Dissipation, residues analysis and risk assessment of metconazole in grapes under field conditions using gas chromatography–tandem mass spectrometry
Main Article Content
Keywords
metconazole, grape, dissipation, residue risk assessment, GC-MS/MS
Abstract
Metconazole (MEZ) is widely used in prevention and control of fruit and vegetable diseases. Here, a simple and reliable gas chromatography–tandem mass spectrometry (GC-MS/MS) method, using modified QuEChERS (“quick, easy, cheap, effective, rugged and safe”) extraction method, was developed for determining the dissipation and residue of MEZ in grapes and soil, and the dietary risk of MEZ residues in grapes was evaluated for Chinese people. The average recoveries of MEZ in two matrices were 80.72–100.36% with relative standard deviations of 1.56–6.16%. The same limits of detection and quantification in grapes and soil were 0.0006 mg/kg and 0.002 mg/kg, respectively. Under field conditions, the half-life of MEZ dissipation in grapes ranged from 11.75 to 20.39 days. The final residues of MEZ in grapes and soil ranged from 0.002 mg/kg to 0.19 mg/kg at pre-harvest intervals of 7, 14 and 21 days. The whole dietary risk assessment indicated acute hazard index and hazard quotient to be less than 1, implying the risk of MEZ was acceptable. This is the first study conducted on the dissipation, residue analysis and risk assessment of MEZ in grapes, thus providing reference for the detection and risk assessment of MEZ in other agricultural products.
References
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Li, J., Duan, Y.B., Bian, C.H., Pan, X.Y., Yao, C.J., Wang, J.X. and Zhou, M.G., 2019. Effects of validamycin in controlling Fusarium head blight caused by Fusarium graminearum: inhibition of DON biosynthesis and induction of host resistance. Pesticide Biochemistry and Physiology, 153: 152–160. 10.1016/j.pestbp.2018.11.012.
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Li, R.J., Liu, T.J., Cui, S.H., Zhang, S.C., Yu, J.L. and Song, G.C., 2017b. Residue behaviors and dietary risk assessment of dinotefuran and its metabolites in Oryza sativa by a new HPLC–MS/MS method. Food Chemistry, 235: 188–193. 10.1016/j.foodchem.2017.04.181.
Liang, H.W., Li, L., Qiu, J., Li, W., Yang, S.M., Zhou, Z.Q. and Qiu, L.H., 2013. Stereo selective transformation of triadimefon to metabolite triadimenol in wheat and soil under field conditions. Journal of Hazardous Materials, 260: 929–936. 10.1016/j.jhazmat.2013.06.046.
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Lopez-Fernandez, O., Rial-Otero, R., Simal-Gandara, J. and Boned, J., 2016. Dissipation kinetics of pre-plant pesticides in greenhouse-devoted soils. Science of the Total Environment, 543: 1–8. 10.1016/j.scitotenv.2015.10.145.
Ma, C., Liu, Z., Qi, Y., Wang, S.S., Cao, X.L., Wang, J., She, Y.X., Shao, Y.X., Shen, J.T. and Zhang, C., 2018. Residue behavior and risk assessment of thifluzamide in the maize field ecosystem. Environmental Science and Pollution Research, 25: 21195–21204. 10.1007/s11356-018-2211-z.
Machado, S.C., Souza, B.M., Marciano, L.P.D., Pereira, A.F.S., De Carvaiho, D.T. and Martins, I., 2019. A sensitive and accurate vortex-assisted liquid-liquid microextraction-gas chromatography-mass spectrometry method for urinary triazoles. Journal of Chromatography A, 1586: 9–17. 10.1016/j.chroma.2018.11.082.
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Mondal, R., Kole, R.K. and Bhttacharyya, A., 2017. Validation of multiresidue method for analysis of 31 pesticides in rice using gas chromatography–tandem mass spectrometry. Journal of AOAC International, 100: 1094–1101. 10.5740/jaoacinct.16-0377.
Shi, K.W., Li, W., Yuan, L.F., Li, L. and Liu, F.M., 2015. Dissipation, terminal residues and risk assessment of fluopicolide and its metabolite in cucumber under field conditions. Environmental Monitoring and Assessment, 187, 698. 10.1007/s10661-015-4924-5.
