Peroxymonosulfate Activation by Co-Doped Magnetic Mn3O4 for Degradation of Oxytetracycline in Water

Peroxymonosulfate Activation by Co-Doped Magnetic Mn3O4 for Degradation of Oxytetracycline in Water | 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 Peroxymonosulfate Activation by Co-Doped Magnetic Mn 3 O 4 for Degradation of Oxytetracycline in Water Liyan He, Hui Li, Jianzhi Wang, Qifei Gao, Xiaoli Li This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-946361/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 30 Jan, 2022 Read the published version in Environmental Science and Pollution Research → Version 1 posted 3 You are reading this latest preprint version Abstract Co-doped magnetic Mn 3 O 4 was synthesized by the solvothermal method and adopted as an effective catalyst for the degradation of oxytetracycline (OTC) in water. Synergistic interactions between Co-Mn 3 O 4 and Fe 3 O 4 not only resulted in the enhanced catalytic activity through the activation of peroxymonosulfate (PMS) to degrade OTC, but also made Fe 3 O 4 /Co-Mn 3 O 4 easy to be separated and recovered from aqueous solution. 94.2% of OTC could be degraded within 60 min at an initial OTC concentration of 10 mg/L, catalyst dosage of 0.2 g/L and PMS concentration of 10 mM, the high efficiency of which was achieved in a wider pH range of 3.0-10.0. The free radical quenching experiments showed that O 2 •- radicals and 1 O 2 played the main role in the degradation process. Co 3+ , Co 2+ , Fe 2+ , Fe 3+ , Mn 4+ , Mn 3+ and Mn 2+ on Fe 3 O 4 /Co-Mn 3 O 4 were identified as catalytic sites based on XPS analysis. Eventually, the intermediates of OTC degradation were examined and the possible decomposition pathways were proposed. The excellent catalytic performance of Fe 3 O 4 /Co-Mn 3 O 4 not only came from the fact that the large specific surface area could provide abundant active sites for the activation of PMS, but also the charged redistribution among atoms to accelerate the reduction of metal ions. The high degradation efficiency of OTC in actual water samples indicated that Fe 3 O 4 /Co-Mn 3 O 4 had good potential for practical application. Environmental Chemistry Toxicology Fe3O4/Co-Mn3O4 OTC Catalytic degradation PPCPs Wastewater treatment Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Full Text Tables Table 1 The specific surface area and pore size distribution of Fe 3 O 4 , Mn 3 O 4 , Co-Mn 3 O 4 , and Fe 3 O 4 /Co-Mn 3 O 4 . Schemes Schemes 1 and 2 are available in the Supplemental Files section. Supplementary Files Scheme1.png Scheme. 1. The synthesis process of Fe3O4/Co-Mn3O4. Scheme2.png Scheme. 2. The possible degradation product of OTC. supplementarymaterial.docx Supplementary Material Cite Share Download PDF Status: Published Journal Publication published 30 Jan, 2022 Read the published version in Environmental Science and Pollution Research → Version 1 posted Reviews received at journal 26 Oct, 2021 Reviewers invited by journal 26 Oct, 2021 First submitted to journal 27 Sep, 2021 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. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-946361","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":59209166,"identity":"7ee587ba-b7b4-4026-bb11-2709acd0d548","order_by":0,"name":"Liyan He","email":"","orcid":"","institution":"Lanzhou University","correspondingAuthor":false,"prefix":"","firstName":"Liyan","middleName":"","lastName":"He","suffix":""},{"id":59209167,"identity":"3f0a8402-d020-4940-96ac-6597b4d53270","order_by":1,"name":"Hui Li","email":"","orcid":"","institution":"Wuhan Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Hui","middleName":"","lastName":"Li","suffix":""},{"id":59209168,"identity":"8770c92a-38de-4b82-9c1f-31320dc6b4b5","order_by":2,"name":"Jianzhi Wang","email":"","orcid":"","institution":"Wuhan Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Jianzhi","middleName":"","lastName":"Wang","suffix":""},{"id":59209169,"identity":"7408cf4e-c617-423f-9fc7-053b642f2ba2","order_by":3,"name":"Qifei