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…

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.

Metabolomic discrimination of grapevine water status for Chardonnay and Pinot noir

Water status impact in viticulture has been widely explored, as it strongly affects grapevine physiology and grape chemical composition. It is considered as a key component of vitivinicultural terroir. Most of the studies concerning grapevine water status have focused on either physiological traits, or berry compounds, or traits involved in wine quality. Here, the response of grapevine to water availability during the ripening period is assessed through non-targeted metabolomics analysis of grape berries by ultra-high resolution mass spectrometry. The grapevine water status has been assessed during 2 consecutive years (2019 & 2020), through carbon isotope discrimination on juices from berries collected at maturity (21.5 brix approx.) for 2 Vitis vinifera cv. Pinot noir (PN) and Chardonnay (CH). A total of 220 grape juices were collected from 5 countries worldwide (Italy; Argentina; France; Germany; Portugal). Measured δ13C (‰) varied from -28.73 to -22.6 for PN, and from -28.79 to -21.67 for CH. These results also clearly revealed higher water stress for the 2020 vintage. The same grape juices have been analysed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Liquid Chromatography coupled to Mass Spectrometry (LC-qTOF-MS), leading to the detection of up to 4500 CHONS containing elemental compositions, and thus likely tens of thousands of individual compounds, which include fatty acids, organic acids, peptides, phenolics, also with high levels of glycosylation. Multivariate statistical analysis revealed that up to 160 elemental compositions, covering the whole range of detected masses (100 –1000 m/z), were significantly correlated to the observed gradients of water status. Examples of chemical markers, which are representative of these complex fingerprints, include various derivatives of the known abscisic acid (ABA), such as phaesic acid or abscisic acid glucose ester, which are significantly correlated with higher water stress, regardless of the variety. Cultivar-specific behaviours could also be identified from these fingerprints. Our results provide an unprecedented representation of the metabolic diversity, which is involved in the water status regulation at the grape level, and which could contribute to a better knowledge of the grapevine mitigation strategy in a climate change context.

Differential responses of red and white grape cultivars trained to a single trellis system – the VSP

Commercial grape production relies on training grapevine cultivars onto a variety of trellis systems. Training allows for well-lit leaves and clusters, maximizing fruit quality in addition to facilitating cultivation, harvesting, and diseases control. Although grapevines can be trained onto an infinite variety of trellis systems, most red and white cultivars are trained to the standard VSP (Vertical Shoot Positioning) system. However, red and white cultivars respond differently to VSP in fruit composition and growth characteristics, which are yet to be fully understood. Therefore, the objective of this study was to examine the influence of the VSP trellis system on fruit composition of three red, Cabernet Sauvignon, Merlot and Syrah, and three white, Chardonnay, Riesling, and Gewurztraminer cultivars grown under uniform growing conditions in the same vineyard. All cultivars were monitored for maturity and harvested at their physiologically maximum possible sugar concentration to compare various fruit quality attributes such as Brix, pH, TA, malic and tartaric acids, glucose and fructose, potassium, YAN, and phenolic compounds including total anthocyanins, anthocyanin profile, and tannins. A distinct pattern in fruit composition was observed in each cultivar. In regards to growth characteristics, Syrah grew vigorously with the highest cluster weight. Although all cultivars developed pyriform seeds, the seed size and weight varied among all cultivars. Also varied were mesocarp cell viability, brush morphology, and cane structure. This knowledge of the canopy architectural characteristics assessed by the widely employed fruit compositional attributes and growth characteristics will aid the growers in better management of the vines in varied situations.

Traditional agroforestry vineyards, sources of inspiration for the agroecological transition of viticulture

A unique “terroir” can be found in southern Bolivia, which combines the specific features of climate, topography and altitude of high valleys, with the management of grapevines staked on trees. It is one of the rare remnants of agroforestry viticulture. A survey was carried out among 29 grapegrowers in three valleys, to characterize the structure and management of these vineyards, and identify the services they expect from trees. Farms were small (2.2 ha on average) and 85% of vineyards were less than 1 ha. Viticulture was associated with vegetable, fruit and fodder production, sometimes in the same fields. Molle trees were found in all plots, together with one or two other native tree species. Traditional grapevine varieties such as Negra Criolla, Moscatel de Alejandría and Vicchoqueña were grown with a large range of densities from 1550 to 9500 vines ha-1. From 18 to 30% of them were staked on trees, with 1.2 to 4.9 vines per tree. The management of these vineyards (irrigation, fertilization and grapevine protection) was described, the most particular technical operation being the coordinated pruning of trees and grapevines. Three types of management could be identified in the three valleys. Grapegrowers had a clear idea of the ecosystem services they expected from trees in their vineyards. The main one was protection against climate hazards (hail, frost, flood). Then they expected benefits in terms of pest and disease control, improvement of soil fertility and resulting yield. At last, some producers claimed that tree-staking was quicker and cheaper than conventional trellising. It can be hypothesized then that agroforestry is a promising technique for the agroecological transition of viticulture. Its contribution to the “terroir” of the high valleys of southern Bolivia and its link with the specificities of the wines and spirits produced there remain to be explored.

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.