IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Study of the evolution of tannins during wine aging by mass spectrometry monitoring of oxidation markers released after chemical depolymerization

Study of the evolution of tannins during wine aging by mass spectrometry monitoring of oxidation markers released after chemical depolymerization

Abstract

Among the many compounds in wine, condensed tannins play an important role in the organoleptic properties of the products; they are partly responsible for astringency, bitterness and also contribute to the color. This research work aims to study the oxidation state of these bio-heteropolymers which is an important lock in the analysis of processed products in order to better control their quality. Indeed, their identification remains at present a challenge because of the large heterogeneity of their degrees of polymerization (DP) based on 4 monomers (epicatechin, catechin, epigallocatechin, epicatechin-3-O-gallate) thus multiplying the number of oxidation products. Due to the difficulties of separation by liquid chromatography and detection by mass spectrometry of tannins with high DP1, tannins were analyzed by UHPLC-ESI-MS after chemical depolymerization. This pre-treatment of the samples allows the cleavage of the interflavanic bonds linking the constituent monomers of the tannins and gives access to the average DP and the proportions of the different monomers. However, in wines, many reactions take place from the beginning of the wine making process to its consumption. Within the tannin structures, the new covalent bonds created by oxidation are resistant to depolymerization conditions and oxidation markers (dimers and trimers) are then obtained. These structural modifications distort to a greater or lesser extent the estimation of the average DP depending on the oxidation state of the tannins. Faced with the complexity and the large number of oxidation products generated, over the last ten years a study conducted on model solutions has allowed the identification of more than one hundred oxidation markers2,3.
Thanks to the detection and identification of these oxidation markers, an in-depth study of the tannin fraction of wines has recently allowed us to understand theirs evolutions during ageing. Three Syrah wines (2018, 2014 and 2010 vintages) were analyzed. An accelerated oxidation of the 2018 vintage sample was also performed in order to evaluate the impact of this oxidation compared to the natural evolution and evaluate the ability of this oxidation to imitate natural evolution. The monitoring of 6 types of extension, extension/terminal and terminal markers at two oxidation levels was investigated. An evolution of the tannin oxidation state during ageing by the increase of the markers of the second oxidation level over the vintages was observed. In the 2018 oxidized wine sample, the first oxidation level markers are similar to the 2014 vintage but the second oxidation level markers are higher than other vintages, indicating a more advanced state of tannin oxidation. This study showed for the first time that it was possible to follow the oxidative evolution of wine tannins by monitoring some relevant dimeric tannin oxidation markers generated after chemical depolymerization.

DOI:

Publication date: June 27, 2022

Issue: IVAS 2022

Type: Poster

Authors

Mouls Laetitia1, Deshaies Stacy1, Garcia François1, Suc Lucas1 and Saucier Cédric1

1SPO, Univ Montpellier, INRAE, Institut Agro

Contact the author

Keywords

Proanthocyanidin, Flavan-3-ol, oxidation marker, wine aging

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

The interplay between grape ripening and weather anomalies – A modeling exercise

Current climate change is increasing inter- and intra-annual variability in atmospheric conditions leading to grapevine phenological shifts as well altered grape ripening and composition at ripeness. This study aims to (i) detect weather anomalies within a long-term time series, (ii) model grape ripening revealing altered traits in time to target specific ripeness thresholds for four Vitis vinifera cultivars, and (iii) establish empirical relationships between ripening and weather anomalies with forecasting purposes. The Day of the Year (DOY) to reach specific grape ripeness targets was determined from time series of sugar concentrations, total acidity and pH collected from a private company in the period 2009-2021 in North-Eastern Italy. Non-linear models for the DOY to reach the specified ripeness thresholds were assessed for model efficiency (EF) and error of prediction (RMSE) in four grapevine cultivars (Merlot, Cabernet Sauvignon, Glera and Garganega). For each vintage and cultivar, advances or delays in DOY to target specified ripeness thresholds were assessed with respect to the average ripening dynamics. Long-term meteorological series monitored at ground weather station by means of hourly air temperature and rainfall data were analyzed. Climate statistics were obtained and for each time period (month, bimester, quarter and year) weather anomalies were identified. A linear regression analysis was performed to assess a possible correlation that may exist between ripening and weather anomalies. For each cultivar, ripeness advances or delays expressed in number of days to target the specific ripening threshold were assessed in relation to registered weather anomalies and the specific reference time period in the vintage. Precipitation of the warmest month and spring quarter are key to understanding the effect of climate change on sugar ripeness. Minimum temperatures of May-June bimester and maximum temperatures of spring quarter best correlate with altered total acidity evolution and pH increment during the ripening process, respectively.

