.031","article-title":"The effect\nof humic acids on biodegradation\nof polycyclic aromatic hydrocarbons depends on the exposure regime","volume":"184","author":"Tejeda-Agredano","year":"2014","journal-title":"Environ. Pollut."},{"key":"2026073021133515900_cit53","doi-asserted-by":"publisher","first-page":"211","DOI":"10.1016\/j.envpol.2015.12.011","article-title":"Influences of humic acid on the bioavailability of phenanthrene and\nalkyl phenanthrenes to early life stages of marine medaka (Oryzias melastigma)","volume":"210","author":"Liu","year":"2016","journal-title":"Environ. Pollut."},{"key":"2026073021133515900_cit54","doi-asserted-by":"publisher","DOI":"10.1038\/srep05295","article-title":"Properties\nof the plant- and manure-derived biochars\nand their sorption of dibutyl phthalate and phenanthrene","volume":"4","author":"Qiu","year":"2014","journal-title":"Sci. Rep."},{"key":"2026073021133515900_cit55","doi-asserted-by":"publisher","DOI":"10.1016\/j.ecoenv.2022.114113","article-title":"Perturbation\nand strengthening effects of DOM on the biochar adsorption pathway","volume":"245","author":"Liu","year":"2022","journal-title":"Ecotoxicol. Environ. 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