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…

Climate projections over France wine-growing region and its potential impact on phenology

Climate change represents a major challenge for the French wine industry. Climatic conditions in French vineyards have already changed and will continue to evolve. One of the notable effects on grapevine is the advancing growing season. The aim of this study is to characterise the evolution of agroclimatic indicators (Huglin index, number of hot days, mean temperature, cumulative rainfall and number of rainy days during the growing season) at French wine-growing regions scale between 1980 and 2019 using gridded data (8 km resolution, SAFRAN) and for the middle of the 21th century (2046-2065) with 21 GCMs statistically debiased and downscaled at 8 km. A set of three phenological models were used to simulate the budburst (BRIN, Smoothed-Utah), flowering, veraison and theoretical maturity (GFV and GSR) stages for two grape varieties (Chardonnay and Cabernet-Sauvignon) over the whole period studied. All the French wine-growing regions show an increase in both temperatures during the growing season and Huglin index. This increase is accompanied by an advance in the simulated flowering (+3 to +9 days), veraison (+6 to +13 days) and theoretical maturity (+6 to +16 days) stages, which are more noticeable in the north-eastern part of France. The climate projections unanimously show, for all the GCMs considered, a clear increase in the Huglin index (+662 to 771 °C.days compared to the 1980-1999 period) and in the number of hot days (+5.6 to 22.6 days) in all the wine regions studied. Regarding rainfall, the expected evolution remains very uncertain due to the heterogeneity of the climates simulated by the 21 models. Only 4 regions out of 21 have a significant decrease in the number of rainy days during the growing season. The two budburst models show a strong divergence in the evolution of this stage with an average difference of 18 days between the two models on all grapevine regions. The theoretical maturity is the most impacted stage with a potential advance between 40 and 23 days according to wine-growing regions.

Effect of partial net shading on the temperature and radiation in the grapevine canopy, consequences on the grape quality of cv. Gros Manseng in PDO Pacherenc-du-vic-Bilh

As elsewhere, southwestern France vineyards face more recurrent summer heat waves these last years. Among the possibilities of adaptation to this climate changing parameter, the use of net shading is a technique that allow for limiting canopy exposure to radiations. In this trial, we tested net shading installed on one face of the canopy, on a north-south row-oriented plot of cv. Gros Manseng trained on VSP system in the PDO Pacherenc-du-Vic-Bilh. The purpose was to characterize the effects on the ambient canopy temperatures and radiations during the season and to observe the consequences on the composition of grapes and wines. Two sorts of net were used with two levels of obstruction (50% and 75%) of the photosynthesis active radiation (PAR). They have been installed on the west side of the canopy and compared to a netless control. Temperature and PAR sensors registered hourly data during the season. On specific summer day (hot and sunny) manual measurements took also place on bunches (temperature) and in different spots of the canopy (PAR). The results showed that, on clear days, the radiation is lowered by the shade nets respecting the supplier criteria. The effects on the ambient canopy temperature were inconstant on this plot when we observed the data from the global period of shading between fruit set and harvest. However, during hot days (>30°C), the temperature in the canopy was reduced during afternoon and the temperature of the bunch surface was reduced as well comparing to the control. A decrease of the maturity parameters of the berries, sugar and acidity, was also observed. Concerning the wine aromatic potential, no differences clearly appeared.

Climate modeling at local scale in the Waipara winegrowing region in the climate change context

