Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

The reliability of using urinary biomarkers to estimate children's exposures to chlorpyrifos and diazinon

Abstract

A few studies have reported concurrent levels of chlorpyrifos (CPF) and diazinon (DZN) and their environmentally occurring metabolites, 3,5,6-trichloro-2-pyridinol (TCP) and 2-isopropyl-6-methyl-4-pyrimidinol (IMP), in food and in environmental media. This information raises questions regarding the reliability of using these same metabolites, TCP and IMP, as urinary biomarkers to quantitatively assess the everyday exposures of children to CPF and DZN, respectively. In this study, we quantified the distributions of CPF, DZN, TCP, and IMP in several environmental and personal media at the homes and day-care centers of 127 Ohio preschool children and identified the important sources and routes of their exposures. The children were exposed to concurrent levels of these four chemicals from several sources and routes at these locations. DZN and IMP were both detected above 50% in the air and dust samples. CPF and TCP were both detected in greater than 50% of the air, dust (solid), food, and hand wipe samples. TCP was detected in 100% of the urine samples. Results from our regression models showed that creatinine levels (<0.001), and dietary (P<0.001) and inhalation (P<0.10) doses of TCP were each significant predictors of urinary TCP, collectively explaining 27% of the urinary TCP variability. This information suggests that measurement of urinary TCP did not reliably allow quantitative estimation of the children's everyday environmental exposures to CPF.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Figure 1

Similar content being viewed by others

References

  • Adgate J.L., Barr D.B., Clayton A., Eberly L.E., Freeman N.C.G., and Lioy P.J., et al. Measurement of children's exposure to pesticides: analysis of urinary metabolite levels in probability-based sample. Environ Health Perspect 2001: 109 (6): 583–590.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Bakke J.E., and Price C.E. Metabolism of OO-dimethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate in sheep and rats and of 3,5,6-trichloro-2-pyridinol in sheep. J Environ Sci Health 1976: B11 (1): 9–22.

    Article  CAS  Google Scholar 

  • Barr D.B., Wilder L.C., Caudill S.P., Gonzalez A.J., Needham L.L., and Pirkle J.L. Urinary creatinine concentrations in the U.S. Population: Implications for urinary biologic monitoring measurements. Environ Health Perspect 2005: 113 (2): 192–200.

    Article  CAS  PubMed  Google Scholar 

  • CDC (Centers for Disease Control and Prevention). Third national report on human exposure to environmental chemicals, 2005: http://www.cdc.gov/exposurereport/.

  • Chuang J.C., Brinkman M., Hart K., Davis D.B., Finegold J., and Gordon S.M. Method refinement and analysis of food data, USEPA. Report to USEPA, Contract 68-D4-0023, WA 4-03. Battelle Memorial Institute, Columbus Ohio, USA, 1999.

  • Eaton D.L., Daroff R.B., Autrup H., Bridges J., Buffler P., and Costa L.G., et al. Review of the toxicology of chlorpyrifos with emphasis on human exposure and neurodevelopment. Crit Rev Toxicol 2008: 38 (1): 1–125.

    Article  CAS  PubMed  Google Scholar 

  • Food and Drug Administration (FDA). FDA's total diet study—monitoring U.S. food supply safety. http://www.fda.gov/Food/FoodSafety/FoodContaminantsAdulteration/TotalDietStudy/ucm186140.htm, 2006.

  • Garfitt S.J., Jones K., Mason H.J., and Cocker M.J. Exposure to the organophosphate diazinon: data from a human volunteer study with oral and dermal doses. Toxicol Lett 2002: 134: 105–113.

    Article  CAS  PubMed  Google Scholar 

  • Griffin P., Mason H., Heywood K., and Cocker J. Oral and dermal absorption of chlorpyrifos: a human volunteer study. Occup Environ Med 1999: 56: 10–13.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Hines C.J., and Deddens J.A. Determinants of chlorpyrifos exposures and urinary 3,5,6-trichloro-2-pyridinol levels among termiticide applicators. Ann Occup Hyg 2001: 45: 309–321.

