Determination of diquat and paraquat in olive oil by ion-pair liquid chromatography–electrospray ionization mass spectrometry (MRM)

Abstract

For the first time a method for determination of herbicides diquat (DQ) and paraquat (PQ) in olive oil was developed utilising liquid chromatography–electrospray ionization mass spectrometry (MRM). n-Hexane/10 mM HFBA aqueous solution partitioning was used as the extraction method. Separation was carried out in an Xterra C8 column (100 × 21 mm, 3 μm), using the gradient mode. Solvent A was a HFBA aqueous solution (5 mM, pH 2) and solvent B acetonitrile/methanol 75/25 (v/v). Peaks used for quantification were m/ z = 157 (diquat) and m/ z = 158 (paraquat). Detection limit found for both diquat and paraquat was 4 μg kg −1. The method can also be applied for determination of chlormequat (CQ, quantification peak m/ z = 58), the detection limit being 0.3 μg kg −1. Such limits are clearly lower than the MCLs commonly applied to olive oil as reference criteria (5 times MCLs in olives). Good reproducibilities (day to day and run to run) were obtained. The method allowed us to check that even though DQ and PQ residues had been detected in soils from olive grove plantations, they did not pass to olive oil.