Role of Ferrate(IV) and Ferrate(V) in Activating Ferrate(VI) by Calcium Sulfite for Enhanced Oxidation of Organic Contaminants

  • Binbin Shao
    Binbin Shao
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
    More by Binbin Shao
  • Hongyu Dong
    Hongyu Dong
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
    More by Hongyu Dong
  • Bo Sun
    Bo Sun
    Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
    More by Bo Sun
  • , and 
  • Xiaohong Guan*
    Xiaohong Guan
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
    International Joint Research Center for Sustainable Urban Water System, Tongji University, Shanghai 200092, P. R. China
    *E-mail: [email protected]. Tel: +86-21-65980956. Fax: 86-21-65986313.
Cite this: Environ. Sci. Technol. 2019, 53, 2, 894–902
Publication Date (Web):December 20, 2018
https://doi.org/10.1021/acs.est.8b04990
Copyright © 2018 American Chemical Society
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Abstract

Although the Fe(VI)–sulfite process has shown great potential for the rapid removal of organic contaminants, the major active oxidants (Fe(IV)/Fe(V) versus SO4•–/OH) involved in this process are still under debate. By employing sparingly soluble CaSO3 as a slow-releasing source of SO32–, this study evaluated the oxidation performance of the Fe(VI)–CaSO3 process and identified the active oxidants involved in this process. The process exhibited efficient oxidation of a variety of compounds, including antibiotics, pharmaceuticals, and pesticides, at rates that were 6.1–173.7-fold faster than those measured for Fe(VI) alone, depending on pH, CaSO3 dosage, and the properties of organic contaminants. Many lines of evidence verified that neither SO4•– nor OH was the active species in the Fe(VI)–CaSO3 process. The accelerating effect of CaSO3 was ascribed to the direct generation of Fe(IV)/Fe(V) species from the reaction of Fe(VI) with soluble SO32– via one-electron steps as well as the indirect generation of Fe(IV)/Fe(V) species from the self-decay of Fe(VI) and Fe(VI) reaction with H2O2, which could be catalyzed by uncomplexed Fe(III). Besides, the Fe(VI)–CaSO3 process exhibited satisfactory removal of organic contaminants in real water, and inorganic anions showed negligible effects on organic contaminant decomposition in this process. Thus, the Fe(VI)–CaSO3 process with Fe(IV)/Fe(V) as reactive oxidants may be a promising method for abating various micropollutants in water treatment.

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