An evaporation-assisted dispersive liquid–liquid microextraction technique as a simple tool for high performance liquid chromatography tandem–mass spectrometry determination of insecticides in wine

Abstract

A sample pre-treatment technique based on evaporation-assisted dispersive liquid–liquid microextraction (EVA-DLLME), followed by HPLC–MS/MS has been developed for the determination of organophosphate insecticides (malathion, diazinon, phosalone) in wine samples. The procedure includes the addition of mixture of organic solvents (with density higher than water), consisting of the extraction (low density) and volatile (high density) solvents, to aqueous sample followed by heating of the mixture obtained, what promotes the volatile solvent evaporation and moving extraction solvent droplets from down to top of the aqueous sample and, as a consequence, microextraction of target analytes. To initiate the evaporation process an initiator is required. It was established that hexanol (extraction solvent) and dichloromethane (volatile solvent) mixture (1:1, v/v) provides effective microextraction of the insecticides from wine samples with recovery from 92 to 103%. The conditions of insecticides’ microextraction such as selection of extraction solvent, ratio of hexanol/dichloromethane and hexanol/sample, type and concentration of initiator, and effect of ethanol as one of the main components of wine have been studied. Under optimal experimental conditions the linear detection ranges were found to be 10−7–10−3gL−1 for malathion, 10−9–10−4gL−1 for diazinon, and 10−6–10−2gL−1 for phosalone. The LODs, calculated from a blank test, based on 3σ, found to be 3×10−8gL−1 for malathion, 3×10−10gL−1 for diazinon and 3×10−7gL−1 for phosalone. The advantages of EVA-DLLME are the rapidity, simplicity, high sample throughput and low cost. As an outcome, the analytical results agreed fairly well with the results obtained by a reference GC–MS method.