SpringerLink
Log in

A sensitive and efficient procedure for the high-throughput determination of nine urinary metabolites of pyrethroids by GC-MS/MS and its application in a sample of Japanese children

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Four pyrethroids (PYRs), metofluthrin, profluthrin, tefluthrin, and transfluthrin, which were newly developed and have relatively high vapor activity at ambient temperature, are now playing a key role in safely controlling insects in our daily lives. We developed a sensitive and high-throughput determination method for urinary metabolites derived from the newly developed PYR, e.g., 2,3,5,6-tetrafluoro-1,4-benzenedimethanol (HOCH2-FB-Al), 2,3,5,6-tetrafluorobenzyl alcohol (FB-Al), and other PYR metabolites such as trans-chrysanthemumdicarboxylic acid (trans-CDCA) and 3-phenoxybenzoic acid (3PBA). After high temperature acid hydrolysis of 2 mL urine sample in 24-deep well plate, the PYR metabolites were extracted by semi-automated liquid-liquid extraction with tert-butyl methyl ether. N,O-Bis (trimethylsilyl) trifluoroacetamide containing 1% trimethylchlorosilane or 1,1,1,3,3,3-hexafluoroisopropanol were used for the derivatization of PYR metabolites, and the derivatized metabolites were analyzed separately by GC-MS/MS equipped with dual injector system (DB-5MS and mid- to high-polarity phase Rtx-65 columns). The derivatization and evaporation conditions were mainly optimized for improving sensitivity and reproducibility. The mean within-run day precisions were less than 18.4% (relative standard deviation, %RSD) with low detection limits ranging from 0.01 μg/L for HOCH2-FB-Al to 0.06 μg/L for trans-CDCA. This method was successfully applied to urine samples obtained from 50 3-year-old children with high detection frequencies (e.g., 82% for HOCH2-FB-Al and 84% for FB-Al). This method may be a pivotal tool for develo** risk assessment from PYR exposure in the general population.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Brazil)

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Food and Agriculture Organization of the United Nations, The Statistics Division. http://faostat.fao.org/site/424/default.aspx#ancor. Accessed 2 Nov 2017.

  2. Scott TW, Chow E, Strickman D, Kittayapong P, Wirtz RA, Lorenz LH, et al. Blood-feeding patterns of Aedes aegypti (Diptera: Culicidae) collected in a rural Thai village. J Med Entomol. 1993;30:922–7.

    Article  CAS  PubMed  Google Scholar 

  3. Scott TW, Clark GG, Lorenz LH, Amerasinghe PH, Reiter P, Edman JD. Detection of multiple blood feeding in Aedes aegypti (Diptera: Culicidae) during a single gonotrophic cycle using a histologic technique. J Med Entomol. 1993;30:94–9.

    Article  CAS  PubMed  Google Scholar 

  4. Coffey LL, Failloux A-B, Weaver SC. Chikungunya virus-vector interactions. Viruses. 2014;6:4628–63.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Soderlund DM, Clark JM, Sheets LP, Mullin LS, Piccirillo VJ, Sargent D, et al. Mechanisms of pyrethroid neurotoxicity: implications for cumulative risk assessment. Toxicology. 2002;171:3–59.

    Article  CAS  PubMed  Google Scholar 

  6. Furlong MA, Barr DB, Wolff MS, Engel SM. Prenatal exposure to pyrethroid pesticides and childhood behavior and executive functioning. Neurotoxicology. 2017;62:231–8.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Quirós-Alcalá L, Mehta S, Eskenazi B. Pyrethroid pesticide exposure and parental report of learning disability and attention deficit/hyperactivity disorder in U.S. children: NHANES 1999-2002. Environ Health Perspect. 2014;122:1336–42.

    Article  Google Scholar 

  8. Perkins A, Walters F, Sievert J, Rhodes B, Morrissey B, Karr CJ. Home use of a pyrethroid-containing pesticide and facial paresthesia in a toddler: a case report. Int J Environ Res Public Health. 2016;13:E829.

