Thanks to their low odor detection thresholds, free varietal thiols (VTs) play a key role in the primary aroma of wines, to which they confer an intense scent reminiscent of box tree, grapefruit, citrus fruits, passionfruit and cat urine odor. Excluding wines from a few VT-rich grapevine cultivars, VTs appear to be present in most cultivars at trace levels, although a comprehensive dataset is still missing. The low concentration of VTs combined with their high reactivity and matrix complexity make their determination in wines a challenging task. In this research an optimized liquid chromatography – tandem mass spectrometry (LC-MS/MS) method was validated and used for the quantification of 4-methyl-4-sulfanylpentan-2-one (4-MSP), 3-sulfanylhexan-1-ol (3-SH), 3-sulfanylhexyl acetate (3-SHA) and ethyl 3-sulfanylpropionate (E3SP) in 246 samples (vintage 2019) representative of 18 monovarietal Italian white wines. VTs were detected in all cultivars even though higher values of 3-SH were found in Lugana, Müller-Thurgau and Verdicchio cultivars. Müller-Thurgau wines showed the highest level of 4- MSP, that was mainly correlated to the odor descriptors of passionfruit and box tree/cat urine. The VTs composition of Müller-Thurgau was confirmed on a second set of 50 wines from different vintages. From a sensory perspective, the samples of Müller-Thurgau showed the best positive correlations between chemical variables and the odor descriptors thiol note, passion fruit and box tree/cat urine. These notes are significantly related to 4-MSP, suggesting that it could play a relevant olfactory role for the aroma of Müller-Thurgau wines. Sorting analysis allowed to group these wines according to their thiolic characteristics. The chemical variables and the odor descriptors attributable to the thiol notes are important for Müller-Thurgau and Lugana wines, while the contribution of thiol notes was sensorially negligible for the other wines.
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