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

Wine aroma is influenced by several viticultural and oenological factors. In this study we used experimental wine making in a full factorial design to determine the impact of grapevine age, must turbidity, and yeast strain on the aroma of Vitis vinifera L. cv. Riesling wines. A recently developed, non-targeted SPME-GC-MS fingerprinting approach for wine volatiles was used. This approach includes the segmentation and mathematical transformation of chromatograms in combination with Parallel Factor Analysis (PARAFAC) and subsequent deconvolution of important chromatogram segments.

Among red wines ethyl esters, those from short hydroxylated and branched-chain aliphatic acids constitute a family with a particular behavior and sensory importance. They have been previously discussed in the literature [1] and recent studies have established that some of them were strongly involved in of red wines’ fruity aroma [2]. As some among them have an asymmetrical carbon atom, it seemed important to separate their different enantiomers to obtain an accurate assessment of their organoleptic impact. Three chiral esters have been identified, presenting alkyl and/or hydroxyle substituants: ethyl 2-hydroxy-4-methylpentanoate, ethyl 2-methylbutanoate, and ethyl 3-hydroxybutanoate.

Vineyard exposure to smoke can lead to grapes and wine which exhibit objectionable smoky and ashy aromas and flavours, more commonly known as ‘smoke taint’ [1, 2]. In the last decade, significant bushfires have occurred around the world, including near wine regions in Australia, Canada, South Africa and the USA, as a consequence of the warmer, drier conditions associated with climate change. Considerable research has subsequently been undertaken to determine the chemical, sensory and physiological consequences of grapevine exposure to smoke. The sensory attributes associated with smoke-tainted wine have been linked to the presence of several smoke-derived volatile phenols, such as guaiacols, syringols and cresols [2].

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).

The composition of wine is largely determined by the composition of pre-fermentation juice, which is influenced by extraction of grape components. Different grape harvesting and processing conditions could affect the extraction of grape components into juice. Among these grape components, pathogenesis-related (PR) proteins are of great concern for white wine maker as they are the main cause of haze formation in finished white wine. If not removed before bottling, these PR proteins may progress into haze through the formation of complex with phenolics under certain conditions. Thaumatin-like proteins (TLPs) and chitinases are the main constituents of PR proteins found in protein haze.