Insights into the Oxidation of Organic Cocontaminants during Cr(VI) Reduction by Sulfite: The Overlooked Significance of Cr(V)

  • Hongyu Dong
    Hongyu Dong
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
    More by Hongyu Dong
  • Guangfeng Wei
    Guangfeng Wei
    School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
  • Tongcheng Cao
    Tongcheng Cao
    School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
  • Binbin Shao
    Binbin Shao
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
    More by Binbin Shao
  • Xiaohong Guan*
    Xiaohong Guan
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering,  International Joint Research Center for Sustainable Urban Water System, Tongji University, Shanghai 200092, China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
    *E-mail: [email protected]. Phone: +86-21-65983869. Fax: +86-21-65986313.
  • , and 
  • Timothy J. Strathmann
    Timothy J. Strathmann
    Department of Civil & Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
Cite this: Environ. Sci. Technol. 2020, 54, 2, 1157–1166
Publication Date (Web):December 20, 2019
https://doi.org/10.1021/acs.est.9b03356
Copyright © 2019 American Chemical Society
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Abstract

Literature works reported that organic cocontaminants could be degraded during Cr(VI), a contaminant, reduction by sulfite (Cr(VI)/sulfite process). However, the role of Cr(V) and Cr(IV) intermediates in the Cr(VI)/sulfite process has been overlooked. In this study, we confirmed the generation of Cr(V) and proposed a new mechanism for the decomposition of coexisting organic contaminants during Cr(VI)/sulfite reactions occurring in oxygenated solutions at pHini 4.0 with the molar ratio of sulfite to Cr(VI) of 10.0. UV–visible and electron paramagnetic resonance (EPR) spectra indicate that Cr(V) was the predominant Cr intermediates in oxygenated solutions, while Cr(IV) accumulated in deoxygenated solutions. The contribution of Cr(V) to the degradation of organic contaminants was verified by the EPR spectra collected at 2 K and using methyl phenyl sulfoxide as a probe compound. Both Cr(V) and SO4•– contributed to the decomposition of organic contaminants in oxygenated solutions, with the relative contributions from each species being strongly dependent on properties of the target organic cocontaminants. The key mechanisms responsible for Cr(V) accumulation were supported by DFT calculations, and the degradation kinetics of organic cocontaminants was simulated with the program Kintecus 6.51. This work advances the fundamental understanding of the oxidative transformation of coexisting organic contaminants in this process.

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  • Chemicals and reagents, stopped flow experiments, competition kinetics experimental procedure, UPLC analysis, procedures for collecting EPR spectra, insignificance of reaction between Cr(VI) and SO3•–, and reactions with real concentrated Cr(VI) electroplating effluent (PDF)

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