Abstract
We report population-based concentrations, stratified by age, sex, and racial/ethnic groups, of dialkyl phosphate (DAP) metabolites of multiple organophosphorus pesticides. We measured dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate (DEP), diethylthiophosphate (DETP), and diethyldithiophosphate (DEDTP) concentrations in 1,949 urine samples collected in U.S. residents 6-59 years of age during 1999 and 2000 as a part of the ongoing National Health and Nutrition Examination Survey (NHANES). We detected each DAP metabolite in more than 50% of the samples, with DEP being detected most frequently (71%) at a limit of detection of 0.2 microg/L. The geometric means for the metabolites detected in more than 60% of the samples were 1.85 microg/L for DMTP and 1.04 microg/L for DEP. The 95th percentiles for each metabolite were DMP, 13 microg/L; DMTP, 46 microg/L; DMDTP, 19 micro g/L; DEP, 13 microg/L; DETP, 2.2 microg/L; and DEDTP, 0.87 microg/L. We determined the molar sums of the dimethyl-containing and diethyl-containing metabolites; their geometric mean concentrations were 49.4 and 10.5 nmol/L, respectively, and their 95th percentiles were 583 and 108 nmol/L, respectively. These data are also presented as creatinine-adjusted concentrations. Multivariate analyses showed concentrations of DAPs in children 6-11 years of age that were consistently significantly higher than in adults and often higher than in adolescents. Although the concentrations between sexes and among racial/ethnic groups varied, no significant differences were observed. These data will be important in evaluating the impact of organophosphorus pesticide exposure in the U.S. population and the effectiveness of regulatory actions.
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- Aprea C., Sciarra G., Orsi D., Boccalon P., Sartorelli P., Sartorelli E. Urinary excretion of alkylphosphates in the general population (Italy). Sci Total Environ. 1996 Jan 5;177(1-3):37–41. doi: 10.1016/0048-9697(95)04857-x. [DOI] [PubMed] [Google Scholar]
- Aprea C., Sciarra G., Sartorelli P., Ceccarelli F., Centi L. Multiroute exposure assessment and excretion of urinary metabolites of fenitrothion during manual operations on treated ornamental plants in greenhouses. Arch Environ Contam Toxicol. 1999 May;36(4):490–497. doi: 10.1007/pl00006622. [DOI] [PubMed] [Google Scholar]
- Aprea C., Sciarra G., Sartorelli P., Desideri E., Amati R., Sartorelli E. Biological monitoring of exposure to organophosphorus insecticides by assay of urinary alkylphosphates: influence of protective measures during manual operations with treated plants. Int Arch Occup Environ Health. 1994;66(5):333–338. doi: 10.1007/BF00378366. [DOI] [PubMed] [Google Scholar]
- Aprea C., Sciarra G., Sartorelli P., Sartorelli E., Strambi F., Farina G. A., Fattorini A. Biological monitoring of exposure to chlorpyrifos-methyl by assay of urinary alkylphosphates and 3,5,6-trichloro-2-pyridinol. J Toxicol Environ Health. 1997 Apr 25;50(6):581–594. doi: 10.1080/15287399709532056. [DOI] [PubMed] [Google Scholar]
- Aprea C., Strambi M., Novelli M. T., Lunghini L., Bozzi N. Biologic monitoring of exposure to organophosphorus pesticides in 195 Italian children. Environ Health Perspect. 2000 Jun;108(6):521–525. doi: 10.1289/ehp.00108521. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Azaroff L. S. Biomarkers of exposure to organophosphorous insecticides among farmers' families in rural El Salvador: factors associated with exposure. Environ Res. 1999 Feb;80(2 Pt 1):138–147. doi: 10.1006/enrs.1998.3877. [DOI] [PubMed] [Google Scholar]
