Multi-residue analysis of pesticides in blood plasma using hollow fiber solvent bar microextraction and gas chromatography with a flame ionization detector

Abstract

The challenges faced on pesticide extraction from biological samples are finding a method that allows a multi-residue extraction, pre-concentration, clean-up, and isolation of analytes in just one step. In this sense, the hollow fiber - liquid phase microextraction method (HF- LPME) in the "solvent bar" mode was used to optimize and validate a method for pesticide multi-residue analysis in blood plasma at trace levels, through gas chromatography coupled with a flame ionization detector (GC-FID). Hollow fiber solvent bar microextraction HF-SBME was carried out with octanol immobilized into the pores of hydrophobic polypropylene fiber and disposed within a matrix of blood plasma, spiked with a mixture of pesticides (monocrotophos, lindane, aldrin, methyl parathion, endosulfan, dieldrin, DDD, DDT, and endrin). The optimization parameters evaluated were: extraction temperature and time, stirring speed, and salt concentration. A principal component analysis was performed to visualize the analytes' behaviour based on their explained variance, and then, a Box-Behnken analysis was generated to identify the optimum parameters. According to the PCA, all pesticides showed similar responses to the extraction method and the response of dieldrin exhibit the lowest variance. Moreover, the stationary points selected from the Box-Behnken analysis were 25.5 °C for the extraction temperature, 870 rpm for stirring speed, 16 min for extraction time, and 8.3 % w/v of salt concentration. Moreover, the validation results proved that HF-SBME is an alternative technique for pesticide multi-residue extraction in blood plasma. The analytes were able to concentrate, reaching 46 fold enrichment. The solvent type, sample and solvent volume were narrowed down without changing the method's precision or accuracy. The relative standard deviation was under 10 %, and the recovery was between 55 % and 105 % for the different analytes excepting lindane, which had lower recovery (27 %). The detection limits were 0.02 until 0.13 μg mL^-1 for most of the pesticides used. Finally, HF-SBME is a good alternative for pesticide multi-residue extraction in complex matrices like plasma.

Keywords: GC-FID; HF-SBME; Multi-residue analysis; Pesticides; Validation methods.