Comparison of Different d-SPE Sorbent Performances Based on Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) Methodology for Multiresidue Pesticide Analyses in Rapeseeds.

Pesticide extraction in rapeseed samples remains a great analytical challenge due to the complexity of the matrix, which contains proteins, fatty acids, high amounts of triglycerides and cellulosic fibers. An HPLC-MS/MS method was developed for the quantification of 179 pesticides in rapeseeds. The performances of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method were evaluated using different dispersive solid-phase extraction (d-SPE) sorbents containing common octadecylsilane silica/primary-secondary amine adsorbent (PSA/C18) and new commercialized d-SPE materials dedicated to fatty matrices (Z-Sep, Z-Sep+, and EMR-Lipid). The analytical performances of these different sorbents were compared according to the SANTE/12682/2019 document. The best results were obtained using EMR-Lipid in terms of pesticide average recoveries (103 and 70 of the 179 targeted pesticides exhibited recoveries within 70-120% and 30-70%, respectively, with low RSD values). Moreover, the limits of quantification (LOQ) range from 1.72 µg/kg to 6.39 µg/kg for 173 of the pesticides. Only the recovery for tralkoxydim at 10 µg/kg level was not satisfactory (29%). The matrix effect was evaluated and proved to be limited between -50% and 50% for 169 pesticides with this EMR-Lipid and freezing. GC-Orbitrap analyses confirmed the best efficiency of the EMR-Lipid sorbent for the purification of rapeseeds.

Comparison of new approach of GC-HRMS (Q-Orbitrap) to GC-MS/MS (triple-quadrupole) in analyzing the pesticide residues and contaminants in complex food matrices.

Performances of multiresidue analysis of one hundred of pesticides and contaminants, using GC-Q-Orbitrap method in full scan mode were compared to those obtained with GC-triple-quadrupole method in multiple reaction monitoring mode. In terms of sensitivity, 86% of molecules exhibited lower limit of detection values using GC-Q-Orbitrap than using GC-triple-quadrupole. For the GC-Q-Orbitrap method, more than 85% of the pesticides and contaminants showed good recovery [70-120%] in wheat samples, with relative standard deviation values < 20%. GC-Q-Orbitrap method appeared the most sensitive for most pesticides studied in wheat with limit of quantification values ranged between 0.1 µg/kg and 4 µg/kg. Moreover, the matrix effect was acceptable in wheat extracts for 84 molecules but strong suppression of the chromatographic signal was observed for 16 molecules for the GC-Q-Orbitrap method. The injection of unpurified wheat extracts spiked at 10 µg/kg proved the potential of the GC-Q-Orbitrap method for use in performing high-throughput pesticide screening.