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Unveiling the Role of Sulfur in Rapid Defluorination of Florfenicol by Sulfidized Nanoscale Zero-Valent Iron in Water under Ambient Conditions

  • Zhen Cao
    Zhen Cao
    College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, China
    More by Zhen Cao
  • Hao Li
    Hao Li
    Department of Chemistry and Oden Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712, United States
    More by Hao Li
  • Gregory V. Lowry
    Gregory V. Lowry
    Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
  • Xiaoyang Shi
    Xiaoyang Shi
    Earth Engineering Center, Center for Advanced Materials for Energy and Environment, Department of Earth and Environmental Engineering, Columbia University, New York, New York 10027, United States
    More by Xiaoyang Shi
  • Xiangcheng Pan
    Xiangcheng Pan
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China
  • Xinhua Xu
    Xinhua Xu
    College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, China
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  • Graeme Henkelman
    Graeme Henkelman
    Department of Chemistry and Oden Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712, United States
  • , and 
  • Jiang Xu*
    Jiang Xu
    College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, China
    Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    *Email: [email protected]
    More by Jiang Xu
Cite this: Environ. Sci. Technol. 2021, 55, 4, 2628–2638
Publication Date (Web):February 2, 2021
https://doi.org/10.1021/acs.est.0c07319
Copyright © 2021 American Chemical Society
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Abstract

Groundwater contamination by halogenated organic compounds, especially fluorinated ones, threatens freshwater sources globally. Sulfidized nanoscale zero-valent iron (SNZVI), which is demonstrably effective for dechlorination of groundwater contaminants, has not been well explored for defluorination. Here, we show that SNZVI nanoparticles synthesized via a modified post-sulfidation method provide rapid dechlorination (∼1100 μmol m–2 day–1) and relatively fast defluorination (∼6 μmol m–2 day–1) of a halogenated emerging contaminant (florfenicol) under ambient conditions, the fastest rates that have ever been reported for Fe0-based technologies. Batch reactivity experiments, material characterizations, and theoretical calculations indicate that coating S onto the metallic Fe surface provides a highly chemically reactive surface and changes the primary dechlorination pathway from atomic H for nanoscale zero-valent iron (NZVI) to electron transfer for SNZVI. S and Fe sites are responsible for the direct electron transfer and atomic H-mediated reaction, respectively, and β-elimination is the primary defluorination pathway. Notably, the Cl atoms in florfenicol make the surface more chemically reactive for defluorination, either by increasing florfenicol adsorption or by electronic effects. The defluorination rate by SNZVI is ∼132–222 times higher with chlorine attached compared to the absence of chlorine in the molecule. These mechanistic insights could lead to new SNZVI materials for in situ groundwater remediation of fluorinated contaminants.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.0c07319.

  • Additional information of dechlorination rate of FF removal by SNZVI with an Fe2+ or Fe3+ precursor; TEM images of NZVI and conventional post-sulfidized SNZVI; TEM images and element distributions of SNZVI; hydrophobicity; Fe0 content; surface area; electrochemical tests and hydrogen evolution of NZVI and SNZVI; FF and its product distribution with or without TBA; and UPLC-MS/MS spectra (PDF)

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This article is cited by 16 publications.

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  2. Ariel Nunez Garcia, Yanyan Zhang, Subhasis Ghoshal, Feng He, Denis M. O’Carroll. Recent Advances in Sulfidated Zerovalent Iron for Contaminant Transformation. Environmental Science & Technology 2021, 55 (13) , 8464-8483. https://doi.org/10.1021/acs.est.1c01251
  3. Jiang Xu, Hao Li, Gregory V. Lowry. Sulfidized Nanoscale Zero-Valent Iron: Tuning the Properties of This Complex Material for Efficient Groundwater Remediation. Accounts of Materials Research 2021, 2 (6) , 420-431. https://doi.org/10.1021/accountsmr.1c00037
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