Simplified pesticide multiresidue analysis in virgin olive oil by gas chromatography with thermoionic specific, electron-capture and mass spectrometric detection

In the present work, an analytical multiresidue method has been developed for the analysis of 32 organochlorine, organophosphorus and organonitrogen pesticides at μg kg−1 levels in virgin olive oil. The method consists of the extraction of the pesticides with acetonitrile saturated in n-hexane followed by a clean-up process based on gel permeation chromatography (GPC) with ethyl acetate–ciclohexane (1:1) as mobile phase to separate the low-molecular mass pesticides from the high-molecular mass fat constituents of the oil. The target compounds were determined in the final extract by gas chromatography (GC) using thermoionic specific (TSD) and electron-capture (ECD) detection. In the case of positive samples, the amounts found were confirmed by GC–MS/MS, being the results in good agreement. Recoveries and RSDs (n = 10) values were 91–124% and 1–8% (GC-ECD), 82–100% and 9–20% (GC-TSD), and 89–105% and 4–14% (GC–MS/MS), respectively. The three proposed methods were applied to samples collected directly in two olive mills located in the Jaén province (Spain). Specifically, 24 samples of virgin olive oil were collected. The most frequently pesticide residues found were the herbicides terbuthylazine and diuron and endosulfan sulfate, a degradation product of the insecticide endosulfan. The herbicide concentration was higher in those oil samples obtained from olives which were collected from the ground after they had fallen down than in those oil samples from olives harvested directly from the tree. The GC–MS/MS developed method was also applied to the analysis of an olive oil sample from a proficiency test spiked with organochlorine pesticides and all the values obtained were within the specified “satisfactory” range.