IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Abstract

3-Sulfanylhexan-1-ol (3SH) is a key impact odorant of white wines such as Sauvignon Blanc. In particular, the varietal characters of Sauvignon Blanc, especially from Marlborough NZ, are strongly influenced by the concentrations of 3SH. Although only trace levels of 3SH are needed to impart perceptible aroma characters of passionfruit and grapefruit, the biogenesis of this compound during fermentation is not yet well understood. The polyfunctional varietal thiols are produced during fermentation by metabolism of non-volatile precursors such as glutathione and cysteine conjugates of 3SH, however the routes by which these precursors are metabolised are complex, and not fully elucidated. 1One precursor of particular interest is the glutathione conjugate to the aldehyde form of 3SH, 3S-glutathionylhexanal (glut-3SH-al). Retention of the aldehyde functional group drastically changes the reactivity of the precursor in wine-like systems. Recent work by this group has shown that this compound can exist as tautomers in solution, suggesting possible new reaction pathways for the metabolism of glut 3SH-al. 2 Additionally, the bisulfite adduct of glut-3SH-al (glut-3SH-SO3) has been identified in wine samples, as SO2 is widely present in wine media. 3,4 The interconversion of glut-3SH-al and glut-3SH-SO3 is of great interest as it is an equilibrium and will be influenced by the concentrations of both glut-3SH-al and free SO2 in the sample. As such, it is thought that glut-3SH-SO3 may exist in finished wines as a potential reservoir for the release of 3SH which could extend the life of the fruity characters which are so desirable in young white wines. 4 We have developed a method for the extraction and quantification of glut-3SH-al and glut-3SH-SO3, using previously synthesised deuterated analogues of these compounds to ensure reliable quantification.5 The compounds are separated using solid-phase extraction (SPE), followed by oxime derivatisation and MRM analysis on an LC-QqQ. This method enables determination of the glut-3SH-al and glut-3SH-SO3 content of a wide range of grape-derived samples, a valuable piece of the puzzle in elucidating 3SH biogenesis.

Using this method, we have analysed the glut-3SH-al and glut-3SH-SO3 content of a wide range of white wines from around NZ, investigating the impact of location, age, and noble rot or late harvest on the precursor content of these wines. This insight into factors impacting glut-3SH-al and glut-3SH-SO3 content in commercial wines, and the possible influence on the finished wine aroma, adds another piece to the puzzle of 3SH and 3SHA biogenesis in wines. Indeed, despite the contribution of these volatile thiols to the aroma of botrytised white wines, these wines contain significantly lower, or negligible, concentrations of glut-3SH-al and glut-3SH-SO3, something which will be explored further in future work

DOI:

Publication date: June 22, 2022

Issue: IVAS 2022

Type: Article

 

Authors

Muhl Jennifer¹, Deed Rebecca¹,², Pilkington Lisa¹ and Fedrizzi Bruno¹

¹The University of Auckland, School of Chemical Sciences

²The University of Auckland, School of Biological Sciences

Contact the author

Keywords

LC-QQQ, 3-sulfanylhexan-1-ol, glut-3SH-al, aroma compound precursors, white wine

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

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.

Grapevine yield-gap: identification of environmental limitations by soil and climate zoning in Languedoc-Roussillon region (south of France)

Grapevine yield has been historically overlooked, assuming a strong trade-off between grape yield and wine quality. At present, menaced by climate change, many vineyards in Southern France are far from the quality label threshold, becoming grapevine yield-gaps a major subject of concern. Although yield-gaps are well studied in arable crops, we know very little about grapevine yield-gaps. In the present study, we analysed the environmental component of grapevine yield-gaps linked to climate and soil resources in the Languedoc Roussillon. We used SAFRAN data and IGP Pays d’Oc wine yields from 2010 to 2018. We selected climate and soil indicators proving to have a significant effect on average wine yield-gaps at the municipality scale. The most significant factors of grapevine yield were the Soil Available Water Capacity; followed by the Huglin Index and the Climatic Dryness Index. The Days of Frost; the Soil pH; and the Very Hot Days were also significant. Then, we clustered geographical zones presenting similar indicators, facilitating the identification of resources yield-gaps. We discussed the number of zones with the experts of IGP Pays d’Oc label, obtaining 7 zones with similar limitations for grapevine yield. Finally, we analysed the main resources causing yield-gaps and the grapevine varieties planted on each zone. Mapping grapevine resource yield-gaps are the first stage for understanding grapevine yield-gaps at the regional scale.

