Native concentrations of α-ionone, β-ionone, and β-damascenone were studied in various authentic and commercial wines. In addition, the enantiomeric distribution of α-ionone was determined and its merits as a potential marker for aroma adulteration in wine were discussed. For extraction of volatiles, headspace solid-phase microextraction (HS-SPME) was applied, followed by heart-cut multidimensional gas chromatography coupled to tandem mass spectrometric detection for trace-level analysis. The enantioselective analysis of α-ionone was achieved with octakis(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin as the chiral selector in the separation column for gas chromatography (GC). In all the authentic wines studied, α-ionone showed a high enantiomeric ratio in favor of the (R)-enantiomer. Since an illegal addition of α-ionone in a racemic form changes the enantiomeric ratio, this ratio may serve as an adulteration marker. Concentrations varied between <LOD to 0.081 μg/L for α-ionone, <LOD to 1.0 μg/L for β-ionone, and 0.03-10.3 μg/L for β-damascenone. Commercial wines of suspiciously strong flavor yielded concentrations up to 4.6 μg/L for α-ionone, 3.6 μg/L for β-ionone, and 4.3 μg/L for β-damascenone. Elevated α- and β-ionone concentrations serve as additional indicators for a potential adulteration. In order to classify the concentrations of the analytes in the context of their odor activity in wine, odor thresholds were determined. Graphical abstract Trace-level analysis of authenticity markers in wine.
Keywords: Adulteration; Authenticity; C13-Norisoprenoids; Enantiodifferentiation; Heart-cut multidimensional gas chromatography; Odor threshold determination; Tandem mass spectrometry.