Abstract
Alpha-cypermethrin (α-cypermethrin), an important chiral pyrethroid insecticide, is frequently detected in human samples. Because of the possible human health risks caused by α-cypermethrin, we studied dynamics, residues, and metabolism of α-cypermethrin in five common vegetables (tomato, cucumber, rape, cabbage, and pepper) on enantiomeric levels after foliar spray. α-Cypermethrin was qualified by a HP-5 column and its enantiomers could be separated by gas chromatograph (GC) using a BGB-172 chiral column. The results of degradation showed that α-cypermethrin dissipated rapidly in vegetables with half-lives being only 2.85–8.88 days. Stereoselective degradation was observed on pepper and cucumber while the two metabolites (cis-DCCA and 3-PBA) of α-cypermethrin were not detected during its dissipation in all plants. This is the first evidence of enantioselective degradation of α-cypermethrin in the five common vegetables and the results should be considered in future environmental risk and food safety evaluations.
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Baker SE, Olsson AO, Barr DB (2004) Isotope dilution high-performance liquid chromatography-tandem mass spectrometry method for quantifying urinary metabolites of synthetic pyrethroid insecticides. Arch Environ Contam Toxicol 46:281
Sereda B, Bouwman H, Kylin H (2009) Comparing water, bovine milk, and indoor residual spraying as possible sources of DDTand pyrethroid residues in breast milk. J Toxicol Environ Health 72:842–851
Barr DB, Olsson AO, Wong LY, Udunka S, Baker SE, Whitehead RD, Magsumbol MS, Williams BL, Needham LL (2010) Urinary concentrations of metabolites of pyrethroid insecticides in the general U.S. population: national health and nutrition examination survey 1999–2002. Environ Health Perspect 118:742–748
Bergerpreiss E, Levsen K, Leng G, Idel H, Sugiri D, Ranft U (2002) Indoor pyrethroid exposure in homes with woollen textile floor coverings. Int J Hyg Environ Health 205:459–472
Diao J, Xu P, Liu D, Lu Y, Zhou Z (2011) Enantiomer-specific toxicity and bioaccumulation of alpha-cypermethrin to earthworm Eisenia fetida. J Hazard Mater 192:1072–1078
Du G, Shen O, Hong S, Fei J, Lu C, Ling S, Xia Y, Wang S, Wang X (2010) Assessing hormone receptor activities of pyrethroid insecticides and their metabolites in reporter gene assays. Toxicol Sci 116:58–66
Gottardi M, Birch MR, Dalhoff K, Cedergreen N (2017) The effects of epoxiconazole and α-cypermethrin on Daphnia magna growth, reproduction, and offspring size. Environ Toxicol Chem 36:2155–2166
Hardt J, Angerer J (2003) Biological monitoring of workers after the application of insecticidal pyrethroids. Int Arch Occup Environ Health 76:492–498
Heudorf U, Angerer J (2001) Metabolites of pyrethroid insecticides in urine specimens: current exposure in an urban population in Germany. Environ Health Perspect 109:213–217
Jin Y, Zheng S, Fu Z (2011) Embryonic exposure to cypermethrin induces apoptosis and immunotoxicity in zebrafish (Danio rerio). Fish Shellfish Immunol 30:1049–1054
Jin Y, Zhang P, Wang X, Xu M, Wang Y, Zhou Z, Zhu W (2015) Stereoselective degradation of alpha-Cypermethrin and its enantiomers in rat liver microsomes. Chirality 28:58–64
Knaak JB, Dary CC, Zhang X, Gerlach RW, Tornero-Velez R, Chang DT, Goldsmith R, Blancato JN (2012): Parameters for pyrethroid insecticide QSAR and PBPK/PD models for human risk assessment. Springer New York, 1–114 pp
Leahey JP (1979) The metabolism and environmental degradation of the pyrethroid insecticides. Outlook Agric 10:135–142
Leicht W, Fuchs R, Londershausen M (2015) Stability and biological activity of cyfluthrin isomers. Pest Manag Sci 48:325–332
Liu W, Gan JJ, Lee S, Werner I (2004) Isomer selectivity in aquatic toxicity and biodegradation of cypermethrin. J Agric Food Chem 52:6233–6238
Liu W, Gan J, Schlenk D, Jury WA (2005) Enantioselectivity in environmental safety of current chiral insecticides. Proc Natl Acad Sci U S A 102:701–706
Łozowicka B, Jankowska M, Kaczyński P (2012) Pesticide residues in Brassica vegetables and exposure assessment of consumers. Food Control 25:561–575
Mckinlay R, Plant JA, Bell JNB, Voulvoulis N (2008) Endocrine disrupting pesticides: implications for risk assessment. Environ Int 34:168–183
Meeker JD, Barr DB, Hauser R (2009) Pyrethroid insecticide metabolites are associated with serum hormone levels in adult men. Reprod Toxicol 27:155–160
