Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

Lu, Xiaohan; Wang, Xingxing; He, Haohua; Liu, Qiuyao; Li, Jinfeng; Zhao, Ziyi; Yang, Peng; Pan, Zezhen; Wang, Zimeng

doi:10.1016/j.jhazmat.2024.137013

Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

Journal Article · Wed Dec 25 00:00:00 EST 2024 · Journal of Hazardous Materials

DOI:https://doi.org/10.1016/j.jhazmat.2024.137013· OSTI ID:2491440

Lu, Xiaohan ^[1]; ^[2]; He, Haohua ^[1]; Liu, Qiuyao ^[1]; Li, Jinfeng ^[1]; Zhao, Ziyi ^[1]; ^[3]; Pan, Zezhen ^[1]; Wang, Zimeng ^[4]

Fudan Univ., Shanghai (China)
Southern University of Science and Technology (SUSTech), Shenzhen (China); Fudan Univ., Shanghai (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Fudan Univ., Shanghai (China); Shanghai Institute of Pollution Control and Ecological Security (China)

Although trivalent manganese (Mn(III)) species have been recognized as crucial intermediates in the degradation of organic contaminants by Mn oxides, quantitative research on their specific roles remains scarce. Here, our study investigated the degradation processes of an organic pollutant, Bisphenol A (BPA), by dissolved Mn(III) and Mn(III)-bearing oxides, and elucidated the differences of the underlying mechanisms and reaction pathways between several Mn oxides and dissolved Mn(III). Our results indicated that BPA degradation rates with Mn(III)-bearing oxides alone follow the order: δ-MnO₂ >> γ-MnOOH > Mn₃O₄. Adding pyrophosphate (PP) significantly enhanced BPA degradation by promoting the formation of Mn(III)-PP complexes and exposing more reactive sites, achieved through destabilizing the crystal structure and mitigating of Mn(II) readsorption, particularly in γ-MnOOH and Mn₃O₄. Our kinetic model revealed that heterogeneous degradation by Mn oxides is the predominant reaction pathway, accounting for 61.4 %, 87.8 %, and 73.8 % of the total degraded BPA for δ-MnO₂, γ-MnOOH, and Mn₃O₄, respectively, even in the presence of significant amount of dissolved Mn(III) intermediates due to high PP concentrations. These results offer mechanistic details on BPA degradation by Mn oxides and the influence of ligand concentration, providing helpful insights for optimizing degradation strategies of organic pollutants.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: China Postdoctoral Science Foundation; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2491440

Journal Information:: Journal of Hazardous Materials, Journal Name: Journal of Hazardous Materials Vol. 486; ISSN 0304-3894

