Macrowine 2021
IVES 9 IVES Conference Series 9 Alternative fate of varietal thiols in wine: identification, formation, and enantiomeric distribution of novel 1,3-oxathianes

Alternative fate of varietal thiols in wine: identification, formation, and enantiomeric distribution of novel 1,3-oxathianes

Abstract

AIM: This study aimed to explore an alternative fate of varietal thiols by identifying and characterising cis-2-methyl-4-propyl-1,3-oxathiane (cis-2-MPO) and cis-2,4,4,6-tetramethyl-1,3-oxathiane (cis-TTMO) in wine. Elucidating these new pathways could aid in explaining the loss of varietal thiols and would further our understanding of the stereochemical relationships between oxathianes and varietal thiols.

METHODS: GC-MS was used to identify cis-2-MPO,1 and a stable isotope dilution assay (SIDA) was developed to quantify its enantiomers after separation with a chiral β-cyclodextrin GC column.2 Varietal thiols and their enantiomers were analysed by SIDA with HPLC-MS/MS to determine their relationship with cis-2-MPO. Production of cis-2-MPO and its correlation with 3-SH, 3-SHA, and acetaldehyde was studied by profiling the evolution of these volatiles during alcoholic fermentation (AF) of Sauvignon blanc (SB) juice fermented with J7, VIN13, and their co-inoculum.3

RESULTS: cis-2-MPO, derived from 3-SH and acetaldehyde, was identified and then measured at up to 460 ng/L (equivalent to 385 ng/L of 3-SH) in a set of wines. Analysis of (2R,4S)-2-MPO and (2S,4R)-2-MPO, arising from thiol enantiomers (3S)-3-SH and (3R)-3-SH, showed respective concentrations of up to 250 and 303 ng/L. The enantiomeric ratio of (2R,4S)-/(2S,4R)-2-MPO was 43:57 whereas that of (3S)-/(3R)-3-SH in the same wines was 51:49.2 Strong correlations were revealed for both 3-SH and cis-2-MPO and their related enantiomeric pairs.The AF study showed cis-2-MPO was produced from an early stage of AF and reached a peak of 847 ng/L (VIN13 ferment) before gradually declining to 50-65 ng/L. Its evolution profile was identical to that of acetaldehyde and 3-SHA, with moderate to strong correlations found for the analytes.Additionally, cis-TTMO, derived from 4-MSPOH and acetaldehyde, was identified in wine as a single enantiomer at concentrations of up to 28 ng/L (equivalent to 23 ng/L of 4-MSPOH). An aroma detection threshold of 14.9 µg/L was determined for cis-TTMO, and this new volatile was described as ‘citrus’, ‘green’, ‘sweet/caramel’, and ‘mango’, shifting toward ‘onion/sweaty’ and ‘sulfurous’ at higher concentrations.2

CONCLUSIONS

The knowledge gained helps rationalise the fate of varietal thiols via the production of oxathianes in wine, and reveals the stereochemical links between these related compounds. A chemical formation pathway to oxathianes was verified and may also apply to other thiols bearing the 1,3-sulfanylalkanol substitution through the reaction with acetaldehyde.

DOI:

Publication date: September 13, 2021

Issue: Macrowine 2021

Type: Article

Authors

Xingchen Wang

Department of Wine Science and Waite Research Institute, The University of Adelaide (UA), PMB 1, Glen Osmond, SA 5064, Australia,Liang, CHEN, Université de Bordeaux, Unité de Recherche Œnologie, EA 4577, USC 1366 INRAE, Institut des Sciences de la Vigne et du Vin, 33882, Villenave d’Ornon cedex, France Dimitra L., CAPONE, Department of Wine Science and Waite Research Institute, Australian Research Council Training Centre for Innovative Wine Production, UA, PMB 1, Glen Osmond, SA 5064, Australia Aurélie, ROLAND, SPO, Univ Montpellier, INRAE, Institut Agro, Montpellier, France David W., JEFFERY, Department of Wine Science and Waite Research Institute, Australian Research Council Training Centre for Innovative Wine Production, UA, PMB 1, Glen Osmond, SA 5064, Australia

Contact the author

Keywords

3-sulfanylhexan-1-ol, 4-methyl-4-sulfanylpentan-2-ol, acetaldehyde, chiral stationary phase, odour detection threshold, sauvignon blanc, stable isotope dilution assay, gas chromatography–mass spectrometry

Citation

Related articles…

Upscaling the integrated terroir zoning through digital soil mapping: a case study in the Designation of Origin Campo de Borja

homogeneous zones by intersecting several partial zonings of major factors that influence vineyard growth. Each of them follows specific process from their corresponding disciplines. Soil zoning specifically refers to a Soil Resource Inventory map that has traditionally been generated by conventional soil mapping methods. These methods have shortcomings in reaching fine cartographic and categorical details and involve significant expenses, which undermines their applicability. A new framework named Digital Soil Mapping has introduced quantitative models by statistical techniques to establish soil-landscape relationships and is able to provide intensive scale cartography.

