Strategies for sample preparation and data handling in GC-MS wine applications

Global warming is accelerating grape ripening, leading to unbalanced wines from fruit with high sugar content but poor aroma and colour development. Reducing the size of the photosynthetic apparatus after veraison has been shown to delay technological ripeness in cool climates, but methods have not been tested in areas with high irradiance and temperature where fruit exposure could have disastrous effects on berry composition. In this Cabernet-Sauvignon trial, we compared the application of an antitranspirant (pinolene), to severe canopy topping and above bunch zone leaf removal, all performed at mid-ripening, with an untouched control. We monitored the vines weekly by measuring stem water potential, gas exchange, fruit zone light exposure. We sampled berries to measure berry weight, total soluble solids, pH, titratable acidity, and the anthocyanin profile. At harvest, we assessed yield components, measured carbon isotope discrimination, rated sunburn on clusters, and produced experimental wines. We submitted harvest samples to metabolomic profiling through PFP-Q Exactive MS/MS and wines to sensory analysis. Application of the antitranspirant significantly reduced stomatal conductance and assimilation rate but did not affect the stem water potential. Inversely, leaf removal and topping increased water potential but did not affect leaf gas exchange. The late topping was the only treatment able to decrease sugar content (up to 2Bx), increase titratable acidity and pH, and improve anthocyanin content because of lower degradation of di-hydroxylated forms. Late leaf removal above the bunch zone increased lightning conditions in the canopy and produced the most significant damage on fruits. Yield components were not affected. This work suggests that late-season canopy management can effectively control ripening speeds and improve grapes and wines. Still, the effect on grape exposure in a critical time must be well balanced to avoid problems with the appropriate technique.

Water status impact in viticulture has been widely explored, as it strongly affects grapevine physiology and grape chemical composition. It is considered as a key component of vitivinicultural terroir. Most of the studies concerning grapevine water status have focused on either physiological traits, or berry compounds, or traits involved in wine quality. Here, the response of grapevine to water availability during the ripening period is assessed through non-targeted metabolomics analysis of grape berries by ultra-high resolution mass spectrometry. The grapevine water status has been assessed during 2 consecutive years (2019 & 2020), through carbon isotope discrimination on juices from berries collected at maturity (21.5 brix approx.) for 2 Vitis vinifera cv. Pinot noir (PN) and Chardonnay (CH). A total of 220 grape juices were collected from 5 countries worldwide (Italy; Argentina; France; Germany; Portugal). Measured δ13C (‰) varied from -28.73 to -22.6 for PN, and from -28.79 to -21.67 for CH. These results also clearly revealed higher water stress for the 2020 vintage. The same grape juices have been analysed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Liquid Chromatography coupled to Mass Spectrometry (LC-qTOF-MS), leading to the detection of up to 4500 CHONS containing elemental compositions, and thus likely tens of thousands of individual compounds, which include fatty acids, organic acids, peptides, phenolics, also with high levels of glycosylation. Multivariate statistical analysis revealed that up to 160 elemental compositions, covering the whole range of detected masses (100 –1000 m/z), were significantly correlated to the observed gradients of water status. Examples of chemical markers, which are representative of these complex fingerprints, include various derivatives of the known abscisic acid (ABA), such as phaesic acid or abscisic acid glucose ester, which are significantly correlated with higher water stress, regardless of the variety. Cultivar-specific behaviours could also be identified from these fingerprints. Our results provide an unprecedented representation of the metabolic diversity, which is involved in the water status regulation at the grape level, and which could contribute to a better knowledge of the grapevine mitigation strategy in a climate change context.

