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…

Modeling the suitability of Pinot Noir in Oregon’s Willamette Valley in a changing climate

Air temperature is the key driver of grapevine phenology and a significant environmental factor impacting yield and quality for a winegrape growing region. In this study the optimal downscaled CMIP5 ensemble for computing thegrowing season average temperature (GST) viticulture climate classification index was determined to spatially compute on a decadal basis predictions of the GST climate index and the grapevine sugar ripeness (GSR) model for Pinot Noir throughout the Willamette Valley (WV) American Viticultural Area (AVA). Forecasts for average temperature and a 220 g/L target sugar concentration level were computed using daily Localized Constructed Analogs (LOCA) downscaled CMIP5 historic and Representative Concentration Pathways (RCP) future climate projections of minimum and maximum daily temperature. We explore spatiotemporal trends of the GST climate classification index and Pinot Noir specific applications of the GSR phenology model for the WV AVA. Spatiotemporal computations of the GST climate index and Pinot Noir specific applications of the GSR model enable the opportunity to explore relationships between their computed values with one intent being to provide updated GST ranges that better align with current temperature-based modeling understanding of Pinot Noir grapevine phenology and the viticultural application of LOCA CMIP5 climate projections for the WV AVA. The Pinot Noir specific applications of the GSR model or the GST index with updated bounds indicate that the percent of the WV AVA area suitable for Pinot Noir production is currently at or near its peak value in the upper 80s to lower 90s of this century.

Spatiotemporal patterns of chemical attributes in Vitis vinifera L. cv. Cabernet Sauvignon vineyards in Central California

Spatial variability of vine productivity in winegrapes is important to characterise as both yield and quality are relevant for the production of different wine styles and products. The objectives were to understand how patterns of variability of Cabernet Sauvignon fruit composition changed over time and space, how these patterns could be characterised with indirect measurements, and how spatial patterns of the variation in fruit compositional attributes can aid in improving management. Prior to the 2017 vintage, 125 data vines were distributed across each of four vineyards in the Lodi American Viticultural Area (AVA) of California. Each data vine was sampled at commercial harvest in 2017, 2018, and 2019. Yield components and fruit composition were measured at harvest for each data vine, and maps of yield and fruit composition were produced for eight ‘objective measures of fruit quality’: total anthocyanins, polymeric tannins, quercetin glycosides, malic acid, yeast assimilable nitrogen, β-damascenone, C6 alcohols and aldehydes, and 3-isobutyl-2-methoxypyrazine. Patterns of variation in anthocyanins and phenolic compounds were found to be most stable over time. Given this relative stability, management decisions focused on fruit quality could be based on zonal descriptions of anthocyanins or phenolics to increase profitability in some vineyards. In each vineyard, dormant season pruning weights and soil cores were collected at each location, elevation and soil apparent electrical conductivity surveys were completed, and remotely sensed imagery was captured by fixed wing aircraft and two satellite platforms at major phenological stages. The data collected were used to develop relationships among biophysical data, soil, imagery, and fruit composition. The standardised and aggregated samples from four vineyards over three seasons were included in the estimation of ‘common variograms’ to assess how this technique could aid growers in producing geostatistically rigorous maps of fruit composition variability without cumbersome, single season sampling efforts.

What are the optimal ranges and thresholds for berry solar radiation for flavonoid biosynthesis?

In wine grape production, canopy management practices are applied to control the source-sink balance and improve the cluster microclimate to enhance berry composition. The aim of this study was to identify the optimal ranges of berry solar radiation exposure (exposure) for upregulation of flavonoid biosynthesis and thresholds for their degradation, to evaluate how canopy management practices such as leaf removal, shoot thinning, and a combination of both affect the grapevine (Vitis vinifera L. cv. Cabernet Sauvignon) yield components, berry composition, and flavonoid profile under context of climate change. First experiment assessed changes in the grape flavonoid content driven by four degrees of exposure. In the second experiment, individual grape berries subjected to different exposures were collected from two cultivars (Cabernet Sauvignon and Petit Verdot). The third experiment consisted of an experiment with three canopy management treatments (i) LR (removal of 5 to 6 basal leaves), (ii) ST (thinned to 24 shoots per vine), and (iii) LRST (a combination of LR and ST) and an untreated control (UNT). Berry composition, flavonoid content and profiles, and 3-isobutyl 2-methoxypyrazine were monitored during berry ripening. Although increasing canopy porosity through canopy management practices can be helpful for other purposes, this may not be the case of flavonoid compounds when a certain proportion of kaempferol was achieved. Our results revealed different sensitivities to degradation within the flavonoid groups, flavonols being the only monitored group that was upregulated by solar radiation. Within different canopy management practices, the main effects were due to the ST. Under environmental conditions given in this trial, ST and LRST hastened fruit maturity; however, a clear improvement of the flavonoid compounds (i.e., greater anthocyanin) was not observed at harvest. Methoxypyrazine berry content decreased with canopy management practices studied. Although some berry traits were improved (i.e. 2.5° Brix increase in berry total soluble solids) due to canopy management practices (ST), this resulted in a four-fold increase in labor operations cost, two-fold decrease in yield with a 10-fold increase in anthocyanin production cost per hectare that should be assessed together as the climate continues to get hot.

A predictive model of spatial Eca variability in the vineyard to support the monitoring of plant status

[lwp_divi_breadcrumbs home_text="IVES" use_before_icon="on" before_icon="||divi||400" module_id="publication-ariane" _builder_version="4.19.4" _module_preset="default" module_text_align="center" module_font_size="16px" text_orientation="center"...

Is wine terroir a valid concept under a changing climate?

The OIV[i] defines terroir as a concept referring to an area in which collective knowledge of the interactions between the physical and biological environment (soil, topography, climate, landscape characteristics and biodiversity features) and vitivinicultural practices develops, providing distinctive wine characteristics. Those are perceptible in the taste of wine, which drives consumer preference and, therefore, wine’s value in the marketplace. Geographical indications (GI) are recognized regulatory constructs formalizing and protecting the nexus between wine taste and the terroir generating it. Despite considering updates, GIs do not consider the nexus as a dynamic one and do not anticipate change, namely of climate. Being climate a fundamental feature of terroir, it strongly impacts wine characteristics, such as taste. According to IPCC[ii], many widespread, rapid and unprecedented changes of climate occurred, some being irreversible over hundreds to thousands of years. Climatic shifts and atmospheric-driven extreme events have been widely reported worldwide. Recent climatic trends are projected to strengthen in upcoming decades, whereas extremes are expected to increase in frequency and intensity, forcing wines away from GI definitions. Geographical shifts of viticultural suitability are projected, often moving into regions and countries different from current ones. Some authors propose adaptation in viticulture, winemaking and product innovation. We show evidence of climate changing wine characteristics in the Douro valley, home of 270-year-old Port GI. We discuss herein resist or adapt stances for when climate changes the nexus between terroir and wine characteristics. Using the MED-GOLD[iii] dashboard, a tool allowing for easy visual navigation of past and future climates, we demonstrate how policymakers can identify future moments, throughout the 21st century under different emission scenarios, when GI specifications will likely need updates (e.g., boundaries, varieties) to reduce climate-change impacts.