    Article  CAS  PubMed  Google Scholar 

  9. Leng G, Gries W. Simultaneous determination of pyrethroid and pyrethrin metabolites in human urine by gas chromatography–high resolution mass spectrometry. J Chromatogr B. 2005;814:285–94.

    Article  CAS  Google Scholar 

  10. Olsson AO, Baker SE, Nguyen JV, Romanoff LC, Udunka SO, Walker RD, et al. A liquid chromatography–tandem mass spectrometry multiresidue method for quantification of specific metabolites of organophosphorus pesticides, synthetic pyrethroids, selected herbicides, and deet in human urine. Anal Chem. 2004;76:2453–61.

    Article  CAS  PubMed  Google Scholar 

  11. Baker SE, Olsson AO, Barr DB. Isotope dilution high-performance liquid chromatography-tandem mass spectrometry method for quantifying urinary metabolites of synthetic pyrethroid insecticides. Arch Environ Contam Toxicol. 2004;46:281–8.

    Article  CAS  PubMed  Google Scholar 

  12. Becker K, Seiwert M, Angerer J, Kolossa-Gehring M, Hoppe H-W, Ball M, et al. GerES IV pilot study: assessment of the exposure of German children to organophosphorus and pyrethroid pesticides. Int J Hyg Environ Health. 2006;209:221–33.

    Article  CAS  PubMed  Google Scholar 

  13. Centers for Disease Control and Prevention. Fourth National Report on Human Exposure to Environmental Chemicals. 2009. http://www.cdc.gov/exposurereport/pdf/FourthReport.pdf. Accessed 31 Oct 2017.

  14. Ueyama J, Kimata A, Kamijima M, Hamajima N, Ito Y, Suzuki K, et al. Urinary excretion of 3-phenoxybenzoic acid in middle-aged and elderly general population of Japan. Environ Res. 2009;109:175–80.

    Article  CAS  PubMed  Google Scholar 

  15. Oulhote Y, Bouchard MF. Urinary metabolites of organophosphate and pyrethroid pesticides and behavioral problems in Canadian children. Environ Health Perspect. 2013;121:1378–84.

    Article  Google Scholar 

  16. Ding G, Shi R, Gao Y, Zhang Y, Kamijima M, Sakai K, et al. Pyrethroid pesticide exposure and risk of childhood acute lymphocytic leukemia in Shanghai. Environ Sci Technol. 2012;46:13480–7.

    Article  CAS  PubMed  Google Scholar 

  17. Yoshida T. Analytical method for pyrethroid metabolites in urine of the non-occupationally exposed population by gas chromatography/mass spectrometry. J Chromatogr Sci. 2017;55:873–81.

    Article  CAS  PubMed  Google Scholar 

  18. Osaka A, Ueyama J, Kondo T, Nomura H, Sugiura Y, Saito I, et al. Exposure characterization of three major insecticide lines in urine of young children in Japan—neonicotinoids, organophosphates, and pyrethroids. Environ Res. 2016;147:89–96.

    Article  CAS  PubMed  Google Scholar 

  19. Wang D, Kamijima M, Imai R, Suzuki T, Kameda Y, Asai K, et al. Biological monitoring of pyrethroid exposure of pest control workers in Japan. J Occup Health. 2007;49:509–14.

    Article  CAS  PubMed  Google Scholar 

  20. Hornung RW, Reed LD. Estimation of average concentration in the presence of nondetectable values. Appl Occup Environ Hyg. 1990;5:46–51.

    Article  CAS  Google Scholar 

  21. World Health Organization. Environmental health criteria 94 permethrin. Kinetics and Metabolism. 1990, http://www.inchem.org/documents/ehc/ehc/ehc94.htm. Accessed 25 Mar 2018.

  22. Ujihara K, Sugano M, Nakada K, Iwakura K, Nishihara K, Katoh H. Discovery and Development of profluthrin (Fairytale®), a new active ingredient of moth proofer. SUMITOMO KAGAKU 2010-II. 1–12. (Japanese). 2010. https://www.sumitomo-chem.co.jp/rd/report/theses/docs/2010-2J_2.pdf. Accessed 31 Oct 2017.

