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…

Underpinning terroir with data: rethinking the zoning paradigm

Agriculture, natural resource management and the production and sale of products such as wine are increasingly data-driven activities. Thus, the use of remote and proximal crop and soil sensors to aid management decisions is becoming commonplace and ‘Agtech’ is proliferating commercially; mapping, underpinned by geographical information systems and complex methods of spatial analysis, is widely used. Likewise, the chemical and sensory analysis of wines draws on multivariate statistics; the efficient winery intake of grapes, subsequent production of wines and their delivery to markets relies on logistics; whilst the sales and marketing of wines is increasingly driven by artificial intelligence linked to the recorded purchasing behaviour of consumers. In brief, there is data everywhere!

Opinions will vary on whether these developments are a good thing. Those concerned with the ‘mystique’ of wine, or the historical aspects of terroir and its preservation, may find them confronting. In contrast, they offer an opportunity to those interested in the biophysical elements of terroir, and efforts aimed at better understanding how these impact on vineyard performance and the sensory attributes of resultant wines. At the previous Terroir Congress, we demonstrated the potential of analytical methods used at the within-vineyard scale in the development of Precision Viticulture, in contributing to a quantitative understanding of regional terroir. For this conference, we take this approach forward with examples from contrasting locations in both the northern and southern hemispheres. We show how, by focussing on the vineyards within winegrowing regions, as opposed to all of the land within those regions, we might move towards a more robust terroir zoning than one derived from a mixture of history, thematic mapping, heuristics and the whims of marketers. Aside from providing improved understanding by underpinning terroir with data, such methods should also promote improved management of the entire wine value chain.

Pruned vine biomass exclusion from a clay loam vineyard soil – examining the impact on physical/chemical properties

The wine industry worldwide faces increasing challenges to achieve sustainable levels of carbon emission mitigation. This project seeks to establish the feasibility of harvesting winter pruned vineyard biomass (PVB) for potential use in carbon footprint reduction, through its use as a renewable biofuel for energy production. In order to make this recommendation, technical issues such as the potential environmental impact, chemical composition and fuel suitability, and logistical challenges of harvesting biomass needs to be understood to compare with the results from similar studies. Of particular interest is the role PVB plays as a carbon source in vineyard soils and what effect annual removal might have on soil carbon sequestration. A preliminary trial was established in the Waite Campus vineyard (University of Adelaide) to test current management strategies. Vines are grown in a Eutrophic, Red Dermosol clay loam soil with well managed midrow swards. A comparison was undertaken of mid-row treatments in two 0.25 Ha blocks (Shiraz and Semillon), including annual cultivation for seed bed preparation, the deliberate exclusion of PVB (25 years) and incorporation of PVB (13 years) at an average of 3.4 and 5.5 Mg/Ha-1 for Shiraz and Semillon respectively. In both 0-10cm and 10-30cm soil core sample depths, combined soil carbon % measures in the desired range of 1.80 to 3.50, were not significantly different between treatments or cultivars and yielded an estimated 42 Mg/ha-1 of sequestered soil carbon. Other key physical and chemical measures were likewise not significantly different between treatments. Preliminary results suggest that in a temperate zone vineyard, managed such as the one used in this study, there is no long term negative impact on soil carbon sequestration through removing PVB. This implies that growers could confidently harvest PVB for use in several end fates including as a bio fuel.

The use of rootstock as a lever in the face of climate change and dieback of vineyard

As viticulture faces challenges such as climate change or vineyard dieback, the choice of the variety and rootstock becomes more and more crucial. To study rootstock levers in the Bordeaux region, a parcel of Cabernet Sauvignon (CS) was planted with four rootstocks in 2014. Twenty repetitions of each of the following four rootstocks were set up: 101-14 MGt, Nemadex AB, 420A MGt and Gravesac. The number of bunches, yields and pruning weights of the vine shoots were measured individually on 240 vines from 2017 to 2021. Since 2020, nitrogen status assessed by assimilable nitrogen level, hydric status assessed by δ13C and berry maturity were measured on 80 samples taken from 20 repetitions of the four rootstocks. A lower yield was measured for CS grafted onto Nemadex AB due to the lower number of bunches and the lower weight of berries. The differences between the other three rootstocks are small, but CS grafted onto 420A MGt was the most productive. The CS grafted onto Nemadex AB had the lowest pruning weight while 101-14 MGt had the highest. In 2020, δ13C showed a more moderate water stress with 101-14 MGt and 420A MGt than with Nemadex AB. Surprisingly, the Gravesac was under more stress than the 101-14 MGt. The nitrogen status in the berries was better for Nemadex AB but this was perhaps due to the significantly lower weight of the berries.Rootstock 101-14 MGt attained the highest accumulation of sugars in the berries while 420A MGt allows to preserve higher acidity. The parcel is still young which may explain some of the results. These measures must therefore be continued over the next several years to fully assess the effects of these rootstocks on the development of the vines and the quality of the production under new climatic conditions.

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.

How can historical cultivars mitigate the effects of climate change?

IFV, INRAe and the national network “Partenaires de la Sélection Vigne” representing 37 organizations from the different wine regions, have been working increasingly closely over the last 2 decades towards the preservation of the French varietal patrimony. There are approximately 600 patrimonial varieties according to INRAe and SupAgro Montpellier experts, including ancient cultivars (400) and intravarietal crossbreeds obtained since the 19th century. In the context of a drastic reduction in such varieties from the mid 1980’s in favor of mainstream varieties, it was essential to carry out an inventory of old vines and vineyards. INRAe Vassal collection plays a key role here as it holds the largest diversity available, along with a rich bibliography and herbariums, offering us the opportunity to document and double check the identity of a cultivar, consolidating the expertise of ampelographers. The work is carried out in several stages, from verifying the existence of a variety in a small region, through to rehabilitation. During this session, the authors present the process that leads to the official registration of a variety. After this, IFV selection center takes over to initiate the process of selection and propagation. A specific focus within regions such as the Alps, Champagne and the South-West will provide details of the full procedure. Bia, Bouysselet, Chardonnay rose, Mecle and the aptly named Tardif, are some of the cultivars that have followed this procedure. Furthermore, a recent regulation established by INAO on “varieties of interest for adaptation purposes” might boost uptake by growers. Since 2006, 36 historical cultivars have been registered. Most of these have been neglected in the past due to late maturity, lack of sugar and high titratable acidity at harvest time. Such characteristics are today considered as positive qualities, not only in mitigation of the effects of climate change, but also as an opportunity for restoring diversity…