Determination of polar pesticides in olive oil and olives by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry

Abstract This article reports the development of two HPLC-MS methods for the determination of polar pesticides in olive oil and olive samples by hydrophilic interaction liquid chromatography (HILIC) separation followed by mass spectrometry detection with tandem mass spectrometry using a triple quadrupole instrument operated in multiple reaction monitoring mode (HILIC-MS/MS) or electrospray time-of-flight mass spectrometry (HILIC-TOFMS). The selected polar pesticides included in the study were: amitrol, cyromazine, diquat, paraquat, mepiquat, trimethylsulfonium (trimesium, glyphosate counterion) and fosetyl aluminium. The simple sample treatment procedure was based on liquid partitioning with methanol. The performance of the sample extraction was evaluated in terms of recovery rates and matrix effects in both olive oil and olives matrices. The results obtained for olive oil were satisfactory while, due to the high complexity of olives, poor recovery rates were obtained for the extraction of diquat, paraquat and amitrol, although with a reasonable precision enabling its use in routine analysis. Similarly, matrix effects were minor in the case of olive oil ( ca. 20% suppression average), while significantly higher suppression was observed for olives (30–50% suppression average). The studied approaches were found to be useful for the determination of the pesticides studied in olive oil and olives with limits of quantitation below 5 µg kg −1 in most cases when tandem mass spectrometry was used, thus being in compliance with MRLs set by current EU regulation.