Chemometrical development and comprehensive validation of a solid phase microextraction/gas chromatography–mass spectrometry methodology for the determination of important free and bound primary aromatics in Greek wines

In this work, a solid-phase microextraction/gas chromatography–mass spectrometry (SPME/GC–MS) methodology was developed for the determination of 21 free and glycosidically-bound volatile varietal aroma compounds in wines. Initially, a comparison was made of 5 commercially available SPME fibers for the isolation/preconcentration of the target compounds in the headspace (HS) and direct immersion (DI) modes. The statistical significance of the microextraction variables was evaluated using a 2-level Plackett–Burman experimental design; the most significant variables were further optimized using a modified Simplex procedure. Using the selected conditions, a GC–MS method was fully validated for the quantitative determination of the 21 free primary aroma compounds. The hydrophilic bound precursors were isolated by solid-phase extraction (SPE), enzymatically hydrolyzed to liberate them as the free compounds and further detected by SPME/GC–MS. The method has been successfully applied to the analysis of 20 Greek white wine samples.