Shi, W.Q., Xiang, L.B., Yu, D.Z., Gong, S.J. and Yang, L.J., 2020. Impact of the biofungicide tetramycin on the development of Fusarium head blight, grain yield and deoxynivalenol accumulation in wheat. World Mycotoxin Journal, 13(2): 235–246. 10.3920/WMJ2019.2494.
Singh, N. and Tandon, S., 2015. Dissipation kinetics and leaching of cyazofamid fungicide in texturally different agricultural soils. International Journal of Environmental Science and Technology, 12: 2475–2484. 10.1007/s13762-014-0608-x.
Szpyrka, E., Kurdziel, A., Matyaszek, A., Podbielska, M., Rupar, J. and Słowik-Borowiec, M., 2015. Evaluation of pesticide residues in fruits and vegetables from the region of south-eastern Poland. Food Control, 48: 137–142. 10.1016/j.foodcont.2014.05.039.
Tateishi, H., Miyake, T., Mori, M., Sakuma, Y. and Saishoji, T., 2014. Effect of application timing of metconazole on Fusarium head blight development and mycotoxin contamination in wheat and barley. Journal of Pesticide Science, 39: 1–6. doi: 10.1584/jpestics.D12-077.
Telenko, D.E.P., Ravellette, J.D. and Wise, K.A., 2020. Assessing late vegetative and tasseling fungicide application timings on foliar disease and yield in Indiana corn. Plant Health Progress, 21: 4. 10.1094/PHP-03-20-0022-RS.
United States Environmental Protection Agency (USEPA), 2007. Pesticide fact sheet. Office of Prevention, Pesticides and Toxic Substances, Washington, DC. Available at: https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=P100C251.txt.
Wang S.W., Sun H.B. and Liu Y.P., 2018a. Residual behavior and risk assessment of tridemorph in banana conditions. Food Chemistry, 244: 71–74. 10.1016/j.foodchem.2017.09.124
Wang, S.Y., Zhang, Q.T., Yu, Y.R., Chen, Y., Zeng, S., Lu, P. and Hu, D.Y., 2018b. Residues, dissipation kinetics, and dietary intake risk assessment of two fungicides in grape and soil. Regulatory Toxicology and Pharmacology, 100: 72–79. 10.1016/j.yrtph.2018.10.015.
World Health Organization (WHO), 2015. A template for the automatic calculation of the IESTI. Available at: http://www.who.int/foodsafety/areas_work/chemical-risks/gems-food/en
Zhang, Y.P., Hu, D.Y., Zeng, S., Lu, P., Zhang, K.K., Chen, L.Z. and Song, B.A., 2016a. Multiresidue determination of pyrethroid pesticide residues in pepper through a modified QuEChERS method and gas chromatography with electron capture detection. Biomedical Chromatography, 30: 142–148. 10.1002/bmc.3528.
Zhang, K.K., Tang, M.M., Zhang, J., Li, Y.J., Han, X.W., Pan, S.Z., Kong, X.X., Li, M.C., Chen, H.Y., Zhang, W., H.J., Zhu, S. Zeng and Hu, D.Y., 2016b. Fate of hexaconazole and isoprothiolane in rice, soil and water under field conditions. International Journal of Environmental Analytical Chemistry, 96: 38–49. 10.1080/03067319.2015.1128535.
Zhu, J.M., Zhang, L.Y., Li, T.T., Ma, D.C., Gao, Y.Y., Mu, W. and Liu, F., 2020. Baseline sensitivity of corynesporacassiicola to metconazole and efficacy of this fungicide. Crop Protection, 130: 1–7. 10.1016/j.cropro.2019.105056.
Barganska, Z., Konieczka, P. and Namiesnik, J., 2018. Comparison of two methods for the determination of selected pesticides in honey and honeybee samples. Molecules 23: 1–13. 10.3390/molecules23102582.
Biswas, S., Mondal, R., Mukherjee, A., Sarkar, M. and Kole, R.K., 2019. Simultaneous determination and risk assessment of fipronil and its metabolites in sugarcane, using GC-ECD and confirmation by GC-MS/MS. Food Chemistry, 272: 559–567. 10.1016/j.foodchem.2018.08.087.