Metwally ES, Osman MS, Al-Rushaid R (1997) A high-performance liquid chromatographic method for the determination of cypermethrin in vegetables and its application to kinetic studies after greenhouse treatment. Food Chem 59:283–290
Moore A, Waring CP (2001) The effects of a synthetic pyrethroid pesticide on some aspects of reproduction in Atlantic salmon (Salmo salar L.). Aquat Toxicol 52:1–12
Mueller MD, Buser HR (1995) Environmental behavior of acetamide pesticide stereoisomers. 2. Stereo- and enantioselective degradation in sewage sludge and soil. Environ Sci Technol 29:2031–2037
Naeher LP, Tulve NS, Egeghy PP, Barr DB, Adetona O, Fortmann RC, Needham LL, Bozeman E, Hilliard A, Sheldon LS (2010) Organophosphorus and pyrethroid insecticide urinary metabolite concentrations in young children living in a southeastern United States city. Sci Total Environ 408:1145–1153
Qu H, Wang P, Ma RX, Qiu XX, Xu P, Zhou ZQ, Liu DH (2014) Enantioselective toxicity, bioaccumulation and degradation of the chiral insecticide fipronil in earthworms (Eisenia feotida). Sci Total Environ 485:415–420
Schettgen T, Heudorf U, Drexler H, Angerer J (2002) Pyrethroid exposure of the general population-is this due to diet. Toxicol Lett 134:141–145
Singleton ST, Lein PJ, Farahat FM, Farahat T, Bonner MR, Knaak JB, Olson JR (2014) Characterization of α-cypermethrin exposure in Egyptian agricultural workers. Int J Hyg Environ Health 217:538–545
Smith SW (2009) Chiral toxicology: it’s the same thing...only different. Toxicol Sci 110:4–30
Solomon KR, Giddings JM, Maund SJ (2001) Probabilistic risk assessment of cotton pyrethroids: I. distributional analyses of laboratory aquatic toxicity data. Environ Toxicol Chem 20:652–659
Starr J, Graham S, Andrews K, Nishioka M (2008) Pyrethroid pesticides and their metabolites in vacuum cleaner dust collected from homes and day-care centers. Environ Res 108:271–279
Sun H, Xu XL, Xu LC, Song L, Hong X, Chen JF, Cui LB, Wang XR (2007) Antiandrogenic activity of pyrethroid pesticides and their metabolite in reporter gene assay. Chemosphere 66:474–479
Sun M, Liu D, Zhou G, Li J, Qiu X, Zhou Z, Wang P (2012) Enantioselective degradation and chiral stability of malathion in environmental samples. J Agric Food Chem 60:372–379
Tyler CR, Beresford N, Woning MVD, Sumpter JP, Thorpe K (2000) Metabolism and environmental degradation of pyrethroid insecticides produce compounds with endocrine activities. Environ Toxicol Chem 19:801–809
Velisek J, Wlasow T, Gomulka P, Svobodova Z, Dobsikova R, Novotny L, Dudzik M (2006): Effects of cypermethrin on rainbow trout (Oncorhynchus mykiss). Veterinarni Medicina - UZPI (Czech Republic) 51: 469
Wolansky MJ, Harrill JA (2008) Neurobehavioral toxicology of pyrethroid insecticides in adult animals: a critical review. Neurotoxicol Teratol 30:55–78
Worthing CR, Walker SB (1983) The pesticide manual, a world compendium. British Crop Protection Council
Xia Y, Han Y, Wu B, Wang S, Gu A, Lu N, Bo J (2008) The relation between urinary metabolite of pyrethroid insecticides and semen quality in humans. Fertil Steril 89:1743–1750
Xu P, Huang L (2017) Effects of α-cypermethrin enantiomers on the growth, biochemical parameters and bioaccumulation in Rana nigromaculata tadpoles of the anuran amphibians. Ecotoxicol Environ Saf 139:431–438
Yao G, Xu J, Wang P, Liu X, Zhou Z, Liu D (2015) Chiral insecticide α-cypermethrin and its metabolites: stereoselective degradation behavior in soils and the toxicity to earthworm eisenia fetida. J Agric Food Chem 63:7714–7720
Ye J, Zhao M, Niu L, Liu W (2015) Enantioselective environmental toxicology of chiral pesticides. Chem Res Toxicol 28:325–338
Ye M, Beach J, Martin JW, Senthilselvan A (2016) Urinary concentrations of pyrethroid metabolites and its association with lung function in a Canadian general population. Occup Environ Med 73:119–126
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This work was supported by the National Natural Science Foundation of China (Contract Grants: 21337005).
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Yao, G., Gao, J., Zhang, C. et al. Enantioselective degradation of the chiral alpha-cypermethrin and detection of its metabolites in five plants. Environ Sci Pollut Res 26, 1558–1564 (2019). https://doi.org/10.1007/s11356-018-3594-6
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DOI: https://doi.org/10.1007/s11356-018-3594-6