Harnessing Magnesium Ion for Innovative Fenton-Like Processes: Greener Multi-Oxidants Strategy to Depollute Water

Harnessing Magnesium Ion for Innovative Fenton-Like Processes: Greener Multi-Oxidants Strategy to Depollute 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 Harnessing Magnesium Ion for Innovative Fenton-Like Processes: Greener Multi-Oxidants Strategy to Depollute Water Aswin Kottapurath Vijay, Gifty Sara Rolly, Vered Marks, Virender K. Sharma, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5288918/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Mar, 2025 Read the published version in Environmental Chemistry Letters → Version 1 posted 4 You are reading this latest preprint version Abstract Organic water pollution poses significant environmental and public health challenges. Fenton reaction process is used as an advanced oxidation process to depolllute water, typically relying on transition metals and effective under acidic conditions of pH 3.0, contributing to secondary pollution. This research presents a Fenton-like process for the first time without applying transition metals that produce multi-oxidative species and are operational around neutral pH conditions. A solution comprising magnesium ions (Mg²⁺), bicarbonate ions (HCO₃⁻), and hydrogen peroxide (H₂O₂) at pH 7.4 generated reactive oxygen species that effectively degrade organic pollutants (e.g. dimethyl sulfoxide and acetamidophenol) in water. Product analysis was conducted using 1 H-NMR and HPLC techniques to determine the efficiency of the oxidation process and to identify transformation products. The findings revealed that the active multi-oxidizing agents, hydroxyl radical and carbonate radical or superoxide and carbonate radical, effectively depolluted water. This study is novel in demonstrating that a Fenton-like process can be achieved with Mg²⁺ serving only as a template to facilitate redox reactions rather than participating directly. These findings suggest a more sustainable approach to remediating water pollutants. The mechanisms for generating oxidizing radicals offer potential applications in both environmental cleanup and biological processes. advanced oxidation processes biology carbonate-radical-anion environmental Fenton-Like-reactions magnesium Figures Figure 1 Figure 2 Figure 3 1. Introduction The growing accumulation of waste in freshwater systems is increasingly threatening both planetary health and societal sustainability (Kuang et al. 2024 ). Currently, there is a sharp increase in waste and pollution due to shifts in human activities following the pandemic. There are growing concerns about the disposal of unused pharmaceuticals and their metabolites, which are often inadequately treated by wastewater treatment plants and could potentially lead to a global health crisis. (Han et al. 2023 ). Researchers are continually developing newer and greener strategies to address the challenge of cleaning water contaminated with pharmaceuticals (Parvulescu et al. 2022 ; Sharma et al. 2023 ). The major focus has been on innovating existing technologies to address the current challenges in water purification. The Fenton and Fenton-like reactions (e.g., Fe 2+ + H 2 O 2 → Fe 3+ + OH − + OH ● ) have been investigated for several decades due to their potential to generate highly reactive hydroxyl radical (OH ● ) in biological systems (Nidheesh et al. 2018 ; Wang et al. 2020 , 2024 ), in environmental processes (Wang et al. 2023 ; Sacchetto et al. 2024 ) and in advanced oxidation processes/technologies, AOPs (Sözen et al. 2020 ; Morin-Crini et al. 2022 ; Farinelli et al. 2024 ). Fenton and Fenton-like reactions are primarily conducted using Fe²⁺ and occasionally involve other transition metal complexes. Transition-metal-based Fenton reactions, often involve the formation of metal complexes and the precipitation of metal oxides/hydroxides (e.g., Fe(OH) 3 ) (Jain et al. 2018 ), which poses treatment efficiency, water quality, and sludge generation challenges. Researchers have been exploring replacing transition metal complexes with other metals (M) like beryllium and aluminum to carry out Fenton-like processes to produce OH ● through reaction (1) (Mandelli et al. 2008 , 2016 ; Kuznetsov et al. 2011 ; Novikov et al. 2016 ). However, reaction (1) typically occurs only in organic solvents with minimal water and requires very high concentrations of hydrogen peroxide (H₂O₂) to proceed. Additionally, an acidic environment must be maintained for the reaction. These stringent conditions make reaction (1) impractical for treating polluted water directly. (H 2 O) k M n ( ● OOH)(H 2 O 2 ) (n−1)+ → (H 2 O) k M n ( ● OOH)(OH − ) (n−1)+ + OH ● (M = Be, Al) (1) We stride out to achieve reaction (1) possible for treating water under neutral conditions. This stems from consideration of the similarity in the redox potentials of the couples (( ● OOH + e − + H + )/(H 2 O 2 ) = 1.46 V versus NHE (Armstrong et al. 2015 ) and (CO 3 •− + e − )/CO 3 2− 1.57 V versus NHE (Armstrong et al. 2015 ), and thus it seemed reasonable to expect the feasibility of the occurrence of reaction (2). (H 2 O) k M n (CO 3 2− )(H 2 O 2 ) (n−2)+ → (H 2 O) k M n ( • OH)(OH − ) (n−1)+ + CO 3 ●− / (H 2 O) k+1 M n (OH − ) (n−1)+ + CO 3 ●− + OH ● (2) Significantly, herein we provide evidence of the occurrence of a Fenton-like reaction in an aqueous environment by using magnesium ion (Mg 2+ ), i.e., without the use of a transition metal complex. Magnesium ion (Mg 2+ ) was intuitively chosen as the cation due to the following reasons: (i) it