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Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry

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Abstract

The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl, metalaxyl, myclobutanil and tebuconazole) was evaluated in different types of water. Two different systems, direct UV photolysis and UVC/H2O2 advanced oxidation process (AOP), were applied for the photodegradation tests. For the monitoring of the target compound degradation, a method based on direct injection liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. Several fungicide photodegradation by-products were tentatively identified by high-resolution mass spectrometry (HRMS) as well. For the photolysis studies, the efficiency of different types of radiation, UVC (λ = 254 nm) and UVA (λ = 365 nm), was compared. UVC photolysis provided the highest removal with a complete degradation for fenhexamide and kresoxim-methyl, and percentages between 48 and 78% for the other compounds, excluding iprovalicarb and myclobutanil with removals <35%, after 30 min of irradiation. Besides, the photodegradation tests were performed with different initial concentrations of fungicides, and the efficiency of two photoreactor systems was compared. In all cases, the kinetics followed pseudo-first order, and the half-life times could also be calculated. The addition of H2O2 under UVC light allowed an improvement of the reaction kinetics, especially for the most recalcitrant fungicides, obtaining in all cases removals higher than 82% in less than 6 min. Finally, in order to evaluate the suitability of the proposed systems, both UVC photolysis and UVC/H2O2 system were tested in different real water matrices (wastewater, tap water, swimming pool water and river water), showing that the UVC/H2O2 system had the highest removal efficiency in less than 6 min, for all water samples.

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Acknowledgements

This research was supported by FEDER funds and projects GPC2014/035, CRETUS (AGRUP2015/02) (Xunta de Galicia), CTQ2013-4645-P and Infrastructure Programme IGDC-1E-2026 (Ministry of Economy and Competitiveness, Spain). R.F. would like to acknowledge the Spanish Ministry of Economy and Competitiveness for her contract. This work was also financially supported by Project POCI-01-0145-FEDER-006984—Associate Laboratory LSRE-LCM funded by FEDER through COMPETE2020—Programa Operacional Competitividade e Internacionalizaçao (POCI)—and by national funds throughFundaçao para a Ciência e a Tecnologia (FCT). V.J.P. Vilar acknowledges the FCT Investigator 2013 Programme (IF/00273/2013).

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Authors and Affiliations

  1. Laboratory of Research and Development of Analytical Solutions (LIDSA), Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Chemistry, Universidade de Santiago de Compostela, Campus Vida, 15782, Santiago de Compostela, Spain

    Maria Celeiro, Rocio Facorro & Maria Llompart

  2. Agronomic and Agrarian Research Centre (INGACAL-CIAM), Unit of Organic Contaminants, Apartado 10, 15080, A Coruña, Spain

    Rocio Facorro & Thierry Dagnac

  3. Laboratory of Separation and Reaction Engineering—Laboratory of Catalysis and Materials (LRSE-LCM), Chemical Engineering Department, Faculty of Engineering, University of Porto, Porto, Portugal

    Vítor J. P. Vilar

Authors
  1. Maria Celeiro
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  2. Rocio Facorro
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  3. Thierry Dagnac
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  4. Vítor J. P. Vilar
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  5. Maria Llompart
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Correspondence to Maria Llompart.

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Responsible editor: Philippe Garrigues

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Celeiro, M., Facorro, R., Dagnac, T. et al. Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry. Environ Sci Pollut Res 24, 19181–19193 (2017). https://doi.org/10.1007/s11356-017-9487-2

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  • DOI: https://doi.org/10.1007/s11356-017-9487-2

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