Non-invasive headspace sorptive extraction for monitoring volatile compounds production by saccharomyces and non-saccharomyces strains throughout alcoholic fermentation

Céline Sparrow a, Christophe Morge a, a SOFRALAB SAS, 79, av. A.A. Thévenet – CS 11031 – 51530 Magenta, France Consumers’ health and security force authorities to limit, in wine as in others food industry products, the concentration in « dangerous » molecules. Therefore the legal limit in heavy metals keeps on decreasing. As per proof EU regulation just decrease the stain concentration in wine from 0,2 to 0,15 mg/l. Certain changes , such as sodium arsenite treatment in vines, disappearance of brass in wineries to the benefit of stainless steel, limit even more the concentration of heavy metals in wines. But the use of copper derivates in vines treatments is difficult to replace. In the case of wine and its elaboration, the problem is even more complex. Indeed, regulation forces the wine producers to control the concentration of certain heavy metals in final wines.

Comprehensive two-dimensional gas chromatography (GCxGC) has emerged as a powerful analytical technique for unraveling the volatile composition of complex matrices. This work will present three applications of GCxGC Tof-MS to the oenological field, aimed to identify novel biomarkers to be used in the quality control process of the wine industry. Comprehensive mapping of volatile compounds was conducted in a large sample of 70 sparkling wines, produced by 48 different wineries across 6 vintages and representative of the two main production areas for premium Italian sparkling wines (Franciacorta (FC) and Trentodoc (TN)), using HS-SPME followed by GCxGC-Tof-MS and multivariate analysis. Selection and identification of 196 putative biomarkers allowed clear separation of sparkling wines from FC and TN.

Bacterial malolactic fermentation (MLF) has a considerable impact on wine quality. The yeast strain used for primary fermentation can consistently stimulate (MLF+ phenotype) or inhibit (MLF- phenotype) malolactic bacteria and the MLF process as a function of numerous winemaking practices, but the molecular evidence behind still remains a mystery. In this study, such evidence was elucidated by the direct comparison of extracellular metabolic profiles of MLF+ and MLF- yeast phenotypes. Untargeted metabolomics combining ultrahigh-resolution FT-ICR-MS analysis, powerful machine learning methods and a comprehensive wine metabolite database, discovered around 800 putative biomarkers and 2500 unknown masses involved in phenotypic distinction.

Recent studies have demonstrated the role of certain lactones, particularly 2-nonen-4-olide, and volatile thiols (3-sulfanylhexan-1-ol) in the over ripped aromas of noble rot sweet wines (Stamatopoulos et al. 2014ab). These compounds are partly formed during the maturation and under the activity of B. cinerea on grapes. This research was carried out in the vineyard of Sauternes with aim to better understand their genesis depending on the grape over-ripening on two different soil types during 3 vintages. Thus, the study was conducted, with the Sémillon grape, during vintages 2012, 2014 & 2015, at 4 stages of over-maturation of the grapes (healthy, pourri plein, pourri roti, pourri roti + 15 days) considering two vineyard plots with different soil characteristics (calcosol & peyrosol) planted with the 315 Sémillon clone and grafted on 101-14 rootstock respectively in 1981 and 1980 and cultivated with the same vineyard management. Volatile lactones were assayed by liquid-liquid extraction followed by GC/MS analysis and the precursors of 3-sulfanylhexanol by an adaptation of the method by Capone et al. 2010 (SPE-
UPLC/FTMS).

Tyrosol (TYR) and hydroxytyrosol (HYT) are bioactive phenols present in olive oil and wine, basic elements of the Mediterranean diet. TYR is reported in the literature for its interesting antioxidant, cardioprotective and anti-inflammatory properties. In wine, its concentration can reach values as high as about 40 mg/L
[Pour Nikfardjam et al. 2007] but, more frequently, this phenol – derived from yeast metabolism of tyrosine during fermentation – is present at lower levels, generally higher in red wines compared to whites. HYT was measured for the first time by Di Tommaso et al. [1998] in Italian wines – with maximum values of 4.20 mg/L and 1.92 mg/L for red and white wines, respectively – while definitely lower concentrations have been found later in Greek samples.