is a small cation and therefore expected to complex with H 2 O 2 better than Fe 2+ , (ii) magnesium salts are soluble in neutral solutions even in the presence of bicarbonate, (iii) magnesium ion plays several important roles in the environment due to its abundance and unique chemical properties,(Karst et al. 2020 ; Chen et al. 2024 ) and (iv) magnesium ions are present in most of the water bodies including tap water and seawater (Werner et al. 2006 ) and thus address the drawbacks of secondary contamination of conventional Fenton reaction processes to treat polluted water. Importantly, reaction (2) directly forms two strong oxidizing radicals: OH ● and carbonate radical anions (CO 3 •− ), resulting in a multi-oxidant system. The CO 3 ●− as an oxidant is of tremendous interest due to its involvement in various catalytic oxidation processes (Patra et al. 2020 ; Kottapurath Vijay et al. 2023b ), some of which are major biological (Illés et al. 2019 ; Meyerstein 2021 ) and water remediation importance (Patra et al. 2020 ; Kottapurath Vijay et al. 2023a ). Significantly, CO 3 ●− radical anions, despite their lower reactivity compared to OH ● radicals, exhibit a specific reactivity towards active moieties of pollutants, establishing their significant role in AOPs (Xiao et al. 2023 ). This study thus aims to provide a greener solution for depolluting water. The solutions containing Mg(H 2 O) 6 2+ , HCO 3 − , and H 2 O 2 could carry the Fenton-like processes effectively. Experiments focused on the oxidation of dimethyl sulfoxide (DMSO) and acetamidophenol were performed to demonstrate a new Fenton-like greener process to decontaminate water. These chosen model reactions serve as representative systems to investigate the intricate mechanisms and dynamics involved in Fenton-like processes in the studied solutions. The implications of these findings in biological processes and the potential for alternative advanced oxidation processes without transitional-metal complexes are briefly discussed. 2. Results and Discussions The experimental procedures are detailed in the supplemental material (Text S1). In an initial experiment, the nature of the formed intermediate oxidizing agents in the reaction mixtures of Mg 2+ and H 2 O 2 in the absence and presence of HCO 3 − was studied. Dimethylsulfoxide ((CH 3 ) 2 SO) was introduced into the reaction mixtures, and the identification of dimethylsulfone (DMSO 2 ) as a product was established through the analysis of 1 H NMR spectra. The results are presented in Fig. 1 . The formation of DMSO 2 was not seen in any solution mixtures except in which both Mg 2+ and HCO 3 − were present together in the solution. The results in Fig. 1 indicate the oxidation of DMSO by OH ● and CO 3 ●− and by HO 2 ● /O 2 ●− . These reactions have been reported to yield CH 3 ● radicals (Herscu-Kluska et al. 2008 ). In this system, the production of radicals is very slow, and therefore CO 3 ●− and O 2 ●− are long-lived and enable their reactions with DMSO (Herscu‐Kluska et al. 2008) and with H 2 O 2 , k (CO 3 ●− + H 2 O 2 ) ~ 4.0 × 10 5 M − 1 s − 1 (Huie 2003 ). The CH 3 ● radicals formed react with H 2 O 2 , k (CH 3 ● + H 2 O 2 → CH 4 + HO 2 ● /(O 2 ●− + H + )) = 2.70 × 10 5 M − 1 s − 1 (Ulanski et al. 1999 ). Thus all the radicals formed in reaction (2) are transformed into HO 2 ● /O 2 ●− radicals that are expected to react with DMSO to yield CH 3 ● and CH 3 S(O)OOH (Herscu‐Kluska et al. 2008). This explains the observed oxidation products in Fig. 1 . The oxidizing properties of a solution containing a mixture of Mg 2+ , HCO 3 − , and H 2 O 2 were further tested to oxidize a well-known micropollutant, acetamidophenol (ACP). The results are presented in Fig. 2 , which clearly shows the efficient oxidation of ACP when all components of the mixture are present. Experiments using four mixtures, HCO 3 − + ACP, Mg 2+ +ACP, H 2 O 2 + ACP, and Mg 2+ + H 2 O 2 + ACP have no oxidation capacity to degrade ACP. The results are adequately explained by the lack of formation of radicals in these reaction media. The observation that the mixture of Mg 2+ and H 2 O 2 does not oxidize the ACP points out that the Shul’pin mechanism (Mandelli et al. 2008 , 2016 ; Kuznetsov et al. 2011 ; Novikov et al. 2016 ) is not operating in aqueous solutions and at low H 2 O 2 concentrations. Whereas H 2 O 2 + HCO 3 − + ACP and Mg 2+ + H 2 O 2 + HCO 3 − + ACP systems showed 25 and 60 percent acetamidophenol degradation respectively. The chromatogram of the major oxidized product (OP) analyzed by HPLC is shown in Fig. 3 . The acetamidophenol was eluted at a retention time of 5.50 and the oxidized product at 6.70. The results point out that oxidizing reactive species are formed in a neutral aqueous solution containing Mg 2+ , H 2 O 2, and HCO 3 − . This suggests that OH ● and CO 3 ●− anion radicals are indeed formed via reaction (2) or CO 3 ●− and HO 2 ● /O 2 ●− via reactions (3)-(6) that are analogous to the proposed mechanism for an analogous system containing Co II aq (Burg et al. 2014 ). (CO 3 )Mg II (H 2 O) 5 + HO 2 − ⇌ (CO 3 )Mg II (HO 2 )(H 2 O) 4 − + H 2 O (3) (CO 3 )Mg II (HO 2 )(H 2 O) 4 − → (CO 4 )Mg II (OH)(H 2 O) 3 − + H 2 O (4) (CO 4 )Mg II (OH)(H 2 O) 3 − + H 2 O 2 → (CO 4 )Mg II (HO 2 )(H 2 O) 3 − + H 2 O (5) (CO 4 )Mg II (HO 2 )(H 2 O) 3 − + H 2 O → CO 3 ●− + Mg II ( • O 2 H)(OH) 2 (H 2 O) (6) The results demonstrate that indeed CO 3 •− are formed via one of these mechanisms. It should be noted that the observed process is considerably slower than the Fenton reaction. 