Urine samples were collected from 51 participants in a study investigating pesticide exposure among farm families in Iowa. Aliquots from the samples were sent to two different labs and analyzed for metabolites of atrazine (atrazine mercapturate), metolachlor (metolachlor mercapturate) and chlorpyrifos (TCP) by two different analytical methods: immunoassay and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). HPLC-MS/MS methods tend to be highly specific, but are costly and time consuming. Immunoassay methods are cheaper and faster, but can be less sensitive due to cross reactivity and matrix effects. Three statistical methods were employed to compare the two analytical methods. Each statistical method differed in how the samples that had results below the limit of detection (LOD) were treated. The first two methods involved an imputation procedure and the third method used maximum likelihood estimation (MLE). A fourth statistical method that modeled each lab separately using MLE was used for comparison. The immunoassay and HPLC-MS/MS methods were moderately correlated (correlation 0.40-0.49), but the immunoassay methods consistently had significantly higher geometric mean (GM) estimates for each pesticide metabolite. The GM estimates for atrazine mercapturate, metolachlor mercapturate, and TCP by immunoassay ranged from 0.16-0.98 microg l(-1), 0.24-0.45 microg l(-1) and 14-14 microg l(-1), respectively and by HPLC-MS/MS ranged from 0.0015-0.0039 microg l(-1), 0.12-0.16 microg l(-1), and 2.9-3.0 microg l(-1), respectively. Immunoassays tend to be cheaper and faster than HPLC-MS/MS, however, they may result in an upward bias of urinary pesticide metabolite levels.
"For a concentration or estimate < LOD, we used a value equal to the LOD divided by the square root of two (Hornung and Reed 1990). Although techniques for imputing values < LOD have been debated in the literature (Caudill et al. 2007; Chen et al. 2011; Curwin et al. 2010; Gillespie et al. 2010; Jain and Wang 2008; Jain et al. 2008), we used this imputation technique consistent with the CDC National Report on Human Exposure to Environmental Chemicals (CDC 2009b). Other imputation techniques may produce slightly different estimates. "
[Show abstract][Hide abstract] 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
[Show abstract][Hide abstract] ABSTRACT: The broad-spectrum organophosphate insecticide chlorpyrifos (CPF)-inducible locus, chpAB, was identified on the endogenous plasmid pSymB in Sinorhizobium meliloti. The S. meliloti chpA promoter was highly induced by CPF and was induced at much lower levels by diazinon and ethion. Transcription of chpA was dependent on chpR, a CadC family transcriptional regulator located upstream of, and divergently transcribed from, chpAB. ChpR was able to mediate the CPF-inducible expression of the S. melilotichpA promoter in Escherichia coli through direct interaction with the chpAB promoter. The chpR-chpA intergenic regions of several bacterial chpRAB operons were aligned and a putative ChpR-binding sequence was proposed. Both the ChpR transcription factor and chpA promoter constitute a good candidate system for genetic-based biosensor development.
Journal of Molecular Microbiology and Biotechnology 04/2010; 18(3):141-7. DOI:10.1159/000308514 · 2.10 Impact Factor
Tianjiao Zhang, Chuanbao Zhang, Wenxiang Chen, Haijian Zhao, Jiangtao Zhang, Weiyan Zhou, Jie Zeng, Jing Wang, Donghuan Wang
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