Grape must quality and mesoclimatic variability in Fruška Gora wine-growing region, Serbia

The Fruška Gora mountain is a traditional wine-growing region in Serbia situated in the Pannonian Basin. Due to such a position, the vicinity of the Danube River and the presence of concave configuration, it is suitable for grape production. This paper provides analyses of spatial variations in meteorological parameters and grape juice quality within Fruška Gora wine region over three consecutive vintages (2018-2020). The examined period can be defined as warm with cool nights during September (AVG 18,9°C; GDD 1918°C; CI 12°CF) and with the presence of mesoclimatic variability. The East part of the study area was somewhat drier and hotter compared to other parts of the region. The analyses of grape must samples (190 in total) of five cultivars (Cabernet-Sauvignon, Merlot, Chardonnay, Sauvignon blanc and Grašac (Welschriesling)) commonly grown across the region (19 sites), were performed using Fourier Transform Infrared Technology (FTIR). Among all cultivars, Sauvignon blanc was harvested first in the East area (DOY=246±5, GDD at harvest=1552±74, 22.2±0.7 °Brix), while the latest harvest was recorded for Cabernet-Sauvignon in the West (DOY=283±5, GDD at harvest=1936±187, 23.4±1.0 °Brix ). Both the red and white cultivars had higher acidity and YAN in the grape must if the vines were grown in the North and East compared to South and West areas. According to PCA analysis, Grašac showed the lowest variation in grape must chemical composition. Thus, the results confirm that Grašac is the most stable cultivar in Fruška Gora. All monitored cultivars reached technological fruit ripeness by the end of the growing season. However, it was difficult to reach full ripeness of red cultivars, mostly beacuse of uncoupling of technolocical and phenolic ripeness. Thus, Cabernet-Sauvignon had higher variations in GDD sums at harvest compared to other cultivars, which probably increased variations in grape must quality.

Evaluation of climate change impacts at the Portuguese Dão terroir over the last decades: observed effects on bioclimatic indices and grapevine phenology

In the last decades the growers of the Portuguese Dão winegrowing region (center of Portugal) are experiencing changes in climate that are influencing either grape phenology berry health and ripening. Aiming to study the relationships between climate indices (CI), seasonal weather and grapevine phenology, in this work long-term climate and phenological data collected at the experimental vineyard of the Portuguese Dão research centre between 1958 and 2019 (61 years) for the red variety Touriga Nacional, was analyzed. The trends over time for the classical temperature-based indices (Growing Season Temperature – GST -, Growing Degree Days – GDD, Huglin Index – HI and Cool Night Index – CI) presented a significantly positive slope while the Dryness Index (DI) showed a negative trend over the last 61 years. Regarding grapevine phenology, an average advance of 4.5 days per decade in the harvest day was observed throughout the last 61 years. Consequently, the weather conditions during the ripening period have changed, showing an increasing trend over time in the average temperature (higher magnitude in the maximum than in the minimum temperature) and a decrease in the accumulated rainfall. A regression analysis showed that ~50% of harvest date variability over years was explained by the temperature-based indices variability. These observed effects of climate change on bioclimatic indices and corresponding anticipation of harvest date can still be considered advantageous for the Dão terroir as it allows to achieve an optimal berry ripening before the common equinox rains and, therefore, avoid the potential negative impacts of the rainfall on berry health and composition.

Mapping and tracking canopy size with VitiCanopy

Understanding vineyard variability to target management strategies, apply inputs efficiently and deliver consistent grape quality to the winery is essential. However, despite inherent vineyard variability, the majority are managed as if they are uniform. VitiCanopy is a simple, grower-friendly tool for precision/digital viticulture that allows users to collect and interpret objective spatial information about vineyard performance. After four years of field and market research, an upgraded VitiCanopy has been created to achieve a more streamlined, technology-assisted vine monitoring tool that provides users with a set of superior new features, which could significantly improve the way users monitor their grapevines. These new features include:
• New user interface
• User authentication
• Batch analysis of multiple images
• Ease the learning curve through enhanced help features
• Reporting via the creation of colour maps that will allow users to assess the spatial differences in canopies within a vineyard.
Use-case examples are presented to demonstrate the quantification and mapping of vineyard variability through objective canopy measurements, ground-truthing of remotely sensed measurements, monitoring of crop conditions, implementation of disease and water management decisions as well as creating a history of each site to forecast quality. This intelligent tool allows users to manage grapevines and make informed management choices to achieve the desired production targets and remain profitable.

Variations of soil attributes in vineyards influence their reflectance spectra

Knowledge on the reflectance spectrum of soil is potentially useful since it carries information on soil chemical composition that can be used to the planning of agricultural practices. If compared with analytical methods such as conventional chemical analysis, reflectance measurement provides non-destructive, economic, near real-time data. This paper reports results from reflectance measurements performed by spectroradiometry on soils from two vineyards in south Brazil. The vineyards are close to each other, are on different geological formations, but were subjected to the same management. The objective was to detect spectral differences between the two areas, correlating these differences to variations in their chemical composition, to assess the technique’s potential to predict soil attributes from reflectance data.To that end, soil samples were collected from ten selected vine parcels. Chemical analysis yield data on concentration of twenty-one soil attributes, and spectroradiometry was performed on samples. Chemical differences significant to a 95% confidence level between the two studied areas were found for six soil attributes, and the average reflectance spectra were separated by this same level along most of the observed spectral domain. Correlations between soil reflectance and concentrations of soil attributes were looked for, and for ten soil traits it was possible to define wavelength domains were reflectance and concentrations are correlated to confidence levels from 95% to 99%. Partial Least Squares Regression (PLSR) analyses were performed comparing measured and predicted concentrations, and for fifteen out of 21 soil traits we found Pearson correlation coefficients r > 0.8. These preliminary results, which have to be validated, suggest that variations of concentration in the investigated soil attributes induce differences in reflectance that can be detected by spectroradiometry. Applications of these observations include the assessment of the chemical content of soils by spectroradiometry as a fast, low-cost alternative to chemical analytical methods.