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Identification, Elucidation, and Toxicity Assessment of Nontarget Disinfection By-products from Fipronil Chlorination

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Abstract

In the present study, fipronil degradation was evaluated in typical chlorination conditions (fipronil: 20 μg L−1; free chlorine concentration: 2 mg L−1; pH 7.5; 25 ○C). Fipronil was quickly degraded by chlorination with half-time life of 2.08 min, achieving 95% of degradation in 15 min of reaction. For identification and elucidation of its disinfection by-products, fipronil solutions (2.0 mg L−1) were chlorinated at different contact times. Six by-products were identified and their structural formulas were elucidated by high-resolution mass spectrometry. Lastly, the toxicity of the unreacted and chlorinated solutions was evaluated using in vitro, in vivo, and in silico assays. Unreacted and chlorinated solutions were toxic to Artemia salina nauplii with an increase on toxic effects after 24 h of reaction time. No estrogenicity and cytotoxicity were observed for the tested solutions using re-engineered bioluminescent yeast estrogen screen and colorimetric MTT assays, respectively. According to quantitative structure-activity relationship methodology, chlorination may produce a more mutagenic compound than the precursor fipronil. The generated disinfection by-products also proved to be developmental toxicant, although it was not possible to measure their relative potency in relation to the parent compound.

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Acknowledgements

The authors would like to thank the Laboratório Brasileiro de Controle de Dopagem (LBCD) – Universidade Federal do Rio de Janeiro (UFRJ), RJ, Brazil for providing its infrastructure and know-how and Laboratório Multiusuário de Proteômica (LMU-ProtBio), from Núcleo de Pesquisas em Ciências Biológicas, Universidade Federal de Ouro Preto, MG, Brazil for providing the required equipment and technical expertise for sample processing and analyses. Finally, we would like to thank Dr. Jason Guy Taylor for reviewing the manuscript for its English usage.

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This work was financially supported by the Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG – TEC-APQ-03205-16); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); and Universidade Federal de Ouro Preto.

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  1. Postgraduation Program in Environmental Engineering (ProAmb), Universidade Federal de Ouro Preto (UFOP), Ouro Preto, MG, 35400-000, Brazil

    André Luis Corrêa de Barros

  2. Multicenter Postgraduation Program in Chemistry – Minas Gerais, Universidade Federal de Ouro Preto, Ouro Preto, MG, 35400-000, Brazil

    Daniel Aparecido da Silva Rodrigues & Camila Cristina Rodrigues Ferreira da Cunha

  3. Department of Biological Sciences, Universidade Federal de Ouro Preto, Ouro Preto, MG, 35400-000, Brazil

    Silvana de Queiroz Silva

  4. Department of Chemistry, Universidade Federal de Ouro Preto, Ouro Preto, MG, 35400-000, Brazil

    Robson José de Cássia Franco Afonso

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All authors have participated in (a) conception and design, or analysis and interpretation of the data; (b) drafting the article or revising it critically for important intellectual content; and (c) approval of the final version. Specifically, the authors’ contribution can be summarized as follows:

André Luis Corrêa de Barrosa: conceptualization; methodology; formal analysis; investigation; and writing—original draft preparation.

Daniel Aparecido da Silva Rodriguesb: methodology; investigation; and writing—review and editing preparation.

Camila Cristina Rodrigues Ferreira da Cunhab: methodology; investigation; and writing—review and editing preparation.

Silvana de Queiroz Silvac: methodology; and investigation.

Robson José de Cássia Franco Afonsod: conceptualization; supervision; project administration; and funding acquisition.

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Correspondence to André Luis Corrêa de Barros.

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de Barros, A.L.C., da Silva Rodrigues, D.A., da Cunha, C.C.R.F. et al. Identification, Elucidation, and Toxicity Assessment of Nontarget Disinfection By-products from Fipronil Chlorination. Water Air Soil Pollut 232, 156 (2021). https://doi.org/10.1007/s11270-021-05102-6

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