Thiol precursors in Catarratto Bianco Comune and Grillo grapes and effect of clarification conditions on the release of varietal thiols in wine

Background and aims: Varietal thiols characterize the typical aroma of several white wines, as Sauvignon blanc. Their presence was suggested in two Sicilian grape cultivars, Catarratto Bianco Comune (CBC) and Grillo, thought it was not analytically proved to date. Methods and Results: Varietal thiol precursors and free varietal thiols were assessed in CBC and Grillo grapes, musts and wines by UPLC/high resolution mass spectrometry (HRMS). The isobaric compounds S-3-(hexanal)-glutathione (GSH-3MHAl) and S-3-(4-mercapto-4-methylpentan-2-one)-glutathione (GSH-4MMP) were discriminated by comparing their accurate masses and HR-MS/MS spectra with those of their synthetic standards. GSH-3MHAl, S-3-(hexan-1-ol)-glutathione (GSH-3MH) and S-3-(hexan-1-ol)-cysteine occurred in grape, must and wine, while GSH-4MMP and its hydrolysed forms did not. Their amounts decreased during the industrial winemaking processes, mostly following the grape pressing. We compared clarification conditions exposing must to either air or CO2 in terms of thiol precursors\u2019 and free thiols\u2019 content in wine. However, negligible differences were observed. Concentrations of free thiols in the range 400\u20131100 ng/L were found in the wines and they were not affected to the two clarification conditions adopted. Conclusion: The isobaric GSH-3MHAl and GSH-4MMP were clearly distinguished for the first time by UPLC-HRMS through their retention times and MS spectra. The varietal thiols were firstly revealed CBC and Grillo wines. The air-free and air- exposed clarification poorly affected the levels of varietal thiols. Significance of the study: This research highlights the major impact of the varietal thiols (mainly 3\u2013mercapto-hexan-1-ol and its acetate form) on the sensory properties of CBC and Grillo wines