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Determination of cis-permethrin, trans-permethrin and associated metabolites in rat blood and organs by gas chromatography–ion trap mass spectrometry

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Abstract

An analytical method was developed to measure cis-permethrin and trans-permethrin in different biological rat matrices and fluids (whole blood, red blood cells, plasma, brain, liver, muscle, testes, kidneys, fat and faeces). The method was also suitable for the simultaneous quantification of their associated metabolites [cis-3-(2,2-dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid (cis-DCCA), trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid (trans-DCCA) and 3-phenoxybenzoic acid (3-PBA)] in blood (whole blood, red blood cells, plasma) and liver. The target analytes were derivatised in samples using a methanolic/hydrochloric acid solution and then extracted with toluene. The analysis was performed by gas chromatography, and detection using ion trap tandem mass spectrometry. The selectivity obtained for complex matrices such as rat organs allowed the use of a purification step to be avoided for most of the matrices investigated. In the case of fat, where permethrin is suspected to accumulate, a dedicated purification step was developed. In fluids, the limits of quantification were at the 50 ng/mL level for the parent compounds and 3-PBA and at 25 ng/mL for cis-DCCA and trans-DCCA. For solid matrices excluding fat, the limits of quantification ranged from 50 ng/g for muscle to 100 ng/g for brain and testes for both cis-permethrin and trans-permethrin. The extraction recoveries ranged primarily between 80 and 120 % for the matrix tested. The stability of blood samples was tested through the addition of 1 % v/v formic acid. The methods developed were applied in a toxicokinetic study in adult rats. cis-Permethrin and the metabolites were detected in all corresponding matrices, whereas trans-permethrin was detected only in blood, plasma and faeces.

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References

  1. Environmental Protection Agency US (2007) Permethrin & resmethrin (pyrethroids), TEACH chemical summary. US Environmental Protection Agency, Washington

    Google Scholar 

  2. Wei BN, Mohan KR, Weisel CP (2012) Exposure of flight attendants to pyrethroid insecticides on commercial flights: urinary metabolite levels and implications. Int J Hyg Environ Health 215(4):465–473

    Article  CAS  Google Scholar 

  3. Morgan MK, Sheldon LS, Croghan CW, Jones PA, Chuang JC, Wilson NK (2007) An observational study of 127 preschool children at their homes and daycare centers in Ohio: Environmental pathways to cis- and trans-permethrin exposure. Environ Res 104(2):266–274

    Article  CAS  Google Scholar 

  4. Feo ML, Eljarrat E, Barcelo D (2010) Determination of pyrethroid insecticides in environmental samples. Trends Anal Chem 29(7):692–705

    Article  CAS  Google Scholar 

  5. Corcellas C, Feo ML, Torres JP, Malm O, Ocampo-Duque W, Eljarrat E, Barcelo D (2012) Pyrethroids in human breast milk: occurrence and nursing daily intake estimation. Environ Int 47:17–22

    Article  CAS  Google Scholar 

  6. Jin YX, Liu JW, Wang LG, Chen RJ, Zhou C, Yang YF, Liu WP, Fu ZW (2012) Permethrin exposure during puberty has the potential to enantioselectively induce reproductive toxicity in mice. Environ Int 42:144–151

    Article  CAS  Google Scholar 

  7. Meeker JD, Barr DB, Hauser R (2008) Human semen quality and sperm DNA damage in relation to urinary metabolites of pyrethroid insecticides. Hum Reprod 23(8):1932–1940

    Article  CAS  Google Scholar 

  8. Wolansky MJ, Harrill JA (2008) Neurobehavioral toxicology of pyrethroid insecticides in adult animals: a critical review. Neurotoxicol Teratol 30(2):55–78

    Article  CAS  Google Scholar 

  9. Zhang SY, Ito Y, Yamanoshita O, Yanagiba Y, Kobayashi M, Taya K, Li C, Okamura A, Miyata M, Ueyama J, Lee CH, Kamijima M, Nakajima T (2007) Permethrin may disrupt testosterone biosynthesis via mitochondrial membrane damage of Leydig cells in adult male mouse. Endocrinology 148(8):3941–3949

    Article  CAS  Google Scholar 

  10. Zhang S-Y, Ueyama J, Ito Y, Yanagiba Y, Okamura A, Kamijima M, Nakajima T (2008) Permethrin may induce adult male mouse reproductive toxicity due to cis isomer not trans isomer. Toxicology 248(2–3):136–141

    Article  CAS  Google Scholar 

  11. Ross MK, Borazjani A, Edwards CC, Potter PM (2006) Hydrolytic metabolism of pyrethroids by human and other mammalian carboxylesterases. Biochem Pharmacol 71(5):657–669

    Article  CAS  Google Scholar 

  12. Soderlund DM, Clark JM, Sheets LP, Mullin LS, Piccirillo VJ, Sargent D, Stevens JT, Weiner ML (2002) Mechanisms of pyrethroid neurotoxicity: implications for cumulative risk assessment. Toxicology 171(1):3–59

    Article  CAS  Google Scholar 

  13. Tornero-Velez R, Davis J, Scollon EJ, Starr JM, Setzer RW, Goldsmith M-R, Chang DT, Xue J, Zartarian V, DeVito MJ, Hughes MF (2012) A pharmacokinetic model of cis- and trans-permethrin disposition in rats and humans with aggregate exposure application. Toxicol Sci 130(1):33–47

