IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Abstract

3-Sulfanylhexan-1-ol (3SH) is a key impact odorant of white wines such as Sauvignon Blanc. In particular, the varietal characters of Sauvignon Blanc, especially from Marlborough NZ, are strongly influenced by the concentrations of 3SH. 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 well understood. The polyfunctional varietal thiols are 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. 1One precursor of particular interest is the glutathione conjugate to the aldehyde form of 3SH, 3S-glutathionylhexanal (glut-3SH-al). Retention 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. 2 Additionally, the bisulfite adduct of glut-3SH-al (glut-3SH-SO3) has been identified in wine samples, as SO2 is widely present in wine media. 3,4 The interconversion of glut-3SH-al and glut-3SH-SO3 is of great interest as it is an equilibrium and 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. 4 We have developed a method for the extraction and quantification of glut-3SH-al and glut-3SH-SO3, using previously synthesised deuterated analogues of these compounds to ensure reliable quantification.5 The compounds are separated using solid-phase extraction (SPE), followed by oxime derivatisation and MRM analysis on an LC-QqQ. This method enables determination of the glut-3SH-al and glut-3SH-SO3 content of a wide range of grape-derived samples, a valuable piece of the puzzle in elucidating 3SH biogenesis.

Using this method, we have analysed the glut-3SH-al and glut-3SH-SO3 content of a wide range of white wines from around NZ, investigating the impact of location, age, and noble rot or late harvest on the precursor content of these wines. This insight into factors impacting glut-3SH-al and glut-3SH-SO3 content in commercial wines, and the possible influence on the finished wine aroma, adds another piece to the puzzle of 3SH and 3SHA biogenesis in wines. Indeed, despite the contribution of these volatile thiols to the aroma of botrytised white wines, these wines contain significantly lower, or negligible, concentrations of glut-3SH-al and glut-3SH-SO3, something which will be explored further in future work

DOI:

Publication date: June 22, 2022

Issue: IVAS 2022

Type: Article

 

Authors

Muhl Jennifer¹, Deed Rebecca¹,², Pilkington Lisa¹ and Fedrizzi Bruno¹

¹The University of Auckland, School of Chemical Sciences

²The University of Auckland, School of Biological Sciences

Contact the author

Keywords

LC-QQQ, 3-sulfanylhexan-1-ol, glut-3SH-al, aroma compound precursors, white wine

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Diagnosis of soil quality and evaluation of the impact of viticultural practices on soil biodiversity in a vineyard in southwestern France

Viticulture is facing two major changes – climate change and agroecological transition. In both cases, soil quality is seen as a lever to move towards a more sustainable viticulture. However, soil biological quality is little considered in the implementation of viticultural practices. Gascogn’Innov (2017-2022) is an Operational Group funded by the European Innovation Partnership for Agriculture. As such, it brings together winegrowers from the south-west of France, scientists, advisors and technicians, around a project focused on viticultural soil biological functioning and the design of technical routes more respectful toward soil heritage. To achieve this, the project aims to acquire references on the impact of viticultural practices on soil biology from a dynamic way, and to test a methodology to integrate information provided by the soil bioindicators to manage farming systems. A set of indicators of soil biological quality are evaluated in the project: microorganisms (bacteria and fungi abundance and diversity), fauna (abundance and diversity of nematodes and earthworms), physico-chemical characteristics, soil structure assessment and degradation rate of organic matter. Based on a network of 13 plots that have been subject to an initial diagnosis in 2017, several agronomical practices to restore soil fertility are experimented to redesign the cropping system (for instance plant cover, organic matter inputs, reduction of herbicides, mineral fertilizers). System redesign was made in collaboration by winegrowers and an interdisciplinary group of experts (agronomists, biologists). Several indicators are measured on vine and soil at each vintage to assess vine health and productivity. At the end of the project (2021), a final diagnosis was carried out. Gascogn’Innov allowed to create a regional database on the quality of wine-growing soils, which permitted to evaluate the effect of practices according to soil types. Especially, decreasing the intensity of tillage and increasing the duration and diversity of grass coverage tends to increase the abundance of all the organisms studied. This project confirmed the value of soil biological quality indicators to drive the sustainability of practices, but also highlighted the key-role of expertise, in both agronomy and soil biology, to help winegrowers understand and appropriate their soil quality diagnoses.

Low-cost sensors as a support tool to monitor soil-plant heat exchanges in a Mediterranean vineyard

Mediterranean viticulture is increasingly exposed to more frequent extreme conditions such as heat waves. These extreme events co-occur with low soil water content, high air vapor pressure deficit and high solar radiant energy fluxes and result in leaf and berry sunburn, lower yield, and berry quality, which is a major constraint for the sustainability of the sector. Grape growers must find ways to proper and effectively manage heat waves and extreme canopy and berry temperatures. Irrigation to keep soil moisture levels and enable adequate plant turgor, and convective and evaporative cooling emerged as a key tool to overcome this major challenge. The effects of irrigation on soil and plant water status are easily quantifiable but the impact of irrigation on soil and canopy temperature and on heat convection from soil to cluster zone remain less characterized. Therefore, a more detailed quantification of vineyard heat fluxes is highly relevant to better understand and implement strategies to limit the effects of extreme weather events on grapevine leaf and berry physiology and vineyards performance. Low-cost sensor technologies emerge as an opportunity to improve monitoring and support decision making in viticulture. However, validation of low-cost sensors is mandatory for practical applicability. A two-year study was carried in a vineyard in Alentejo, south of Portugal, using low-cost thermal cameras (FLIR One, 80×60 pixels and FLIR C5, 160×120 pixels, 8-14 µm, FLIR systems, USA) and pocket thermohygrometers (Extech RHT30, EXTECH instruments, USA) to monitor grapevine and soil temperatures. Preliminary results show that low-cost cameras can detect severe water stress and support the evaluation of vertical canopy temperature variability, providing information on soil surface temperature. All these thermal parameters can be relevant for soil and crop management and be used in decision support systems.

