Automated on-line liquid-liquid extraction in a multisyringe flow injection analysis manifold for migration studies in food-contact materials: analysis of 4,4´-dihydroxybiphenyl.

Packaging may represent a source of food contamination, as different organic compounds and degradation compounds may migrate from packaging to foodstuff. For fatty foods, rectified olive oil is the common simulant, which implies time-consuming and laborious liquid-liquid extraction (LLE) procedures to isolate the contaminant(s) from the oil. Here we propose a Multisyringe Flow Injection Analysis manifold to automate this sample treatment, using the monomer 4,4´-dihydroxybiphenyl as the contaminant. The LLE procedure, using water as extractant, was fully automated. After the on-line LLE, the resulting extract was pumped through a fluorescence detector, inside which a flow-cell filled with C18 silica gel solid support was placed. The analyte was pre-concentrated on the solid support (in which the analytical signal was directly recorded), so improving the sensitivity of the system. Under optimum conditions, the method detection limit is 0.05 mg kg-1, well within the specific migration limit of 6 mg kg-1. The method developed was compared with the standard CEN test method (off-line LLE and HPLC determination) observing savings in sample and reagents of 90% and a 7-fold increase in sample throughput.

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

A 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.

Separation of a binary mixture of pesticides in fruits using a flow-through optosensor.

A flow-through optosensor is here proposed for the determination of mixtures of two widely used pesticides, carbendazim and o-phenylphenol, in fruits. The pesticides are separated on-line using an additional amount of solid support, C18 silica gel, in the flow-through cell. The resolution is performed due to the different retention/desorption kinetics of the analytes when interacting with the C18 microbeads. Therefore, both separation and determination are integrated in the same cell, considerably simplifying the system. In addition, the use of Sequential Injection Analysis provides a high degree of automation and minimum wastes generation. After the analytes are separated, their native fluorescence is measured, obtaining linearity in the 2.0-30 and 1.1-20 mg kg(-1) ranges for carbendazim and o-phenylphenol. The detection limits are 0.60 and 0.33 mg kg(-1) for carbendazim and o-phenylphenol respectively. The proposed method fulfills the maximum residue limits (MRLs) established in Europe and USA for these pesticides in cherries, pineapple, and mango: 5-10 mg kg(-1). In order to demonstrate the suitability of the method, several samples have been analyzed and the obtained results compared with a chromatographic method.