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Kinetics and mechanism of 4-methylbenzylidene camphor degradation by UV-activated persulfate oxidation

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Abstract

4-Methylbenzylidene camphor (4-MBC), a widely used ultraviolet (UV) filter detected in various aquatic environments, has been shown to evoke estrogenic activity. In this study, the use of UV light-activated persulfate for 4-MBC degradation is evaluated for the first time. Our results showed that the combination of UV and persulfate (UV/persulfate) can significantly remove 4-MBC, with a pseudo-first-order rate constant (kobs) of 0.1349 min−1 under the conditions of [4-MBC]0 = 0.4 μM, [persulfate]0 = 12.6 μM, and initial pH = 7. The kobs and persulfate dose exhibited a linear proportional relationship in the persulfate dose range of 4.2–42 μM. The kobs remained similar at pH 5 and pH 7 but significantly decreased at pH 9. A radical scavenging test indicated that SO4−• was the dominant species in 4-MBC degradation; the second-order rate constant of SO4−• with 4-MBC was calculated to be (2.82 ± 0.05) × 109 M−1 s−1. During the UV/persulfate reaction, 4-MBC was continuously degraded, while SO4−• was gradually converted to SO42−. 4-MBC degradation involved the hydroxylation and demethylation pathways, resulting in the generation of transformation byproducts P1 (m/z 271) and P2 (m/z 243), respectively. The Microtox® acute toxicity test (Vibrio fischeri) showed increasing toxicity during the UV/persulfate degradation of 4-MBC. The 4-MBC degradation rate was markedly lower in outdoor swimming pool water than in deionized water.

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Funding

This work was financially supported by the Ministry of Science and Technology through the projects MOST 105-2628-E-002-002-MY3 and MOST 103-2221-E-002-240-MY5 and by National Taiwan University through the Excellence Research Program-Core Consortiums (NTU-CC-108L891305) within the framework of the Higher Education Sprout Project by the Ministry of Education in Taiwan.

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  1. Graduate Institute of Environmental Engineering, National Taiwan University, 71-Chou-shan Road, Taipei, 106, Taiwan

    Sung-Chuan Hsieh, Webber Wei-Po Lai & Angela Yu-Chen Lin

  2. Department of Environmental Science and Engineering, Tunghai University, Taichung, 407, Taiwan

    Webber Wei-Po Lai

  3. International Graduate Program of Molecular Science and Technology, National Taiwan University (NTU-MST), Taipei, 106, Taiwan

    Angela Yu-Chen Lin

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  1. Sung-Chuan Hsieh
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Sung-Chuan Hsieh: writing—original draft, conceptualization, methodology, visualization, investigation.

Webber Wei-Po Lai: conceptualization, methodology, visualization, writing—review and editing.

Angela Yu-Chen Lin: supervision, validation, writing—review and editing, funding acquisition.

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Correspondence to Angela Yu-Chen Lin.

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Hsieh, SC., Lai, W.WP. & Lin, A.YC. Kinetics and mechanism of 4-methylbenzylidene camphor degradation by UV-activated persulfate oxidation. Environ Sci Pollut Res 28, 18021–18034 (2021). https://doi.org/10.1007/s11356-020-11795-9

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