Analytical method for fast screening and confirmation of multi-class veterinary drug residues in fish and shrimp by LC-MS/MS.

A multi-class, multi-residue analytical method based on LC-MS/MS detection was developed for the screening and confirmation of 28 veterinary drug and metabolite residues in flatfish, shrimp and eel. The chosen veterinary drugs are prohibited or unauthorised compounds in Korea, which were categorised into various chemical classes including nitroimidazoles, benzimidazoles, sulfones, quinolones, macrolides, phenothiazines, pyrethroids and others. To achieve fast and simultaneous extraction of various analytes, a simple and generic liquid extraction procedure using EDTA-ammonium acetate buffer and acetonitrile, without further clean-up steps, was applied to sample preparation. The final extracts were analysed by ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The method was validated for each compound in each matrix at three different concentrations (5, 10 and 20 ng g(-1)) in accordance with Codex guidelines (CAC/GL 71-2009). For most compounds, the recoveries were in the range of 60-110%, and precision, expressed as the relative standard deviation (RSD), was in the range of 5-15%. The detection capabilities (CCßs) were below or equal to 5 ng g(-1), which indicates that the developed method is sufficient to detect illegal fishery products containing the target compounds above the residue limit (10 ng g(-1)) of the new regulatory system (Positive List System - PLS).

Highly sensitive electromembrane extraction for the determination of volatile organic compound metabolites in dried urine spot.

Electromembrane extraction coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for determination of ten volatile organic compound metabolites in dried urine spot samples. The dried urine spot approach is a convenient and economical sampling method, wherein urine is spotted onto a filter paper and dried. This method requires only a small amount of sample, but the analysis sometimes suffers from low sensitivity, which can lead to analytical problems in the detection of minor components in samples. The newly developed dried urine spot analysis using electromembrane extraction exhibited improved sensitivity and extraction, and enrichment of the sample was rapidly achieved in one step by applying an electric field. Aliquots of urine were spotted onto Bond Elut DMS cards and dried at room temperature. After drying, the punched out dried urine spot was eluted with water. Volatile organic compound metabolites were extracted from the sample through a supported liquid membrane into an alkaline acceptor solution inside the lumen of a hollow fiber with the help of an electric potential. The optimum extraction conditions were determined by using design of experiments (fractional factorial design and response surface methodology). Satisfactory sensitivity was achieved and the limits of quantification (LOQ) obtained were lower than the regulatory threshold limits. The method was validated by assessing the linearity, precision, accuracy, recovery, reproducibility, stability, and matrix effects. The results were acceptable, and the developed method was successfully applied to biological exposure monitoring of volatile organic compound metabolites in fifty human urine samples.