IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 An Ag+ SPE method combined with Deans’ switch heart-cutting MDGC–MS/Olfactometry approach for identifying unknown volatile thiols in wine

An Ag+ SPE method combined with Deans’ switch heart-cutting MDGC–MS/Olfactometry approach for identifying unknown volatile thiols in wine

Abstract

Wine aroma is a crucial quality criterion. A multitude of volatile compounds have been identified and correlated to the aroma attributes perceived in wine. Volatile thiols are a category of volatile sulfur compounds that are well-recognized as potent aroma-impacting odorants contributing to various aroma attributes of many wines because of their low odor detection thresholds (ng/L). However, volatile thiols are highly reactive and generally present at ultra-trace concentrations (ng/L) in wines, causing major analytical difficulties. For more than two decades, the identifications of new volatile thiols were nearly exclusively achieved by the use of organomercuric compounds for thiol extraction, followed by conventional gas chromatography and mass spectrometry/olfactometry (GC–MS/O) for chromatographic separation, odorous zone profiling, and MS detection. However, such analytical protocols required the use of highly toxic organomercuric chemicals and are often laborious. Meanwhile, olfactometry data of other unknown thiol odorous zones has been reported but their identities were not pursued.
This work focused on the aroma of premium red wines and aimed to identify unknown volatile thiols. First, we developed a silver ion solid-phase extraction (Ag+ SPE) method for thiol isolation. Ag+ SPE cartridge selectivity, cartridge wettability, reservoir material, and elution reagent were evaluated. The developed Ag+ SPE method was safe, simple, scalable, selective, and artefact resistant, suitable for qualitative identification tasks. Low thermal mass (LTM) Deans’ switch (DS) heart-cutting multidimensional GC–MS/O (H/C MDGC–MS/O) was optimized for its performance using three model volatile thiol analytes. Significant impacts of instrument parameters including main host oven temperature, H/C width, and cryogenic trapping on the separation and detection were observed. Main host oven at high temperature was required to maintain flow balance for H/C operation. Narrow H/C width was selected to avoid irregular chromatographic behavior. Cryogenic trapping at the optimal temperature was needed to effectively capture the H/C effluent at the inlet of second column and to significantly enhance peak detection. The development of the Ag+ SPE H/C MDGC–MS/O protocol was applied to screen a selection of several premium Bordeaux red wines presenting a bouquet with intense empyreumatic nuances. In selected wines, a number of odorous zones with such aroma descriptors were characterized. Supported by olfactometric results, retention data, and corresponding mass spectra, the identification of odorous thiols that were not previously reported in wine was described. The identification of unknown thiols expands our understanding of the volatile molecular markers contributing to the aroma quality of premium wines

DOI:

Publication date: June 22, 2022

Issue: IVAS 2022

Type: Article

Authors

Chen Liang¹* and Darriet Philippe¹

¹Univ. Bordeaux, INRAE, Bordeaux INP, UMR1366 Œnologie, ISVV, F-33140 Villenave d’Ornon, France

Contact the author

Keywords

red wine, aroma, volatile thiols, extraction, identification

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

A spatial explicit inventory of EU wine protected designation of origin to support decision making in a changing climate

Winemaking areas recognized as protected designations of origin (PDOs) shape important economic, environmental and cultural values that are tied to closely defined geographic locations. To preserve wine products and wine-growing practices adopted in different PDOs these areas are strictly regulated by legal specifications. However, quality viticulture is increasingly under pressure from climate change, which is altering the local conditions of many winegrowing areas. Therefore, maintaining traditional wine products will require the adoption of tailored adaptation strategies, including possible changes in the legal regulation of protected wines. To this end, it is necessary to have a comprehensive knowledge on PDOs including their extension, products and allowed practices. While there have been efforts to build databases that summarize the characteristics for individual wine PDO areas and to quantify the related effects of climate change, much information is still included only in the official documentation of the EU geographical indication register and has never been collected in a comprehensive manner. With this study we aim at filling this gap by building a spatial inventory of European wine PDOs that supports decision making in viticulture in the context of climate change. To map and characterize European wine PDOs, we analysed their legal documents and extracted relevant information useful for climate change adaptation. The output consists of a comprehensive geographical dataset that identifies the boundaries of all 1200 European wine PDOs at unprecedented spatial resolution and includes a set of legally binding regulations, such as authorized vine varieties, maximum yields and planting density. The inventory will allow researchers to analyse the impacts of climate change on European wine PDOs and support decision makers in developing tailored adaptation strategies. This includes, among others, the evaluation of new vineyard site selection, the expansion of cultivated varieties or the authorization of irrigation in vineyards.

Analysis of some environmental factors and cultural practices that affect the production and quality of the Manto Negro, Callet and Prensal Blanc varieties

45 non irrigated vineyards distributed in the DO (Denomination) Pla i Llevant de Mallorca and the DO Binissalem Mallorca were used to investigate the characteristics of production and quality and their relationships certain environmental factors and cultural practices. The grape varieties investigated are autochthonous to the island of Mallorca, Manto Negro and Callet as red and Prensal Blanc as white. All plants were measured for four consecutive years in the main production and quality parameters. Among the environmental factors, the type of soil has been studied, more specifically its water retention capacity, the planting density, the age of the vineyard and the level of viral infection. The presence or absence of virus seems to have no effect on any component studied in the varieties studied. For the white variety Prensal Blanc age is negatively correlated with production and the number of bunches, nevertheless it does not cause any effect on the required quality parameters. However, for the red varieties Callet and Manto Negro, the age of the plantation is the variable that best correlates with the quality parameters, therefore the old vines should be the object of preservation by the viticulturists and winemakers in order to guarantee its contribution to the quality of the wines made with these varieties.