Chen, X.X., Fan, X.Q., Ma, Y.C. and Hu, J.Y., 2018. Dissipation behaviour, residue distribution and dietary risk assessment of tetraconazole and kresoxim-methyl in greenhouse strawberry via RRLC-QqQ-MS/MS technique. Ecotoxicology and Safety, 148: 799–804. 10.1016/j.ecoenv.2017.11.019
Chen, X.J., Meng, Z.Y., Zhang, Y.Y., Gu, H.T., Ren, Y.J. and Lu, C.L., 2016. Degradation kinetics and pathways of spirotetramat in different parts of spinach plant and in the soil. Environmental Science and Pollution Research, 23: 15053–15062. 10.1007/s11356-016-6665-6
Chen, S.S., Zhou, M.X., Zhang, Z.F. and Zhang, W.B., 2017. New and convenient approach for synthesis of metconazole. Research on Chemical Intermediates, 43: 6293–6298. 10.1007/s11164-017-2989-1
Chinese Ministry of Agriculture, 2021. National food safety standard—maximum residue limits for pesticides in food, GB-2763–2021. Beijing China: Chinese Ministry of Agriculture (MOA).
Council of the European Union 2016. European pesticides database. Bruxelles, Brussel: EU. Available at: https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/active-substances/?event=as.details&as_id=211#inline-nav-3.
Deng, Y., Liu, R., Wang, Z.K., Zhang, L.Y., Yu, S.M., Zhou, Z.Q. and Diao, J.L., 2021. The stereoselectivity of metconazole on wheat grain filling and harvested seeds germination: Implication for the application of triazole chiral pesticides. Journal of Hazardous Materials, 416: 1–11. 10.1016/j.jhazmat.2021.125911.
Duan, Y.B., Tao, X., Zhao, H.H., Xiao, X.M., Li, M. X., Wang, J.X. and Zhou, M.G., 2019. Activity of demethylation inhibitor fungicide metconazole on Chinese fusarium graminearum species complex and its application in carbendazim-resistance management of fusarium head blight in wheat. Plant Disease, 103: 929–937. 10.1094/PDIS-09-18-1592-RE.
Fantke, P. and Juraske, R., 2013. Variability of pesticide dissipation half-lives in plants. Environment Science and Technology, 47: 3548–35560. 10.1021/es303525x.
Food and Agriculture Organization/World Health Organization (FAO/WHO), 2009. Dietary exposure assessment of chemicals in food. In: Principles and methods for the risk assessment of chemicals in food. Rome, Italy: FAO, Chap 6, p. 98. ISBN 9789241572408, ISSN 250-863X.
Freitas, L.A.D., Vieira, A.C., Mendonca, J.A.F.R. and Figueiredo, E.C., 2014. Molecularly imprinted fibers with renewable surface for solid-phase microextraction of triazoles from grape juice samples followed by gas chromatography mass spectrometry analysis. Analyst, 139: 626–632. 10.1039/C3AN01756G.
Grayson, B.T., Boyd, S.L., Sampson, A.J., Drummond, J. and Walter, D., 1995. Effect of adjuvants on the performance of the new cereal fungicide, metconazole. I glasshouse trials. Pesticide Science, 45: 153–160. 10.1002/ps.2780450209.
He, R., Fan, J., Tan, Q., Lai, Y., Chen, X., Wang, T., Jiang, Y., Zhang, Y. and Zhang, W. 2017. Enantio selective determination of metconazole in multi matrices by high-performance liquid chromatography. Talanta, 178: 980–986. 10.1016/j.talanta.2017.09.045.
Hernandez, F., Cervera, M.I, Portoles, T., Beltran, J. and Pitarch, E., 2013. The role of GC-MS/MS with triple quadrupole in pesticide residue analysis in food and the environment. Analytical Methods, 5: 5875–5894. 10.1039/c3ay41104d.
