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Herein, second-order rate constants (k) for Fe(IV) reactions with DOM and DOM-relevant model compounds were determined under acidic conditions using a competition kinetics method performed on self-assembled quenched-flow apparatuses. At pH 3.0, k for 15 DOM isolates ranged from (2.1 \u00b1 0.2) \u00d7 104 MC\u20131 s\u20131 to (11.6 \u00b1 0.9) \u00d7 104 MC\u20131 s\u20131 and correlated strongly with the electron-donating capacity of DOM. Similarly, k for nine para-substituted phenolic compounds correlated linearly with the Hammett constant \u03c3+, EHOMO, and vertical ionization potential, supporting Fe(IV) selectivity toward electron-rich substrates. Across pH 1.0\u20133.5, k for DOM increased monotonically from the 104 to 105 MC\u20131 s\u20131 scale. In contrast, k for 11 model compounds representing major DOM moieties spanned 101\u2013107 M\u20131 s\u20131 and exhibited moiety-specific pH dependences, indicating that individual DOM components contribute differently to overall Fe(IV)-DOM reactivity. Fluorescence spectroscopy revealed broad-spectrum oxidation of DOM fluorophores, whereas high-resolution mass spectrometry showed that Fe(IV) preferentially transformed unsaturated moieties, oxidized nitrogen\/sulfur-containing functionalities, and fragmented moderate-molecular-weight molecules. These findings provide a bulk-to-molecular kinetic and mechanistic basis for predicting Fe(IV) fate in DOM-containing waters and optimizing Fe(IV)-based advanced oxidation processes.<\/jats:p>","DOI":"10.1021\/acs.est.6c08622","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T05:06:03Z","timestamp":1787375163000},"page":"24520-24532","source":"Crossref","is-referenced-by-count":0,"title":["Transformation of\nDissolved Organic Matter by Aqueous\nFe(IV) under Acidic Conditions: Bulk-to-Molecular Insights into Reaction\nKinetics and Mechanisms"],"prefix":"10.1021","volume":"60","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0818-4118","authenticated-orcid":true,"given":"Zhen","family":"Wang","sequence":"first","affiliation":[{"name":"Guangdong University of Technology , , ,","place":["Guangzhou, China, 510006"]},{"name":"Gwangju Institute of Science and Technology (GIST) , , ,","place":["Gwangju, Republic of Korea, 61005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenbo","family":"Liu","sequence":"additional","affiliation":[{"name":"Guangdong University of Technology , , ,","place":["Guangzhou, China, 510006"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5923-4897","authenticated-orcid":true,"given":"Yunho","family":"Lee","sequence":"additional","affiliation":[{"name":"Gwangju Institute of Science and Technology (GIST) , , ,","place":["Gwangju, Republic of Korea, 61005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jin","family":"Jiang","sequence":"additional","affiliation":[{"name":"Guangdong University of Technology , , ,","place":["Guangzhou, China, 510006"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,21]]},"reference":[{"issue":"42","key":"2026090307145706900_cit1","doi-asserted-by":"publisher","first-page":"6871","DOI":"10.1002\/anie.200502686","article-title":"Aqueous FeIV=O: Spectroscopic identification\nand oxo-group exchange","volume":"44","author":"Pestovsky","year":"2005","journal-title":"Angew. 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Technol."},{"issue":"2","key":"2026090307145706900_cit29","doi-asserted-by":"publisher","first-page":"814","DOI":"10.1021\/ic051868z","article-title":"Aqueous ferryl(IV)\nion: Kinetics of oxygen atom transfer to substrates\nand oxo exchange with solvent water","volume":"45","author":"Pestovsky","year":"2006","journal-title":"Inorg.\nChem."},{"issue":"42","key":"2026090307145706900_cit30","doi-asserted-by":"publisher","first-page":"13757","DOI":"10.1021\/ja0457112","article-title":"Reactivity of aqueous Fe(IV) in hydride and hydrogen atom transfer\nreactions","volume":"126","author":"Pestovsky","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"2026090307145706900_cit31","doi-asserted-by":"publisher","first-page":"488","DOI":"10.1002\/kin.10076","article-title":"Kinetic study of\nthe reactions of oxoiron(IV) with\naromatic substrates in aqueous solutions","volume":"34","author":"Ma\u0301rtire","year":"2002","journal-title":"Int.\nJ. Chem. Kinet."},{"issue":"3","key":"2026090307145706900_cit32","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1002\/(SICI)1097-4601(1998)30:3&lt;215::AID-KIN7&gt;3.0.CO;2-V","article-title":"Reactions of the ferryl ion with\nsome compounds found in cloud water","volume":"30","author":"Jacobsen","year":"1998","journal-title":"Int. J.\nChem. Kinet."},{"issue":"6","key":"2026090307145706900_cit33","doi-asserted-by":"publisher","first-page":"725","DOI":"10.1016\/1359-0197(90)90169-I","article-title":"Studies of the\nkinetic, spectral and chemical properties\nof Fe(IV) pyrophosphate by pulse radiolysis","volume":"36","author":"Melton","year":"1990","journal-title":"Radiat. Phys. Chem."},{"issue":"46","key":"2026090307145706900_cit34","doi-asserted-by":"publisher","first-page":"11529","DOI":"10.1021\/jp012223x","article-title":"Sequential one-electron\nreduction\nof Fe(V) to Fe(III) by cyanide in alkaline medium","volume":"105","author":"Sharma","year":"2001","journal-title":"J. Phys. 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