Towards multi-purpose valorisation of polyphenols from grape pomace: Pressurized liquid extraction coupled to purification by membrane processes

Recent studies have demonstrated the role of certain lactones, particularly 2-nonen-4-olide, and volatile thiols (3-sulfanylhexan-1-ol) in the over ripped aromas of noble rot sweet wines (Stamatopoulos et al. 2014ab). These compounds are partly formed during the maturation and under the activity of B. cinerea on grapes. This research was carried out in the vineyard of Sauternes with aim to better understand their genesis depending on the grape over-ripening on two different soil types during 3 vintages. Thus, the study was conducted, with the Sémillon grape, during vintages 2012, 2014 & 2015, at 4 stages of over-maturation of the grapes (healthy, pourri plein, pourri roti, pourri roti + 15 days) considering two vineyard plots with different soil characteristics (calcosol & peyrosol) planted with the 315 Sémillon clone and grafted on 101-14 rootstock respectively in 1981 and 1980 and cultivated with the same vineyard management. Volatile lactones were assayed by liquid-liquid extraction followed by GC/MS analysis and the precursors of 3-sulfanylhexanol by an adaptation of the method by Capone et al. 2010 (SPE-
UPLC/FTMS).

Elemental sulfur is a fungicide used by grape growers to control the development of powdery mildew, caused by the fungus Erysiphe necator. This compound is effective, cheap and has a low toxicity with no withholding period recommended. However, high levels of S0 residues in the harvested grapes can lead to the formation of reductive sulfur compounds that can impart taints and faults to the wine. Hydrogen sulphide (H2S) is a very volatile and unpleasant sulfur compound which formation is connected to high residues of S0 in juice (10 – 100 mg/L).

From the standpoint of wine aroma oxidation there are two effects observed: aroma degradation of oxygen sensitive compounds (polyfunctional mercaptans) and the appearance of new substances with high aromatic power (acetaldehyde, methional, phenylacetaldehyde, sotolon, alkenals, isobutanal and 2, 3-metylbutanals) (1-5). According to our experience, Strecker aldehydes are compounds with highest sensory relevance in the oxidative degradation of many wines (5-7).

Light-struck taste is a defect prevalent in white wines bottled in clear glass light-exposed for a considerable amount of time leading to a loss of color and appearance of sulfur-like odors. The reaction involves riboflavin (RF), a highly photosensitive compound that undergoes to intermolecular photoreduction by the uptake of two electron equivalents from an external donor, the methionine. The reaction includes different steps forming methional which is extremely unstable and decomposes to methane thiol and acrolein. The reaction of two molecules of methane thiol yields dimethyl disulfide. Methane thiol is highly volatile, has a low perception threshold (2 to 10 µg/L in wine) and confers aroma-like rotten eggs or cabbage.

Glutathione is a tripeptide (γ-Glu-Cys-Gly), which can occur in grapes, in must and in wine prevalently in the reduced form as well as in the oxidized form as glutathione disulfide. The importance of the reduced form of glutathione lies in its antioxidant activity. In must, it limits browning by reducing o-quinones produced by polyphenol oxidase activity on hydroxycinnamic acids; in wine, it exerts a protective effect on various aromatic compounds. Glutathione concentration in wine is lower than in grape juice and variable as it depends on several factors, ranging from the native content of grapes to winemaking technique.