Macrowine 2021
IVES 9 IVES Conference Series 9 First quantification of glut-3SH-SO3 and glut-3SH-al in juice and wine

First quantification of glut-3SH-SO3 and glut-3SH-al in juice and wine

Abstract

3-Sulfanylhexan-1-ol (3SH) is a key impact odorant of white wines such as Sauvignon Blanc.[1] In particular, the varietal characters of Sauvignon Blanc, especially from Marlborough New Zealand, are strongly influenced by the concentrations of 3SH.[2,3] 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 fully understood.[1,4] The polyfunctional varietal thiols can be 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.[4]

One precursor of particular interest is the glutathione conjugate to the aldehyde form of 3SH, 3S-glutathionylhexanal (glut-3SH-al). The presence 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. Additionally, the bisulfite adduct of glut-3SH-al (glut-3SH-SO3) has been identified in wine samples.[5,6] The interconversion of glut-3SH-al and glut-3SH-SO3 is of great interest as this equilibrium 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.[6]

A method for the extraction and quantification of glut-3SH-al and glut-3SH-SO3 has been developed, using previously synthesised deuterated analogues of these compounds to ensure reliable quantification.[7] The compounds are separated using solid phase extraction (SPE), followed by oxime derivatisation and MRM analysis on an LC-QqQ. This method has been validated using standard addition of synthetic glut-3SH-al and was found to be linear up to 1000 ppb.

Using this method, we have analysed the glut-3SH-al and glut-3SH-SO3 content of laboratory scale synthetic grape media samples before, during, and after fermentation, as well as a selection of commercial wines and grape juices. With the SPE and LC-QqQ analysis described here, the glut-3SH-al and glut-3SH-SO3 content of a wide range of grape derived samples can be measured, a valuable piece of the puzzle in elucidating 3SH biogenesis.

DOI:

Publication date: September 7, 2021

Issue: Macrowine 2021

Type: Article

Authors

Jennifer Muhl

School of Chemical Sciences, The University of Auckland,Lisa PILKINGTON, School of Chemical Sciences, The University of Auckland  Bruno FEDRIZZI, School of Chemical Sciences, The University of Auckland  Rebecca DEED, School of Chemical Sciences, School of Biological Sciences, The University of Auckland

Contact the author

Keywords

3-sulfanylhexan-1-ol, Aroma Precursors, Analytical Method, Isotopic Labelling, LC-MS/MS

Citation

Related articles…

Simulating climate change impact on viticultural systems in historical and emergent vineyards

Global climate change affects regional climates and hold implications for wine growing regions worldwide. Although winegrowers are constantly adapting to internal and external factors, it seems relevant to develop tools, which will allow them to better define actual and future agro-climatic potentials. Within this context, we develop a modelling approach, able to simulate the impact of environmental conditions and constraints on vine behaviour and to highlight potential adaptation strategies according to different climate change scenarios. Our modeling approach, named SEVE (Simulating Environmental impacts on Viticultural Ecosystems), provides a generic modeling framework for simulating grapevine growth and berry ripening under different conditions and constraints (slope, aspect, soil type, climate variability…) as well as production strategies and adaptation rules according to climate change scenarios. Each activity is represented by an autonomous agent able to react and adapt its reaction to the variability of environmental constraints. Using this model, we have recently analyzed the evolution of vineyards’ exposure to climatic risks (frost, pathogen risk, heat wave) and the adaptation strategies potentially implemented by the winegrowers. This approach, implemented for two climate change scenarios, has been initiated in France on traditional (Loire Valley) and emerging (Brittany) vineyards. The objective is to identify the time horizons of adaptations and new opportunities in these two regions. Carried out in collaboration with wine growers, this approach aims to better understand the variability of climate change impacts at local scale in the medium and long term.

Projected changes in vine phenology of two varieties with different thermal requirements cultivated in La Mancha DO (Spain) under climate change scenarios

The aim of this work was to analyze the phenology variability of Tempranillo and Chardonnay cultivars, related to the climatic characteristics in La Mancha Designation of Origin, and their potential changes under climate change scenarios. Phenological dates referred to budbreak, flowering, veraison and harvest were analyzed for the period 2000-2019. The weather conditions at daily time scale, recorded during the same period, were also evaluated. The thermal requirements to reach each of these phenological stages were calculated and expressed as the GDD accumulated from DOY=60. Changes in phenology were projected by 2050 and 2070 taking into account those values and the projected temperatures and precipitation, simulated under two Representative Concentration Pathway (RCP) scenarios –RCP4.5 and RCP8.5– using an ensemble of models. The average phenological dates during the period under study were, April 16th ± 6.6 days and April 5th ± 6.0 days for budbreak, May 31st ± 6.0 days and May 27th ± 5.3 days for flowering, July 26th ± 5.6 days and July 25th ± 5.8 days for veraison, and Ago 23rd ± 10.8 days and Ago 17th ± 9.0 days for harvest, respectively, for Tempranillo and Chardonnay. The projected changes in temperature imply an average change in the maximum growing season (April-August) temperatures of 1.2 and 1.9°C by 2050, and 1.6 and 2.6°C by 2070, under the RCP4.5 and RCP8.5 scenarios, respectively. A reduction in precipitation is predicted, which vary between 15% for 2050 under RCP4.5 scenario and up to 30% by 2070 under RCP8.5. The advance of the phenological dates for 2050, could be of 6, 7, 7, and 8 days for Tempranillo and 4, 6, 6 and 9 days for Chardonnay, respectively for budbreak, flowering, veraison and harvest under the RCP4.5 scenario. Under the RCP8.5 emission scenario, the advance could be up to 30% higher.

