Abstract

An accurate, rapid, and reliable multiresidue QuEChERS method based on gas chromatography coupled with tandem mass spectrometry was developed for the determination of 235 pesticides in challenging, dry, complex herb matrices (Centaurea cyanus L., Matricaria chamomilla L., Thymus vulgaris L.). Sample mass and the type of cleanup sorbent used to estimate the procedure’s effectiveness were optimized. Purification steps with ChloroFiltr, ENVI-Carb, GCB, octadecyl, PSA, and Z-Sep as cleanup sorbents and a step without purification were compared. To minimize the matrix effect and obtain acceptable recoveries for pesticides, 2 g of herb sample and 10 mL acetonitrile, followed by d-SPE cleanup step with a combination of 150 mg PSA/45 mg ENVI-Carb/900 mg MgSO₄, and additionally 50 μL of 5% formic acid and some droplets of dodecane, were needed. Matrix effects for the vast majority of pesticides were reduced (> 20%), showing suppression or enhancement. Most recoveries were in the range of 70–120% (RSD < 18%), reaching the quantification limit of 0.001 to 0.002 mg kg⁻¹. There was excellent linearity within the range from 0.001 to 2.00 μg mL⁻¹, and a correlation coefficient higher than 0.999 was obtained. Expanded measurement uncertainty was estimated to be between 4 and 43%. Finally, the developed method was successfully employed to identify and quantify pesticide residues in the analysis of 46 real herb samples.