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…

Use of multispectral satellite for monitoring vine water status in mediterranean areas

The development of new generations of multispectral satellites such as Sentinel-2 opens possibilities as to vine water status assessment (Cohen et al., 2019). Based on a three years field campaign, a model of Stem Water Potential (SWP) estimation on vine using four satellite bands in Red, Red-Edge, NIR and SWIR domains was developed (Laroche-Pinel et al., 2021). The model relies on SWP field measures done using a pressure chamber (Scholander et al., 1965), which is a common, robust and precise method to assess vine water status (Acevedo-Opazo et al., 2008). The model was mainly developed from from SWP measures on Syrah N (Laroche Pinel E., 2021).

A large scale monitoring was organized in different vineyards in the Mediterranean region in 2021. 10 varieties amongst the most represented in this area were monitored (Cabernet sauvignon N, Chardonnay B, Cinsault N, Grenache N, Merlot N, Mourvèdre N, Sauvignon B, Syrah N, Vermentino B, Viognier B). The model was used to produce water status maps from Sentinel-2 images, starting from the beginning of June (fruit set) up to September (harvest). The average estimated SWP for each vine was compared to actual field SWP measures done by wine growers or technicians during usual monitoring of irrigation programs. The correlations between mean estimated SWP and mean measured SWP were at the same level than expected by the model. (Laroche Pinel, 2021) The general SWP kinetics were comparable. The estimated SWP would have led to same irrigation decisions concerning the date of first irrigation in comparison with measured SWP.

Acevedo-Opazo, C., Tisseyre, B., Ojeda, H., Ortega-Farias, S., Guillaume, S. (2008). Is it possible to assess the spatial variability of vine water status? OENO One, 42(4), 203.
Cohen, Y., Gogumalla, P., Bahat, I., Netzer, Y., Ben-Gal, A., Lenski, I., … Helman, D. (2019). Can time series of multispectral satellite images be used to estimate stem water potential in vineyards? In Precision agriculture ’19, The Netherlands: Wageningen Academic Publishers, pp. 445–451.
Laroche-Pinel, E., Duthoit, S., Albughdadi, M., Costard, A. D., Rousseau, J., Chéret, V., & Clenet, H. (2021). Towards vine water status monitoring on a large scale using sentinel-2 images. remote sensing, 13(9), 1837.
Laroche-Pinel,E. (2021). Suivi du statut hydrique de la vigne par télédétection hyper et multispectrale. Thèse INP Toulouse, France.
Scholander, P.F., Bradstreet, E.D., Hemmingsen, E.A., & Hammel, H.T. (1965). Sap pressure in vascular plants: Negative hydrostatic pressure can be measured in plants. Science, 148(3668), 339–346.

Use of a new, miniaturized, low-cost spectral sensor to estimate and map the vineyard water status from a mobile 

Optimizing the use of water and improving irrigation strategies has become increasingly important in most winegrowing countries due to the consequences of climate change, which are leading to more frequent droughts, heat waves, or alteration of precipitation patterns. Optimized irrigation scheduling can only be based on a reliable knowledge of the vineyard water status.

In this context, this work aims at the development of a novel methodology, using a contactless, miniaturized, low-cost NIR spectral tool to monitor (on-the-go) the vineyard water status variability. On-the-go spectral measurements were acquired in the vineyard using a NIR micro spectrometer, operating in the 900–1900 nm spectral range, from a ground vehicle moving at 3 km/h. Spectral measurements were collected on the northeast side of the canopy across four different dates (July 8th, 14th, 21st and August 12th) during 2021 season in a commercial vineyard (3 ha). Grapevines of Vitis vinifera L. Graciano planted on a VSP trellis were monitored at solar noon using stem water potential (Ψs) as reference indicators of plant water status. In total, 108 measurements of Ψs were taken (27 vines per date).

Calibration and prediction models were performed using Partial Least Squares (PLS) regression. The best prediction models for grapevine water status yielded a determination coefficient of cross-validation (r2cv) of 0.67 and a root mean square error of cross-validation (RMSEcv) of 0.131 MPa. This predictive model was employed to map the spatial variability of the vineyard water status and provided useful, practical information towards the implementation of appropriate irrigation strategies. The outcomes presented in this work show the great potential of this low-cost methodology to assess the vineyard stem water potential and its spatial variability in a commercial vineyard.

Measurement of redox potential as a new analytical winegrowing tool

Excell laboratory has initiated the development of an analytical method based on electrochemistry to evaluate the ability of wines to undergo or resist to oxidative phenomena. Electrochemistry is a powerful tool to probe reactions involving electron transfers and offers possibility of real-time measurements. In that context, the laboratory has implemented electrochemical analysis to assess oxidation state of different wine matrices but also in order to evaluate oxidative or reduced character of leaf and soil. Initially, our laboratory focused on dosage of compounds involved in responses of plant stresses and we were also interested in microbiological activity of soils. These analyses were compared with the measurement of redox potential (Eh) and pH which are two fundamental variables involved in the modulation of plant metabolism. Indeed, the variation of redox states of the plant reflects its biological activity but also its capacity to absorb nutriments. The Eh-pH conditions mainly determine metabolic processes involved in soil and leaf and our goal is to determine if this combined analytical approach will be sufficiently precise to detect biological evolutions (plant health, parasitic attack…).

Comparison of imputation methods in long and varied phenological series. Application to the Conegliano dataset, including observations from 1964 over 400 grape varieties

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.

Influence of agronomic practices in soil water content in mid-mountain vineyards

In the context of LIFE project MIDMACC (LIFE18 CCA/ES/001099), several pilots have been installed in vineyards in mid mountain areas of Catalonia (NE Spain) to test well stablished agronomic practices to increase the adaptation of Mediterranean mid mountain to climate change. Soil water content (SWC) at three different depths (15, 30 and 45cm) was measured in continuum from August 2020. One pilot (WC) included a well-established green cover (GC), a new GC (NC) and a conventional soil management (CM, tilling+herbicides). NC presented an intermediate state between WC and CM, responding similarly to CM in autumn but quickly reaching similar SWC to WC, then following the same evolution till next spring, with CM presenting lower values along autumn and winter. Then vegetation activation decreased SWC in all plots, (much slower in CM, lacking GC). Sensibility to spring rains is again intermediate for NC, which joins SWC evolution of CM by the end of spring till next autumn. It is expected that NC will resemble WC more and more as its GC develops. In the pilot combining vine training (VSP vs Gobelet) and hillside management (slope vs terrace), no clear pattern could be related with these conditions. However, both terraces seem to be more sensitive to spring rains. A third pilot included new vineyards (7 and 1 year old). In the new vineyard (N), higher canopy development, a spontaneous green cover and row straw resulted in a slower SWC dynamic, not so sensitive to rains but conserving more soil water in spring and most of summer, even with presumably a higher water extraction by vines. In the newest vineyard (VN) the deepest sensor is still sensitive to rain events all over the year and SWC is always highest at this depth, revealing small water capture by vines.