- Barr Dana B., Turner Wayman E., DiPietro Emily, McClure P. Cheryl, Baker Samuel E., Barr John R., Gehle Kimberly, Grissom Raymond E., Jr, Bravo Roberto, Driskell W. Jack. Measurement of p-nitrophenol in the urine of residents whose homes were contaminated with methyl parathion. Environ Health Perspect. 2002 Dec;110 (Suppl 6):1085–1091. doi: 10.1289/ehp.02110s61085. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Bradway D. E., Shafik T. M. Malathion exposure studies. Determination of mono- and dicarboxylic acids and alkyl phosphates in urine. J Agric Food Chem. 1977 Nov-Dec;25(6):1342–1344. doi: 10.1021/jf60214a002. [DOI] [PubMed] [Google Scholar]
- Bravo Roberto, Driskell William J., Whitehead Ralph D., Jr, Needham Larry L., Barr Dana B. Quantitation of dialkyl phosphate metabolites of organophosphate pesticides in human urine using GC-MS-MS with isotopic internal standards. J Anal Toxicol. 2002 Jul-Aug;26(5):245–252. doi: 10.1093/jat/26.5.245. [DOI] [PubMed] [Google Scholar]
- Castorina Rosemary, Bradman Asa, McKone Thomas E., Barr Dana B., Harnly Martha E., Eskenazi Brenda. Cumulative organophosphate pesticide exposure and risk assessment among pregnant women living in an agricultural community: a case study from the CHAMACOS cohort. Environ Health Perspect. 2003 Oct;111(13):1640–1648. doi: 10.1289/ehp.5887. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Charnley Gail. Pesticide exposures and children's risk tradeoffs. Environ Health Perspect. 2003 Oct;111(13):A689–A691. doi: 10.1289/ehp.111-a689a. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Cocker J., Mason H. J., Garfitt S. J., Jones K. Biological monitoring of exposure to organophosphate pesticides. Toxicol Lett. 2002 Aug 5;134(1-3):97–103. doi: 10.1016/s0378-4274(02)00168-6. [DOI] [PubMed] [Google Scholar]
- Curl Cynthia L., Fenske Richard A., Kissel John C., Shirai Jeffry H., Moate Thomas F., Griffith William, Coronado Gloria, Thompson Beti. Evaluation of take-home organophosphorus pesticide exposure among agricultural workers and their children. Environ Health Perspect. 2002 Dec;110(12):A787–A792. doi: 10.1289/ehp.021100787. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Davies J. E., Peterson J. C. Surveillance of occupational, accidental, and incidental exposure to organophosphate pesticides using urine alkyl phosphate and phenolic metabolite measurements. Ann N Y Acad Sci. 1997 Dec 26;837:257–268. doi: 10.1111/j.1749-6632.1997.tb56879.x. [DOI] [PubMed] [Google Scholar]
- Drevenkar V., Radić Z., Vasilić Z., Reiner E. Dialkylphosphorus metabolites in the urine and activities of esterases in the serum as biochemical indices for human absorption of organophosphorus pesticides. Arch Environ Contam Toxicol. 1991 Apr;20(3):417–422. doi: 10.1007/BF01064413. [DOI] [PubMed] [Google Scholar]
- Duncan R. C., Griffith J. Monitoring study of urinary metabolites and selected symptomatology among Florida citrus workers. J Toxicol Environ Health. 1985;16(3-4):509–521. doi: 10.1080/15287398509530759. [DOI] [PubMed] [Google Scholar]
