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…

Legacy of land-cover changes on soil erosion and microbiology in Burgundian vineyards

Soils in vineyards are recognized as complex agrosystems whose characteristics reflect complex interactions between natural factors (lithology, climate, slope, biodiversity) and human activities. To date, most of the unknown lies in an incomplete understanding of soil ecosystems, and specifically in the microbial biodiversity even though soil microbiota is involved in many key functions, such as nutrient cycling and carbon sequestration. Soil biological properties are indicative of soil quality. Therefore, understanding how soil communities are related to soil ecosystem functioning is becoming an essential issue for soil strategy conservation. Here, we propose to assess the importance of land-cover history on the present-day microbiological and physico-chemical properties. The studied area was selected in the Burgundian vineyards (Pernand-Vergelesses, Burgundy, France) where land occupation has been reconstructed over the last 40 years. Soil samples were collected in five areas reflecting various land cover history (forest, vineyards, shifting from forest to vineyards). For each area, physico-chemical parameters (pH, C, N, P, grain size) were measured and DNA was extracted to characterize the abundance and diversity of microbial communities. The obtained results show significant differences in the five areas suggesting that present-day microbial molecular biomass and bacterial taxonomic is partly inherited from past land occupation. Over longer period of time, such study of land-uses legacies may help to better assess ecosystem recovery and the impact of management practices for a better soil quality and vineyards sustainability.

Organic recycled mulches in sustainable viticulture: assessment of spontaneous plants communities and weed coverage

In recent years, developing more efficient and sustainable viticulture management has been essential due to the impact of climate change in semiarid regions. For this reason, the use of recycled organic mulching (ROM) in the vineyard has become an interesting strategy to cope with water stress, isolated soil from extreme temperatures and improving soil humidity, control the presence of weeds and therefore reduce the inputs of herbicides and improve soil fertility. This work aimed to analyse the effect of three different organic mulches [straw (S), grape pruning debris (GPD) and spent mushroom compost (SMC)] and two traditional soil management techniques [herbicide (H) and interrow (IN)] on weed coverage and the spontaneous plant communities’ presence. Data sampling was collected throughout the vine vegetative cycle of 2021 in La Rioja, Spain. The different soil management techniques had a clear effect on weed coverage and his development during the vine vegetative cycle. SMC and H were the treatments with the highest and the lowest coverage percentage, respectively. IN had a delayed weed emergence at the beginning of the vine vegetative cycle, but finally it reached maximum values nearby SMC. GPD and S had similar effects on weed emergence, reaching 25-30% of the maximum coverage values. A total of 29 herbaceous species were identified during the vegetative cycle, some of them very isolated and occasional. Principal component analysis (PCAs) showed a good association between spontaneous species and treatments, furthermore, specific species-treatment associations were found. Moreover, three clear groups of herbaceous communities were identified by cluster analysis. This study provides interesting information about the effect of different alternative soil management on herbaceous plant coverage and weed species communities which could contribute to making more sustainable viticulture.

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.

Second pruning as a strategy to delay maturation in cv. ‘Touriga nacional’ in the Portuguese Douro region

The advance in maturation of wine grapes is an important climate change risk related effect that could affect warm regions like Portuguese Douro Wine Region. Indeed, the climate analysis over the past years registered a decrease in the precipitation, significant higher average temperatures, and a more frequent occurrence of extreme weather events, including heat waves. In these conditions the length from anthesis until maturation is shortened and the uncoupling of technical and phenolic maturity results in berries with higher sugar concentration (and lower acidity), but lower anthocyanins, tannins, and total phenolic concentration, which produce unbalanced wines.
In this work, an innovative strategy of crop forcing, based on forcing vine regrowth after a second pruning of green shoots, was tested, aimed at delaying ripening until the temperature becomes lower and, therefore, preventing acidity loss and increasing anthocyanin-to-sugar ratio. The experiments were conducted in 2019 and 2020 in a commercial vineyard of ‘Touriga Nacional’ located in the Douro Region. Crop forcing was conducted 15 (CF1) to 30 (CF2) days after fruit set. Vines pruned with conventional methods were used as control (CF0). Results confirmed that fruit ripening was shifted from the hot season (August/September), until a cooler period (October through early-November). At harvest, grapevine berries from CF1 and CF2 presented lower pH and higher acidity, than control, with no significant differences in colour intensity and phenolic levels composition. Sugar content was lower in CF2-treated vines in both seasons. However, in CF-treated vines the number and size of clusters were significantly lower (up to 88% reduction) than in control plants. A metabolomics analysis of mature berries from CF-treated vines and control is underway. Crop forcing was indeed effective in producing a more balance berry composition but severely reduced grapevine yield,

Spatial variability of temperature is linked to grape composition variability in the Saint-Emilion winegrowing area

Elevated temperature during the grape maturation period is a major threat for grape quality and thus wine quality. Therefore, characterizing the grape composition response to temperature at a larger scale would represent a crucial step towards adaptation to climate change. In response to changes in temperature, various physiological mechanisms regulate grape composition. Primary and secondary metabolisms are both involved in this response, with well-known effects, for example on anthocyanins, and lesser known effects, for example on aromas or aroma precursors. At the field scale or at the regional scale, however, numerous environmental or plant-specific factors intervene to make the effects of temperature difficult to distinguish from overall variability. In this study, it was attempted to overcome this difficulty by selecting well-characterized situations with differing temperatures.
A long-term study of air temperature variability across several Merlot vineyards in the Saint-Emilion and Pomerol wine producing area found significant temperature differences and gradients at various time scales linked to environmental factors. From this study area, a few sites were selected with similar age, soil and training system conditions, and with repeated and contrasted temperature differences during the maturation period. The average temperature difference during the maturation period was about 2°C between cooler and warmer sites, a difference similar to that expected under future climate change scenarios. In close vicinity to the temperature sensors at each site, grape berries were sampled at different times until full maturity during 2019 and 2020. Also, berries from bunches on either side of the row were analyzed separately, allowing an investigation of bunch exposure effect associated with the coupling of berry temperature and solar radiation. Four replicates of pooled berries for each time – site – bunch exposure combination were obtained and analyzed for biochemical composition. Analyses of variance of the biochemical composition data collected at different sampling times reveal significant effects associated with temperature, site, and bunch azimuth. For instance, anthocyanins in grape skins are clearly influenced by temperature and solar radiation exposure, with up to 30% reduction in warmer conditions.