  23. Toshima H, Yoshinaga J, Shiraishi H, Ito Y, Kamijima M, Ueyama J. Comparison of different urine pretreatments for biological monitoring of pyrethroid insecticides. J Anal Toxicol. 2015;39:133–6.

    Article  CAS  PubMed  Google Scholar 

  24. Abe J, Nagahori H, Omori R, Mikata K, Kurosawa M, Tomigahara Y, et al. Metabolism of (Z)-(1R,3R)-Profluthrin in rats. J Agric Food Chem. 2015;63:8651–61.

    Article  CAS  PubMed  Google Scholar 

  25. Takaku T, Mikata K, Matsui M, Nishioka K, Isobe N, Kaneko H. In vitro metabolism of trans-permethrin and its major metabolites, PBalc and PBacid, in humans. J Agric Food Chem. 2011;59:5001–5.

    Article  CAS  PubMed  Google Scholar 

  26. Wong HNC, Hon MY, Tse CW, Yip YC, Tanko J, Hudlicky T. Use of cyclopropanes and their derivatives in organic synthesis. Chem Rev. 1989;89:165–98.

    Article  CAS  Google Scholar 

  27. Yoshida T. Analytical method for urinary metabolites of the fluorine-containing pyrethroids metofluthrin, profluthrin and transfluthrin by gas chromatography/mass spectrometry. J Chromatogr B Anal Technol Biomed Life Sci. 2013;913–914:77–83.

    Article  CAS  Google Scholar 

  28. Saito S, Ueyama J, Kondo T, Saito I, Shibata E, Gotoh M, et al. A non-invasive biomonitoring method for assessing levels of urinary pyrethroid metabolites in diapered children by gas chromatography-mass spectrometry. J Expo Sci Environ Epidemiol. 2013;24:200–7.

    Article  CAS  PubMed  Google Scholar 

  29. Schisterman EF, Little RJ. Opening the black box of biomarker measurement error. Epidemiology. 2010;21(Suppl 4):S1–3.

    Article  PubMed  PubMed Central  Google Scholar 

  30. Fortin M-C, Bouchard M, Carrier G, Dumas P. Biological monitoring of exposure to pyrethrins and pyrethroids in a metropolitan population of the province of Quebec, Canada. Environ Res. 2008;107:343–50.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This research was supported in part by Grants-in-Aid of Scientific Research (Grant Number, 17H04132) from the Japan Society for the Promotion of Science.

Author information

Authors and Affiliations

  1. Department of Pathophysiological Laboratory Sciences, Field of Radiological and Medical Laboratory Sciences, Nagoya University Graduate School of Medicine, 1-1-20 Daiko-minami, Higashi-ku, Nagoya, 461-8673, Japan

    Yuko Ueda, Masaya Oda, Risa Hamada, Takaaki Kondo & Jun Ueyama

  2. Food Safety and Quality Research Center, Tokai COOP Federation, 1–173 Sagamine, Yazako, Nagakute, Aichi, 480–1103, Japan

    Isao Saito

  3. Department of Occupational and Environmental Health, Nagoya City University Graduate School of Medical Sciences, 1 Kawasumi, Mizuho-cho, Mizuho-ku, Nagoya, 467-8601, Japan

    Michihiro Kamijima

Authors
  1. Yuko Ueda
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Masaya Oda
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Isao Saito
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Risa Hamada
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Takaaki Kondo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Michihiro Kamijima
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jun Ueyama
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jun Ueyama.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ueda, Y., Oda, M., Saito, I. et al. A sensitive and efficient procedure for the high-throughput determination of nine urinary metabolites of pyrethroids by GC-MS/MS and its application in a sample of Japanese children. Anal Bioanal Chem 410, 6207–6217 (2018). https://doi.org/10.1007/s00216-018-1229-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1229-x

Keywords

Search

Navigation