- Eskenazi B., Bradman A., Castorina R. Exposures of children to organophosphate pesticides and their potential adverse health effects. Environ Health Perspect. 1999 Jun;107 (Suppl 3):409–419. doi: 10.1289/ehp.99107s3409. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Fenske R. A., Lu C., Simcox N. J., Loewenherz C., Touchstone J., Moate T. F., Allen E. H., Kissel J. C. Strategies for assessing children's organophosphorus pesticide exposures in agricultural communities. J Expo Anal Environ Epidemiol. 2000 Nov-Dec;10(6 Pt 2):662–671. doi: 10.1038/sj.jea.7500116. [DOI] [PubMed] [Google Scholar]
- Franklin C. A., Muir N. I., Moody R. P. The use of biological monitoring in the estimation of exposure during the application of pesticides. Toxicol Lett. 1986 Oct;33(1-3):127–136. doi: 10.1016/0378-4274(86)90077-9. [DOI] [PubMed] [Google Scholar]
- García A. M., Sabater M. C., Mendoza M. T., Ballester F., Carrasco J. M. Exposure to organophosphate pesticides in a general population living in a rice growing area: an exploratory study. Bull Environ Contam Toxicol. 2000 Dec;65(6):764–771. doi: 10.1007/s0012800188. [DOI] [PubMed] [Google Scholar]
- Griffith J. G., Duncan R. C. Alkyl phosphate residue values in the urine of Florida citrus fieldworkers compared to the National Health and Nutrition Examination Survey (HANES) sample. Bull Environ Contam Toxicol. 1985 Feb;34(2):210–215. doi: 10.1007/BF01609726. [DOI] [PubMed] [Google Scholar]
- Hardt J., Angerer J. Determination of dialkyl phosphates in human urine using gas chromatography-mass spectrometry. J Anal Toxicol. 2000 Nov-Dec;24(8):678–684. doi: 10.1093/jat/24.8.678. [DOI] [PubMed] [Google Scholar]
- Heudorf U., Angerer J. Metabolites of organophosphorous insecticides in urine specimens from inhabitants of a residential area. Environ Res. 2001 May;86(1):80–87. doi: 10.1006/enrs.2001.4237. [DOI] [PubMed] [Google Scholar]
- Koch Denise, Lu Chensheng, Fisker-Andersen Jennifer, Jolley Lance, Fenske Richard A. Temporal association of children's pesticide exposure and agricultural spraying: report of a longitudinal biological monitoring study. Environ Health Perspect. 2002 Aug;110(8):829–833. doi: 10.1289/ehp.02110829. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Krieger Robert I., Dinoff Travis M., Williams Ryan L., Zhang Xiaofei, Ross John H., Aston Linda S., Myers Gosia. Correspondence: preformed biomarkers in produce inflate human organophosphate exposure assessments. Environ Health Perspect. 2003 Oct;111(13):A688–A91. doi: 10.1289/ehp.111-a688. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Lin W. C., Kuei C. H., Wu H. C., Yang C. C., Chang H. Y. Method for the determination of dialkyl phosphates in urine by strong anion exchange disk extraction and in-vial derivatization. J Anal Toxicol. 2002 Apr;26(3):176–180. doi: 10.1093/jat/26.3.176. [DOI] [PubMed] [Google Scholar]
- Loewenherz C., Fenske R. A., Simcox N. J., Bellamy G., Kalman D. Biological monitoring of organophosphorus pesticide exposure among children of agricultural workers in central Washington State. Environ Health Perspect. 1997 Dec;105(12):1344–1353. doi: 10.1289/ehp.971051344. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Lu C., Fenske R. A., Simcox N. J., Kalman D. Pesticide exposure of children in an agricultural community: evidence of household proximity to farmland and take home exposure pathways. Environ Res. 2000 Nov;84(3):290–302. doi: 10.1006/enrs.2000.4076. [DOI] [PubMed] [Google Scholar]