In viticulture, a warming climate can have a very significant impact on grapevine development and therefore on the quality and characteristics of wines across different spatial scales, ranging from global to local. In order to adapt wine-growing to climate change, global climate models can be used to define future scenarios, but only at the scale of major wine regions. Despite the huge progress made over the last ten years in terms of the spatial resolution of climate models (now downscaled to a few square kilometres), they are not yet sufficiently precise to account for the local climate variability associated with such parameters as local topography, in spite of these parameters being decisive for vine and wine characteristics. This study describes a method to downscale future climate scenarios to vineyard scale. Networks of data loggers have been used to collect air temperature at canopy level in the Waipara winegrowing region (New Zealand) over five growing seasons. These measurements allow the creation of fine-scale geostatistical models and maps of temperature (at 100 m resolution) for the growing season. In order to model climate change at pilot site scale, these geostatistical models have been combined with regional climate change predictions for the periods 2031-2050 and 2081-2100 based on the RCP8.5 climate change scenario. The integration of local climate variability with regionalized climate change simulations allows assessment of the impacts of climate change at the vineyard scale. The improved knowledge gained using this methodology results from the increased horizontal resolution that better addresses the concerns of winegrowers. The results provide the local winegrowers with information necessary to understand current processes, as well as historical and future viticulture trends at the scale of their site, thereby facilitating decisions about future response strategies.

Sustainable fertilisation of the vineyard in Galicia (Spain)

Excessive fertilization of the vineyard leads to low quality grapes, increased costs and a negative impact on the environment. In order to establish an integrated management system aimed at a sustainable fertilization of the vineyards, nutritional reference levels were established. For this purpose, 30 representative vineyards of the Albariño variety were studied, in which soil and petiole analyses were carried out for two years and grape yield and quality at harvest were measured. In both years of study, soil pH, calcium, sodium and cation exchange capacity were positively correlated with calcium content and negatively correlated with manganese in grapes. Irrigated vineyards had higher levels of aluminium in soil and lower levels of calcium in petiole. Climatic conditions were very different in the years of the study. The year 2019 was colder than usual, in 2020 there was a marked water stress with high summer temperatures. This resulted in medium-high acidity in grapes in 2019 and low acidity in 2020, with sugar levels being similar both years. A very marked decrease in must amino nitrogen was observed in 2020, with ammonia nitrogen remaining stable. The correlation of acidity and sugar values in grapes with soil and petiole analysis data made it possible to establish reference levels for the nutritional diagnosis of the Albariño variety in this region. Based on these results, an easy-to-use TIC application is currently being created for grapegrowers, aimed at improving the sustainability of the vineyard through reasoned fertilization. This study has now been extended to other Galician vine varieties.

Phenolic composition of Tempranillo Blanco grapes changes after foliar application of urea

Our research aimed to determine the effect and efficiency of foliar application of urea on the phenolic composition of Tempranillo Blanco grapes. The field experiment was carried out in 2019 and 2020 seasons and the plot was located in D.O.Ca Rioja (North of Spain). The vineyard was Vitis vinifera L. Tempranillo Blanco and grafted on Richter-110 rootstock. The treatments were control (C), whose plants were sprayed with water and three doses of urea: plants were sprayed with urea 3 kg N/ha (U3), 6 kg N/ha (U6) and 9 kg N/ha (U9). The applications were performed in two phenological stages, pre-veraison (Pre) and veraison (Ver). Also, each of the treatments was repeated one week later. Control and treatments were performed in triplicate and arranged in a randomised block design. Grapes were harvested at optimum ripening stage. High-performance liquid chromatography was used to analyse the phenolic composition of the grapes. Finally, the results obtained from the analytical determinations – flavonols, flavanols and non-flavonoid (hydroxybenzoic acids, hydroxycinnamic acids and stilbenes) – were studied statistically by analysis of variance. The results showed that, in 2019, U6-Pre and U9-Pre treatments increased the hydroxybenzoic acid content in grapes, and also all foliar treatments applied at Pre enhanced the stilbene concentration. Moreover, U3-Ver was the only treatment that rose flavonol and stilbene contents in the Tempranillo Blanco grapes. In 2020, all treatments applied at Pre enhanced the flavonol concentration in grapes. Furthermore, U3-Pre and U9-Pre treatments increased stilbene content in grapes. Nevertheless, the hydroxybenzoic acid content was improved by U6-Ver and U9-Ver and besides, hydroxycinnamic acid concentration in grapes was increased by all treatments applied at Ver. In conclusion, the lower and highest dose of urea (U3 and U9), applied at pre-veraison, were the best treatments to improve the Tempranillo Blanco grape phenolic composition.