Macrowine 2021
IVES 9 IVES Conference Series 9 Macrowine 9 Macrowine 2021 9 Chemical diversity of 'special' wine styles: fortified wines, passito style, botrytized and ice wines, orange wines, sparkling wines 9 Identification and quantification of molecular ellagitannins in cognac eaux-de-vie by a mass spectrometry method: barrel toasting and aging impact

Identification and quantification of molecular ellagitannins in cognac eaux-de-vie by a mass spectrometry method: barrel toasting and aging impact

Abstract

AIM: Ellagitannins are the main oak wood phenolic compounds that contribute to wine and spirits organoleptic quality (color, astringency, bitterness)(1-3). Given the lack of knowledge regarding their composition and evolution in spirits, the objectives were to follow their extraction kinetic in Cognac “eaux-de-vie” matured in barrel representing different toasting and to observe their evolution and structural modifications during aging.

METHODS: Eight different toasting levels were used for studying the impact of the toasting on ellagitannins composition. Two verticals (1978-2018) of “eaux-de-vie” samples coming from two terroirs were analyzed in order to observe ellagitannins evolution during aging. The above analyses were conducted using HPLC-Triple Quadrupole mass spectrometer (4) and the unknown compounds were identified by UPLC-Q-TOF, purified by preparative HPLC prior to 1D/2D-NMR analysis.

RESULTS: A general trend between the toasting levels and the individual ellagitannins content and composition was observed. Indeed “Eau-de-vie” aged in light toasted barrel has 40% higher castalagin content than in high toasting. During spirit aging, native ellagitannins content decreases over time. After two years, only castalagin remains quantifiable, suggesting that they undergo transformations leading to the formation of new compounds. Among them, whisky tannin B and A ([M-H]- ion peak at m/z 977.0896 and m/z 675.0834 respectively), resulting from the ethanol/castalagin or castalin reaction as well as some ellagitannin oxidation products like dehydrocastalagin and dehydroroburin D were identified for the first time in Cognac “eaux-de-vie” samples. The kinetic of the above compounds is in progress and the influence of both aging and barrel toasting is being researched.

CONCLUSIONS:

This work brings new insights on the Cognac ellagitannins content and how these molecules are influenced by aging and barrel toasting. Tastings will be performed to understand the organoleptic impact of these compounds.

DOI:

Publication date: September 15, 2021

Issue: Macrowine 2021

Type: Article

Authors

Mathilde Gadrat, Joel Lavergne, Catherine Emo, Pierre-Louis Teissedre, Kléopatra Chira,

1. Unité de recherche Œnologie, EA 4577, USC 1366 INRAE, ISVV, Univ. Bordeaux, Bordeaux INP, F33882 Villenave d’Ornon France 
2.   Courvoisier SAS, 2 places du château, 16200 Jarnac, France ,
Unité de recherche Œnologie, EA 4577, USC 1366 INRAE, ISVV, Univ. Bordeaux, Bordeaux INP, F33882 Villenave d’Ornon France 

Contact the author

Keywords

cognac, ellagitannins, mass spectrometry, toasting

Citation

Related articles…

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.

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.

Using δ13C and hydroscapes as a tool for discriminating cultivar specific drought response

Measurement of carbon isotope discrimination in berry juice sugars at maturity (δ13C) provides an integrated assessment of water use efficiency (WUE) during the period of berry ripening, and when collected over multiple seasons can be used as an indication of drought stress response. Berry juice δ13C measurements were carried out on 48 different varieties planted in a common garden experiment in Bordeaux, France from 2014 through 2021 and were paired with midday and predawn leaf water potential measurements on the same vines in a subset of six varieties. The aim was to discriminate a large panel of varieties based on their stomatal behaviour and potentially identify hydraulic traits characterizing drought tolerance by comparing δ13C and hydroscapes (the visualisation of plant stomatal behaviour as a response to predawn water potential). Cluster analysis found that δ13C values are likely affected by the differing phenology of each variety, resulting in berry ripening of different varieties taking place under different stress conditions within the same year. We accounted for these phenological differences and found that cluster analysis based on specific δ13C metrics created a classification of varieties that corresponds well to our current empirical understanding of their relative drought tolerances. In addition, we analysed the water potential regulation of the subset of six varieties (using the hydroscape approach) and found that it was well correlated with some δ13C metrics. Surprisingly, a variety’s water potential regulation (specifically its minimum critical leaf water potential under water deficit) was strongly correlated to δ13C values under well-watered conditions, suggesting that base WUE may have a stronger impact on drought tolerance than WUE under water deficit. These results give strong insights on the innate WUE of a very large panel of varieties and suggest that studies of drought tolerance should include traits expressed under non-limiting conditions.

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.

Deconstructing the soil component of terroir: from controversy to consensus

Wine terroir describes the collectively recognized relation between a geographical area and the distinctive organoleptic characteristics of the wines produced in it. The overriding objective in terroir studies is therefore to provide scientific proof relating the properties of terroir components to wine quality and typicity. In scientific circles, the role of climate (macro-, meso- and micro-) on grape and wine characteristics is well documented and accepted as the most critical. Moreover, there has been increasing interest in recent years about new elements with possible importance in shaping wine terroir like berry/leaf/soil microbiology or even aromatic plants in proximity to the vineyard conferring flavors to the grapes. However, the actual effect of these factors is also dependent on complex interactions with plant material (variety/clone, rootstock, vine age) and with human factors.
The contribution of soil, although a fundamental component of terroir and extremely popular among wine enthusiasts, remains a much-debated issue among researchers. The role of geology is probably the one mostly associated by consumers with the notion of terroir with different parent rocks considered to give birth to different wine styles. However, the relationship between wine properties and the underlying parent material raises a lot of controversy especially regarding the actual existence of rock-derived flavors in the wine (e.g. minerality). As far as the actual soil properties are concerned, the effect of soil physical properties is generally regarded as the most significant (e.g sandy soils being associated with lighter wines while those on clay with colored and tannic ones) mostly through control of water availability which ultimately modifies berry ripening conditions either directly by triggering biosynthetic pathways, or indirectly by altering vigor and yield components. The role of soil chemistry seems to be weakly associated to wine sensory characteristic, although N, K, S and Ca, but also soil pH, are often considered important in the overall soil effect.
Recently, in the light of evidence provided by precision agriculture studies reporting a high variability of vineyard soils, the spatial scale should also be taken into consideration in the evaluation of the soil effects on wines. While it is accepted that soil effects become more significant than climate on a local level, it is not clear whether these micro-variations of vineyard soils are determining in the terroir effect. Moreover, as terroir is not a set of only natural factors, the magnitude of the contribution of human-related factors (irrigation, fertilization, soil management) to the soil effect still remains ambiguous. Lastly, a major shortcoming of the majority of works about soil effects on wine characteristics is the absence of connection with actual vine physiological processes since all soil effects on grape and wine chemistry and sensorial properties are ultimately mediated through vine responses.
This article attempts to breakdown the main soil attributes involved in the terroir effect to suggest an improved understanding about soil’s true contribution to wine sensory characteristics. It is proposed that soil parameters per se are not as significant determining factors in the terroir effect but rather their mutual interactions as well as with other natural and human factors included in the terroir concept. Consequently, similarly to bioclimatic indices, composite soil indices (i.e. soil depth, water holding capacity, fertility, temperature etc), incorporating multiple soil parameters, might provide a more accurate and quantifiable means to assess the relative weight of the soil component in the terroir effect.