Matrix Effect Evaluation in GC/MS-MS Analysis of Multiple Pesticide Residues in Selected Food Matrices

Multi-analyte methods based on QuEChERS sample preparation and chromatography/mass spectrometry determination are indispensable in monitoring pesticide residues in the feed and food chain. QuEChERS method, even though perceived as convenient and generic, can contribute to sample matrix constituents' introduction to the measuring system and possibly affect analytical results. In this study, matrix effects (ME) were investigated in four food matrices of plant origin (apples, grapes, spelt kernels, and sunflower seeds) during GC-MS/MS analysis of >200 pesticide residues using QuEChERS sample preparation. Data analysis revealed considerable analyte signal enhancement and suppression: strong enhancement was observed for the majority of analytes in two matrices within the commodity groups with high water content-apples, and high acid and water content-grapes (73.9% MES and 72.5% MEA, and 77.7% MES and 74.9% MEA, respectively), while strong suppression was observed for matrices within the commodity groups with high starch/protein content and low water and fat content-spelt kernels, and high oil content and very low water content-sunflower seeds (82.1% MES and 82.6% MEA, and 65.2% MES and 70.0% MEA, respectively). Although strong matrix effects were the most common for all investigated matrices, the use of matrix-matched calibration for each sample type enabled satisfactory method performance, i.e., recoveries for the majority of analytes (up to roughly 90%, depending on the fortification level and matrix type), which was also externally confirmed through participation in proficiency testing schemes for relevant food commodity groups with the achieved z-scores within acceptable range ≤ |2|.