Reaction Mechanisms of Copper and Iron with Hydrogen Sulfide and Thiols in Model Wine

Copper and iron are known to substantially impact wine stability through oxidative, reductive or colloidal phenomena. However, the binding of metal ions to different wine components under wine conditions, and the impact of this binding on the ability of the metal ions to induce spoilage processes, is not well understood. This study surveyed a range of red and white wines for an understanding of the variability of broad metal categories within the wines. The techniques utilized included an electrochemical constant current stripping potentiometry technique (ccSP), and solid phase extraction (SPE) fractionation of wine with subsequent analysis of the metal content of each fraction by inductively coupled plasma – optical emission spectroscopy (ICP-OES).

With climate change, it is progressively more often to obtain grapes with an acceptable content in sugars or acids but with immature tannins described as green, aggressive or hard (noted as GAH onwards). During winemaking, the oenologist has to make decisions related to the elaboration of such grapes based mainly on empirical experience, given the lack of objective criteria to this concern. An increase in the chemical and sensory knowledge of immature tannins would allow managing this GAH character of grapes with the maximum possible efficiency during winemaking processes. The present work aims at isolating and identifying the group of compounds responsible for the GAH character present in wines.

During wine aging, several complex phenomena of gas transfer take place in barrels due to the wine/oak contact. The efficiency of this gas transfer varies according to oak wood’s intrinsic physical properties. This research aims to better understand oxygen transfer phenomena through dry oak staves and especially through stave gaps, in order to reevaluate the importance of barrel-making on a barrel’s supply of oxygen. Experimentation was based on the development of an innovative permeameter of laboratory scale, for which the principal operating conditions concerning applied pressure, the choice of liquid phase/gas phase, and the grain type of oak are taken into account and investigated. With a specially developed tightening system, the existing pressure at stave gaps in a barrel could be reproduced on a laboratory scale in order to estimate its influence on oxygen transfer efficiency.

Despite the extensive research performed during the last decades, the multifactorial mechanism responsible for the white wine protein haze formation is not fully characterized. Herein, a new model is proposed, which is based on the experimental identification of sulfur dioxide as a major modulating factor inducing wine protein haze upon heating. As opposed to other reducing agents, such as 2-mercaptoethanol, dithiothreitol and tris(2-carboxyethyl)phosphine hydrochloride (TCEP), the addition of SO2 to must/wine upon heating cleaves intraprotein disulfide bonds, hinders thiol-disulfide exchange during protein interactions and can lead to the formation of novel inter/intraprotein disulfide bonds. Those are eventually responsible for wine protein aggregation which follows a nucleation-growth kinetic model as shown by dynamic light scattering [1].

Wine oxidation is a problem that affects the freshness, the aromatic profile, the colour and also the mouthfeel of the wine. It mainly concerns white wines. Oxygen interactions with wine compounds lead to the phenomena cited above that are responsible for the depreciation of these wines. Barrel aging is a crucial step in the wine process because it allows many modifications as wine enrichment, colour stabilization, clarification and also a slow oxygenation of the wine. Effects of the oak barrel have to be known to prevent oxidation of the wine. We have been interested in the main antioxidant compounds released by oak barrels to the wine and we have developed an innovative method to reach directly these antioxidant compounds at the oak stave surface.