THE EFFECT OF COPPER ON THE PRODUCTION OF VARIETAL THIOLS DURING THE ALCOHOLIC FERMENTATION OF COLOMBARD AND GROS MANSENG GRAPE JUICES

Abstract

Nowadays, the rapid growth of vineyards with organic practices and the use of copper as the only fungicide against downy mildew raises again the question of the effect of copper on varietal thiols in wine, especially 3-sulfanylhexan-1-ol (3SH) and its acetate (3SHA). A few decades ago, several works indicated that the use of copper in the vineyard had a negative effect on the content of varietal thiols in Sauvignon blanc wines [1, 2]. However, these studies only considered the concentration of the reduced form (RSH) of varietal thiols, without quantifying the oxidised ones. For this purpose, we proposed to monitor both reduced and oxidised forms of varietal thiols in wine under copper stress during alcoholic fermentation to have a more complete picture of the biological and chemical mechanisms. In the present work, Colombard and Gros Manseng grape juices were fermented under different copper levels (from 0.2 to 3.88 mg/L) to mimic the consequences of organic practices on grape and must. The consumption of thiol precursors and the release of varietal thiols (both free and oxidised forms of 3SH and 3SHA) were monitored by LC-MS/MS according to previously published methods [3, 4]. It was found that the highest copper content (3.6 and 3.88 mg/L for Colombard and Gros Manseng, respectively) significantly increased yeast consumption of precursors (by 9.0 and 7.6% for Colombard and Gros Manseng, respectively). Surprisingly, this higher consumption of precursors was not associated to higher thiol concentrations. Indeed, for both varieties, the content of free thiols in the wine decreased significantly (by 84 and 47% for Colombard and Gros Manseng, respectively) with the increase of copper in the starting must, as already described in the literature [1, 2]. However, the sum “reduced+oxidized” forms of 3SH produced during fermentation was constant for the Colombard must regardless of the copper conditions, which means that the effect of copper was only oxidative for this variety. In Gros Manseng, on the other hand, the sum “reduced+oxidized” forms of 3SH increased with the copper content, up to 90%. This last result suggests that copper probably modifies the regulation of the production pathways of varietal thiols and has also a key role of oxidation. These results complement our knowledge on the effect of copper during thiol-oriented fermentation and the importance of considering both “reduced+oxidized” forms to distinguish chemical from biological effects.