3. Conclusions The results clearly showed that the solutions of Mg 2+ , H 2 O 2, and HCO 3 − generate reactive oxygen species, OH • and CO 3 ●− , or CO 3 ●− and HO 2 ● /O 2 ●− under neutral pH conditions. In these systems, the central cation acts only as a template for a redox process between its ligands. Hence, the presented Fenton-lie reaction system without transition metal ions opens the door to new advantageous AOPs. The results point out that carbonate radical anions are formed also, via the mechanism reported herein, in oceans and other natural waters that contain high concentrations of Mg 2+ and HCO 3 − . ( Mg 2+ is present in high concentrations in oceans.) Furthermore, the presence of Mg 2+ in biological systems, where it typically acts as an antioxidant due to complex biological mechanisms, raises intriguing questions. The possibility that the Fenton-like processes reported herein may have been overlooked in biological systems is a noteworthy point. This opens avenues for further research into the role of Mg 2+ in biological processes and whether it contributes to radical-induced degradation in living organisms. MgCO 3 is a common additive in pharmacological preparations and foods. Thus it has to be investigated whether the new Fenton-like process reported herein plays a role in the radical-induced degradation of pharmaceuticals and foods. Further studies are crucial to gain a clearer understanding of the phenomena and their implications. Overall, the findings lead to the development of new advanced oxidation processes that do not require transition metal complexes as catalysts. The advantage of bicarbonate as a co-catalyst in the process is that it did not decompose in the catalytic oxidation processes. Declarations Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments This study was enabled by grants from the Pazy Foundation and Ariel University. References Armstrong DA, Huie RE, Koppenol WH, et al (2015) Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report). Pure Appl Chem 87:1139–1150. https://doi.org/10.1515/pac-2014-0502 Burg A, Shamir D, Shusterman I, et al (2014) The role of carbonate as a catalyst of Fenton-like reactions in AOP processes: CO 3 ˙ − as the active intermediate. Chem Commun 50:13096–13099. https://doi.org/10.1039/C4CC05852F Chen J, Wang Y, Su A (2024) Composition characteristics of magnesium isotopes in groundwater and their application prospects in water cycle processes. 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Chem Eng J 474:145245. https://doi.org/10.1016/j.cej.2023.145245 Supplementary Files SupplementaryMaterial.docx Cite Share Download PDF Status: Published Journal Publication published 01 Mar, 2025 Read the published version in Environmental Chemistry Letters → Version 1 posted Reviewers agreed at journal 11 Nov, 2024 Reviewers invited by journal 11 Nov, 2024 Editor assigned by journal 19 Oct, 2024 First submitted to journal 18 Oct, 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-5288918","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":376556363,"identity":"0b919364-4db6-4027-babe-fda476f97669","order_by":0,"name":"Aswin Kottapurath Vijay","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABDUlEQVRIie2QMUsDMRiGUw7sknKOkUL7F+6WoHBcf4hLQqAuFnHrUORqIY6uFfwLgpNzIFCXaNYPuvR2h5PuYu6sY3odBfNM7/A+efmCUCDwR1EIkQihznxTTTNUB3WgEi3SpRnXStGq7OjKfk/q30f8xPcm1dfytBsvuezjI5s/3Wm3MsvOfQqBy0Q/SBIR4IuzR7wWL4Y7ZTWeFD4Hes8aG3cL8Dl8kLWgyimdQnuVoX37UYbAC4KTd0FtuV9J1MQpUxIlwG9PMFM5hZaVFK6qRklN6T5ZCUbBrbA9twzsSmxxciMGrxfl5vMrH1HrQjXL/OfvEOiYNYE3TdZSr8lRrJowOqAcCAQC/4xvRe5qNg6Jf+kAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0003-1477-2573","institution":"Gdansk University of Technology: Politechnika Gdanska","correspondingAuthor":true,"prefix":"","firstName":"Aswin","middleName":"Kottapurath","lastName":"Vijay","suffix":""},{"id":376556364,"identity":"25b7e778-8334-468f-85f8-7f29e218f8cc","order_by":1,"name":"Gifty Sara Rolly","email":"","orcid":"","institution":"Ariel University","correspondingAuthor":false,"prefix":"","firstName":"Gifty","middleName":"Sara","lastName":"Rolly","suffix":""},{"id":376556365,"identity":"a1920978-c392-4597-8d18-9df4c0d2eb43","order_by":2,"name":"Vered Marks","email":"","orcid":"","institution":"Ariel University","correspondingAuthor":false,"prefix":"","firstName":"Vered","middleName":"","lastName":"Marks","suffix":""},{"id":376556366,"identity":"716bef87-c401-4b3a-bc9c-063ce88c2e77","order_by":3,"name":"Virender K. Sharma","email":"","orcid":"","institution":"Texas A\u0026M University","correspondingAuthor":false,"prefix":"","firstName":"Virender","middleName":"K.","lastName":"Sharma","suffix":""},{"id":376556367,"identity":"d2d664f4-5852-4a12-b056-93eca83c06ba","order_by":4,"name":"Dan Meyerstein","email":"","orcid":"https://orcid.org/0000-0002-5429-8901","institution":"Ariel University","correspondingAuthor":false,"prefix":"","firstName":"Dan","middleName":"","lastName":"Meyerstein","suffix":""}],"badges":[],"createdAt":"2024-10-18 11:07:19","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5288918/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5288918/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10311-025-01828-5","type":"published","date":"2025-03-01T15:57:38+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":70106071,"identity":"6756e07b-0433-4708-ba8b-148ffe484aed","added_by":"auto","created_at":"2024-11-28 11:28:24","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":541999,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectra of the products of the reactions of Mg\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e with dimethylsulfoxide\u0026nbsp; (DMSO) at pH 7.40 with and without HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e. Measured one week after preparation of samples, de-aerated solutions (Experimental conditions: [H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e] = 5.0 mM, [HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e] = 5.0 mM, [Mg\u003csup\u003e2+\u003c/sup\u003e] = 1.0 mM, and [DMSO] = 25.0 mM). The results show that the DMSO is oxidized by both OH\u003csup\u003e●\u003c/sup\u003e and CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●-\u003c/sup\u003e radicals, as well as by HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●-\u003c/sup\u003e species. These reactive species contribute to the oxidation processes observed.