There is an increasing concern about the negative impacts of veterinary drugs in beehive compartments. This study evaluates the presence and distribution of chemical residues in beeswax, bee bread and honey and determinates in what extension honeybees are exposed to them. Samples were analyzed by LC-MS/MS and GC-MS/MS with a wide scope of 322 chemical residues. Samples were collected from apiaries located in rural and forest areas, showing no difference in contamination of phytosanitary applications. Residues of acaricides used for sanitary treatments, coumaphos and two transformation products of amitraz (DMF and DMPF), were quantified at higher levels in wax and bee bread than in honey in most cases. Coumaphos, DMF and DMPF were detected in honey in the range 6-36 µg.kg-1; 45-541 µg.kg-1; 15-107 µg.kg-1, respectively. All, except one sample, were below the EU MRLs, 396/2005 Regulation. Other pesticide residues were detected in beeswax and bee bread at various levels.

Food analysis is a tremendously broad field that is constantly evolving. New methods have emerged to increase productivity, such as modern miniaturized and robotic analytical techniques. In this paper, a micro-solid-phase extraction system (µ-SPE) for clean-up was combined with a robotic autosampler to yield ready-to-analyze extracts. The system was evaluated for its applicability in routine laboratories. The new, automated, high-throughput µ-SPE clean-up method was applied to acetonitrile extracts and was developed for the analysis of pesticide residues in cereals by gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap-MS). The µ-SPE clean-up efficiency was demonstrated in the removal of matrix-interfering components and in the recovery of pesticides. The sorbent bed mixture consisted of magnesium sulfate, primary-secondary amine, C18, and CarbonX, and effectively retained matrix components without loss of target analytes. Analysis of five types of cereals (barley, oat, rice, rye, and wheat) by GC-Orbitrap-MS showed that the method removed more than 70% of matrix components. The clean-up method was validated for 170 pesticides in rye, 159 pesticides in wheat, 142 pesticides in barley, 130 pesticides in oat, and 127 pesticides in rice. Spike recovery values were 70-120% for all pesticides and the repeatability, calculated as the relative standard deviation, was less than 20%. The limits of quantitation achieved were 0.005 mg kg-1 for almost all analytes, ensuring compliance with the maximum residue limits.