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 mcg/L, respectively. Adolescents were two to three times more likely to have diethylphosphate concentrations above the 95th percentile estimate of 15.5 mcg/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.

Organophosphorus (OP) pesticides kill by disrupting a targeted pest's brain and nervous systems. But if humans and other animals are sufficiently exposed, OP pesticides can have the same effect on them. We developed a fast and accurate high-performance liquid chromatography-tandem mass spectrometry method for the quantitative measurement of the following six common dialkylphosphate (DAP) metabolites of organophosphorus insecticides: dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate, (DEP), diethylthiophosphate (DETP), and diethyldithiophosphate (DEDTP). The general sample preparation included 96-well plate solid phase extraction using weak anion exchange cartridges. The analytical separation was performed by high-performance liquid chromatography with a HILIC column. Detection involved a triple quadrupole mass spectrometer with an ESI probe in negative ion mode using multiple reaction monitoring. Repeated analyses of urine samples spiked at 150, 90 and 32ng/mL with the analytes gave relative standard deviations of less than 22%. The extraction efficiency ranged from 40% to 98%. The limits of detection were in the range of 0.04-1.5ng/mL. The throughput is 1152 samples per week, effectively quadrupling our previous throughput. The method is safe, quick, and sensitive enough to be used in environmental and emergency biological monitoring of occupational and nonoccupational exposure to organophosphates.

We have developed a gas chromatography-high resolution mass spectrometry method for measuring pyrethroid, organophosphorus, carbamate and fipronil pesticides and the synergist piperonyl butoxide in human plasma. Plasma samples were extracted using solid phase extraction and were then concentrated for injection and analysis using isotope dilution gas chromatography-high resolution mass spectrometry. The limits of detection ranged from 10 to 158pg/mL with relative recoveries at concentrations near the LODs (e.g., 25 or 250pg/mL) ranging from 87% to 156% (9 of the 16 compounds were within +/-15% of 100%). The extraction recoveries ranged from 20% to 98% and the overall method relative standard deviations were typically less than 20% with some exceptions. Analytical characteristics were determined at 25, 250, and 1000pg/mL.

Dialkylphosphates (DAPs) are urinary metabolites and breakdown products of organophosphorous (OP) pesticides. Urinary DAPs are widely used to assess exposure to OP pesticides in epidemiologic studies. Recent evidence suggests that preformed DAPs are present in food and that they may also be present in other parts of the environment. Thus, DAP concentrations observed in urine may reflect a person's exposure to both parent OP pesticides and preformed DAPs in food and other environmental media. The presence of preformed DAPs in multiple media may indicate that previous studies have overestimated exposure to OP pesticides and that the use of urinary DAPs as biomarkers of exposure for OP pesticides may not accurately characterize exposure in non-acute settings. To establish the presence of DAPs in environmental and food media, we developed analytical methods to measure six DAPs in dust and orange juice. The limits of detection (LOD) for the dimethyl phosphates (dimethylphosphate (DMP), dimethylthiophosphate, and dimethyldithiophosphate) ranged from 2.8-9.9 ng g-1 and 0.2-0.4 ng mL-1 in dust and juice, respectively. The LODs for the diethyl phosphates (diethylphosphate (DEP), diethylthiophosphate, diethyldithiophosphate) ranged from 5.2-10.4 ng g -1 and 0.5-3.0 ng mL-1 in dust and juice, respectively. The extraction efficiencies for the analytes ranged from 23% to 91% and from 41% to 85% in dust and orange juice, respectively. DMP was detected in about half of the dust samples whereas DEP was detected in 80% of the dust samples tested. Other DAPs were less frequently detected in dust. Less than 3% of intact pesticide present in the matrices was converted to their respective DAPs during the pre-analytic and analytic process. Evaluation of the conversion of intact pesticides in the samples to DAPs will help us to better understand the contribution of preformed DAPs to urinary DAP concentrations. copyright 2009 The Royal Society of Chemistry.