Characterization of variety-specific changes in bulk stomatal conductance in response to changes in atmospheric demand and drought stress

In wine growing regions around the world, climate change has the potential to affect vine transpiration and overall vineyard water use due to related changes in atmospheric demand and soil water deficits. Grapevines control their transpiration in response to a changing environment by regulating conductance of water through the soil-plant-atmosphere continuum. Most vineyard water use models currently estimate vine transpiration by applying generic crop coefficients to estimates of reference evapotranspiration, but this does not account for changes in vine conductance associated with water stress, nor differences thought to exist between varieties. The response of bulk stomatal conductance to daily weather variability and seasonal drought stress was studied on Cabernet-Sauvignon, Merlot, Tempranillo, Ugni blanc, and Semillon vines in a non-irrigated vineyard in Bordeaux France. Whole vine sap flow, temperature and humidity in the vine canopy, and net radiation absorbed by the vine canopy were measured on 15-minute intervals from early July through mid-September 2020, together with periodic measurement of leaf area, canopy porosity, and predawn leaf water potential. From this data, bulk stomatal conductance was calculated on 15-minute intervals, and multiple regression analysis was performed to identify key variables and their relative effect on conductance. Attention was focused on addressing multicollinearity and time-dependency in the explanatory variables and developing regression models that were readily interpretable. Variability of vapor pressure deficit over the day, and predawn water potential over the season explained much of the variability in conductance, with relative differences in response coefficients observed across the five varieties. By characterizing this conductance response, the dynamics of vine transpiration can be better parameterized in vineyard water use modeling of current and future climate scenarios.

Making sense of available information for climate change adaptation and building resilience into wine production systems across the world

Effects of climate change on viticulture systems and winemaking processes are being felt across the world. The IPCC 6thAssessment Report concluded widespread and rapid changes have occurred, the scale of recent changes being unprecedented over many centuries to many thousands of years. These changes will continue under all emission scenarios considered, including increases in frequency and intensity of hot extremes, heatwaves, heavy precipitation and droughts. Wine companies need tools and models allowing to peer into the future and identify the moment for intervention and measures for mitigation and/or avoidance. Previously, we presented conceptual guidelines for a 5-stage framework for defining adaptation strategies for wine businesses. That framework allows for direct comparison of different solutions to mitigate perceived climate change risks. Recent global climatic evolution and multiple reports of severe events since then (smoke taint, heatwave and droughts, frost, hail and floods, rising sea levels) imply urgency in providing effective tools to tackle the multiple perceived risks. A coordinated drive towards a higher level of resilience is therefore required. Recent publications such as the Australian Wine Future Climate Atlas and results from projects such as H2020 MED-GOLD inform on expected climate change impacts to the wine sector, foreseeing the climate to expect at regional and vineyard scale in coming decades. We present examples of practical application of the Climate Change Adaptation Framework (CCAF) to impacts affecting wine production in two wine regions: Barossa (Australia) and Douro (Portugal). We demonstrate feasibility of the framework for climate adaptation from available data and tools to estimate historical climate-induced profitability loss, to project it in the future and to identify critical moments when disruptions may occur if timely measures are not implemented. Finally, we discuss adaptation measures and respective timeframes for successful mitigation of disruptive risk while enhancing resilience of wine systems.

Impact of changes in pruning practices on vine growth and yield

A gradual decline in vineyards has been observed over the past twenty years worldwide. This might be explained by the climate change, practices change or the increase of dieback diseases. To increase the longevity of vines, we studied the impact of different pruning strategies in four adult and four young vineyards located in France and Spain. In France, vineyards were planted with Cabernet franc on 3309C while Spanish trials were planted with Tempranillo grafted on 110R. Vegetative expression, yield, quality of berries and wood vessels conductivity were measured. The distribution of vegetative expression, yield and berry composition between primary and secondary vegetation were quantified. Finally, tomography was used to evaluate the implication of the treatments on sap flows.
First results show that i) the respectful pruning leads to an increase of 30 to 50% more secondary shoots than the aggressive pruning in France and between 15 and 20% in Spain, ii) there is no major effect on the yield over the first two years following the implementation of the new pruning practices, although the proportion of clusters from suckers is higher on the respectful pruning method. On young vines, the development of the trunk according to a respectful pruning leads to a loss of harvest 2 years after planting. This is due to the removal, on the future trunk, of the green suckers which carrying bunches. This operation carried out in spring rather than during winter pruning, would promote a better leaf / fruit balance when the plant comes into production, and could lead to better hydraulic conduction in the vessels of the trunk. Maintaining these trials for several years will provide more robust data to assess the impact of these practices on the vines over the long term.