Comparison of immunoassay and HPLC-MS/MS used to measure urinary metabolites of atrazine, metolachlor, and chlorpyrifos from farmers and non-farmers in Iowa.
ABSTRACT 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.
- SourceAvailable from: Travert CarineJOMT. 01/2010; 6:3.
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ABSTRACT: Chlorpyrifos is the most common organophosphate insecticide registered for use in Vietnam and is widely used in agriculture, particularly rice farming. However, chlorpyrifos exposure to and adverse effects on farmers has not been evaluated. In this study, biological monitoring of chlorpyrifos exposure in a group of rice farmers was conducted after a typical application event using back-pack spraying. Urine samples (24 h) were collected from the rice farmers before and post insecticide application. Samples were analysed for 3,5,6-trichloropyridinol (TCP), the major urinary metabolite of chlorpyrifos, using an enzymatic pre-treatment before extraction followed by HPLC-MS/MS. Absorbed Daily Dose (ADD) of chlorpyrifos for farmers were then estimated from urinary TCP levels, expressed as μg g(-1)creatinine. The analytical method for urinary TCP had a low detection limit (0.6 μg L(-1)), acceptable recovery values (80-114%), and low relative percentage differences in duplicate and repeated samples. Post-application chlorpyrifos ADD of farmers varied from 0.4 to 94.2 μg kg(-1) (body weight) d(-1) with a mean of 19.4 μg kg(-1) d(-1) which was approximately 80-fold higher than the mean baseline exposure level (0.24 μg kg(-1) d(-1)). Hazard Quotients (ratio of the mean ADD for rice farmers to acute oral reference dose) calculated using acute oral reference doses recommended by United States and Australian agencies varied from 2.1 (Australian NRA), 4.2 (US EPA) to 6.9 (ATSDR). Biological monitoring using HPLC-MS/MS analysis of urinary TCP (24 h) was found to be an effective method for measuring chlorpyrifos exposure among farmers. This case study found that Vietnamese rice farmers had relatively high exposures to chlorpyrifos after application, which were likely to have adverse health effects.Chemosphere 12/2011; 87(4):294-300. · 3.14 Impact Factor
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ABSTRACT: Pesticides have been widely used to control pest and pest-related diseases in agriculture, fishery, forestry and the food industry. In this review, we identify a number of respiratory symptoms and diseases that have been associated with occupational pesticide exposures. Impaired lung function has also been observed among people occupationally exposed to pesticides. There was strong evidence for an association between occupational pesticide exposure and asthma, especially in agricultural occupations. In addition, we found suggestive evidence for a link between occupational pesticide exposure and chronic bronchitis or COPD. There was inconclusive evidence for the association between occupational pesticide exposure and lung cancer. Better control of pesticide uses and enforcement of safety behaviors, such as using personal protection equipment (PPE) in the workplace, are critical for reducing the risk of developing pesticide-related symptoms and diseases. Educational training programs focusing on basic safety precautions and proper uses of personal protection equipment (PPE) are possible interventions that could be used to control the respiratory diseases associated with pesticide exposure in occupational setting.International Journal of Environmental Research and Public Health 12/2013; 10(12):6442-71. · 1.99 Impact Factor