Huang, J.X., Liu, C.Y., Lu, D.H., Chen, J.J., Deng, Y.C. and Wang, F.H., 2015. Residue behavior and risk assessment of mixed formulation of imidacloprid and chlorfenapyr in chieh-qua under field conditions. Environmental Monitoring and Assessment, 187, 650. 10.1007/s10661-015-4846-2.
Jin, S.G., 2008. The tenth report of nutrition and health status for China residents: nutrition and health status of annual 2002. Beijing, China: People’s Medical Publishing House.
Li, J., Duan, Y.B., Bian, C.H., Pan, X.Y., Yao, C.J., Wang, J.X. and Zhou, M.G., 2019. Effects of validamycin in controlling Fusarium head blight caused by Fusarium graminearum: inhibition of DON biosynthesis and induction of host resistance. Pesticide Biochemistry and Physiology, 153: 152–160. 10.1016/j.pestbp.2018.11.012.
Li, Z.N., Li, F.F., Wei, Y., Fan, Y., Ma, Y., Wang, W., Liu, Y., Zhao, T., Lu, P., Zhang, Y.P. and Hu, D.Y., 2017a. Dissipation rates of saisentong residues in fresh tobacco, tobacco powder and soil determined by high-performance liquid chromatography coupled with diode array detection. International Journal of Environmental Analytical Chemistry, 97: 355–367. 10.1080/03067319.2017.1315111.
Li, R.J., Liu, T.J., Cui, S.H., Zhang, S.C., Yu, J.L. and Song, G.C., 2017b. Residue behaviors and dietary risk assessment of dinotefuran and its metabolites in Oryza sativa by a new HPLC–MS/MS method. Food Chemistry, 235: 188–193. 10.1016/j.foodchem.2017.04.181.
Liang, H.W., Li, L., Qiu, J., Li, W., Yang, S.M., Zhou, Z.Q. and Qiu, L.H., 2013. Stereo selective transformation of triadimefon to metabolite triadimenol in wheat and soil under field conditions. Journal of Hazardous Materials, 260: 929–936. 10.1016/j.jhazmat.2013.06.046.
Liu, S.M., Fu, L.Y., Chen, J.P., Wang, S., Liu, J.L., Jiang, J., Che, Z.P., Tian, Y. and Chen, G.Q., 2021. Baseline sensitivity of Sclerotiniasclerotiorum to metconazole and the analysis of cross-resistance with carbendazim, dimethachlone, boscalid, fluazinam, and fludioxonil. Phytoparasitica, 49: 123–130. 10.1007/s12600-020-00867-8.
Liu, G., Qiao, X., Tao, C., He, Y., Gong, Y., Qin, D., Zhu, G., Qin, S., Li, Y. and Song, W., 2004. Guideline on pesticide residue trials. The industry standard of P.R. China (NY/T 788-2004). China Agricultural Publisher, Beijing, China.
Lopez-Fernandez, O., Rial-Otero, R., Simal-Gandara, J. and Boned, J., 2016. Dissipation kinetics of pre-plant pesticides in greenhouse-devoted soils. Science of the Total Environment, 543: 1–8. 10.1016/j.scitotenv.2015.10.145.
Ma, C., Liu, Z., Qi, Y., Wang, S.S., Cao, X.L., Wang, J., She, Y.X., Shao, Y.X., Shen, J.T. and Zhang, C., 2018. Residue behavior and risk assessment of thifluzamide in the maize field ecosystem. Environmental Science and Pollution Research, 25: 21195–21204. 10.1007/s11356-018-2211-z.
Machado, S.C., Souza, B.M., Marciano, L.P.D., Pereira, A.F.S., De Carvaiho, D.T. and Martins, I., 2019. A sensitive and accurate vortex-assisted liquid-liquid microextraction-gas chromatography-mass spectrometry method for urinary triazoles. Journal of Chromatography A, 1586: 9–17. 10.1016/j.chroma.2018.11.082.
Malhat, F., Badawy, H., Barakat, D. and Saber, A., 2013. Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD. Journal of Environmental Science and Health, Part B 48: 331–335. 10.1080/03601234.2013.742371.
