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…

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.

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.

Biodiversity in the vineyard agroecosystem: exploring systemic approaches

Biodiversity conservation and restoration are essential for guarantee the provision of ecosystem services associated to vineyard agroecosystem such as climate regulation trough carbon sequestration and control of pests and diseases. Most of published research dealing with the complexity of the vineyard agroecosystems emphasizes the necessity of innovative approaches, including the integration of information at different temporal and spatial scales and development of systemic analysis based on modelling. A biodiversity survey was conducted in the Franciacorta wine-growing area (Lombardy, Italy), one of the most important Italian wine-growing regions for sparkling wine production, considering a portion of the territory of 112 ha. The area was divided into several Environmental Units (EUs), defined as a whole vineyard or portion of vineyard homogenous in terms of four agronomic characteristics: planting year, planting density, cultivar, and training system. In each EU a set of compartments was identified and characterised by specific variables. The compartments are meteorology, morphology (altitude, slope, aspect, row orientation, and solar irradiance), ecological infrastructures and management. The landscape surrounding EU was also characterised in terms of land-use in a buffer zone of 500 m. For each component a specific methodology was identified and applied. Different statistical approaches were used to evaluate the method to integrate the information related to different compartments within the EU and related to the buffer zone. These approaches were also preliminarily evaluated for their ability to describe the contribution of biodiversity and landscape components to ecosystem services. This methodological exploration provides useful indication for the development of a fully systemic approach to structural and functional biodiversity in vineyard agroecosystems, contributing to promote a multifunctional perspective for the all wine-growing sector.

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.

Climate change impacts: a multi-stress issue

With the aim of producing premium wines, it is admitted that moderate environmental stresses may contribute to the accumulation of compounds of interest in grapes. However the ongoing climate change, with the appearance of more limiting conditions of production is a major concern for the wine industry economic. Will it be possible to maintain the vineyards in place, to preserve the current grape varieties and how should we anticipate the adaptation measures to ensure the sustainability of vineyards? In this context, the question of the responses and adaptation of grapevine to abiotic stresses becomes a major scientific issue to tackle. An abiotic stress can be defined as the effect of a specific factor of the physico-chemical environment of the plants (temperature, availability of water and minerals, light, etc.) which reduces growth, and for a crop such as the vine, the yield, the composition of the fruits and the sustainability of the plants. Water stress is in many minds, but a systemic vision is essential for at least two reasons. The first reason is that in natural environments, a single factor is rarely limiting, and plants have to deal with a combination of constraints, as for example heat and drought, both in time and at a given time. The second reason is that plants, including grapevine, have central mechanisms of stress responses, as redox regulatory pathways, that play an important role in adaptation and survival. Here we will review the most recent studies dealing with this issue to provide a better understanding of the grapevine responses to a combination of environmental constraints and of the underlying regulatory pathways, which may be very helpful to design more adapted solutions to cope with climate change.