Fast analysis of quaternary ammonium pesticides in food and beverages using cation-exchange chromatography coupled with isotope-dilution high-resolution mass spectrometry

A fast separation based on cation-exchange liquid chromatography coupled with high-resolution mass spectrometry is proposed for simultaneous determination of chlormequat, difenzoquat, diquat, mepiquat and paraquat in several food and beverage commodities. Solid samples were extracted using a mix of water/methanol/formic acid (69.6:30:0.4 v/v/v), while liquid samples were ten-times diluted with the same solution. Separation was carried out on an experimental length-modified IonPac CS17 column (2 × 15 mm) which allowed the use of formic acid and acetonitrile as mobile phase. Detection limits for food and beverage matrices were established at 1.5 μg L−1 for chlormequat, difenzoquat and mepiquat, and 3 μg L−1 for diquat and paraquat, while for drinking water a pre-analytical sample concentration allowed detection limits of 9 and 20 ng L−1, respectively. Precision, as repeatability (RSD%), ranged from 0.2 to 24%, with a median value of 6%, and trueness, as recovery, ranged from 64 to 118%, with a median value of 96%. The method developed was successfully applied to investigate the presence of herbicide residues in commercial commodities (mineral water, orange juice, beer, tea, green coffee bean, toasted coffee powder, cocoa bean, white corn flour, rice and sugar samples).