Gao","email":"","orcid":"","institution":"Lanzhou University","correspondingAuthor":false,"prefix":"","firstName":"Qifei","middleName":"","lastName":"Gao","suffix":""},{"id":59209170,"identity":"8e23b0e0-5460-4a52-9947-f597b9c052d2","order_by":4,"name":"Xiaoli Li","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzklEQVRIie3RsQrCMBCA4QuBZIl2PaG+Q6UghQq+SrrYRZw7OAQK7SL4SimBTnV3dXFy0M1FsbYguLQFF4f8y5HhIxcCYLP9YWMKoAEC4fDmTPsJawmKSTqYtAPBM4MJFzN9T9D1DT8jJGGk+EH3LMZksatQzA2sEKo4UmIjewjVepQ1pESSmUih8HoIUcWjJn5KMiTPQYRq877Fo5QhUYMIk8at34KG0UCWsZ+JdTdxnMq/XZLF0snz0/G6Dad7XnWT7yR8fspms9lsv/QC+bw2Ygr3ougAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-4797-8271","institution":"Lanzhou University","correspondingAuthor":true,"prefix":"","firstName":"Xiaoli","middleName":"","lastName":"Li","suffix":""}],"badges":[],"createdAt":"2021-09-28 19:02:26","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-946361/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-946361/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11356-022-18929-1","type":"published","date":"2022-01-31T03:52:26+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":15029140,"identity":"e173cf28-7fda-4897-9444-01259597f867","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":342418,"visible":true,"origin":"","legend":"The SEM images of Fe3O4 (a) and Fe3O4/Co-Mn3O4 (b); TEM images of Fe3O4 (c)and Fe3O4/Co-Mn3O4 (d); SEM images of Mn3O4 (e) and Co-Mn3O4 (f); and the elemental mapping (Fe, Co and Mn elements) of Fe3O4/Co-Mn3O4 (g-j).","description":"","filename":"Fig1.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/d709b2c54af4b2d0c6ae6002.png"},{"id":15029141,"identity":"3522977d-9799-4c8b-ae30-fbc094d194e8","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":172497,"visible":true,"origin":"","legend":"The N2 adsorption-desorption isotherms of Fe3O4, Mn3O4, Co-Mn3O4 and Fe3O4/Co-Mn3O4 (a); XRD patterns of Fe3O4, Fe3O4/Co-Mn3O4 (b) and the illustration were XRD patterns of Mn3O4 and Co-Mn3O4; FTIR spectra of Fe3O4 and Fe3O4/Co-Mn3O4 before OTC degradation and the FTIR spectra of Fe3O4/Co-Mn3O4 after OTC degradation (c); Magnetization curves of Fe3O4 and Fe3O4/Co-Mn3O4 (d).","description":"","filename":"Fig2.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/4f2dace6d1c740308633a0fd.png"},{"id":15029149,"identity":"f0e042e6-61de-4dbf-85ac-fb7d8ff8f218","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":173847,"visible":true,"origin":"","legend":"The comparison diagram of different components (a) and its kinetic fitting curve (b); the optimization of different Fe3O4 contents (c) and their rate constant kobs (d).","description":"","filename":"Fig3.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/ccde22680c38b5a76e9cfd06.png"},{"id":15030585,"identity":"19d79ca9-6c6b-4674-90ea-26eb32bf3dff","added_by":"auto","created_at":"2021-10-29 15:19:44","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":180405,"visible":true,"origin":"","legend":"The optimization of different Co contents (a) and their rate constant kobs (b); the (Ct/C0) -t curves of different dosing amounts (c) and their rate constant kobs (d).","description":"","filename":"Fig4.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/58d39527a02db6841fdf00ec.png"},{"id":15029150,"identity":"98bcad9c-930f-44db-9e57-aff4180b7252","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":148987,"visible":true,"origin":"","legend":"The (Ct/C0) -t curves of different pH values (a) and their rate constant kobs (b); the (Ct/C0) -t curves of different pH values (c), their kinetic fitting (d).","description":"","filename":"Fig5.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/e5e37994e8afc8ddac582cbc.png"},{"id":15030587,"identity":"0a93e5b8-7f12-4324-bf4d-3d281cbfc269","added_by":"auto","created_at":"2021-10-29 15:19:44","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":128953,"visible":true,"origin":"","legend":"and effects of water background compounds (a); the UV-vis absorption spectra of OTC at 350 nm (b); the free radical quenching experiment (c) and their rate constant kobs (d).","description":"","filename":"Fig6.