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Nanostructured Alkaline-Cation-Containing δ-MnO ₂ for Photocatalytic Water Oxidation Boppana, Venkata Bharat Ram; Yusuf, Seif; Hutchings, Gregory S. Advanced Functional Materials, Vol. 23, Issue 7 https://doi.org/10.1002/adfm.201202141	journal	September 2012
Hydrogen Bonding and Jahn–Teller Distortion in Groutite,α-MnOOH, and Manganite,γ-MnOOH, and Their Relations to the Manganese Dioxides Ramsdellite and Pyrolusite Kohler, Thomas; Armbruster, Thomas; Libowitzky, Eugen Journal of Solid State Chemistry, Vol. 133, Issue 2 https://doi.org/10.1006/jssc.1997.7516	journal	November 1997
Crystal structure refinement and reflectance measurements of hausmannite, Mn3O4 Jarosch, D. Mineralogy and Petrology, Vol. 37, Issue 1 https://doi.org/10.1007/BF01163155	journal	August 1987
Transformation of bisphenol A by manganese oxide-coated sand Lin, Kunde; Peng, Yiwen; Huang, Xinwen Environmental Science and Pollution Research, Vol. 20, Issue 3 https://doi.org/10.1007/s11356-012-1049-z	journal	July 2012
Nonequilibrium models for predicting forms of precipitated manganese oxides Hem, John D.; Lind, Carol J. Geochimica et Cosmochimica Acta, Vol. 47, Issue 11 https://doi.org/10.1016/0016-7037(83)90219-3	journal	November 1983
Precipitation and complex formation in the system Mn(ClO4)2-Na4P2O7−-pH (295 K, I = 0.5 and I ≈ 0 mol dm−3) Bilinski, Halka Polyhedron, Vol. 2, Issue 5 https://doi.org/10.1016/S0277-5387(00)83928-5	journal	January 1983
Thermodynamics, kinetics, and activation energy studies of the sorption of chromium(III) and chromium(VI) to a Mn3O4 nanomaterial Cantu, Yvette; Remes, Abril; Reyna, Alejandra Chemical Engineering Journal, Vol. 254 https://doi.org/10.1016/j.cej.2014.05.110	journal	October 2014
Dissolution and phase transformation processes of hausmannite in acidic aqueous systems under anoxic conditions Luo, Yao; Tan, Wenfeng; Suib, Steven L. Chemical Geology, Vol. 487 https://doi.org/10.1016/j.chemgeo.2018.04.016	journal	May 2018
Enhanced degradation mechanism of tetracycline by MnO2 with the presence of organic acids Sun, Siyang; Wang, Yuhan; Zhou, Lin Chemosphere, Vol. 286 https://doi.org/10.1016/j.chemosphere.2021.131606	journal	January 2022
Removal of bisphenol A via a hybrid process combining oxidation on β-MnO2 nanowires with microfiltration Zhang, Tong; Zhang, Xiwang; Yan, Xiaoli Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 392, Issue 1 https://doi.org/10.1016/j.colsurfa.2011.09.056	journal	December 2011
Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B Peña, Jasquelin; Duckworth, Owen W.; Bargar, John R. Geochimica et Cosmochimica Acta, Vol. 71, Issue 23 https://doi.org/10.1016/j.gca.2007.03.043	journal	December 2007
Structural response of phyllomanganates to wet aging and aqueous Mn(II) Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G. Geochimica et Cosmochimica Acta, Vol. 192 https://doi.org/10.1016/j.gca.2016.07.035	journal	November 2016
Soluble Mn(III)–L complexes are abundant in oxygenated waters and stabilized by humic ligands Oldham, Véronique E.; Mucci, Alfonso; Tebo, Bradley M. Geochimica et Cosmochimica Acta, Vol. 199 https://doi.org/10.1016/j.gca.2016.11.043	journal	February 2017
Oxidative dissolution of orpiment and realgar induced by dissolved and solid Mn(III) species Wang, Xingxing; Wang, Jiajia; Lu, Xiaohan Geochimica et Cosmochimica Acta, Vol. 332 https://doi.org/10.1016/j.gca.2022.06.028	journal	September 2022
Occurrence and estrogenic potency of eight bisphenol analogs in sewage sludge from the U.S. EPA targeted national sewage sludge survey Yu, Xiaohua; Xue, Jingchuan; Yao, Hong Journal of Hazardous Materials, Vol. 299 https://doi.org/10.1016/j.jhazmat.2015.07.012	journal	December 2015
Impact of Mn2+ in bisphenol A degradation by chelating agents-assisted manganese dioxide: Mechanism understanding and efficiency evaluation Jia, Daqing; Brigante, Marcello; Zhang, Changbo Journal of Water Process Engineering, Vol. 56 https://doi.org/10.1016/j.jwpe.2023.104388	journal	December 2023
A kinetic approach to assess the strengths of ligands bound to soluble Mn(III) Luther, George W.; Madison, Andrew S.; Mucci, Alfonso Marine Chemistry, Vol. 173 https://doi.org/10.1016/j.marchem.2014.09.006	journal	July 2015
Role of dissolved Mn(III) in transformation of organic contaminants: Non-oxidative versus oxidative mechanisms Hu, Erdan; Zhang, Ya; Wu, Shuyan Water Research, Vol. 111 https://doi.org/10.1016/j.watres.2017.01.013	journal	March 2017
