UV/Nitrilotriacetic Acid Process as a Novel Strategy for Efficient Photoreductive Degradation of Perfluorooctanesulfonate

  • Zhuyu Sun
    Zhuyu Sun
    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 Zhuyu Sun
  • Chaojie Zhang*
    Chaojie Zhang
    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
    *Tel: +86 21 65981831. Fax: +86 21 65983869. E-mail: [email protected]
  • Lu Xing
    Lu Xing
    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 Lu Xing
  • Qi Zhou
    Qi Zhou
    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 Qi Zhou
  • Wenbo Dong
    Wenbo Dong
    Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433, China
    More by Wenbo Dong
  • , and 
  • Michael R. Hoffmann
    Michael R. Hoffmann
    Linde-Robinson Laboratories, California Institute of Technology, Pasadena, California 91125, United States
Cite this: Environ. Sci. Technol. 2018, 52, 5, 2953–2962
Publication Date (Web):February 3, 2018
Copyright © 2018 American Chemical Society
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Supporting Info (1)»


Perfluorooctanesulfonate (PFOS) is a toxic, bioaccumulative, and highly persistent anthropogenic chemical. Hydrated electrons (eaq) are potent nucleophiles that can effectively decompose PFOS. In previous studies, eaq are mainly produced by photoionization of aqueous anions or aromatic compounds. In this study, we proposed a new photolytic strategy to generate eaq and in turn decompose PFOS, which utilizes nitrilotriacetic acid (NTA) as a photosensitizer to induce water photodissociation and photoionization, and subsequently as a scavenger of hydroxyl radical (OH) to minimize the geminate recombination between OH and eaq. The net effect is to increase the amount of eaq available for PFOS degradation. The UV/NTA process achieved a high PFOS degradation ratio of 85.4% and a defluorination ratio of 46.8% within 10 h. A pseudo-first-order rate constant (k) of 0.27 h–1 was obtained. The laser flash photolysis study indicates that eaq is the dominant reactive species responsible for PFOS decomposition. The generation of eaq is greatly enhanced and its half-life is significantly prolonged in the presence of NTA. The electron spin resonance (ESR) measurement verified the photodissociation of water by detecting OH. The model compound study indicates that the acetate and amine groups are the primary reactive sites.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.7b05912.

  • Schematic diagram of the photochemical reactor; technical data of the low-pressure mercury lamp; additional details on analytical methods; kinetics for PFOS degradation; abbreviation and chemical structure of model compounds; time profiles of PFOS degradation products; mass balance of F; NTA and NTA degradation products; NTA degradation pathway; effect of N2O; UV–vis absorption spectra; ESR spectra; effect of NTA degradation products and effect of NTA concentration; and discussion on the effect of NTA concentration (PDF)

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