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/984c7eed8f76b74095f3aedc.png"},{"id":15029992,"identity":"6728a2fa-f8ad-498e-8c27-11916d997f97","added_by":"auto","created_at":"2021-10-29 15:16:44","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":160489,"visible":true,"origin":"","legend":"XPS total absorption peak spectra before and after catalysis (a), and XPS absorption peak spectra of Mn (b), Co (c) and Fe (d) element before and after catalysis.","description":"","filename":"Fig7.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/2940c1a5c9ca23825c8a31ef.png"},{"id":15029146,"identity":"93072235-0df6-48a5-b0a1-1183a5a04452","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":144232,"visible":true,"origin":"","legend":"The removal efficiency of OTC and TOC (a); the reuse experiment (b); catalysis spectra (c) of Yellow River water, the changes of dosage (d) (the illustration showed the rate constant of Yellow River and deionized water at 15 mg), and concentration (e) (the illustration showed the rate constant of Yellow River and deionized water at 20 mg and 10 mg/L).","description":"","filename":"Fig8.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/0d83070c43ad71cebcc6b3a3.png"},{"id":15029993,"identity":"099a4c5c-732c-4184-8fab-6a5d95f7b627","added_by":"auto","created_at":"2021-10-29 15:16:44","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":256808,"visible":true,"origin":"","legend":"The possible degradation process of OTC.","description":"","filename":"Fig9.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/ec14377f8a655149844a19f2.png"},{"id":17792411,"identity":"35ed8e3a-1c61-41db-a672-3cf3de160be5","added_by":"auto","created_at":"2022-01-31 03:52:41","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":896247,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1_covered.pdf"},{"id":15031454,"identity":"e76decbc-9b7a-48d4-a2a4-a41279c7c2e4","added_by":"auto","created_at":"2021-10-29 15:22:52","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":890961,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1_covered.pdf"},{"id":15029139,"identity":"abf499da-65c3-4a55-aaed-c18f3a0b2c04","added_by":"auto","created_at":"2021-10-29 15:13:44","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":164681,"visible":true,"origin":"","legend":"Scheme. 1. The synthesis process of Fe3O4/Co-Mn3O4.","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/edb7990c7fd3af1f9bc238a7.png"},{"id":15031413,"identity":"383f003c-7732-43e0-8a99-80e8ade56106","added_by":"auto","created_at":"2021-10-29 15:22:44","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":121286,"visible":true,"origin":"","legend":"Scheme. 2. The possible degradation product of OTC.","description":"","filename":"Scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/8c59c8b1638f48d74b4ef867.png"},{"id":15029988,"identity":"a0138ec1-3acf-4903-a908-0da45cb8aabc","added_by":"auto","created_at":"2021-10-29 15:16:44","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":164540,"visible":true,"origin":"","legend":"Supplementary Material","description":"","filename":"supplementarymaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-946361/v1/bf043d67e77af7d277235513.docx"}],"financialInterests":"","formattedTitle":"\u003cp\u003ePeroxymonosulfate Activation by Co-Doped Magnetic Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e for Degradation of Oxytetracycline in Water\u003c/p\u003e","fulltext":[{"header":"Full Text","content":"This preprint is available for \u003ca href='/article/rs-946361/latest.pdf' target='_blank'\u003edownload as a PDF\u003c/a\u003e."},{"header":"Tables","content":"\u003cp\u003eTable 1 The specific surface area and pore size distribution of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, and Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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1 and 2 are available in the Supplemental Files section.