    Article  CAS  Google Scholar 

  14. Anadon A, Martinezlarranaga MR, Diaz MJ, Bringas P (1991) Toxicokinetics of Permethrin in the Rat. Toxicol Appl Pharmacol 110(1):1–8

    Article  CAS  Google Scholar 

  15. Crow JA, Borazjani A, Potter PM, Ross MK (2007) Hydrolysis of pyrethroids by human and rat tissues: examination of intestinal, liver and serum carboxylesterases. Toxicol Appl Pharmacol 221(1):1–12

    Article  CAS  Google Scholar 

  16. Nakamura Y, Sugihara K, Sone T, Isobe M, Ohta S, Kitamura S (2007) The in vitro metabolism of a pyrethroid insecticide, permethrin, and its hydrolysis products in rats. Toxicology 235(3):176–184

    Article  CAS  Google Scholar 

  17. Choi J, Rose RL, Hodgson E (2002) In vitro human metabolism of permethrin: the role of human alcohol and aldehyde dehydrogenases. Pestic Biochem Physiol 74(3):117–128

    Article  CAS  Google Scholar 

  18. Scollon EJ, Starr JM, Godin SJ, DeVito MJ, Hughes MF (2009) In vitro metabolism of pyrethroid pesticides by rat and human hepatic microsomes and cytochrome P450 isoforms. Drug Metab Dispos 37(1):221–228

    Article  CAS  Google Scholar 

  19. Starr JM, Scollon EJ, Hughes MF, Ross DG, Graham SE, Crofton KM, Wolansky MJ, DeVito MJ, Tornero-Velez R (2012) Environmentally relevant mixtures in cumulative assessments: an acute study of toxicokinetics and effects on motor activity in rats exposed to a mixture of pyrethroids. Toxicol Sci 130(2):309–318

    Article  CAS  Google Scholar 

  20. Du JJ, Yan HY, She DD, Liu BM, Yang GL (2010) Simultaneous determination of cypermethrin and permethrin in pear juice by ultrasound-assisted dispersive liquid-liquid microextraction combined with gas chromatography. Talanta 82(2):698–703

    Article  CAS  Google Scholar 

  21. Leng G, Kuhn KH, Idel H (1997) Biological monitoring of pyrethroids in blood and pyrethroid metabolites in urine: applications and limitations. Sci Total Environ 199(1–2):173–181

    Article  CAS  Google Scholar 

  22. Schettgen T, Koch HM, Drexler H, Angerer J (2002) New gas chromatographic-mass spectrometric method for the determination of urinary pyrethroid metabolites in environmental medicine. J Chromatogr B 778(1–2):121–130

    Article  CAS  Google Scholar 

  23. Baker SE, Olsson AO, Barr DB (2003) Isotope dilution high-performance liquid chromatography-tandem mass spectrometry method for quantifying urinary metabolites of synthetic pyrethroid insecticides. Arch Environ Contam Toxicol 46(3):281–288

    Google Scholar 

  24. Corrion ML, Ostrea EM, Bielawski DM, Posecion NC, Seagraves JJ (2005) Detection of prenatal exposure to several classes of environmental toxicants and their metabolites by gas chromatography–mass spectrometry in maternal and umbilical cord blood. J Chromatogr B 822(1–2):221–229

    Article  CAS  Google Scholar 

  25. Leng G, Gries W (2005) Simultaneous determination of pyrethroid and pyrethrin metabolites in human urine by gas chromatography-high resolution mass spectrometry. J Chromatogr B 814(2):285–294

    Article  CAS  Google Scholar 

  26. Le Grand R, Dulaurent S, Gaulier JM, Saint-Marcoux F, Moesch C, Lachatre G (2012) Simultaneous determination of five synthetic pyrethroid metabolites in urine by liquid chromatography-tandem mass spectrometry: application to 39 persons without known exposure to pyrethroids. Toxicol Lett 210(2):248–253

    Article  Google Scholar 

  27. Standard NF EN 1528 (1997) Fatty food. Determination of pesticides and polychlorinated biphenyls (PCBs)

  28. Rawn DFK, Judge J, Roscoe V (2010) Application of the QuEChERS method for the analysis of pyrethrins and pyrethroids in fish tissues. Anal Bioanal Chem 397(6):2525–2531

    Article  CAS  Google Scholar 

  29. EU Reference Laboratories for Residues of Pesticides (2012) Document no. SANCO/12495/2011: method validation & quality control procedures for pesticide residues analysis in food & feed

Download references

Acknowledgments

This work was supported by La Fondation UTC pour l’Innovation (Project ToxOnChip) of the University of Technology of Compiègne and the French Ministry of Ecology and Sustainable Development.

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Correspondence to F. Lestremau.

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Lestremau, F., Willemin, ME., Chatellier, C. et al. Determination of cis-permethrin, trans-permethrin and associated metabolites in rat blood and organs by gas chromatography–ion trap mass spectrometry. Anal Bioanal Chem 406, 3477–3487 (2014). https://doi.org/10.1007/s00216-014-7774-z

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  • DOI: https://doi.org/10.1007/s00216-014-7774-z

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