Mn(III)-mediated bisphenol a degradation: Mechanisms and products Sun, Yanchen; Wang, Chao; May, Amanda L. Water Research, Vol. 235 https://doi.org/10.1016/j.watres.2023.119787	journal	May 2023
Enzymes, Manganese, or Iron? Drivers of Oxidative Organic Matter Decomposition in Soils Jones, Morris E.; LaCroix, Rachelle E.; Zeigler, Jacob Environmental Science & Technology, Vol. 54, Issue 21 https://doi.org/10.1021/acs.est.0c04212	journal	October 2020
Oxidation of Mn(III) Species by Pb(IV) Oxide as a Surrogate Oxidant in Aquatic Systems Wang, Xingxing; Wang, Qihuang; Yang, Peng Environmental Science & Technology, Vol. 54, Issue 21 https://doi.org/10.1021/acs.est.0c05459	journal	October 2020
A Critical Review on the Multiple Roles of Manganese in Stabilizing and Destabilizing Soil Organic Matter Li, Hui; Santos, Fernanda; Butler, Kristen Environmental Science & Technology, Vol. 55, Issue 18 https://doi.org/10.1021/acs.est.1c00299	journal	September 2021
Rates of Abiotic Mn^II Oxidation by O₂: Influence of Various Multidentate Ligands at High pH Morgan, James J.; Schlautman, Mark A.; Bilinski, Halka Environmental Science & Technology, Vol. 55, Issue 21 https://doi.org/10.1021/acs.est.1c01795	journal	July 2021
Roles of MnO₂ Colloids and Mn(III) during the Oxidation of Organic Contaminants by Permanganate Wang, Shuchang; Chen, Jie; Sun, Yuankui Environmental Science & Technology, Vol. 57, Issue 2 https://doi.org/10.1021/acs.est.2c07399	journal	December 2022
Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species Kim, Juhee; Wang, Junyue; Ashley, Daniel C. Environmental Science & Technology, Vol. 57, Issue 47 https://doi.org/10.1021/acs.est.3c00765	journal	May 2023
Influence of Divalent Cation Inhibition and Dissolved Organic Matter Enhancement on Phenol Oxidation Kinetics by Manganese Oxides Swenson, Jenna T.; Ginder-Vogel, Matthew; Remucal, Christina K. Environmental Science & Technology, Vol. 58, Issue 5 https://doi.org/10.1021/acs.est.3c08273	journal	January 2024
Identification of 4-Hydroxycumyl Alcohol As the Major MnO ₂ -Mediated Bisphenol A Transformation Product and Evaluation of Its Environmental Fate Im, Jeongdae; Prevatte, Carson W.; Campagna, Shawn R. Environmental Science & Technology, Vol. 49, Issue 10 https://doi.org/10.1021/acs.est.5b00372	journal	May 2015
Synergistic Effect of Reductive and Ligand-Promoted Dissolution of Goethite Wang, Zimeng; Schenkeveld, Walter D. C.; Kraemer, Stephan M. Environmental Science & Technology, Vol. 49, Issue 12 https://doi.org/10.1021/acs.est.5b01191	journal	May 2015
Synergistic Effects between Biogenic Ligands and a Reductant in Fe Acquisition from Calcareous Soil Schenkeveld, Walter D. C.; Wang, Zimeng; Giammar, Daniel E. Environmental Science & Technology, Vol. 50, Issue 12 https://doi.org/10.1021/acs.est.6b01623	journal	June 2016
Spectroscopic Investigation of Interfacial Interaction of Manganese Oxide with Triclosan, Aniline, and Phenol Shaikh, Nabil; Taujale, Saru; Zhang, Huichun Environmental Science & Technology, Vol. 50, Issue 20 https://doi.org/10.1021/acs.est.6b02673	journal	October 2016
Structural Transformation of MnO ₂ during the Oxidation of Bisphenol A Balgooyen, Sarah; Alaimo, Peter J.; Remucal, Christina K. Environmental Science & Technology, Vol. 51, Issue 11 https://doi.org/10.1021/acs.est.6b05904	journal	May 2017
Does Soluble Mn(III) Oxidant Formed in Situ Account for Enhanced Transformation of Triclosan by Mn(VII) in the Presence of Ligands? Gao, Yuan; Jiang, Jin; Zhou, Yang Environmental Science & Technology, Vol. 52, Issue 8 https://doi.org/10.1021/acs.est.8b00120	journal	March 2018
Effect of MnO ₂ Phase Structure on the Oxidative Reactivity toward Bisphenol A Degradation Huang, Jianzhi; Zhong, Shifa; Dai, Yifan Environmental Science & Technology, Vol. 52, Issue 19 https://doi.org/10.1021/acs.est.8b03383	journal	September 2018
Manganese-Driven Carbon Oxidation at Oxic–Anoxic Interfaces Jones, Morris E.; Nico, Peter S.; Ying, Samantha Environmental Science & Technology, Vol. 52, Issue 21 https://doi.org/10.1021/acs.est.8b03791	journal	September 2018
Geochemical Stability of Dissolved Mn(III) in the Presence of Pyrophosphate as a Model Ligand: Complexation and Disproportionation Qian, Ao; Zhang, Wen; Shi, Cheng Environmental Science & Technology, Vol. 53, Issue 10 https://doi.org/10.1021/acs.est.9b00498	journal	April 2019
Enhancement and Inhibition of Oxidation in Phenolic Compound Mixtures with Manganese Oxides Trainer, Emma Leverich; Ginder-Vogel, Matthew; Remucal, Christina K. ACS ES&T Water, Vol. 2, Issue 12 https://doi.org/10.1021/acsestwater.2c00261	journal	October 2022