Local ancient grapevine cultivars to face future viticulture

Among the different strategies to cope with the negative impacts of climate change on viticulture, the exploitation of genetic diversity is one of the most promising to adapt to new conditions and maintain wine production and quality. One of the biggest concerns in the context of climate change is to improve water use efficiency (WUE). In this way, the use of genotypes that present a better response to drought and high WUE is a key issue. In this work, physiological performance analysis was conducted to compare the water deficit stress (WDS) responses of local and widespread grapevines cultivars. Leaf gas exchange, water use efficiency (WUE) at different levels (leaf and long-term WUE (∆13C)), leaf osmotic adjustment and other water relations parameters were determined in plants under well-watered and WDS conditions alongside assessment of the levels of foliar hormones concentrations. Results denote that local cultivars displayed better physiological performance under WDS as compared to the widely-distributed ones. he results corroborate the hypothesis that better stomatal control allows increasing leaf WUE under drought as occurred in the local Callet cv.; but the minority local cultivar Escursac cv. showed high WUE under both treatments. In this case, high WUE can be related to maintaining higher photosynthetic activity under drought. The different mechanisms underlying the better performance under WDS and high WUE of minority local cultivars are discussed.

Making sense of available information for climate change adaptation and building resilience into wine production systems across the world

Effects of climate change on viticulture systems and winemaking processes are being felt across the world. The IPCC 6thAssessment Report concluded widespread and rapid changes have occurred, the scale of recent changes being unprecedented over many centuries to many thousands of years. These changes will continue under all emission scenarios considered, including increases in frequency and intensity of hot extremes, heatwaves, heavy precipitation and droughts. Wine companies need tools and models allowing to peer into the future and identify the moment for intervention and measures for mitigation and/or avoidance. Previously, we presented conceptual guidelines for a 5-stage framework for defining adaptation strategies for wine businesses. That framework allows for direct comparison of different solutions to mitigate perceived climate change risks. Recent global climatic evolution and multiple reports of severe events since then (smoke taint, heatwave and droughts, frost, hail and floods, rising sea levels) imply urgency in providing effective tools to tackle the multiple perceived risks. A coordinated drive towards a higher level of resilience is therefore required. Recent publications such as the Australian Wine Future Climate Atlas and results from projects such as H2020 MED-GOLD inform on expected climate change impacts to the wine sector, foreseeing the climate to expect at regional and vineyard scale in coming decades. We present examples of practical application of the Climate Change Adaptation Framework (CCAF) to impacts affecting wine production in two wine regions: Barossa (Australia) and Douro (Portugal). We demonstrate feasibility of the framework for climate adaptation from available data and tools to estimate historical climate-induced profitability loss, to project it in the future and to identify critical moments when disruptions may occur if timely measures are not implemented. Finally, we discuss adaptation measures and respective timeframes for successful mitigation of disruptive risk while enhancing resilience of wine systems.

How does aromatic composition of red wines, resulting from varieties adapted to climate change, modulate fruity aroma?

One of the major issues for the wine sector is the impact of climate change linked to the increasing temperatures which affects physicochemical parameters of the grape varieties planted in Bordeaux vineyard and consequently, the quality of wine. In some varietals, the attenuation of their fresh fruity character is accompanied by the accentuation of dried-fruit notes [1]. As a new adaptive strategy on climate change, some winegrowers have initiated changes in the Bordeaux blend of vine varieties [2]. This study intends to explore the fruitiness in wines produced from grape varieties adapted to the future climate of Bordeaux. 10 commercial single–varietal wines from 2018 vintage made from the main grape varieties in the Bordeaux region (Cabernet franc, Cabernet-Sauvignon and Merlot) as well as from indigenous grape varieties from the Mediterranean basin, such as Cyprus (Yiannoudin), France (Syrah), Greece (Agiorgitiko and Xinomavro), Portugal (Touriga Nacional) and Spain (Garnacha and Tempranillo), were selected among 19 samples using sensory descriptive analyses. Both sensory and instrumental analyses were coupled, to investigate their fruity aroma expression. For sensory analysis, samples were prepared from wine, using a semi preparative HPLC method which preserves wine aroma and isolates fruity characteristics in 25 specific fractions [3,4]. Fractions of interest with intense fruity aromas were sensorially selected for each wine by a trained panel and mixed with ethanol and microfiltered water to obtain fruity aromatic reconstitutions (FAR) [5]. A free sorting task was applied to categorize FAR according to their similarities or dissimilarities, and different clusters were highlighted. Instrumental analysis of the different FAR and wines demonstrated variations in their molecular composition. Results obtained from sensory and gas chromatography analysis enrich the knowledge of the fruity expression of red wines from “new” grape varieties opening up new perspectives in wine technology, including blending, thus providing new tools for producers.