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Atomic-Level Structural Differences between Fe(III) Coprecipitates Generated by the Addition of Fe(III) Coagulants and by the Oxidation of Fe(II) Coagulants Determine Their Coagulation Behavior in Phosphate and DOM Removal

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Environ. Sci. Technol. 2023, 57, 33, 12489-12500
    Physico-Chemical Treatment and Resource Recovery

    Atomic-Level Structural Differences between Fe(III) Coprecipitates Generated by the Addition of Fe(III) Coagulants and by the Oxidation of Fe(II) Coagulants Determine Their Coagulation Behavior in Phosphate and DOM Removal
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    • Bingqian Yang
      Bingqian Yang
      State Key Laboratory of Environmental Aquatic Chemistry, Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People’s Republic of China
      University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
      More by Bingqian Yang
    • Nigel Graham
      Nigel Graham
      Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
      More by Nigel Graham
    • Peng Liu
      Peng Liu
      School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
      More by Peng Liu
      Orcidhttps://orcid.org/0000-0002-2870-7193
    • Mengjie Liu
      Mengjie Liu
      State Key Laboratory of Environmental Aquatic Chemistry, Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People’s Republic of China
      University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
      More by Mengjie Liu
    • John Gregory
      John Gregory
      Department of Civil, Environmental and Geomatic Engineering, University College London, Gower Street, London WC1E 6BT, U.K.
      More by John Gregory
      Orcidhttps://orcid.org/0000-0003-4528-0432
    • Wenzheng Yu*
      Wenzheng Yu
      State Key Laboratory of Environmental Aquatic Chemistry, Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People’s Republic of China
      *Email: [email protected]
      More by Wenzheng Yu
      Orcidhttps://orcid.org/0000-0001-9776-8021
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    Environmental Science & Technology

    Cite this: Environ. Sci. Technol. 2023, 57, 33, 12489–12500
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    https://doi.org/10.1021/acs.est.3c03463
    Published August 8, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    In situ Fe(III) coprecipitation from Fe2+ oxidation is a widespread phenomenon in natural environments and water treatment processes. Studies have shown the superiority of in situ Fe(III) (formed by in situ oxidation of a Fe(II) coagulant) over ex situ Fe(III) (using a Fe(III) coagulant directly) in coagulation, but the reasons remain unclear due to the uncertain nature of amorphous structures. Here, we utilized an in situ Fe(III) coagulation process, oxidizing the Fe(II) coagulant by potassium permanganate (KMnO4), to treat phosphate-containing surface water and analyzed differences between in situ and ex situ Fe(III) coagulation in phosphate removal, dissolved organic matter (DOM) removal, and floc growth. Compared to ex situ Fe(III), flocs formed by the natural oxidizing Fe2+ coagulant exhibited more effective phosphate removal. Furthermore, in situ Fe(III) formed through accelerated oxidation by KMnO4 demonstrated improved flocculation behavior and enhanced removal of specific types of DOM by forming a more stable structure while still maintaining effective phosphate removal. Fe K-edge extended X-ray absorption fine structure spectra (EXAFS) of the flocs explained their differences. A short-range ordered strengite-like structure (corner-linked PO4 tetrahedra to FeO6 octahedra) was the key to more effective phosphorus removal of in situ Fe(III) than ex situ Fe(III) and was well preserved when KMnO4 accelerated in situ Fe(III) formation. Conversely, KMnO4 significantly inhibited the edge and corner coordination between FeO6 octahedra and altered the floc-chain-forming behavior by accelerating hydrolysis, resulting in a more dispersed monomeric structure than ex situ Fe(III). This research provides an explanation for the superiority of in situ Fe(III) in phosphorus removal and highlights the importance of atomic-level structural differences between ex situ and in situ Fe(III) coprecipitates in water treatment.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.3c03463.

    • Coagulants and raw water properties (Text S1); coagulation experimental process and details (Text S2); kinetic analysis and results of phosphate removal (Text S3); PARAFAC analysis methods and details (Text S4); 2D-COS analysis methods and details (Text S5); wavelet transform analysis methods and details (Text S6); DLVO analysis methods and details (Text S7); wavelet transform analysis of a pure mineral structure (Text S8); shell-fitting analysis methods and details of EXAFS data (Text S9); OpenFluor matches for PARAFAC components (Table S1); peak splitting results of XPS carbon spectra (Table S2); average elemental component results of EDS spectra (Table S3); Fe XANES LCF results for sediment samples (Table S4); Fe EXAFS fitting results (Table S5); coagulation experimental design (Figure S1); kinetics of phosphate removal by different flocs by coprecipitation or adsorption (Figure S2); equilibrium flocculation index (FI) formed by different Fe coagulation systems with/without phosphate (Figure S3); XRD results of nanoparticles formed by different coagulants (Figure S4); TEM results of nanoparticles formed by different coagulants (Figure S5); HRTEM of flocs formed under different conditions (Figure S6); DLVO calculation results (Figure S7); FiUV254 absorbance results in phosphate-containing surface water before and after treatment with different coagulants (Figure S8); fluorescence EEM contours of three PARAFAC components identified from surface water (Figure S9); adsorption model of phosphate on different floc surfaces (Figure S10); high-resolution N XPS spectra of the flocs (Figure S11); high-resolution Fe and C XPS spectra of the flocs (Figure S12); high-resolution P XPS spectra of the flocs (Figure S13); high-resolution Mn XPS spectra of the flocs (Figure S14); EDS-mapping (HAADF) results of nanoparticles formed by different coagulants (Figure S15); EDS-mapping results of nanoparticles formed by different coagulants (Figure S16); wavelet transform results of standard minerals and samples (η = 12 and σ = 1) (Figure S17); wavelet transform results of standard minerals and samples (η = 4 and σ = 1) (Figure S18); and Wavelet Transform results of goethite and Fe-OM (Figure S19) (PDF)

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    Environmental Science & Technology

    Cite this: Environ. Sci. Technol. 2023, 57, 33, 12489–12500
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.est.3c03463
    Published August 8, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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