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-5288918/v1/b47c2e9ec4eb4ce10e133894.png"},{"id":70106231,"identity":"e267f640-2ed1-4711-9f03-c6abe374af08","added_by":"auto","created_at":"2024-11-28 11:36:24","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1136739,"visible":true,"origin":"","legend":"\u003cp\u003eRemoval efficiency of acetamidophenol (ACP) was obtained for the systems: HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e + ACP, Mg\u003csup\u003e2+\u003c/sup\u003e+ ACP, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003e+ ACP, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e + HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e + ACP, Mg\u003csup\u003e2+\u003c/sup\u003e+ H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003e+ ACP, and Mg\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e + HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e + ACP. ([HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e], [H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e], and [MgCl\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e.\u003c/sup\u003e6H\u003csub\u003e2\u003c/sub\u003eO] = 10.0 mM, [ACP = acetamidophenol] = 0.25 mM). All samples were at pH 7.40, de-aerated, and analyzed by HPLC after one week of preparation. The results indicate that the removal efficiency of\u0026nbsp; ACP was evaluated in various systems, including HCO₃⁻, Mg²⁺, H₂O₂, and their combinations with ACP. HPLC analysis revealed varying levels of ACP removal for each system, with the most complex system (Mg²⁺ + H₂O₂ + HCO₃⁻ + ACP) showing significant removal efficiency.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-5288918/v1/3a8e0986d6c99bac7c2cfe79.png"},{"id":70106072,"identity":"3c73c1c0-4315-4392-a18c-b8ed0c27924a","added_by":"auto","created_at":"2024-11-28 11:28:24","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":345081,"visible":true,"origin":"","legend":"\u003cp\u003eHPLC-UV Chromatograms were obtained for the acetamidophenol degradation in the systems: ACP (green), H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e + HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e + ACP (purple), and Mg\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e + HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e + ACP (orange). The lines are shifted horizontally for better vision. The figure indicates the HPLC chromatogram of the major oxidized product (OP) of ACP. ACP eluted at a retention time of 5.50 minutes, while the oxidized product was observed at 6.70 minutes, indicating successful oxidation.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-5288918/v1/bf15a73e12701d6aa8a754a1.png"},{"id":77622476,"identity":"febb417d-9a50-4d11-acec-435f30639c91","added_by":"auto","created_at":"2025-03-03 16:07:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2531683,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5288918/v1/2ce25b45-848d-474d-ad5d-07ad3c21f82a.pdf"},{"id":70106068,"identity":"ec72aa98-88bd-4061-9002-6d5e84349f2b","added_by":"auto","created_at":"2024-11-28 11:28:24","extension":"docx","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":26057,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-5288918/v1/c82f8ebc01b5dce8ede0c0eb.docx"}],"financialInterests":"","formattedTitle":"Harnessing Magnesium Ion for Innovative Fenton-Like Processes: Greener Multi-Oxidants Strategy to Depollute Water","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe growing accumulation of waste in freshwater systems is increasingly threatening both planetary health and societal sustainability (Kuang et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). Currently, there is a sharp increase in waste and pollution due to shifts in human activities following the pandemic. There are growing concerns about the disposal of unused pharmaceuticals and their metabolites, which are often inadequately treated by wastewater treatment plants and could potentially lead to a global health crisis. (Han et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). Researchers are continually developing newer and greener strategies to address the challenge of cleaning water contaminated with pharmaceuticals (Parvulescu et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Sharma et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). The major focus has been on innovating existing technologies to address the current challenges in water purification.