A fast and sensitive direct immersion-solid-phase microextraction-gas chromatography-time-of-flight mass spectrometry (DI-SPME-GC-ToFMS) method for the determination of multiresidue pesticides in grapes employing a PDMS-modified PDMS/DVB coating was developed utilizing multivariate approaches for optimization of the most important factors affecting SPME performance. A comprehensive investigation of appropriate internal standards using a bottom-up approach led to the selection of suitable compounds that adequately covered a range of 40 pesticides pertaining to various classes. The validated method yielded good accuracy, precision, and sensitivity and has been successfully applied to the analysis of commercial samples. With regard to the limitations of the proposed method, the DI-SPME method did not provide a satisfactory performance toward more polar pesticides (e.g., acephate, omethoate, dimethoate) and highly hydrophobic pesticides, such as pyrethroids. Despite the challenges and limitations encountered by this method, the practical aspects of the PDMS-modified coating demonstrated here create new opportunities for SPME applied in food analysis.
Keywords: coating; gas chromatography−time-of-flight mass spectrometry (GC-TOFMS); grapes; multiresidue pesticides; solid-phase microextraction (SPME).