Mn(III) Center Availability as a Rate Controlling Factor in the Oxidation of Phenol and Sulfide on δ-MnO ₂ Nico, Peter S.; Zasoski, Robert J. Environmental Science & Technology, Vol. 35, Issue 16 https://doi.org/10.1021/es001848q	journal	August 2001
Cation Effects on the Layer Structure of Biogenic Mn-Oxides Zhu, Mengqiang; Ginder-Vogel, Matthew; Parikh, Sanjai J. Environmental Science & Technology, Vol. 44, Issue 12 https://doi.org/10.1021/es1009955	journal	June 2010
Reduction of Carbadox Mediated by Reaction of Mn(III) with Oxalic Acid Chen, Wan-Ru; Liu, Cun; Boyd, Stephen A. Environmental Science & Technology, Vol. 47, Issue 3 https://doi.org/10.1021/es303895w	journal	January 2013
Oxidative UO ₂ Dissolution Induced by Soluble Mn(III) Wang, Zimeng; Xiong, Wei; Tebo, Bradley M. Environmental Science & Technology, Vol. 48, Issue 1 https://doi.org/10.1021/es4037308	journal	December 2013
Reductive Dissolution of Manganese(III/Iv) Oxides by Substituted Phenols Stone, Alan T. Environmental Science & Technology, Vol. 21, Issue 10 https://doi.org/10.1021/es50001a011	journal	October 1987
Oxidative Removal of Bisphenol A by Manganese Dioxide: Efficacy, Products, and Pathways Lin, Kunde; Liu, Weiping; Gan, Jay Environmental Science & Technology, Vol. 43, Issue 10 https://doi.org/10.1021/es900235f	journal	May 2009
Importance of Mn(III) Availability on the Rate of Cr(III) Oxidation on δ-MnO ₂ Nico, Peter S.; Zasoski, Robert J. Environmental Science & Technology, Vol. 34, Issue 16 https://doi.org/10.1021/es991462j	journal	August 2000
Structure–Property Relationship of Bifunctional MnO ₂ Nanostructures: Highly Efficient, Ultra-Stable Electrochemical Water Oxidation and Oxygen Reduction Reaction Catalysts Identified in Alkaline Media Meng, Yongtao; Song, Wenqiao; Huang, Hui Journal of the American Chemical Society, Vol. 136, Issue 32 https://doi.org/10.1021/ja505186m	journal	August 2014
Evidence for the presence of Mn(III) intermediates in the bacterial oxidation of Mn(II) Webb, S. M.; Dick, G. J.; Bargar, J. R. Proceedings of the National Academy of Sciences, Vol. 102, Issue 15 https://doi.org/10.1073/pnas.0409119102	journal	March 2005
Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation Birkner, N.; Nayeri, S.; Pashaei, B. Proceedings of the National Academy of Sciences, Vol. 110, Issue 22 https://doi.org/10.1073/pnas.1306623110	journal	May 2013
Importance of trivalency and the eg1 configuration in the photocatalytic oxidation of water by Mn and Co oxides Maitra, U.; Naidu, B. S.; Govindaraj, A. Proceedings of the National Academy of Sciences, Vol. 110, Issue 29 https://doi.org/10.1073/pnas.1310703110	journal	July 2013
Redox properties of birnessite from a defect perspective Peng, Haowei; McKendry, Ian G.; Ding, Ran Proceedings of the National Academy of Sciences, Vol. 114, Issue 36 https://doi.org/10.1073/pnas.1706836114	journal	August 2017
Transformation of Bisphenol A in the Presence of Manganese Dioxide Gao, Na; Hong, Jianwen; Yu, Zhiqiang Soil Science, Vol. 176, Issue 6 https://doi.org/10.1097/SS.0b013e31821d0b97	journal	January 2011
Soluble Mn(III) in Suboxic Zones Trouwborst, R. E. Science, Vol. 313, Issue 5795 https://doi.org/10.1126/science.1132876	journal	September 2006
Manganese Redox Chemistry Revisited Johnson, Kenneth S. Science, Vol. 313, Issue 5795 https://doi.org/10.1126/science.1133496	journal	September 2006
Oxidation of Phenol in Acidic Aqueous Suspensions of Manganese Oxides Ukrainczyk, Ljerka Clays and Clay Minerals, Vol. 40, Issue 2 https://doi.org/10.1346/CCMN.1992.0400204	journal	January 1992
Relationship between Pb²⁺ adsorption and average Mn oxidation state in synthetic birnessites Zhao, Wei; Cui, Haojie; Liu, Fan Clays and Clay Minerals, Vol. 57, Issue 5 https://doi.org/10.1346/CCMN.2009.0570501	journal	October 2009
Hydrolysis of Pyrophosphate in a Highly Calcareous Soil: A Solid-State Phosphorus-31 NMR Study McBeath, T. M.; Smernik, R. J.; Lombi, E. Soil Science Society of America Journal, Vol. 70, Issue 3 https://doi.org/10.2136/sssaj2005.0184	journal	May 2006
Synergistic Dissolution of Manganese Oxides as Promoted by Siderophores and Small Organic Acids Saal, Lauren B.; Duckworth, Owen W. Soil Science Society of America Journal, Vol. 74, Issue 6 https://doi.org/10.2136/sssaj2009.0465	journal	November 2010

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
Bisphenol A
Dissolved Mn(III)
Kinetic modeling
Manganese oxides
Pyrophosphate

Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

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