In the present study, a microzoning at 1:10.000 scale is generated from an initial zoning, where the conventional soil map with polytaxic map units is replaced by a new one from digital techniques that disaggregates them. The comparison between the zonings considers a quantitative evaluation of capability for each Homogeneous Terroir Unit by means of the Viticultural Quality Index and its categorization based on its distribution by map. The spatial intersection of both maps gives rise to a confusion matrix in which the flows of class variations after the substitution are assessed.

The results show a five-fold increase in the number of Homogeneous Terroir Units identified and a larger differentiation among them, evidenced by a wider range in the capability index distribution. Both elements are accompanied by an increase in the detection of areas of higher potential within previously undervalued uniform zones.These features are a direct effect of the improvements brought by Digital Soil Mapping techniques and would verify the advantages of their implementation in the Integrated Terroir zoning. Eventually, such new highly detailed terroir units would benefit precision viticulture and sustainable management practices.

Understanding graft union formation by using metabolomic and transcriptomic approaches during the first days after grafting in grapevine

Since the arrival of Phyloxera (Daktulosphaira vitifolia) in Europe at the end of the 19th century, grafting has become essential to cultivate Vitis vinifera. Today, grafting provides not only resistance to this aphid, but it used to adapt the cultivars according to the type of soil, environment, or grape production requirements by using a panel of rootstocks. As part of vineyard decline, it is often mentioned the importance of producing quality grafted grapevine to improve vineyard longevity, but, to our knowledge, no study has been able to demonstrate that grafting has a role in this context. However, some scion/rootstock combinations are considered as incompatible due to poor graft union formation and subsequently high plant mortality soon after grafting. In a context of climate change where the creation of new cultivars and rootstocks is at the centre of research, the ability of new cultivars to be grafted is therefore essential. The early identification of graft incompatibility could allow the selection of non-viable plants before planting and would have a beneficial impact on research and development in the nursery sector. For this reason, our studies have focused on the identification of metabolic and transcriptomic markers of poor grafting success during the first days/week after grafting; we have identified some correlations between some specialized metabolites, especially stilbenes, and grafting success, as well as an accumulation of some amino acids in the incompatible combination. The study of the metabolome and the transcriptome allowed us to understand and characterise the processes involved during graft union formation.

Elevational range shifts of mountain vineyards: Recent dynamics in response to a warming climate

Increasing temperatures worldwide are expected to cause a change in spatial distribution of plant species along elevational gradients and there are already observable shifts to higher elevations as a consequence of climate change for many species. Not only naturally growing plants, but also agricultural cultivations are subject to the effects of climate change, as the type of cultivation and the economic viability depends largely on the prevailing climatic conditions. A shift to higher elevations therefore represents a viable adaptation strategy to climate change, as higher elevations are characterized by lower temperatures. This is especially important in the case of viticulture because a certain wine-style can only be achieved under very specific climatic conditions. Although there are several studies investigating climatic suitability within winegrowing regions or longitudinal shifts of winegrowing areas, little is known about how fast vineyards move to higher elevations, which may represent a viable strategy for winegrowers to maintain growing conditions and thus wine-style, despite the effects of climate change. We therefore investigated the change in the spatial distribution of vineyards along an elevational gradient over the past 20 years in the mountainous wine-growing region of Alto Adige (Italy). A dataset containing information about location and planting year of more than 26000 vineyard parcels and 30 varieties was used to perform this analysis. Preliminary results suggest that there has been a shift to higher elevations for vineyards in general (from formerly 700m to currently 850 m a.s.l., with extreme sites reaching 1200 m a.s.l.), but also that this development has not been uniform across different varieties and products (i.e. vitis vinifera vs hybrid varieties and still vssparkling wines). This is important for climate change adaptation as well as for rural development. Mountain areas, especially at mid to high elevations, are often characterized by severe land abandonment which can be avoided to some degree if economically viable and sustainable land management strategies are available.

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.

Better understand the soil wet bulb formation with subsurface or aerial drip irrigation in viticulture

The gradual change in rainfall patterns experienced in the south of France vineyards, especially around the Mediterranean sea, means that the vines are increasingly subject to summer drought. The winegrowers developped the use of irrigation techniques to ensure the maintenance of competitive yields in the production of wines under Protected Geographical Indication label. In practice, drip irrigation pipes can be installed above the ground or buried into the soil as well as at different distances from the vine row. The objective of this study was to examine the profiles of the wet bulbs of the soil obtained from two drip irrigation systems : aerial drip located under the vine row and subsurface drip placed in the middle of the inter-row. This experiment took place over two consecutive seasons (2020-2021) on a 3.4 ha Viognier plot in the Mediterranean region (PGI Oc, France) on sandy clay soil. The annual rainfalls were less than 400 mm. Soil water content probes were installed at different depths (20 – 40 – 60 – 80 cm) and at different lateralities from the vine row (30 – 60 – 90 – 120 cm) to control the formation of the soil wet bulb during irrigation. The mapping and the analysis of the data allowed a better understanding and differentiation of the water percolation when irrigating with subsurface or aerial drip. For the same amount of water and without differences of vine water status, it is shown that in a subsurface drip irrigation situation, the size of the wet bulb formed is larger than in aerial drip irrigation system.