\u003c/p\u003e \u003cp\u003eThe Fenton and Fenton-like reactions (e.g., Fe\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e \u0026rarr; Fe\u003csup\u003e3+\u003c/sup\u003e + OH\u003csup\u003e\u0026minus;\u003c/sup\u003e + OH\u003csup\u003e●\u003c/sup\u003e) have been investigated for several decades due to their potential to generate highly reactive hydroxyl radical (OH\u003csup\u003e●\u003c/sup\u003e) in biological systems (Nidheesh et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2020\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2024\u003c/span\u003e), in environmental processes (Wang et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Sacchetto et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) and in advanced oxidation processes/technologies, AOPs (S\u0026ouml;zen et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Morin-Crini et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Farinelli et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). Fenton and Fenton-like reactions are primarily conducted using Fe\u0026sup2;⁺ and occasionally involve other transition metal complexes. Transition-metal-based Fenton reactions, often involve the formation of metal complexes and the precipitation of metal oxides/hydroxides (e.g., Fe(OH)\u003csub\u003e3\u003c/sub\u003e) (Jain et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2018\u003c/span\u003e), which poses treatment efficiency, water quality, and sludge generation challenges.\u003c/p\u003e \u003cp\u003eResearchers have been exploring replacing transition metal complexes with other metals (M) like beryllium and aluminum to carry out Fenton-like processes to produce OH\u003csup\u003e●\u003c/sup\u003e through reaction (1) (Mandelli et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2008\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Kuznetsov et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Novikov et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). However, reaction (1) typically occurs only in organic solvents with minimal water and requires very high concentrations of hydrogen peroxide (H₂O₂) to proceed. Additionally, an acidic environment must be maintained for the reaction. These stringent conditions make reaction (1) impractical for treating polluted water directly.\u003c/p\u003e \u003cp\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003ek\u003c/sub\u003eM\u003csup\u003en\u003c/sup\u003e(\u003csup\u003e●\u003c/sup\u003eOOH)(H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e)\u003csup\u003e(n\u0026minus;1)+\u003c/sup\u003e \u0026rarr; (H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003ek\u003c/sub\u003eM\u003csup\u003en\u003c/sup\u003e(\u003csup\u003e●\u003c/sup\u003eOOH)(OH\u003csup\u003e\u0026minus;\u003c/sup\u003e)\u003csup\u003e(n\u0026minus;1)+\u003c/sup\u003e + OH\u003csup\u003e●\u003c/sup\u003e (M\u0026thinsp;=\u0026thinsp;Be, Al) (1)\u003c/p\u003e \u003cp\u003eWe stride out to achieve reaction (1) possible for treating water under neutral conditions. This stems from consideration of the similarity in the redox potentials of the couples ((\u003csup\u003e●\u003c/sup\u003eOOH\u0026thinsp;+\u0026thinsp;e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csup\u003e+\u003c/sup\u003e)/(H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e)\u0026thinsp;=\u0026thinsp;1.46 V versus NHE (Armstrong et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) and (CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e + e\u003csup\u003e\u0026minus;\u003c/sup\u003e )/CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e 1.57 V versus NHE (Armstrong et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), and thus it seemed reasonable to expect the feasibility of the occurrence of reaction (2).\u003c/p\u003e \u003cp\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003ek\u003c/sub\u003eM\u003csup\u003en\u003c/sup\u003e(CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e)(H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e)\u003csup\u003e(n\u0026minus;2)+\u003c/sup\u003e \u0026rarr; (H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003ek\u003c/sub\u003eM\u003csup\u003en\u003c/sup\u003e(\u003csup\u003e\u0026bull;\u003c/sup\u003eOH)(OH\u003csup\u003e\u0026minus;\u003c/sup\u003e)\u003csup\u003e(n\u0026minus;1)+\u003c/sup\u003e + CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e/\u003c/p\u003e \u003cp\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003ek+1\u003c/sub\u003eM\u003csup\u003en\u003c/sup\u003e(OH\u003csup\u003e\u0026minus;\u003c/sup\u003e)\u003csup\u003e(n\u0026minus;1)+\u003c/sup\u003e + CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e + OH\u003csup\u003e●\u003c/sup\u003e (2)\u003c/p\u003e \u003cp\u003eSignificantly, herein we provide evidence of the occurrence of a Fenton-like reaction in an aqueous environment by using magnesium ion (Mg\u003csup\u003e2+\u003c/sup\u003e), i.e., without the use of a transition metal complex. Magnesium ion (Mg\u003csup\u003e2+\u003c/sup\u003e) was intuitively chosen as the cation due to the following reasons: (i) it is a small cation and therefore expected to complex with H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e better than Fe\u003csup\u003e2+\u003c/sup\u003e\u003csub\u003e,\u003c/sub\u003e (ii) magnesium salts are soluble in neutral solutions even in the presence of bicarbonate, (iii) magnesium ion plays several important roles in the environment due to its abundance and unique chemical properties,(Karst et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Chen et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) and (iv) magnesium ions are present in most of the water bodies including tap water and seawater (Werner et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2006\u003c/span\u003e) and thus address the drawbacks of secondary contamination of conventional Fenton reaction processes to treat polluted water.