    Article  CAS  PubMed  Google Scholar 

  • Koch H., and Angerer J. Analysis of 3,5,6-trichloro-2-pyridinol in urine samples from the general population using gas chromatography-mass spectrometry after steam distillation and solid-phase extraction. J Chromatogr B 2001: 759: 43–49.

    Article  CAS  Google Scholar 

  • Lu C., Bravo R., Caltabiano L.M., Irish R.M., Weerasekera G., and Barr D.B. The presence of dialkylphosphates in fresh fruit juices: implications for organophosphorus pesticide exposure and risk assessments. J Toxicol Environ Health A 2005: 68 (3): 209–227.

    Article  CAS  PubMed  Google Scholar 

  • Miller L.A., and Stapleton F.B. Urinary volume in children with urolithiasis. J Urol 1989: 141 (4): 918–920.

    Article  CAS  PubMed  Google Scholar 

  • Morgan M.K., Sheldon L.S., Croghan C.W., Chuang J.C., Lordo R., and Wilson N.K., et al. A pilot study of children's total exposure to persistent pesticides and other persistent organic pollutants (CTEPP). EPA/600/R-041/193. http://www.epa.gov/heasd/ctepp/ctepp_report.pdf, 2004.

  • Morgan M.K., Sheldon L.S., Croghan C.W., Jones P.A., Robertson G.L., and Chuang J.C., et al. Exposures of preschool children to chlorpyrifos and its degradation product 3,5,6-trichloro-2-pyridinol in their everyday environments. J Expo Anal Environ Epidemiol 2005: 15: 297–309.

    Article  CAS  PubMed  Google Scholar 

  • Nolan R.J., Rick D.L., Freshour N.L., and Saunders J.H. Chlorpyrifos: pharmacokinetics in human volunteers. Toxicol Appl Pharmacol 1984: 73: 8–15.

    Article  CAS  PubMed  Google Scholar 

  • Poet T., Kousba A., Dennison S., and Timchalk C. Physiologically based pharmacokinetic/pharmacodynamic model for the organophosphorus pesticide diazinon. Neurotoxicology 2004: 25 (6): 1013–1030.

    Article  CAS  PubMed  Google Scholar 

  • Racke K.D. Environmental fate of chlorpyrifos. Rev Environ Contam Toxicol 1993: 131: 1–150.

    CAS  PubMed  Google Scholar 

  • Raina R., and Sun L. Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry. J Environ Sci Health B 2008: 43 (4): 323–332.

    Article  CAS  PubMed  Google Scholar 

  • Rigas M.L., Okino M.S., and Quackenboss J.J. Use of a pharmacokinetic model to assess chlorpyrifos exposure and dose in children, based on urinary biomarker measurements. Toxicol Sci 2001: 61: 374–381.

    Article  CAS  PubMed  Google Scholar 

  • Ross J.H., Driver J.H., Cockran R.C., Thongsinthusak T., and Kreiger R.I. Could pesticide toxicology studies be more relevant to occupational risk assessment? Ann Occup Hyg 2001: 45 (1001): S5–S17.

    Article  CAS  PubMed  Google Scholar 

  • Szabo L., and Fegyverneki S. Maximum and average urine flow rates in normal children—the Miskoln nomograms. Br J Urol 1995: 76 (1): 16–20.

    Article  CAS  PubMed  Google Scholar 

  • Timchalk C., Busby A., Campbell J.A., Needham L.L., and Barr D.B. Comparative pharmacokinetics of the organophosphorus insecticide chlorpyrifos and its major metabolites diethylphosphate, diethythiophosphate and 3,5,6-trichloro-2-pyridinol in the rat. Toxicology 2007: 237 (1-3): 145–157.

    Article  CAS  PubMed  Google Scholar 

  • Timchalk C., Poet T.S., Hinman M.N., Busby A.L., and Kousba A.A. Pharmacokinetics and pharmacodynamics interaction for a binary mixture of chlorpyrifos and diazinon in the rat. Toxicol Appl Pharmacol 2005: 205 (1): 31–42.

