Evaluation of two-dimensional gas chromatography–time-of-flight mass spectrometry for the determination of multiple pesticide residues in fruit

Abstract

In recent years, comprehensive two-dimensional gas chromatography (GC×GC) has attained increasing attention for its outstanding separation potential and capability to solve demanding analytical tasks. Trace level analysis of pesticides residues in complex food matrices represents such a demanding task. For some commodities, such as baby food, the requirements on method detection limits are very strict and the unambiguous confirmation of the pesticide presence based on mass spectrometric detection is required. In this work, GC×GC coupled to time-of-flight mass spectrometry (TOF MS) has been evaluated for the determination of pesticides residues in fruit samples. Twenty modern pesticides with a broad range of physico-chemical properties were analysed in apple and peach samples. It has been demonstrated that the application of comprehensive two-dimensional gas chromatography brings distinct advantages such as enhanced separation of target pesticides from matrix co-extracts as well as their improved detectability. The limits of detection of the pesticides comprised in the study (determined at S/N=5) ranged from 0.2 to 30 pg, injected with the exception of the last eluted deltamethrin, for which 100 pg could be detected. When compared to one-dimentional GC–TOF MS analysis under essentially the same conditions the detectability enhancement was 1.5–50-fold. Full mass spectral information by time-of-flight mass spectrometry and the deconvolution capability of the dedicated software allowed for reliable identification of most pesticides at levels below 0.01 mg/kg (<10 pg injected) in fruit. Performance characteristics of the GC×GC–TOF MS method, such as linearity of calibration curves, repeatability of (summed) peak areas, as well as repeatability of first and second dimension retention times, were shown to fully satisfy the requirements for trace level analysis of the pesticide residues in food.