Discrimination of white wines by Raman spectroscopy coupled with chemometric methods

The grape variety Gewürztraminer is known to be affected by two physiological disorders namely berry shrivel and bunch stem necrosis. During the season 2014 we noticed a new symptomatology type of ripening disorder on the variety. The new symptom showed not all berries fallowing the normal maturation stages, but single berries remaining at a soft but green stage till harvest. The broad distribution of these so called “green berries” symptoms in different production sites of our region, caused huge damage due to the difficulty of eliminating single berries per bunch before harvesting. Therefore, the Research Centre Laimburg began to investigate the reasons and origins of this new symptom. This work shows the results of first attempts to find causes for the symptom as well as the resulting approach to mitigate symptoms. Applications of magnesium leaf fertilizer showed first promising results against this putative disorder. To study the causal effect of the green berries 30 symptomatic vineyards in 2014 have been selected for a monitoring during the season 2016. To evaluate the foliar nutrient treatment two vineyards have been selected for application of magnesium sulfate and magnesium chloride. Leaf and berry nutrient analysis, as well as the main quality parameters during ripening have been performed. As soon as “green berries” symptoms appeared, incidence and severity have been evaluated. Most of the symptomatic vineyards of the 2016 monitoring showed light to clear magnesium deficit symptoms on their foliage. Only during the seasons 2020 and 2021 “green berries” symptoms could be found in the leaf fertilizer treatment vineyards. Both seasons showed a significant effect of the magnesium treatments to reduce the incidence and severity of the symptom. It seems that the appearance of the “green berries” symptom on Gewürztraminer is correlated to a disturbed uptake of magnesium of the vines.

Climate influence on grapevine physiology is prevalent and this influence is only expected to increase with climate change. Although governed by a general determinism, climate influence on grapevine physiology may present variations according to the terroir. In addition, these site-specific differences are likely to be enhanced when climate influence is studied using farm data. Indeed, farm data integrate additional sources of variation such as a varying representativity of the conditions actually experienced in the field. Nevertheless, there is a real challenge in valuing farm data to enable grape growers to understand their own terroir and consequently adapt their practices to the local conditions. In such a context, this article proposes a framework to site-specifically study climate influence on grapevine physiology using farm data. It focuses on improving the analysis of time series of weather data. The analytical framework includes the synchronization of time series using site-specific thermal indices computed with an original method called Extended Growing Degree Days (eGDD). Synchronized time series are then analyzed using a Bayesian functional Linear regression with Sparse Steps functions (BLiSS) in order to detect site-specific periods of strong climate influence on yield development. The article focuses on temperature and rain influence on grape yield development as a case study. It uses data from three commercial vineyards respectively situated in the Bordeaux region (France), California (USA) and Israel. For all vineyards, common periods of climate influence on yield development were found. They corresponded to already known periods, for example around veraison of the year before harvest. However, the periods differed in their precise timing (e.g. before, around or after veraison), duration and correlation direction with yield. Other periods were found for only one or two vineyards and/or were not referred to in literature, for example during the winter before harvest.

In the study of terroir, a separate analysis of its many component factors can be of great help in accurately identifying a vineyard’s natural elements that impact wine quality and typicity. This research used a dedicated pluri-disciplinary approach to investigate the ecological characteristics, including geology and geographical features, of 14 vineyards that produce Gewürztraminer and Sauvignon Blanc cultivars in the alpine Alto Adige DOC wine region. Both the geopedological method using Vineyards Geological Identity (VGI) and the new Solar Radiaton Identity (SRI) topoclimatic classification method were used to provide analytical measurements and qualitative/quantitative characterisations. In addition, wide-ranging targeted and untargeted oenological and chemical analyses were carried out on grapes, musts and wines to correlate the soils’ geomineral and physical conditions with the biochemical properties of their fruits and wines. The research identified strong correlations between vineyard geo-identity and wine biofingerprint, confirming a mineral traceability of strontium rubidium ratio and some minerals distinctive to the local geology, such as K, Ca, Ag, Ba and Mn.  The study also discovered that particular geomineral and physical soil conditions of the studied vineyards are related to the different amount of amino acids, primary varietal aromas and polyphenols found in grapes, musts and wines. The research confirmed that winemaking technologies support oenological quality, although in some cases, human practices can overpower certain characteristic elements in wine, erasing the typical imprint left by the vineyards’ natural terroir, which becomes less traceable. Terroir abiotic ecological factors and vineyard identity can be classified in detail using the new VGI and SRI analysis methods to discover interrelationships between geo-pedological and topoclimatic conditions that impact wine quality. These methods are also helpful in identifying which ecological elements are exclusive to a particular vineyard or wine sub-region.

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.

A large varietal collection including over 1700 varieties was maintained in Conegliano, ITA, since the 1950s. Phenological data on a subset of 400 grape varieties including wine grapes, table grapes, and raisins were acquired at bud break, flowering, veraison, and ripening since 1964. Despite the efforts in maintaining and acquiring data over such an extensive collection, the data set has varying degrees of missing cases depending on the variety and the year. This is ubiquitous in phenology datasets with significant size and length. In this work, we evaluated four state-of-the-art methods to estimate missing values in this phenological series: k-Nearest Neighbour (kNN), Multivariate Imputation by Chained Equations (mice), MissForest, and Bidirectional Recurrent Imputation for Time Series (BRITS). For each phenological stage, we evaluated the performance of the methods in two ways. 1) On the full dataset, we randomly hold-out 10% of the true values for use as a test set and repeated the process 1000 times (Monte Carlo cross-validation). 2) On a reduced and almost complete subset of varieties, we varied the percentage of missing values from 10% to 70% by random deletion. In all cases, we evaluated the performance on the original values using normalized root mean squared error. For the full dataset we also obtained performance statistics by variety and by year. MissForest provided average errors of 17% (3 days) at budbreak, 14% (4 days) at flowering, 14.5% (7 days) at veraison, and 17% (3 days) at maturity. We completed the imputations of the Conegliano dataset, one of the world’s most extensive and varied phenological time series and a steppingstone for future climate change studies in grapes. The dataset is now ready for further analysis, and a rigorous evaluation of imputation errors is included.