    Article  CAS  PubMed  Google Scholar 

  • USEPA. Chlorpyrifos-methyl, 2000: http://www.epa.gov/oppsrrd1/reregistration/chlorpyrifos-methyl/.

  • USEPA. Chlorpyrifos facts, 2002: http://www.epa.gov/oppsrrd1/REDs/factsheets/chlorpyrifos_fs.htm.

  • USEPA. Diazinon, 2008: http://www.epa.gov/opp00001/reregistration/diazinon/.

  • Weerasekera G., Smith K.D., Quiros-Alcala L., Fernandez C., Bradman A., Eskenazi B., Needham L.L., and Barr D.B. A mass spectrometry-based method to measure dialkylphosphate degradation products of organophosphorous insecticides in dust and orange juice. J Environ Monit 2009: 11: 1345–1351.

    Article  CAS  PubMed  Google Scholar 

  • Wilson N.K., Chuang J.C., Iachan R., Lyu C., Gordon S.M., and Morgan M.K., et al. Design and sampling methodology for a large study of preschool children's aggregate exposures to persistent organic pollutants in their everyday environments. J Expo Anal Environ Epidemiol 2004: 14: 260–274.

    Article  CAS  PubMed  Google Scholar 

  • Wilson N.K., Chuang J.C., and Lyu C. Levels of persistent organic pollutants in several child day care centers. J Expo Anal Environ Epidemiol 2001: 11: 449–458.

    Article  CAS  PubMed  Google Scholar 

  • Wilson N.K., Chuang J.C., Lyu C., Menton R., and Morgan M.K. Aggregate exposures of nine preschool children to persistent organic pollutants at daycare and at home. J Expo Anal Environ Epidemiol 2003: 13 (1): 187–202.

    Article  CAS  PubMed  Google Scholar 

  • Wilson N.K., Chuang J.C., Strauss W., Lyu C., Iroz-Elardo N., and Pivetz T. Pesticide Exposures of Preschool Children Over Time (PEPCOT), National Center for Environmental Research, Washington DC. Final Report, STAR Grant R829363 2008.

  • Wilson N.K., Strauss W.J., Iroz-Elardo N., and Chuang J.C. Exposures of preschool children to chlorpyrifos, diazinon, pentachlorophenol, and 2,4-diphenoxyacetic acid over 3 years from 2003 to 2005: A longitudinal model. J Expo Sci Environ Epidemiol 2009 (advance online publication, 2 September 2009; doi:10.1038/jes.2009.45).

    Article  Google Scholar 

  • Zhang X., Driver J.H., Li Y., Ross J.H., and Kreiger R.I. Dialklphosphate (DAPs) in fruits and vegetables may confound biomonitoring in organophosphorus insecticide exposure and risk assessment. J Agric Food Chem 2008: 56: 10638–10645.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

We thank the participants for participating in this important observational human exposure measurements study. We also thank J. Sobus from the USEPA for his technical guidance in the advanced statistical analyses of these data. In addition, we would also like to thank Battelle staff members, particularly C. Lyu, J. Satola, R. Lordo, and Y. Chou, for their valuable contributions to the success of this study.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Marsha K Morgan.

Ethics declarations

Competing interests

The authors declare no conflict of interest.

Additional information

Disclaimer

The United States Environmental Protection Agency, through its Office of Research and Development, funded and managed the research described here under Contract #68-D-99-011 to Battelle. It has been subjected to Agency review and approved for publication.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Morgan, M., Sheldon, L., Jones, P. et al. The reliability of using urinary biomarkers to estimate children's exposures to chlorpyrifos and diazinon. J Expo Sci Environ Epidemiol 21, 280–290 (2011). https://doi.org/10.1038/jes.2010.11

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/jes.2010.11

Keywords

This article is cited by

Search

Quick links