\u003c/p\u003e \u003cp\u003eImportantly, reaction (2) directly forms two strong oxidizing radicals: OH\u003csup\u003e●\u003c/sup\u003e and carbonate radical anions (CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e), resulting in a multi-oxidant system. The CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e as an oxidant is of tremendous interest due to its involvement in various catalytic oxidation processes (Patra et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Kottapurath Vijay et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2023b\u003c/span\u003e), some of which are major biological (Ill\u0026eacute;s et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Meyerstein \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2021\u003c/span\u003e) and water remediation importance (Patra et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Kottapurath Vijay et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2023a\u003c/span\u003e). Significantly, CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e radical anions, despite their lower reactivity compared to OH\u003csup\u003e●\u003c/sup\u003e radicals, exhibit a specific reactivity towards active moieties of pollutants, establishing their significant role in AOPs (Xiao et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThis study thus aims to provide a greener solution for depolluting water. The solutions containing Mg(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e, HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e, and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e could carry the Fenton-like processes effectively. Experiments focused on the oxidation of dimethyl sulfoxide (DMSO) and acetamidophenol were performed to demonstrate a new Fenton-like greener process to decontaminate water. These chosen model reactions serve as representative systems to investigate the intricate mechanisms and dynamics involved in Fenton-like processes in the studied solutions. The implications of these findings in biological processes and the potential for alternative advanced oxidation processes without transitional-metal complexes are briefly discussed.\u003c/p\u003e"},{"header":"2. Results and Discussions","content":"\u003cp\u003eThe experimental procedures are detailed in the supplemental material (Text S1). In an initial experiment, the nature of the formed intermediate oxidizing agents in the reaction mixtures of Mg\u003csup\u003e2+\u003c/sup\u003e and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e in the absence and presence of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e was studied. Dimethylsulfoxide ((CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eSO) was introduced into the reaction mixtures, and the identification of dimethylsulfone (DMSO\u003csub\u003e2\u003c/sub\u003e) as a product was established through the analysis of \u003csup\u003e1\u003c/sup\u003eH NMR spectra. The results are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The formation of DMSO\u003csub\u003e2\u003c/sub\u003e was not seen in any solution mixtures except in which both Mg\u003csup\u003e2+\u003c/sup\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e were present together in the solution.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe results in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e indicate the oxidation of DMSO by OH\u003csup\u003e●\u003c/sup\u003e and CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e and by HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e. These reactions have been reported to yield CH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e radicals (Herscu-Kluska et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). In this system, the production of radicals is very slow, and therefore CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e and O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e are long-lived and enable their reactions with DMSO (Herscu‐Kluska et al. 2008) and with H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, \u003cem\u003ek\u003c/em\u003e(CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e)\u0026thinsp;~\u0026thinsp;4.0 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003es\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Huie \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). The CH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e radicals formed react with H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, \u003cem\u003ek\u003c/em\u003e(CH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e \u0026rarr; CH\u003csub\u003e4\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/(O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e + H\u003csup\u003e+\u003c/sup\u003e))\u0026thinsp;=\u0026thinsp;2.70 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003es\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Ulanski et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e1999\u003c/span\u003e). Thus all the radicals formed in reaction (2) are transformed into HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e radicals that are expected to react with DMSO to yield CH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e and CH\u003csub\u003e3\u003c/sub\u003eS(O)OOH (Herscu‐Kluska et al. 2008). This explains the observed oxidation products in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe oxidizing properties of a solution containing a mixture of