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…

Green berries on Gewürztraminer (Vitis vinifera L.) in South Tyrol (Italy)

The grape variety Gewürztraminer is known to be affected by two physiological disorders namely berry shrivel and bunch stem necrosis. During the season 2014 we noticed a new symptomatology type of ripening disorder on the variety. The new symptom showed not all berries fallowing the normal maturation stages, but single berries remaining at a soft but green stage till harvest. The broad distribution of these so called “green berries” symptoms in different production sites of our region, caused huge damage due to the difficulty of eliminating single berries per bunch before harvesting. Therefore, the Research Centre Laimburg began to investigate the reasons and origins of this new symptom. This work shows the results of first attempts to find causes for the symptom as well as the resulting approach to mitigate symptoms. Applications of magnesium leaf fertilizer showed first promising results against this putative disorder. To study the causal effect of the green berries 30 symptomatic vineyards in 2014 have been selected for a monitoring during the season 2016. To evaluate the foliar nutrient treatment two vineyards have been selected for application of magnesium sulfate and magnesium chloride. Leaf and berry nutrient analysis, as well as the main quality parameters during ripening have been performed. As soon as “green berries” symptoms appeared, incidence and severity have been evaluated. Most of the symptomatic vineyards of the 2016 monitoring showed light to clear magnesium deficit symptoms on their foliage. Only during the seasons 2020 and 2021 “green berries” symptoms could be found in the leaf fertilizer treatment vineyards. Both seasons showed a significant effect of the magnesium treatments to reduce the incidence and severity of the symptom. It seems that the appearance of the “green berries” symptom on Gewürztraminer is correlated to a disturbed uptake of magnesium of the vines.

Phenological characterization of a wide range of Vitis Vinifera varieties

In order to study the impact of climate change on Bordeaux grape varieties and to assess the adaptation capacities of candidates to the grape varieties of this wine region to the new climatic conditions, an experimental block design composed of 52 grape varieties was set up in 2009 at the INRAE Bordeaux Aquitaine center. Among the many parameters studied, the three main phenological stages of the vine (budburst, flowering and veraison) have been closely monitored since 2012. Observations for each year, stage and variety were carried out on four independent replicates. Precocity indices have been calculated from the data obtained over the 2012-2021 period (Barbeau et al. 1998). This work allowed to group the phenological behaviour of the grapevine varieties, not only based on the timing of the subsequent developmental stages, but also on the overall precocity of the cycle and the total length of the cycle between budburst and veraison. Results regarding the variability observed among the different grape varieties for these phenological stages are presented as heat maps.

Ecophysiological performance of Vitis rootstocks under water stress

The use of rootstocks tolerant to soil water deficit is an interesting strategy to cope with limited water availability. Currently, several nurseries are breeding new genotypes, but the physiological basis of its responses under water stress are largely unknown. To this end, an ecophysiological assessment of the conventional 110-Richter (110R) and SO4, and the new M1 and M4 rootstocks was carried out in potted ungrafted plants. During one season, these Vitis genotypes were grown under greenhouse conditions and subjected to two water regimes, well-watered and water deficit. Water potentials of plants under water deficit down to < -1.4 MPa, and net photosynthesis (AN) <5 μmol m-2 s-1 did not cause leaf oxidative stress damage compared to well-watered conditions in any of the genotypes. The antioxidant capacity was sufficient to neutralize the mild oxidative stress suffered. Under both treatments, gravimetric differences in daily water use were observed among genotypes, leading to differences in the biomass of root, shoot and leaf. Under well-watered conditions, SO4 and 110R were the most vigorous and M1 and M4 the least. However, under water stress, SO4 exhibited the greatest reduction in biomass while M4 showed the lowest. Remarkably, under these conditions, SO4 reached the least negative stem water potential (Ψstem), while M1 reduced stomatal conductance (gs) and AN the most. In addition, SO4 and M1 genotypes also showed the highest and lowest hydraulic conductance values, respectively. Our results suggest that there are differences in water use regulation among genotypes, not only attributed to differences in stomatal regulation or intrinsic water use efficiency at the leaf level. Therefore, because no differences in canopy-to-root ratio were achieved, it is hypothesized that xylem vessel anatomical differences may be driving the reported differences among rootstocks performance. Results demonstrate that each Vitis rootstock differs in its ecophysiological responses under water stress.

Bioclimatic shifts and land use options for Viticulture in Portugal

Land use, plays a relevant role in the climatic system. It endows means for agriculture practices thus contributing to the food supply. Since climate and land are closely intertwined through multiple interface processes, climate change may lead to significant impacts in land use. In this study, 1-km observational gridded datasets are used to assess changes in the Köppen–Geiger and Worldwide Bioclimatic (WBCS)

Variations of soil attributes in vineyards influence their reflectance spectra

Knowledge on the reflectance spectrum of soil is potentially useful since it carries information on soil chemical composition that can be used to the planning of agricultural practices. If compared with analytical methods such as conventional chemical analysis, reflectance measurement provides non-destructive, economic, near real-time data. This paper reports results from reflectance measurements performed by spectroradiometry on soils from two vineyards in south Brazil. The vineyards are close to each other, are on different geological formations, but were subjected to the same management. The objective was to detect spectral differences between the two areas, correlating these differences to variations in their chemical composition, to assess the technique’s potential to predict soil attributes from reflectance data.To that end, soil samples were collected from ten selected vine parcels. Chemical analysis yield data on concentration of twenty-one soil attributes, and spectroradiometry was performed on samples. Chemical differences significant to a 95% confidence level between the two studied areas were found for six soil attributes, and the average reflectance spectra were separated by this same level along most of the observed spectral domain. Correlations between soil reflectance and concentrations of soil attributes were looked for, and for ten soil traits it was possible to define wavelength domains were reflectance and concentrations are correlated to confidence levels from 95% to 99%. Partial Least Squares Regression (PLSR) analyses were performed comparing measured and predicted concentrations, and for fifteen out of 21 soil traits we found Pearson correlation coefficients r > 0.8. These preliminary results, which have to be validated, suggest that variations of concentration in the investigated soil attributes induce differences in reflectance that can be detected by spectroradiometry. Applications of these observations include the assessment of the chemical content of soils by spectroradiometry as a fast, low-cost alternative to chemical analytical methods.