Pesticide Multiresidue Analysis in Cereal Grains Using Modified QuEChERS Method Combined with Automated Direct Sample Introduction GC-TOFMS and UPLC-MS/MS Techniques†

The QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation method was modified to accommodate various cereal grain matrices (corn, oat, rice, and wheat) and provide good analytical results (recoveries in the range of 70-120% and RSDs <20%) for the majority of the target pesticides (about 180 analytes). The method consists of a 1 h shaking of a milled sample (2.5-5 g) in 20 mL of 1:1 (v/v) water/acetonitrile (or 25 mL of 1.5:1 water/acetonitrile in the case of rice) to provide simultaneous matrix swelling and analyte extraction. Then, a MgSO(4)/NaCl salt mixture (4:1, w/w) is added to the extract to induce phase separation and force the pesticides into the upper acetonitrile layer, a 1 mL aliquot of which is subsequently cleaned up using dispersive solid phase extraction with 150 mg of PSA, 50 mg of C(18), and 150 mg of MgSO(4). GC-amenable pesticides were analyzed using gas chromatography combined with time-of-flight mass spectrometry (GC-TOFMS) and the automated direct sample introduction technique for a large volume injection of the extracts. Ultraperformance liquid chromatography coupled to triple-quadrupole tandem mass spectrometry (UPLC-MS/MS) was employed for the analysis of LC-amenable pesticides. This method was implemented in a routine laboratory, providing about 3-fold increased sample throughput, 40-50% reduction in the cost of disposable materials and in the operation costs, 1:100 solvent waste reduction, and increased scope of the analysis versus the traditional approach based on the Luke method.