Development of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry: II. Improvement and extension to new analytes

Abstract

This paper describes the extension and re-validation of a previously published multi-residue method to currently 140 pesticides and 4 pesticide degradation products in cereals and feedingstuffs. The pesticides were extracted using buffered QuEChERS (“quick, easy, cheap, rugged, effective and safe”) method and then cleaned up using dispersive solid-phase extraction with Bondesil PSA and C18 sorbents, and optionally by a freezing-out clean-up step. The final extracts were analyzed in a single injection gas chromatographic-tandem quadrupole mass spectrometric (GC–MS/MS) acquisition method. A high degree of confidence was achieved by entering two multiple reaction monitoring transitions per compound. In this way, quantification of analytical results and unequivocal identification of pesticide residues in compliance with the recent European Union criteria could be done in a single analysis. Thorough optimization of the GC–MS/MS acquisition conditions and application of an effective clean-up procedure has resulted in a remarkable enhancement of the validation parameters. The linearity of the calibration curves was excellent in matrix-matched standards, and yielded the coefficients of determination ( R 2) ≥ 0.99 for approximately 96% of the target analytes. Average recoveries of the pesticides spiked at 0.01 mg kg −1 into a feed mixture and wheat grain were in the range 70–120% with associated RSD values ≤20% for approximately 60% and 67% of the compounds, respectively. At the higher spiking levels of 0.05, 0.1 and 0.5 mg kg −1 average recoveries and RSDs readily met the validation criteria for nearly all the studied pesticides. Based on these results, the proposed approach has been proven to be highly efficient and suitable for routine determinations of multi-class pesticides in a range of cereal and related matrices. Up to now, 145 samples of matrices of differing complexity including cereals grain, bran, whole ears, straw, hay, feed mixtures and other samples such as malt, starch and dry vegetables have been analyzed. A total of 15 different pesticides have been detected, among which pirimiphos methyl (19 cases), deltamethrin (14 cases), tolylfluanid (5 cases), dichlofluanid (5 cases), and tebuconazole (4 cases) were the most frequently encountered ones.