Mondal, R., Kole, R.K. and Bhttacharyya, A., 2017. Validation of multiresidue method for analysis of 31 pesticides in rice using gas chromatography–tandem mass spectrometry. Journal of AOAC International, 100: 1094–1101. 10.5740/jaoacinct.16-0377.
Shi, K.W., Li, W., Yuan, L.F., Li, L. and Liu, F.M., 2015. Dissipation, terminal residues and risk assessment of fluopicolide and its metabolite in cucumber under field conditions. Environmental Monitoring and Assessment, 187, 698. 10.1007/s10661-015-4924-5.
Shi, W.Q., Xiang, L.B., Yu, D.Z., Gong, S.J. and Yang, L.J., 2020. Impact of the biofungicide tetramycin on the development of Fusarium head blight, grain yield and deoxynivalenol accumulation in wheat. World Mycotoxin Journal, 13(2): 235–246. 10.3920/WMJ2019.2494.
Singh, N. and Tandon, S., 2015. Dissipation kinetics and leaching of cyazofamid fungicide in texturally different agricultural soils. International Journal of Environmental Science and Technology, 12: 2475–2484. 10.1007/s13762-014-0608-x.
Szpyrka, E., Kurdziel, A., Matyaszek, A., Podbielska, M., Rupar, J. and Słowik-Borowiec, M., 2015. Evaluation of pesticide residues in fruits and vegetables from the region of south-eastern Poland. Food Control, 48: 137–142. 10.1016/j.foodcont.2014.05.039.
Tateishi, H., Miyake, T., Mori, M., Sakuma, Y. and Saishoji, T., 2014. Effect of application timing of metconazole on Fusarium head blight development and mycotoxin contamination in wheat and barley. Journal of Pesticide Science, 39: 1–6. doi: 10.1584/jpestics.D12-077.
Telenko, D.E.P., Ravellette, J.D. and Wise, K.A., 2020. Assessing late vegetative and tasseling fungicide application timings on foliar disease and yield in Indiana corn. Plant Health Progress, 21: 4. 10.1094/PHP-03-20-0022-RS.
United States Environmental Protection Agency (USEPA), 2007. Pesticide fact sheet. Office of Prevention, Pesticides and Toxic Substances, Washington, DC. Available at: https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=P100C251.txt.
Wang S.W., Sun H.B. and Liu Y.P., 2018a. Residual behavior and risk assessment of tridemorph in banana conditions. Food Chemistry, 244: 71–74. 10.1016/j.foodchem.2017.09.124
Wang, S.Y., Zhang, Q.T., Yu, Y.R., Chen, Y., Zeng, S., Lu, P. and Hu, D.Y., 2018b. Residues, dissipation kinetics, and dietary intake risk assessment of two fungicides in grape and soil. Regulatory Toxicology and Pharmacology, 100: 72–79. 10.1016/j.yrtph.2018.10.015.
World Health Organization (WHO), 2015. A template for the automatic calculation of the IESTI. Available at: http://www.who.int/foodsafety/areas_work/chemical-risks/gems-food/en
Zhang, Y.P., Hu, D.Y., Zeng, S., Lu, P., Zhang, K.K., Chen, L.Z. and Song, B.A., 2016a. Multiresidue determination of pyrethroid pesticide residues in pepper through a modified QuEChERS method and gas chromatography with electron capture detection. Biomedical Chromatography, 30: 142–148. 10.1002/bmc.3528.
Zhang, K.K., Tang, M.M., Zhang, J., Li, Y.J., Han, X.W., Pan, S.Z., Kong, X.X., Li, M.C., Chen, H.Y., Zhang, W., H.J., Zhu, S. Zeng and Hu, D.Y., 2016b. Fate of hexaconazole and isoprothiolane in rice, soil and water under field conditions. International Journal of Environmental Analytical Chemistry, 96: 38–49. 10.1080/03067319.2015.1128535.
Zhu, J.M., Zhang, L.Y., Li, T.T., Ma, D.C., Gao, Y.Y., Mu, W. and Liu, F., 2020. Baseline sensitivity of corynesporacassiicola to metconazole and efficacy of this fungicide. Crop Protection, 130: 1–7. 10.1016/j.cropro.2019.105056.
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