\u003c/p\u003e"}],"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":true,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Fe3O4/Co-Mn3O4, OTC, Catalytic degradation, PPCPs, Wastewater treatment","lastPublishedDoi":"10.21203/rs.3.rs-946361/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-946361/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCo-doped magnetic Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was synthesized by the solvothermal method and adopted as an effective catalyst for the degradation of oxytetracycline (OTC) in water. Synergistic interactions between Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e not only resulted in the enhanced catalytic activity through the activation of peroxymonosulfate (PMS) to degrade OTC, but also made Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003eeasy to be separated and recovered from aqueous solution. 94.2% of OTC could be degraded within 60 min at an initial OTC concentration of 10 mg/L, catalyst dosage of 0.2 g/L and PMS concentration of 10 mM, the high efficiency of which was achieved in a wider pH range of 3.0-10.0. The free radical quenching experiments showed that O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e•-\u003c/sup\u003e radicals and \u003csup\u003e1\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e played the main role in the degradation process. Co\u003csup\u003e3+\u003c/sup\u003e, Co\u003csup\u003e2+\u003c/sup\u003e, Fe\u003csup\u003e2+\u003c/sup\u003e, Fe\u003csup\u003e3+\u003c/sup\u003e, Mn\u003csup\u003e4+\u003c/sup\u003e, Mn\u003csup\u003e3+\u003c/sup\u003e and Mn\u003csup\u003e2+\u003c/sup\u003e on Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e were identified as catalytic sites based on XPS analysis. Eventually, the intermediates of OTC degradation were examined and the possible decomposition pathways were proposed. The excellent catalytic performance of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e not\u0026nbsp;only came from the fact that the large specific surface area could provide abundant active sites for the activation of PMS, but also the charged redistribution among atoms to accelerate the reduction of metal ions. The high degradation efficiency of OTC in actual water samples indicated that Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/Co-Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e had\u0026nbsp;good potential\u0026nbsp;for\u0026nbsp;practical application.\u003c/p\u003e","manuscriptTitle":"Peroxymonosulfate Activation by Co-Doped Magnetic Mn3O4 for Degradation of Oxytetracycline in Water","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2021-10-29 15:13:42","doi":"10.21203/rs.3.rs-946361/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"editorInvitedReview","content":"","date":"2021-10-26T14:49:46+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2021-10-26T11:29:44+00:00","index":"","fulltext":""},{"type":"submitted","content":"Environmental Science and Pollution Research","date":"2021-09-27T08:21:59+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"2ad063f5-67e4-4b7e-aa42-84fc7ba819d1","owner":[],"postedDate":"October 29th, 2021","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":8187462,"name":"Environmental Chemistry"},{"id":8187463,"name":"Toxicology"}],"tags":[],"updatedAt":"2022-01-31T03:52:26+00:00","versionOfRecord":{"articleIdentity":"rs-946361","link":"https://doi.org/10.1007/s11356-022-18929-1","journal":{"identity":"environmental-science-and-pollution-research","isVorOnly":false,"title":"Environmental Science and Pollution Research"},"publishedOn":"2022-01-31 03:52:26","publishedOnDateReadable":"January 31st, 2022"},"versionCreatedAt":"2021-10-29 15:13:42","video":"","vorDoi":"10.1007/s11356-022-18929-1","vorDoiUrl":"https://doi.org/10.1007/s11356-022-18929-1","workflowStages":[]},"version":"v1","identity":"rs-946361","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-946361","identity":"rs-946361","version":["v1"]},"buildId":"_2-kVJe1T_tPrBINL-cwx","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}