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

Wine is a widely consumed alcoholic beverage with a high commercial value. More specifically, the worldwide consumption of rosé wine has increased by 20% since 2002[1]. But because of its high commercial value, it can become a subject of fraud, and authenticity control is necessarily required. More than one hundred polyphenols have been recently quantified in various rosé wines [2]. They are key components defining color, taste and quality of wines. Their amount and composition depend on many different factors such as grape variety, winemaking and age of the wine. In this study, the influence of geographic origin of some rosé French wines was investigated. An original and very fast UPLC-QTOF-MS method was developed and used to predict the geographic origin authenticity of rosé wines.

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).

The chemical mechanisms involved in oxidation/reduction potential of wine during winemaking and aging are affecting its color, aroma and taste. Chemical oxidation is one of the major causes of development of off-flavors during ageing1. Thus, the chemical changes in wine during storage should be controlled to ensure the sensory quality of the product and avoid consumer rejection that will compromise the economic value of the product. The 1-hydroxyethyl radical has been recognized as the key radical intermediate in the oxidative reactions in wine2. Based on the kinetic study of POBN-1-hydroxyethyl spin adduct formation in wines initiated via the Fenton reaction, a novel tool was recently developed in our laboratory to quantify the resistance of wines against oxidation3.

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].

Barrel ageing is a crucial step in the wine process because it allows many changes to the wine as enrichment, colour stabilization, clarification and also a slow oxygenation. Effects of the oak barrel have to be known to prevent oxidation of the wine. The type of bung used during ageing is also a parameter to consider. Ageing sweet wines in barrel is a real challenge. These wines may need some oxygen at the beginning of ageing but they should be protected at the end of their maturation, to avoid oxidation.