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…

Effects of graft quality on growth and grapevine-water relations

Climate change is challenging viticulture worldwide compromising its sustainability due to warmer temperatures and the increased frequency of extreme events. Grafting Vitis vinifera L.

Estimating bulk stomatal conductance of grapevine canopies

In response to changes in their environment, grapevines regulate transpiration using various physiological mechanisms that alter conductance of water through the soil-plant-atmosphere continuum. Expressed as bulk stomatal conductance at the canopy scale, it varies diurnally in response to changes in vapor pressure deficit and net radiation, and over the season to changes in soil water deficits and hydraulic conductivity of both soil and plant. It is necessary to characterize the response of conductance to these variables to better model how vine transpiration also responds to these variables. Furthermore, to be relevant for vineyard-scale modeling, conductance is best characterized using data collected in a vineyard setting. Applying a crop canopy energy flux model developed by Shuttleworth and Wallace, bulk stomatal conductance was estimated using measurements of individual vine sap flow, temperature and humidity within the vine canopy, and estimates of net radiation absorbed by the vine canopy. These measurements were taken on several vines in a non-irrigated vineyard in Bordeaux France, using equipment that did not interfere with ongoing vineyard operations. An inverted Penman-Monteith equation was then used to calculate bulk stomatal conductance on 15-minute intervals from July to mid-September 2020. Time-series plots show significant diurnal variation and seasonal decreases in conductance, with overall values similar to those in the literature. Global sensitivity analysis using non-parametric regression found transpiration flux and vapor pressure deficit to be the most important input variables to the calculation of bulk stomatal conductance, with absorbed net radiation and bulk boundary layer conductance being much less important. Conversely, bulk stomatal conductance was one of the most important inputs when calculating vine transpiration, further emphasizing the need for characterizing its response to environmental changes for use in vineyard water use modeling.

Spatial variability of temperature is linked to grape composition variability in the Saint-Emilion winegrowing area

Elevated temperature during the grape maturation period is a major threat for grape quality and thus wine quality. Therefore, characterizing the grape composition response to temperature at a larger scale would represent a crucial step towards adaptation to climate change. In response to changes in temperature, various physiological mechanisms regulate grape composition. Primary and secondary metabolisms are both involved in this response, with well-known effects, for example on anthocyanins, and lesser known effects, for example on aromas or aroma precursors. At the field scale or at the regional scale, however, numerous environmental or plant-specific factors intervene to make the effects of temperature difficult to distinguish from overall variability. In this study, it was attempted to overcome this difficulty by selecting well-characterized situations with differing temperatures.
A long-term study of air temperature variability across several Merlot vineyards in the Saint-Emilion and Pomerol wine producing area found significant temperature differences and gradients at various time scales linked to environmental factors. From this study area, a few sites were selected with similar age, soil and training system conditions, and with repeated and contrasted temperature differences during the maturation period. The average temperature difference during the maturation period was about 2°C between cooler and warmer sites, a difference similar to that expected under future climate change scenarios. In close vicinity to the temperature sensors at each site, grape berries were sampled at different times until full maturity during 2019 and 2020. Also, berries from bunches on either side of the row were analyzed separately, allowing an investigation of bunch exposure effect associated with the coupling of berry temperature and solar radiation. Four replicates of pooled berries for each time – site – bunch exposure combination were obtained and analyzed for biochemical composition. Analyses of variance of the biochemical composition data collected at different sampling times reveal significant effects associated with temperature, site, and bunch azimuth. For instance, anthocyanins in grape skins are clearly influenced by temperature and solar radiation exposure, with up to 30% reduction in warmer conditions.

Photoselective shade films affect grapevine berry secondary metabolism and wine composition

Grapevine physiology and production are challenged by forecasted increases in temperature and water deficits. Within this scenario, photoselective overhead shade films are promising tools in warm viticulture areas to overcome climate change related factors. The aim of this study was to evaluate the vulnerability of ‘Cabernet Sauvignon’ grape berry to solar radiation overexposure and optimize shade film use for berry integrity. A randomized complete block design field study was conducted across two years (2020-2021) in Oakville, Napa Valley, CA, with four shade films (D1, D3, D4, D5) differing in the percent of radiation spectra transmitted and compared to an uncovered control (C0). Integrals for gas exchange parameters and mid-day stem water potential were unaffected by the shade films in 2020 and 2021. By harvest, berries from uncovered and shaded vines did not differ in their size or primary metabolism in either year. Despite precipitation exclusion during the dormant season in the shaded treatments, yield did not differ between them and the control in either season. In 2020, total skin anthocyanins (mg/g fresh mass) in the shaded treatments was greater than C0 during berry ripening and at harvest. Conversely, flavonol concentrations in 2020 were reduced in shaded vines compared to C0. The 2020 growing season highlighted the impact of heat degradation on flavonoids. Flavonoid concentrations in 2021 increased until harvest while flavonoid degradation was apparent from veraison to harvest in 2020 across shaded and control vines. Wine analyses highlighted the importance of light spectra to modify wine composition. Wine color intensity, tonality and anthocyanin values were enhanced in D4 whereas antioxidant properties were enhanced in C0 and D5 wines. Altogether, our results highlighted the need of new approaches in warm viticulture areas given the impact that composition of light has on berry and wine quality.

Climate change impacts on Douro Region viticulture and adaptation measures

Climate has a significant impact in the success of any agricultural system, with a direct influence on the crops suitability to a given region, interfering on yield and quality and also with the economic sustainability of the productive activity. In the Douro Demarcated Region (RDD), as in most regions of the Mediterranean climate, the scarce precipitation (33% has less than 600 mm per year), and your high variability, associated with high rates of evapotranspiration during the summer, is usually one of the fundamental factors that limit the grapevine development, as well as the production and quality of the harvest. Thus, facing the scenario in temperature changes for the next decades (1.5-2.5°C) and confirming the predictions of precipitation decreases and/or great variability in the occurrence of heat waves and intense rainfall, the consequences for slope stability in mountain viticulture and sustainability of all operations involved, are risks to be taken into account. In this way, a deepest and sustained knowledge regarding the adaptation measures to adverse environmental conditions is of a crucial importance, enabling a more efficient adaptation of plant growth conditions and the optimization of production and quality of the grapevines. The development of this work, carried out in two commercial vineyards, one located in Soutelo do Douro, São João da Pesqueira, Cima Corgo sub-region, and another located in Numão, Vila Nova de Foz Côa, Douro Superior sub-region, it seeks to establish a relationship between climatic elements and physiological, productive and qualitative parameters, as well as to evaluate the effectiveness of adaptation measures, including different types of deficit irrigation (2002-2019) and the application of shading nets (2019-2020) in the physiological, viticultural and oenological behavior in the Touriga Nacional and Moscatel Galego Branco varieties, respectively. The results showed that the application of deficit irrigation allowed to significantly reduce the impact of the adverse weather conditions at key moments in the development of the grapevine, particularly in the period immediately before veráison and maturation, reducing the negative effects on the physiological processes and productivity, without compromise the must quality parameters. On the other hand, the application of shading nets significantly reduced de leaves temperature, allowing to increase the water potential, stomatal conductance and photosynthetic rate of grapes, which was reflected in the yield increase in the 2nd year of the study. For the maturation indicators, higher levels of total acidity, malic acid and assimilable nitrogen were obtained. The last measure presents a huge potential, being essential to carry out more years of trials to obtain stronger conclusions in terms of production parameters, but also in characteristics as important as the grape ripening components and the organoleptic characteristics of wines.