Assessing the relationship between cordon strangulation, dieback, and fungal trunk disease symptom expression

Grapevine trunk diseases including Eutypa dieback are a major factor in the decline of vineyards and may lead to loss of productivity, reduced income, and premature reworking or replanting. Several studies have yielded results indicating that vines may be more likely to express symptoms of vascular disease if their health is already compromised by stress. In Australia and many other wine-growing regions it is a common practice for canes to be wrapped tightly around the cordon wire during the establishment of permanent cordon arms. It is likely that this practice may have a negative effect on health and longevity, as older cordons that have been trained in this manner often display signs of decay and dieback, with the wire often visibly embedded within the wood of the cordon. It is possible that adopting a training method which avoids constriction of the vasculature of the cordon may help to limit the onset of vascular disease symptom expression. A survey was conducted during the spring of two consecutive growing seasons on vineyards in South Australia displaying symptoms of Eutypa lata infection when symptomless shoots were 50–100 cm long. Vines were assessed as follows: (i) the proportion of cordon exhibiting dieback was rated using a 0–100% scale; (ii) the proportion of canopy exhibiting foliar symptoms of Eutypa dieback was rated using a 0–100% scale; (iii) the severity of strangulation was rated using a 0–4 point scale. Images were also taken of each vine for the purpose of measuring plant area index (PAI) using the VitiCanopy App. The goal of the survey was to determine if and to what extent any correlation exists between severity of strangulation and cordon dieback, in addition to Eutypa dieback foliar symptom expression.

Towards adaptation to climate change in Rioja: Quality evaluation of wines obtained from Grenache x Tempranillo selections

The wine sector is of great relevance and tradition in Mediterranean countries, however, it may be most susceptible to climate change. In recent years, wine production is facing changes worldwide, both at environmental as well as commercial levels, due to global warming and the shift in consumers’ preferences. Wine growers and wine makers are in search of solutions that allow to face these new challenges. One of the most promising initiatives in the long term is the introduction of new plant materials, specifically intraspecific hybridizations between premium varieties that may improve traditional germplasm in its adaptation to climate change. These inter-varietal crosses have the potential to generate quality wines, whilst maintaining the regional typicity, and constitute an attractive alternative for the consumer due to their sensory attributes. In this study, we have evaluated wines from 29 intraspecific Garnacha x Tempranillo hybrids in two different locations, with the aim to assess their oenological potential and sensory attributes. Thirteen of the selections were white and 16 were red. Microvinifications were conducted with two or three replications depending on grape availability. Conventional oenological parameters were determined for all wines. The sensory evaluation and hedonic scores were given by five experts. Red selections obtained higher quality scores than white ones. Among the white selections with higher quality scores, GT-41 Varea and GT-159 Varea outstand, due to their high total acidity and high malic acid content. Regarding red selections, GT-57 Varea and GT-57 UR were perceived as higher in quality, highlighted for their moderate alcoholic and high anthocyanin content. Our results indicate that intraspecific hybridization may be a powerful tool for adapting traditional cultivars to climate change in Rioja.

Metabolomic discrimination of grapevine water status for Chardonnay and Pinot noir

Water status impact in viticulture has been widely explored, as it strongly affects grapevine physiology and grape chemical composition. It is considered as a key component of vitivinicultural terroir. Most of the studies concerning grapevine water status have focused on either physiological traits, or berry compounds, or traits involved in wine quality. Here, the response of grapevine to water availability during the ripening period is assessed through non-targeted metabolomics analysis of grape berries by ultra-high resolution mass spectrometry. The grapevine water status has been assessed during 2 consecutive years (2019 & 2020), through carbon isotope discrimination on juices from berries collected at maturity (21.5 brix approx.) for 2 Vitis vinifera cv. Pinot noir (PN) and Chardonnay (CH). A total of 220 grape juices were collected from 5 countries worldwide (Italy; Argentina; France; Germany; Portugal). Measured δ13C (‰) varied from -28.73 to -22.6 for PN, and from -28.79 to -21.67 for CH. These results also clearly revealed higher water stress for the 2020 vintage. The same grape juices have been analysed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Liquid Chromatography coupled to Mass Spectrometry (LC-qTOF-MS), leading to the detection of up to 4500 CHONS containing elemental compositions, and thus likely tens of thousands of individual compounds, which include fatty acids, organic acids, peptides, phenolics, also with high levels of glycosylation. Multivariate statistical analysis revealed that up to 160 elemental compositions, covering the whole range of detected masses (100 –1000 m/z), were significantly correlated to the observed gradients of water status. Examples of chemical markers, which are representative of these complex fingerprints, include various derivatives of the known abscisic acid (ABA), such as phaesic acid or abscisic acid glucose ester, which are significantly correlated with higher water stress, regardless of the variety. Cultivar-specific behaviours could also be identified from these fingerprints. Our results provide an unprecedented representation of the metabolic diversity, which is involved in the water status regulation at the grape level, and which could contribute to a better knowledge of the grapevine mitigation strategy in a climate change context.