Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid–liquid microextraction combined with liquid chromatography-tandem mass spectrometry

Abstract

The objective of this study was to develop analytical method based on optimized dispersive liquid–liquid microextraction (DLLME) as a pretreatment procedure combined with reversed phase liquid chromatographic separation on C18 column and isocratic elution for simultaneous MS/MS determination of selected neonicotinoid insecticides in honey. The LC–MS/MS parameters were optimized to unequivocally provide good chromatographic separation, low detection (LOD, 0.5–1.0μgkg−1) and quantification (LOQ, 1.5–2.5μgkg−1) limits for acetamiprid, clothianidin, thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different types (chloroform, dichloromethane) and volumes of extraction (0.5–3.0mL) and dispersive (acetonitrile; 0.0–1.0mL) solvent and by mathematical modeling it was possible to establish the optimal sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the concentration range of LOQ-100.0μgkg−1 were used to compensate the matrix effect and to fulfill the requirements of SANCO/12495/2011 for the accuracy (R 74.3–113.9%) and precision (expressed in terms of repeatability (RSD 2.74–11.8%) and within-laboratory reproducibility (RSDs 6.64–16.2%)) of the proposed method. The rapid (retention times 1.5–9.9min), sensitive and low solvent consumption procedure described in this work provides reliable, simultaneous, and quantitative method applicable for the routine laboratory analysis of seven neonicotinoid residues in real honey samples.