Mg\u003csup\u003e2+\u003c/sup\u003e, HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e, and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e were further tested to oxidize a well-known micropollutant, acetamidophenol (ACP). The results are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, which clearly shows the efficient oxidation of ACP when all components of the mixture are present. Experiments using four mixtures, HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + ACP, Mg\u003csup\u003e2+\u003c/sup\u003e+ACP, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;ACP, and Mg\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;ACP have no oxidation capacity to degrade ACP. The results are adequately explained by the lack of formation of radicals in these reaction media. The observation that the mixture of Mg\u003csup\u003e2+\u003c/sup\u003e and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e does not oxidize the ACP points out that the Shul\u0026rsquo;pin mechanism (Mandelli et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2008\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Kuznetsov et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Novikov et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) is not operating in aqueous solutions and at low H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e concentrations. Whereas H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + ACP and Mg\u003csup\u003e2+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + ACP systems showed 25 and 60 percent acetamidophenol degradation respectively. The chromatogram of the major oxidized product (OP) analyzed by HPLC is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The acetamidophenol was eluted at a retention time of 5.50 and the oxidized product at 6.70.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe results point out that oxidizing reactive species are formed in a neutral aqueous solution containing Mg\u003csup\u003e2+\u003c/sup\u003e, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2,\u003c/sub\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e. This suggests that OH\u003csup\u003e●\u003c/sup\u003e and CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e anion radicals are indeed formed via reaction (2) or CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e and HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e via reactions (3)-(6) that are analogous to the proposed mechanism for an analogous system containing Co\u003csup\u003eII\u003c/sup\u003e\u003csub\u003eaq\u003c/sub\u003e (Burg et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2014\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e(CO\u003csub\u003e3\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e5\u003c/sub\u003e + HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e ⇌ (CO\u003csub\u003e3\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(HO\u003csub\u003e2\u003c/sub\u003e)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO (3)\u003c/p\u003e \u003cp\u003e(CO\u003csub\u003e3\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(HO\u003csub\u003e2\u003c/sub\u003e)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; (CO\u003csub\u003e4\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(OH)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO (4)\u003c/p\u003e \u003cp\u003e(CO\u003csub\u003e4\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(OH)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e \u0026rarr; (CO\u003csub\u003e4\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(HO\u003csub\u003e2\u003c/sub\u003e)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO (5)\u003c/p\u003e \u003cp\u003e(CO\u003csub\u003e4\u003c/sub\u003e)Mg\u003csup\u003eII\u003c/sup\u003e(HO\u003csub\u003e2\u003c/sub\u003e)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO \u0026rarr; CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e + Mg\u003csup\u003eII\u003c/sup\u003e(\u003csup\u003e\u0026bull;\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003eH)(OH)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO) (6)\u003c/p\u003e \u003cp\u003eThe results demonstrate that indeed CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e are formed via one of these mechanisms. It should be noted that the observed process is considerably slower than the Fenton reaction.\u003c/p\u003e"},{"header":"3. Conclusions","content":"\u003cp\u003eThe results clearly showed that the solutions of Mg\u003csup\u003e2+\u003c/sup\u003e, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2,\u003c/sub\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e generate reactive oxygen species, OH\u003csup\u003e\u0026bull;\u003c/sup\u003e and CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e, or CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e and HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u003c/sup\u003e/O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e under neutral pH conditions. In these systems, the central cation acts only as a template for a redox process between its ligands. Hence, the presented Fenton-lie reaction system without transition metal ions opens the door to new advantageous AOPs.