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…

Grape berry size is a key factor in determining New Zealand Pinot noir wine composition

Making high quality but affordable Pinot noir (PN) wine is challenging in most terroirs and New Zealand’s (NZ) situation is no exception. To increase the probability of making highly typical PN wines producers choose to grow grapes in cool climates on lower fertility soils while adopting labour intensive practices. Stringent yield targets and higher input costs necessarily mean that PN wine cost is high, and profitability lower, in line-priced varietal wine ranges. To understand the reasons why higher yielding vines are perceived to produce wines of lower quality we have undertaken an extensive study of PN in NZ. Since 2018, we established a network of twelve trial sites in three NZ regions to find individual vines that produced acceptable commercial yields (above 2.5kg per vine) and wines of composition comparable to “Icon” labels. Approximately 20% of 660 grape lots (N = 135) were selected from within a narrow juice Total Soluble Solids (TSS) range and made into single vine wines under controlled conditions. Principal Component Analysis of the vine, berry, juice and wine parameters from three vintages found grape berry mass to be most effective clustering variable. As berry mass category decreased there was a systematic increase in the probability of higher berry red colour and total phenolics with a parallel increase in wine phenolics, changed aroma fraction and decreased juice amino acids. The influence of berry size on wine composition would appear stronger than the individual effects of vintage, region, vineyard or vine yield. Our observations support the hypothesis that it is possible to produce PN wines that fall within an “Icon” benchmark composition range at yields above 2.5kg per vine provided that the Leaf Area:Fruit Weight ratio is above 12cm2 per g, mean berry mass is below 1.2g and juice TSS is above 22°Brix.

Extreme canopy management for vineyard adaptation to climate change: is it a good idea?

Climate change constitutes an enormous challenge for humankind and for all human activities, viticulture not being an exception. Long-term strategic changes are probably needed the most, but growers also need to deal with short-term changes: summers that are getting progressively warmer, earlier harvest dates and higher pH in musts and wines. In the last 10-15 years, a relevant corpus of research is being developed worldwide in order to evaluate to which extent extreme canopy management operations, aimed at reducing leaf area and, thus, limiting the source to sink ratio, could be useful to delay ripening. Although extreme canopy management can result in relevant delays in harvest dates, longer term studies, as well as detailed analysis of their implications on carbohydrate reserves, bud fertility and future yield are desirable before these practices can be recommended.

The plantation frame as a measure of adaptation to climate change

The mechanization of vineyard work originally led to a reduction in planting densities due to the lack of machinery adapted to the vineyard. The current availability of specific machinery makes it possible to establish higher planting densities. In this work, three planting densities (1.40×0.80 m, 1.80×1 m and 2.20×1.20 m, corresponding to 8928, 5555 and 3787 plants/ha respectively) were studied with four varieties autochthonous of Galicia (northwestern Spain): Albariño and Treixadura (white), Sousón and Mencía (red). The vines were trained in a vertical shoot positioning system using a single Royat cordon, and pruned to spurs with two buds each. Agronomic data (yield, pruning wood weight, Ravaz index) and oenological data in must were collected. The higher planting density (1.40×0.80 m) had no significant effect on grape yield per vine in white varieties, although production per hectare was much higher due to the greater number of plants. In red varieties, this planting density resulted in a significantly lower production per vine, compensated by the greater number of plants. In addition, it significantly reduced the Brix degree in the must of the Albariño, Treixadura and Sousón varieties, and increased the total acidity in the latter two and Mencía. It also caused an increase in extractable and total anthocyanins and IPT in red grapes. The effects of high planting density on grapes are of great interest for the adaptation of varieties in the context of climate change. In the future, it could be advisable to modify the limits imposed by the appellations of origin on the planting density of these varieties in order to obtain more balanced wines.

Terroir traceability in grapes, musts and wine: results of research on Gewürztraminer and Sauvignon Blanc grape varieties in northern Italy

In the study of terroir, a separate analysis of its many component factors can be of great help in accurately identifying a vineyard’s natural elements that impact wine quality and typicity. This research used a dedicated pluri-disciplinary approach to investigate the ecological characteristics, including geology and geographical features, of 14 vineyards that produce Gewürztraminer and Sauvignon Blanc cultivars in the alpine Alto Adige DOC wine region. Both the geopedological method using Vineyards Geological Identity (VGI) and the new Solar Radiaton Identity (SRI) topoclimatic classification method were used to provide analytical measurements and qualitative/quantitative characterisations. In addition, wide-ranging targeted and untargeted oenological and chemical analyses were carried out on grapes, musts and wines to correlate the soils’ geomineral and physical conditions with the biochemical properties of their fruits and wines. The research identified strong correlations between vineyard geo-identity and wine biofingerprint, confirming a mineral traceability of strontium rubidium ratio and some minerals distinctive to the local geology, such as K, Ca, Ag, Ba and Mn.  The study also discovered that particular geomineral and physical soil conditions of the studied vineyards are related to the different amount of amino acids, primary varietal aromas and polyphenols found in grapes, musts and wines. The research confirmed that winemaking technologies support oenological quality, although in some cases, human practices can overpower certain characteristic elements in wine, erasing the typical imprint left by the vineyards’ natural terroir, which becomes less traceable. Terroir abiotic ecological factors and vineyard identity can be classified in detail using the new VGI and SRI analysis methods to discover interrelationships between geo-pedological and topoclimatic conditions that impact wine quality. These methods are also helpful in identifying which ecological elements are exclusive to a particular vineyard or wine sub-region.

Under-vine management effects on grapevine production, soil properties and plant communities in South Australia

Under-vine (UV) management has traditionally consisted of synthetic herbicide use to limit competition between weeds and grapevines. With growing global interest towards non-synthetic chemical use, this study aimed to capture the effects of alternative UV management at two commercial Shiraz vineyards in South Australia, where the sole management variables were UV management since 2016. In adjacent treatment blocks, cultivation (CU) was compared to spontaneous vegetation (SV) in McLaren Vale (MV), and herbicide was compared to SV in Eden Valley (EV). Soil water infiltration rates were slower and grapevine stem water potential was lower in CU compared to SV in MV, with the latter having a plant community dominated by soursob (Oxalis pes-caprae) during winter; while in EV, there was little separation between the treatments. Yields were affected at both sites, with SV being higher in MV and HE being higher in EV. In MV, the only effect on grape must was a lower 13C:12C isotope ratio in CU, indicating greater grapevine water stress. In the grape must at EV, SV had higher total soluble solids, total phenolics, anthocyanins, and yeast available nitrogen; and lower pH and titratable acidity. Pruning weights were not affected by the treatments in MV, while they were higher in HE at EV. Assessments revealed that the differing soil types at the two sites were likely the main determinants of the opposing production outcomes associated with UV management. In the silty loam soil of MV, the higher yields in SV were likely due to more plant-available water, as a potential result of the continuous soil bio-pores formed by winter UV vegetation. Conversely, in the loamy sand soils of EV with a lower cation exchange capacity, the lower yields and pruning weights in SV suggest the UV vegetation competed significantly with the grapevines for available water and nutrients.