- Lu C., Knutson D. E., Fisker-Andersen J., Fenske R. A. Biological monitoring survey of organophosphorus pesticide exposure among pre-school children in the Seattle metropolitan area. Environ Health Perspect. 2001 Mar;109(3):299–303. doi: 10.1289/ehp.01109299. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Mileson B. E., Chambers J. E., Chen W. L., Dettbarn W., Ehrich M., Eldefrawi A. T., Gaylor D. W., Hamernik K., Hodgson E., Karczmar A. G. Common mechanism of toxicity: a case study of organophosphorus pesticides. Toxicol Sci. 1998 Jan;41(1):8–20. doi: 10.1006/toxs.1997.2431. [DOI] [PubMed] [Google Scholar]
- Mills P. K., Zahm S. H. Organophosphate pesticide residues in urine of farmworkers and their children in Fresno County, California. Am J Ind Med. 2001 Nov;40(5):571–577. doi: 10.1002/ajim.10007. [DOI] [PubMed] [Google Scholar]
- Murphy R. S., Kutz F. W., Strassman S. C. Selected pesticide residues or metabolites in blood and urine specimens from a general population survey. Environ Health Perspect. 1983 Feb;48:81–86. doi: 10.1289/ehp.834881. [DOI] [PMC free article] [PubMed] [Google Scholar]
- O'Rourke M. K., Lizardi P. S., Rogan S. P., Freeman N. C., Aguirre A., Saint C. G. Pesticide exposure and creatinine variation among young children. J Expo Anal Environ Epidemiol. 2000 Nov-Dec;10(6 Pt 2):672–681. doi: 10.1038/sj.jea.7500119. [DOI] [PubMed] [Google Scholar]
- Richter E. D., Kowalski M., Leventhal A., Grauer F., Marzouk J., Brenner S., Shkolnik I., Lerman S., Zahavi H., Bashari A. Illness and excretion of organophosphate metabolites four months after household pest extermination. Arch Environ Health. 1992 Mar-Apr;47(2):135–138. doi: 10.1080/00039896.1992.10118767. [DOI] [PubMed] [Google Scholar]
- Royster Michael O., Hilborn Elizabeth D., Barr Dana, Carty Cara L., Rhoney Scott, Walsh Debra. A pilot study of global positioning system/geographical information system measurement of residential proximity to agricultural fields and urinary organophosphate metabolite concentrations in toddlers. J Expo Anal Environ Epidemiol. 2002 Nov;12(6):433–440. doi: 10.1038/sj.jea.7500247. [DOI] [PubMed] [Google Scholar]
- Shafik T., Bradway D. E., Enos H. F., Yobs A. R. gas-liquid chromatographic analysis of alkyl phosphate metabolites in urine. J Agric Food Chem. 1973 Jul-Aug;21(4):625–629. doi: 10.1021/jf60188a036. [DOI] [PubMed] [Google Scholar]
- Shalat Stuart L., Donnelly Kirby C., Freeman Natalie C. G., Calvin James A., Ramesh Sowmya, Jimenez Marta, Black Kathleen, Coutinho Catriona, Needham Larry L., Barr Dana B. Nondietary ingestion of pesticides by children in an agricultural community on the US/Mexico border: preliminary results. J Expo Anal Environ Epidemiol. 2003 Jan;13(1):42–50. doi: 10.1038/sj.jea.7500249. [DOI] [PubMed] [Google Scholar]
- Takamiya K. Monitoring of urinary alkyl phosphates in pest control operators exposed to various organophosphorus insecticides. Bull Environ Contam Toxicol. 1994 Feb;52(2):190–195. doi: 10.1007/BF00198487. [DOI] [PubMed] [Google Scholar]
- Whyatt R. M., Barr D. B. Measurement of organophosphate metabolites in postpartum meconium as a potential biomarker of prenatal exposure: a validation study. Environ Health Perspect. 2001 Apr;109(4):417–420. doi: 10.1289/ehp.01109417. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Wilson Nancy K., Chuang Jane C., Lyu Christopher, Menton Ronald, Morgan Marsha K. Aggregate exposures of nine preschool children to persistent organic pollutants at day care and at home. J Expo Anal Environ Epidemiol. 2003 May;13(3):187–202. doi: 10.1038/sj.jea.7500270. [DOI] [PubMed] [Google Scholar]
