Urinary Concentrations of Dialkylphosphate Metabolites of Organophosphorus Pesticides: National Health and Nutrition Examination Survey 1999–2004

Emory University, Rollins School of Public Health, Atlanta, GA 30322, USA.
International Journal of Environmental Research and Public Health (Impact Factor: 2.06). 08/2011; 8(8):3063-98. DOI: 10.3390/ijerph8083063
Source: PubMed


Organophosphorus (OP) insecticides were among the first pesticides that EPA reevaluated as part of the Food Quality Protection Act of 1996. Our goal was to assess exposure to OP insecticides in the U.S. general population over a six-year period. We analyzed 7,456 urine samples collected as part of three two-year cycles of the National Health and Nutrition Examination Survey (NHANES) from 1999-2004. We measured six dialkylphosphate metabolites of OP pesticides to assess OP pesticide exposure. In NHANES 2003-2004, dimethylthiophosphate was detected most frequently with median and 95th percentile concentrations of 2.03 and 35.3 μg/L, respectively. Adolescents were two to three times more likely to have diethylphosphate concentrations above the 95th percentile estimate of 15.5 μg/L than adults and senior adults. Conversely, for dimethyldithiophosphate, senior adults were 3.8 times and 1.8 times more likely to be above the 95th percentile than adults and adolescents, respectively, while adults were 2.1 times more likely to be above the 95th percentile than the adolescents. Our data indicate that the most vulnerable segments of our population-children and older adults-have higher exposures to OP pesticides than other population segments. However, according to DAP urinary metabolite data, exposures to OP pesticides have declined during the last six years at both the median and 95th percentile levels.

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    • "Given the 1990 census data, we estimate that about one quarter of the participants in the NHANES III call-back cohort was not 20–59 years of age. Barr et al. (2011) demonstrated that adults ≥ 60 years of age tended to have higher urinary DAP concentrations than did younger adults in NHANES 2001–2004. Assuming that a similar age effect was observed in the NHANES III call-back cohort, the urinary DAP estimates presented here may overestimate those of the adult population 20–59 years of age during 1988–1994 because of the influence of samples from older adults. "
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    ABSTRACT: The Food Quality Protection Act (FQPA) was signed into law in 1996 to strengthen the regulation of pesticide tolerances in food. Organophosphorus (OP) insecticides were the first group of pesticides reviewed by the U.S. Environmental Protection Agency (EPA) under the new law. Our goal was to determine whether urinary concentrations of dialkylphosphate (DAP) metabolites of OP pesticides declined between the National Health and Nutrition Examination Survey (NHANES) III and NHANES 1999-2004. Using mass spectrometry-based methods, we analyzed urine samples from a nationally representative sample of 2,874 adults 20-59 years of age in NHANES 1999-2004 and samples from a non-nationally representative sample of 197 adult participants for NHANES III (1988-1994) for six common DAP metabolites of OP pesticides. Median urinary DAP concentrations decreased by more than half between NHANES III and NHANES 2003-2004. Reductions of about 50%-90% were also observed for 95th percentile concentrations of five of the six metabolites. Frequencies of detection (FODs) decreased in all six metabolites (< 50% reduction). On average, median and 95th percentile concentrations and FODs showed a larger decrease in diethylphosphate metabolites than dimethylphosphate metabolites. Human exposure to OP insecticides as assessed by urinary DAP concentrations has decreased since the implementation of the FQPA, although we cannot be certain that U.S. EPA actions in response to the FQPA directly caused the decrease in DAP concentrations.
    Environmental Health Perspectives 01/2012; 120(4):521-5. DOI:10.1289/ehp.1104323 · 7.98 Impact Factor
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    ABSTRACT: Low levels of pesticides and their metabolites/degradates occur in produce when pesticides are used in conventional or organic crop protection. Human dietary and nonoccupational urine biomonitoring studies may be confounded by preformed pesticide biomarkers in the diet. The extent of formation of putative urine biomarkers, including malathion specific (MMA, MDA; malathion mono- and diacids), organophosphorus generic (DMP, DMTP, DMDTP; dimethyl-, dimethylthio-, and dimethydithiophosphate), pyrethroid generic (3-PBA; 3-phenoxybenzoic acid), and captan-specific metabolites (THPI; tetrahydrophthalimide), was measured in produce samples containing the parent pesticide. Every produce sample of 19 types of fruits and vegetables contained biomarkers of potential human exposure. A total of 134 of 157 (85%) samples contained more molar equivalent biomarkers than parent pesticide. Malathion and fenpropathrin were sprayed (1 lb/A), and the time-dependent formation of pesticide biomarkers in strawberries was investigated under field conditions typical of commercial production in California. Malathion and fenpropathrin residues were always below established residue tolerances. Malathion, MMA, and MDA dissipated, while DMP, DMTP, and DMDTP increased, during a 20 day study period following the preharvest interval. The mole ratios of biomarkers/(malathion + malaoxon) were always greater than 1 and increased from day 4 to day 23 postapplication. Fenpropathrin and 3-PBA also dissipated in strawberries during each monitoring period. The mole ratios of 3-PBA/fenpropathrin were always less than 1 and decreased from day 4 to day 14. The absorption of pesticide biomarkers in produce and excretion in urine would falsely indicate consumer pesticide exposure if used to reconstruct dose for risk characterization.
    Journal of Agricultural and Food Chemistry 08/2012; 60(36):9342-51. DOI:10.1021/jf303116p · 2.91 Impact Factor
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    ABSTRACT: Recent epidemiological studies have claimed to associate a variety of toxicological effects of organophosphorus insecticides (OPs) and residential OP exposure based on the dialkyl phosphates (DAPs; metabolic and environmental breakdown products of OPs) levels in the urine of pregnant females. A key premise in those epidemiology studies was that the level of urinary DAPs was directly related to the level of parent OP exposure. Specific chemical biomarkers and DAPs representing absorbed dose of OPs are invaluable to reconstruct human exposures in prospective occupational studies and even in non-occupational studies when exposure to a specific OP can be described. However, measurement of those detoxification products in urine without specific knowledge of insecticide exposure is insufficient to establish OP insecticide exposure. DAPs have high oral bioavailability and are ubiquitously present in produce at concentrations several-fold greater than parent OPs. Studies relying on DAPs as an indicator of OP exposure that lack credible information on proximate OP exposure are simply measuring DAP exposure and misattributing OP exposure.
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