\u003c/p\u003e \u003cp\u003eThe results point out that carbonate radical anions are formed also, via the mechanism reported herein, in oceans and other natural waters that contain high concentrations of Mg\u003csup\u003e2+\u003c/sup\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e. ( Mg\u003csup\u003e2+\u003c/sup\u003e is present in high concentrations in oceans.) Furthermore, the presence of Mg\u003csup\u003e2+\u003c/sup\u003e in biological systems, where it typically acts as an antioxidant due to complex biological mechanisms, raises intriguing questions. The possibility that the Fenton-like processes reported herein may have been overlooked in biological systems is a noteworthy point. This opens avenues for further research into the role of Mg\u003csup\u003e2+\u003c/sup\u003e in biological processes and whether it contributes to radical-induced degradation in living organisms. MgCO\u003csub\u003e3\u003c/sub\u003e is a common additive in pharmacological preparations and foods. Thus it has to be investigated whether the new Fenton-like process reported herein plays a role in the radical-induced degradation of pharmaceuticals and foods. Further studies are crucial to gain a clearer understanding of the phenomena and their implications. Overall, the findings lead to the development of new advanced oxidation processes that do not require transition metal complexes as catalysts. The advantage of bicarbonate as a co-catalyst in the process is that it did not decompose in the catalytic oxidation processes.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAcknowledgments\u003c/h2\u003e \u003cp\u003eThis study was enabled by grants from the Pazy Foundation and Ariel University.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eArmstrong DA, Huie RE, Koppenol WH, et al (2015) Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report). 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Environ Chem Lett 22:1327\u0026ndash;1343. https://doi.org/10.1007/s10311-024-01701-x\u003c/li\u003e\n\u003cli\u003eWerner JJ, Arnold WA, McNeill K (2006) Water Hardness as a Photochemical Parameter: Tetracycline Photolysis as a Function of Calcium Concentration, Magnesium Concentration, and pH. Environ Sci Technol 40:7236\u0026ndash;7241. https://doi.org/10.1021/es060337m\u003c/li\u003e\n\u003cli\u003eXiao R, Meng Y, Fu Y, et al (2023) The overlooked carbonate radical in micropollutant degradation: An insight into hydration interaction. Chem Eng J 474:145245. https://doi.org/10.1016/j.cej.2023.145245\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"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":"advanced oxidation processes, biology, carbonate-radical-anion, environmental Fenton-Like-reactions, magnesium","lastPublishedDoi":"10.21203/rs.3.rs-5288918/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5288918/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOrganic water pollution poses significant environmental and public health challenges. Fenton reaction process is used as an advanced oxidation process to depolllute water, typically relying on transition metals and effective under acidic conditions of pH 3.0, contributing to secondary pollution. This research presents a Fenton-like process for the first time without applying transition metals that produce multi-oxidative species and are operational around neutral pH conditions. A solution comprising magnesium ions (Mg\u0026sup2;⁺), bicarbonate ions (HCO₃⁻), and hydrogen peroxide (H₂O₂) at pH 7.4 generated reactive oxygen species that effectively degrade organic pollutants (e.g. dimethyl sulfoxide and acetamidophenol) in water. Product analysis was conducted using \u003csup\u003e1\u003c/sup\u003eH-NMR and HPLC techniques to determine the efficiency of the oxidation process and to identify transformation products. The findings revealed that the active multi-oxidizing agents, hydroxyl radical and carbonate radical or superoxide and carbonate radical, effectively depolluted water. This study is novel in demonstrating that a Fenton-like process can be achieved with Mg\u0026sup2;⁺ serving only as a template to facilitate redox reactions rather than participating directly. These findings suggest a more sustainable approach to remediating water pollutants. The mechanisms for generating oxidizing radicals offer potential applications in both environmental cleanup and biological processes.\u003c/p\u003e","manuscriptTitle":"Harnessing Magnesium Ion for Innovative Fenton-Like Processes: Greener Multi-Oxidants Strategy to Depollute Water","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-28 11:28:19","doi":"10.21203/rs.3.rs-5288918/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-11-11T16:35:19+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-11-11T09:45:05+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-10-19T12:44:54+00:00","index":"","fulltext":""},{"type":"submitted","content":"Environmental Chemistry Letters","date":"2024-10-18T07:06:45+00:00","index":"","fulltext":""}],"status":"published","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}}],"origin":"","ownerIdentity":"90e98579-29f0-4a52-a000-83d1161465a3","owner":[],"postedDate":"November 28th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-03-03T16:01:40+00:00","versionOfRecord":{"articleIdentity":"rs-5288918","link":"https://doi.org/10.1007/s10311-025-01828-5","journal":{"identity":"environmental-chemistry-letters","isVorOnly":false,"title":"Environmental Chemistry Letters"},"publishedOn":"2025-03-01 15:57:38","publishedOnDateReadable":"March 1st, 2025"},"versionCreatedAt":"2024-11-28 11:28:19","video":"","vorDoi":"10.1007/s10311-025-01828-5","vorDoiUrl":"https://doi.org/10.1007/s10311-025-01828-5","workflowStages":[]},"version":"v1","identity":"rs-5288918","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5288918","identity":"rs-5288918","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}