Constraining the yields and pathways of long-lived photo-oxidants: Suggestion of a formation process not involving organic matter triplet states

Constraining the yields and pathways of long-lived photo-oxidants: Suggestion of a formation process not involving organic matter triplet states | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Constraining the yields and pathways of long-lived photo-oxidants: Suggestion of a formation process not involving organic matter triplet states Davide Vittorio Vione, Marcello Brigante This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4018178/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 05 Nov, 2024 Read the published version in Environmental Chemistry Letters → Version 1 posted 4 You are reading this latest preprint version Abstract Long-lived photo-oxidants (LLPOs) are reactive transients photoproduced by chromophoric dissolved organic matter in sunlit surface waters, and play important roles in the photodegradation of contaminants such as phenols and anilines. Previous works identified LLPOs with phenoxy radicals, tentatively assuming they are formed upon oxidation of organic-matter phenols by the excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*). In this work we generated reactive (electron-poor) phenoxy radicals by direct UVA photolysis of 2-nitrophenol and 4-nitrophenol, and determined their reactivity with 2,4,6-trimethylphenol in water. Our main findings are: (i) LLPOs are unlikely to derive only from 3 CDOM* because, to explain 2,4,6-trimethylphenol degradation, one should assume quite long LLPO lifetimes (equal to the proposed upper limits), very elevated reactivity (comparable to the most unstable/reactive phenoxy radicals), and the involvement in LLPO generation of most 3 CDOM* that escape quenching by O 2 ; (ii) results are more easily explained by assuming that LLPOs are also formed by direct photolysis of organic-matter phenols that absorb environmental UV radiation. Aquatic photochemistry Sunlit surface waters Photochemically produced reactive intermediates Phenolic moieties of natural organic matter Photochemical self-depuration Full Text Cite Share Download PDF Status: Published Journal Publication published 05 Nov, 2024 Read the published version in Environmental Chemistry Letters → Version 1 posted Reviewers agreed at journal 18 Mar, 2024 Reviewers invited by journal 18 Mar, 2024 Editor assigned by journal 06 Mar, 2024 First submitted to journal 05 Mar, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4018178","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":280860014,"identity":"a09637a9-84fa-47c6-a638-36f7d6f5dfd3","order_by":0,"name":"Davide Vittorio Vione","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA8ElEQVRIiWNgGAWjYDCCA0DEA6TZQJwPIAY7KVoYZ4AYzERoYeCBspnBDEJa+I6fMTzwpoIhsY+99+Bjm1/b5PmYGRg/fMzBrUXyTI7BwTlnGBLbeM4lG+f23TZsY2Zglpy5DbcWgwNpCYd52xiM2SRyzKRze24zArWwMfPi03L+GVDLP7AW89+WPbftCWu5kXzgMG8DgxzIFmaGH7cTCWqRvPH4wME5xyTk2HjOGEv2NtxObmNmbMbrF77zic0f3tTY8Mi39xh++PHntu389uaDHz7i0QIFEhCKsQ1MNhBUjwT+kKJ4FIyCUTAKRgoAAPpATzh81X+lAAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0002-2841-5721","institution":"University of Turin: Universita degli Studi di Torino","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Davide","middleName":"Vittorio","lastName":"Vione","suffix":""},{"id":280860015,"identity":"914e5ecb-b1ac-41ff-b1b9-d55e2536a252","order_by":1,"name":"Marcello Brigante","email":"","orcid":"","institution":"Clermont-Université: Universite Clermont Auvergne et associes","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Marcello","middleName":"","lastName":"Brigante","suffix":""}],"badges":[],"createdAt":"2024-03-05 17:28:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4018178/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4018178/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10311-024-01786-4","type":"published","date":"2024-11-05T15:57:30+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":68750373,"identity":"128fd540-63e5-48c8-b202-7ba5818d56fa","added_by":"auto","created_at":"2024-11-11 16:11:56","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":418092,"visible":true,"origin":"","legend":"","description":"","filename":"LLPO.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4018178/v1_covered_19db62ce-b369-4925-82fc-9396e2980b47.pdf"}],"financialInterests":"","formattedTitle":"Constraining the yields and pathways of long-lived photo-oxidants: Suggestion of a formation process not involving organic matter triplet states","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"environmental-chemistry-letters","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"ecle","sideBox":"Learn more about [Environmental Chemistry Letters](https://www.springer.com/journal/10311)","snPcode":"10311","submissionUrl":"https://submission.nature.com/new-submission/10311/3","title":"Environmental Chemistry Letters","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Aquatic photochemistry, Sunlit surface waters, Photochemically produced reactive intermediates, Phenolic moieties of natural organic matter, Photochemical self-depuration","lastPublishedDoi":"10.21203/rs.3.rs-4018178/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4018178/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eLong-lived photo-oxidants (LLPOs) are reactive transients photoproduced by chromophoric dissolved organic matter in sunlit surface waters, and play important roles in the photodegradation of contaminants such as phenols and anilines. 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