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Determination of pyrethroid metabolites in human urine using liquid phase microextraction coupled in-syringe derivatization followed by gas chromatography/electron capture detection

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Abstract

Metabolites of synthetic pyrethroids such as cis-3-(2,2-dibromovinyl)-2,2-di-methylcyclo-propane-1-carboxylic acid, cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid), 3-phenoxybenzoic acid (3-PBA), and 4-fluoro-3-PBA are biomarkers for exposure to phenothrin, tetramethrin, cyfluthrin, cypermethrin, deltamethrin, and permethrin. In this study, the pyrethroid metabolites in workers’ urine samples were monitored for the first time with a novel sample pretreatment process combining hollow fiber liquid phase microextraction (HF-LPME) and in-syringe derivatization (ISD) followed by gas chromatography–electron capture detector (GC-ECD) analysis. A micro-syringe pre-filled with derivatizing agents and syringe needle connected to an extracting solvent impregnated hollow fiber segment was used as the LPME probe. Pyrethroid metabolites were extracted and enriched simultaneously from urine samples by HF-LPME sampling and acid hydrolysis at 70 °C for 10 min. After sampling, the ISD was performed by mixing the extracting solution and derivatizing agents through plunger movements, followed by GC-ECD analysis. Parameters influencing the HF-LPME efficiency and ISD were investigated and optimized. Under optimum conditions, the method provided enrichment factors of 69.8–154.6, repeatability from 5.0 to 12% (n = 5), and good linearity (R 2 = 0.9980–0.9998) for interested analytes spiked in urine samples. The method detection limits ranged from 1.6 to 17 ng/mL. A comparison was performed between the proposed method and conventional methods. The proposed method was applied to analyze pyrethroid metabolites in the urine samples collected from workers of pesticide formulation plants. The results suggested that the proposed HF-LPME coupled ISD method was a rapid, simple, efficient, and eco-friendly technique in the biomonitoring of metabolites of pyrethroids in workers’ urine.

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Acknowledgment

The authors thank the National Science Council of Taiwan (grant no. NSC 94-2113-M-005-002, NSC-98-2113-M-005-016-MY3) and the Council of Agriculture (COA) in Taiwan (grant no. 90AS-1.2.2-PI-P2(3)) for financial support.

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Authors and Affiliations

  1. Department of Chemistry, National Chung Hsing University, Taichung City, 402, Taiwan

    Chiu-Hwa Lin, Ponnusamy Vinoth Kumar & Jen-Fon Jen

  2. Residue Control Department, Taiwan Agricultural Chemicals and Toxic Substances Research Institute, Council of Agriculture (TACTRI/COA), Wu-Fung, Taichung City, 413, Taiwan

    Chiu-Hwa Lin & Hong-Ping Li

  3. Department of Occupational Safety and Health, Chung-Shan Medical University, Taichung, 402, Taiwan

    Cheing-Tong Yan

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  1. Chiu-Hwa Lin
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  2. Cheing-Tong Yan
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  3. Ponnusamy Vinoth Kumar
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  4. Hong-Ping Li
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Correspondence to Jen-Fon Jen.

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Lin, CH., Yan, CT., Kumar, P.V. et al. Determination of pyrethroid metabolites in human urine using liquid phase microextraction coupled in-syringe derivatization followed by gas chromatography/electron capture detection. Anal Bioanal Chem 401, 927–937 (2011). https://doi.org/10.1007/s00216-011-5122-0

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  • DOI: https://doi.org/10.1007/s00216-011-5122-0

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