Multiresidue Determination of Fungicides in Wine by Solvent Demulsification-Dispersive Liquid-Liquid Microextraction and Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

Fungicides are applied from plant development to grape production, transport, and storage. Even after fruit processing, residues of these compounds can be present in grape by-products such as wine and juice. In this way, a fast and straightforward method based on solvent demulsification-dispersive liquid-liquid microextraction (SD-DLLME) sample preparation was developed, validated, and applied for the multiresidue determination of 30 fungicides in wine using ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The evaluated SD-DLLME parameters were agitation types, extraction and dispersive solvent type, extraction and dispersive solvent volume, sample pH, and salt types. Sample preparation using SD-DLLME avoids the centrifugation step. Validation was performed using spiked blank sample and satisfactory results for accuracy, with recoveries ranging from 70 to 117% and precision in terms of relative standard deviation <= 20%, except for three compounds at the lowest spiked level. For most of the compounds, the practical method limits of detection and quantification were 0.03 and 0.1 mu g L-1, respectively. The method was successfully applied in commercial wine samples in which several pesticides were found at concentrations ranging from 0.109 to 10.6 mu g L-1.