The reproducibility of elemental profile in wines produced across multiple vintages has been previously reported using grapes from a single scion clone of Vitis vinifera L. cv. Pinot noir. The grapevines were grown on fourteen different vineyard sites, from Oregon to southern California in the U.S.A., which span distances from approximately hundreds of meters to 1450 km, while elevations range from near sea level to nearly 500 m. In addition, sensorial (i.e. aroma, taste, and mouthfeel) and chemical (i.e. polyphenolic and volatile) differences across the different vineyard sites have also been observed among these wines at two aging time points. While strong evidence exists to support that grapes grown in different regions can produce wines with unique chemical and sensorial profiles, even when a single clone is used, the understanding of growing site characteristics that result in this reproducible differentiation continues to emerge. One hypothesis is that the elemental profile that a vineyard site imparts to the grape berries and the resulting wine is an important contributor to this differentiation in chemistry and sensory of wines. For example, various classes of enzymes that catalyze the formation of key aroma compounds or their precursors require specific metals. In this work, we begin to report correlations between elemental and volatile aroma profiles of site-specific Pinot noir wines, made under standardized winemaking conditions, that have been previously shown to be distinguished separately by these chemical analyses.

homogeneous zones by intersecting several partial zonings of major factors that influence vineyard growth. Each of them follows specific process from their corresponding disciplines. Soil zoning specifically refers to a Soil Resource Inventory map that has traditionally been generated by conventional soil mapping methods. These methods have shortcomings in reaching fine cartographic and categorical details and involve significant expenses, which undermines their applicability. A new framework named Digital Soil Mapping has introduced quantitative models by statistical techniques to establish soil-landscape relationships and is able to provide intensive scale cartography.

In the present study, a microzoning at 1:10.000 scale is generated from an initial zoning, where the conventional soil map with polytaxic map units is replaced by a new one from digital techniques that disaggregates them. The comparison between the zonings considers a quantitative evaluation of capability for each Homogeneous Terroir Unit by means of the Viticultural Quality Index and its categorization based on its distribution by map. The spatial intersection of both maps gives rise to a confusion matrix in which the flows of class variations after the substitution are assessed.

The results show a five-fold increase in the number of Homogeneous Terroir Units identified and a larger differentiation among them, evidenced by a wider range in the capability index distribution. Both elements are accompanied by an increase in the detection of areas of higher potential within previously undervalued uniform zones.These features are a direct effect of the improvements brought by Digital Soil Mapping techniques and would verify the advantages of their implementation in the Integrated Terroir zoning. Eventually, such new highly detailed terroir units would benefit precision viticulture and sustainable management practices.

Vitis vinifera L. ‘Gewürztraminer’ is a historical grape variety of Alto Adige (Südtirol), Italy, which is widely grown in the area of Tramin an der Weinstraße, but is also grown globally. It produces highly aromatic wines that are strongly influenced by the terroir of the vineyard sites where they are grown. This study looked at musts and young wines from ‘Gewürztraminer’ grapes harvested in seven distinct vineyards near Tramin and then processed at Cantina di Termeno, minimizing winemaking protocol variability. Samples were profiled using bidimensional gas chromatography–time-of-flight mass spectrometry, liquid chromatography coupled to electrochemical detection, and near-IR spectrometry. The data were subjected to Principle Component Analysis and Hierarchical Clustering Analysis. Sensory discriminant testing was undertaken using the sorting method with a semi-trained panel, and the data were processed using Multidimensional Scaling. Seven must/wine pairs could be distinguished based on their untargeted volatilome profiles and on sensory evaluation. As expected, there were greater differences in the volatile compounds between the wines than between the musts. The wines from vineyards 4 and 5 were nonetheless quite homogenous in terms of chemical and sensory analyses, as were the wines from vineyards 1 and 3. For the phenolic profile, differences were noted between the musts and wines of vineyards 2, 3, and 4, but the musts from vineyards 5 and 7 were similar. Sensory analysis showed the wines from vineyards 6 and 7 to be distinct from the rest. These results reinforce that the composition of ‘Gewürztraminer’ musts and wines is strongly determined by vineyard site, even in a small geographic area with high variability of the terroir (soil and microclimate), and that these differences are apparent in the flavours and aromas of the finished wines. Further confirmation would require a larger sample of wines, preferably from several vintages.