Low transition temperature mixture-based extraction of 14 pesticides from tomato samples and their high-performance...

The extensive use of pesticides to control pest infestations has led to the development of analytical methods to determine pesticide residues in food matrices to prevent food exposure. However, most developed analytical methods do not consider impact on the environment in terms of the toxicity of the chemicals used and the amount of waste produced. An environmentally-friendly method, based on a miniaturized matrix solid-phase dispersion followed by high-performance liquid chromatography-tandem mass spectrometry, for the analysis of fourteen pesticides in tomatoes, was exploited. For the recovery of pesticides from tomato samples, a low transition temperature mixture (LTTM), containing choline chloride and sesamol 1:3 molar ratio, was employed. Extraction parameters like sample-to-dispersant ratio, extraction solvent volume and LTTM volume were optimized through a Box-Behnken design. The 1:4 sample-to-dispersant ratio, 900 µL of ethanol as extraction solvent and 50 µL of LTTM ensured the best result considering the pesticides' peak areas. The optimized analytical method was validated obtaining the following results: linearity range was between LOQ and 5 mg kg^-1 with a minimum R² of 0.9944 for tebufenozide, values in the range of 0.001-0.023 and 0.004-0.076 mg kg^-1 were obtained for LOD and LOQ respectively, while peak areas intra-day and inter-day repeatability were maximum of 10.19 and 9.15 %, respectively. The analytical method was then applied to real samples studying whole, pulp and peel tomato pool. The analysis of whole and tomato pulp revealed the presence of seven and eight of the fourteen investigated pesticides, respectively. However, their concentration was lower than the limit of quantification. In tomato peel, five pesticides, namely dimethomorph, methoxyfenozide, pyraclostrobin, pyriproxyfen, and spiromesifen were quantified and their concentrations were below maximum residue levels.