Novel sequential separation and determination of a quaternary mixture of fungicides by using an automatic fluorimetric optosensor

Abstract

ABSTRACTA versatile flow-through multi-optosensor is proposed for the separation and spectrofluorimetric determination of mixtures of four widely used pesticides: carbendazim, thiabendazole, carbaryl and o-phenylphenol at µg g−1 levels in fruits. The flow system is based on the online pre-concentration and separation of the pesticides on a solid sensing microzone, followed by the sequential measurement of their native fluorescence. The separation of the pesticides takes place on a solid support located in the same flow cell, on which analytes are temporarily immobilized and separated from the matrix due to their different retention/desorption kinetics when they interact with the C18 silica gel microbeads. Suitable analytical parameters were obtained for the selected analytes, with method detection and quantification limits ranging between 0.1–0.5 and 0.2–1.6 µg g−1, respectively. These values comply with the maximum residue limits (MRLs) established by the Codex Alimentarius for these commodities; in addition, carbendazim, thiabendazole and ortho-phenylphenol comply with the MRLs of The European Union. The developed method was applied to the analysis of citrus fruits by performing recovery studies. Recoveries between 85% and 115% were obtained in all cases, and the results were confirmed by a liquid chromatography–mass spectrometry reference method.