Grapevine varietal diversity as mitigation tool for climate change: Agronomic and oenologic potential of 14 foreign varieties grown in Languedoc region (France)

Climate change effects in Languedoc include an expected rise in temperatures, increased evapotranspiration as well as more severe and frequent climatic hazards, such as frost, drought periods and heat waves. For winegrowers theses phenomena impact both yield and quality, resulting in more frequent unbalanced wines. Research on identified mitigation tools for vineyard management is necessary to improve resilience of grapevine agrosystems. Varietal assortment is one of them. This study focuses on agronomic and oenologic potential of 14 foreign varieties grown in Languedoc French region. Fourteen grapevine varieties were monitored during 2021 from June until harvest on eight different sites, some of which occurring on more than one site adding up to 21 different modalities: 7 white varieties Alvarinho B, Assyrtiko B (2), Malvasia Istriana B, Parellada B, Verdejo B, Verdelho B, Xarello B, and 7 black varieties Saperavi N (2), Touriga nacional N, Baga N, Aleatico N, Montepulciano N (2), Primitivo N (3), Calabrese N (3). Varietals were compared through the following parameters: phenology was assessed by using the information collected in the Database Network of French Vine Conservatories (INRAE-SupAgro-IFV, 2005-2015). The number of inflorescences for shoots from secondary buds and bourillons and suckers were observed to assess post-bud break frost tolerance potential. Grapevine water status was studied through stem water potential measurement, observation of foliage symptoms of drought, and 𝛿13C on must. Frequencies and intensities of downy mildew, powdery mildew, and black rot attacks were estimated before harvest on leaves and clusters and botrytis at harvest to assess disease susceptibilities. Berry composition was monitored from end of veraison until harvest. Yield and mean bunch weight were also calculated. Varieties were then ranked on a 1-4 scale for each parameter and compared through PCA. Forty two stations of the Mediterranean basin were compared by PCA with the Multicriteria Climatic Classification indicators in order to confront the collected information during 2021 campaign to the hypothesis that plants coming from dry and hot regions are genetically adapted to such climatic conditions.

Copper contamination in vineyard soils of Bordeaux: spatial risk assessment for the replanting of vines and crops

Copper (Cu) is widely and historically used in viticulture as a fungicide against mildew. Cu has a strong affinity for soil organic matter and accumulates in topsoil horizons. Thus, Cu may negatively affect soil organisms and plants, consequently reducing soil fertility and productivity. The Bordeaux vineyards have the largest vineyard surfaces (26%) within French controlled appellation and a great proportion of French wine production (around 5 million hl per year). Considering the local context of vineyard surfaces decreasing (vine uprooting) and possible new crop plantation, the issue of Cu potential toxicity rises. Therefore, the aims of this work are firstly to evaluate the Cu contamination in vineyard soils of Bordeaux, secondly to produce a risk assessment map for new vine or crop plantation. We used soil analyses from several local studies to build a database with 4496 soil horizon samples. The database was enhanced by means of pedotransfer functions in order to estimate the bioaccessible (EDTA-extractable) Cu in soils of samples without measurements. From this database, 1797 georeferenced samples with CuEDTA concentrations in the topsoil (0-50 cm depth) were used for kriging interpolation in order to produce the spatial distribution map of CuEDTA in vineyard soils. Then, the spatial distribution of Cu was crossed with vine uprooting surfaces and municipality boundaries. CuEDTAconcentrations ranged from 0.52 to 459 mg/kg and showed clear anomalies. Our results from spatial analysis showed that almost 50% of vineyard soil surfaces have CuEDTA concentrations higher than 30 mg/kg (moderate risk for new plantation) and 20% with concentrations higher than 50 mg/kg (high risk for new plantation). A decision-support map based on municipalities was realised to provide a simple tool to stakeholders concerned by land use management.

Assessing the climate change vulnerability of European winegrowing regions by combining exposure, sensitivity and adaptive capacity indicators

Winegrowing regions recognized as protected designations of origin (PDOs) are closely tied to well defined geographic locations with a specific set of pedoclimatic attributes and strictly regulated by legal specifications. However, climate change is increasingly threatening these regions by changing local conditions and altering winegrowing processes. The vulnerability to these changes is largely heterogenous across different winegrowing regions because it is determined by individual characteristics of each region, including the capacity to adapt to new climatic conditions and the sensitivity to climate change, which depend not only on natural, but also socioeconomic and legal factors. Accurate vulnerability assessments therefore need to combine information about adaptive capacity and climate change sensitivity with projected exposure to new climatic conditions. However, most existing studies focus on specific impacts neglecting important interactions between the different factors that determine climate change vulnerability. Here, we present the first comprehensive vulnerability assessment of European wine PDOs that spatially combines multiple indicators of adaptive capacity and climate change sensitivity with high-resolution climate projections. We found that the climate change vulnerability of PDO areas largely depends on the complex interactions between physical and socioeconomic factors. Homogenous topographic conditions and a narrow varietal spectrum increase climate change vulnerability, while the skills and education of farmers, together with a good economic situation, decrease their vulnerability. Assessments of climate change consequences therefore need to consider multiple variables as well as their interrelations to provide a comprehensive understanding of the expected impacts of climate change on European PDOs. Our results provide the first vulnerability assessment for European winegrowing regions at high spatiotemporal resolution that includes multiple factors related to climate exposure, sensitivity, and adaptive capacity on the level of single winegrowing regions. They will therefore help to identify hot spots of climate change vulnerability among European PDOs and efficiently direct adaptation strategies.