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…

The modification of cultural practices in grapevine cv. Syrah, does it modify the characteristics of the musts?

The work shows the results of a year of experimentation (2020) in a Syrah variety vineyard in La Roda (Castilla-La Mancha, Spain). The trial approach was on a randomized block design with two factors: Irrigation (I) and Pruning (P).
Irrigation schedules were adjusted to apply amounts close to 1,500 m3/ha. With this provision, 2 different irrigation treatments were proposed: I1) Start of irrigation from pea-sized grape to post-harvest (providing at least 20 % of the total amount of irrigation water to be provided post-harvest); I2) Start of irrigation from pea-sized grape to harvest (usual irrigation practice in the study area). Pruning was proposed with two treatments, one at the end of January (P1), which is pruning on a conventional date; and P2) pruning carried out at the beginning of budding. In total, 4 repetitions were designed with 4 elementary plots, each one of them representing one of the proposed treatments (I1P1; I1P2; I2P1; I2P2). In total, 16 plots were worked on and each elementary plot consisted of 30 strains, distributed in 3 lines.
The productive response was evaluated with the yield results of the harvest harvested at 23 ºBrix. The qualitative response was measured in the musts through the indices of technological (acidity, pH and potassium) and phenolic maturity and aromatic compounds in free and glycosylated fractions. The treatments tested had, in general, an effect on the different variables analyzed.

A blueprint for managing vine physiological balance at different spatial and temporal scales in Champagne

In Champagne, the vine adaptation to different climatic and technical changes during these last 20 years can be seen through physiological balance disruptions. These disruptions emphasize the general grapevine decline. Since the 2000s, among other nitrogen stress indicators, the must nitrogen has been decreasing. The combination of restricted mineral fertilizers and herbicide use, the growing variability of spring rainfall, the increasing thermal stress as well as the soil type heterogeneity are only a few underlying factors that trigger loss of physiological balance in the vineyards. It is important to weigh and quantify the impact of these factors on the vine. In order to do so, the Comité Champagne uses two key-tools: networking and modelization. The use of quantitative and harmonized ecophysiological indicators is necessary, especially in large spatial scales such as the Champagne appellation. A working group with different professional structures of Champagne has been launched by the Comité Champagne in order to create a common ecophysiology protocol and thus monitor the vine physiology, yearly, around 100 plots, with various cultural practices and types of soil. The use of crop modelling to follow the vine physiological balance within different pedoclimatic conditions enables to understand the present balance but also predict the possible disruptions to come in future climatic scenarios. The physiological references created each year through the working group, benefit the calibration of the STICS model used in Champagne. In return, the model delivers ecophysiology indicators, on a daily scale and can be used on very different types of soils. This study will present the bottom-up method used to give accurate information on the impacts of soil, climate and cultural practices on vine physiology.

Under-vine management effects on grapevine production, soil properties and plant communities in South Australia

Under-vine (UV) management has traditionally consisted of synthetic herbicide use to limit competition between weeds and grapevines. With growing global interest towards non-synthetic chemical use, this study aimed to capture the effects of alternative UV management at two commercial Shiraz vineyards in South Australia, where the sole management variables were UV management since 2016. In adjacent treatment blocks, cultivation (CU) was compared to spontaneous vegetation (SV) in McLaren Vale (MV), and herbicide was compared to SV in Eden Valley (EV). Soil water infiltration rates were slower and grapevine stem water potential was lower in CU compared to SV in MV, with the latter having a plant community dominated by soursob (Oxalis pes-caprae) during winter; while in EV, there was little separation between the treatments. Yields were affected at both sites, with SV being higher in MV and HE being higher in EV. In MV, the only effect on grape must was a lower 13C:12C isotope ratio in CU, indicating greater grapevine water stress. In the grape must at EV, SV had higher total soluble solids, total phenolics, anthocyanins, and yeast available nitrogen; and lower pH and titratable acidity. Pruning weights were not affected by the treatments in MV, while they were higher in HE at EV. Assessments revealed that the differing soil types at the two sites were likely the main determinants of the opposing production outcomes associated with UV management. In the silty loam soil of MV, the higher yields in SV were likely due to more plant-available water, as a potential result of the continuous soil bio-pores formed by winter UV vegetation. Conversely, in the loamy sand soils of EV with a lower cation exchange capacity, the lower yields and pruning weights in SV suggest the UV vegetation competed significantly with the grapevines for available water and nutrients.

Elevational range shifts of mountain vineyards: Recent dynamics in response to a warming climate

Increasing temperatures worldwide are expected to cause a change in spatial distribution of plant species along elevational gradients and there are already observable shifts to higher elevations as a consequence of climate change for many species. Not only naturally growing plants, but also agricultural cultivations are subject to the effects of climate change, as the type of cultivation and the economic viability depends largely on the prevailing climatic conditions. A shift to higher elevations therefore represents a viable adaptation strategy to climate change, as higher elevations are characterized by lower temperatures. This is especially important in the case of viticulture because a certain wine-style can only be achieved under very specific climatic conditions. Although there are several studies investigating climatic suitability within winegrowing regions or longitudinal shifts of winegrowing areas, little is known about how fast vineyards move to higher elevations, which may represent a viable strategy for winegrowers to maintain growing conditions and thus wine-style, despite the effects of climate change. We therefore investigated the change in the spatial distribution of vineyards along an elevational gradient over the past 20 years in the mountainous wine-growing region of Alto Adige (Italy). A dataset containing information about location and planting year of more than 26000 vineyard parcels and 30 varieties was used to perform this analysis. Preliminary results suggest that there has been a shift to higher elevations for vineyards in general (from formerly 700m to currently 850 m a.s.l., with extreme sites reaching 1200 m a.s.l.), but also that this development has not been uniform across different varieties and products (i.e. vitis vinifera vs hybrid varieties and still vssparkling wines). This is important for climate change adaptation as well as for rural development. Mountain areas, especially at mid to high elevations, are often characterized by severe land abandonment which can be avoided to some degree if economically viable and sustainable land management strategies are available.

How can historical cultivars mitigate the effects of climate change?

IFV, INRAe and the national network “Partenaires de la Sélection Vigne” representing 37 organizations from the different wine regions, have been working increasingly closely over the last 2 decades towards the preservation of the French varietal patrimony. There are approximately 600 patrimonial varieties according to INRAe and SupAgro Montpellier experts, including ancient cultivars (400) and intravarietal crossbreeds obtained since the 19th century. In the context of a drastic reduction in such varieties from the mid 1980’s in favor of mainstream varieties, it was essential to carry out an inventory of old vines and vineyards. INRAe Vassal collection plays a key role here as it holds the largest diversity available, along with a rich bibliography and herbariums, offering us the opportunity to document and double check the identity of a cultivar, consolidating the expertise of ampelographers. The work is carried out in several stages, from verifying the existence of a variety in a small region, through to rehabilitation. During this session, the authors present the process that leads to the official registration of a variety. After this, IFV selection center takes over to initiate the process of selection and propagation. A specific focus within regions such as the Alps, Champagne and the South-West will provide details of the full procedure. Bia, Bouysselet, Chardonnay rose, Mecle and the aptly named Tardif, are some of the cultivars that have followed this procedure. Furthermore, a recent regulation established by INAO on “varieties of interest for adaptation purposes” might boost uptake by growers. Since 2006, 36 historical cultivars have been registered. Most of these have been neglected in the past due to late maturity, lack of sugar and high titratable acidity at harvest time. Such characteristics are today considered as positive qualities, not only in mitigation of the effects of climate change, but also as an opportunity for restoring diversity…