VOLATILE COMPOSITION OF WINES USING A GC/TOFMS: HS-SPME VS MICRO LLE AS SAMPLE PREPARATION METHODOLOGY

It is well known that the vinification of grapes at full maturation can produce rich, full-bodied wines,
with intense and complex flavour profiles. However, the juice obtained from such grapes may have very
high sugar concentration, resulting in wines with an excessive concentration of ethanol. In addition, the decoupling between technological maturity and phenolic/aromatic one due to global warming, exacerbates this problem in some wine-growing regions. In parallel with the increase of the mean alcohol content of wines on the market, also the demand for reduced alcohol beverages has increased in recent years, mainly as a result of health and social concerns about the risks related to the consumption of alcohol.

In a recent study several genes controlling the acidification properties of the wine yeast Saccharomyces cerevisiae have been identified by a QTL approach [1]. Many of these genes showed allelic variations that affect the metabolism of malic acid and the pH homeostasis during the alcoholic fermentation. Such alleles have been used for driving genetic selection of new S. cerevisiae starters that may conversely acidify or deacidify the wine by producing or consuming large amount of malic acid [2]. This particular feature drastically modulates the final pH of wine with difference of 0.5 units between the two groups.

Barrel fermentation and barrel-ageing of wine are commonly utilised practices in premium wine production. The wine aroma compounds related to barrel contact are varied and can enhance a range of wine aromas and flavours, such as ‘struck flint’, ‘caramel’, ‘red berry’, ‘toasty’ and ‘nutty’, as well as conventional oaky characters such as ‘vanilla’, ‘spice’, ‘smoky’ and ‘coconut’. A survey of commercially produced premium Shiraz, Cabernet Sauvignon, Pinot Noir and Chardonnay wines was conducted, assessing the prevalence of compounds that have been proposed as barrel-ageing markers¹ including oak lactones, volatile phenols, furanones, aldehydes, thiazoles2,3, phenylmethanethiol⁴ and 2-furylmethanethiol.⁵

Malic acid has a strong impact on wine pH and the contribution of fermenting yeasts to modulate its concentration has been intensively investigated in the past. Recent advances in yeast genetics have shed light on the unexpected property of some strains to produce large amounts of malic acid (“acidic strains”) while most of the wine starters consume it during the alcoholic fermentation. Being a key metabolite of the central carbohydrate metabolism, malic acid participates to TCA and glyoxylate cycles as well as neoglucogenesis. Although present at important concentrations in grape juice, the metabolic fate of malic acid has been poorly investigated.

According to winemakers, wine experts and sommeliers, aromas of wet stone, mineral, struck match and flint in white wines styles, such as those produced from Vitis vinifera L. cv. Chardonnay, are considered to be hallmarks of positive reduction.1,2 In recent years, the production of Chardonnay styles defined by aroma characteristics related to positive reduction has become more desirable among wine experts and consumers. The chemical basis of positive reduction is thought to originate from the concentration of specific volatile sulfur compounds (VSCs), including methanethiol (MeSH) imparting mineral and chalk notes,3 and benzenemethanethiol (BMT) responsible for struck match and flint.1,4