IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 UHPLC-HRMS analysis for the evaluation of formation and degradation of polysulfides in wine 

UHPLC-HRMS analysis for the evaluation of formation and degradation of polysulfides in wine 

Abstract

The contribution of sulfur compounds to wine aroma has been studied for several years, as their role can be either positive, contributing to the fruitiness and typicity of some white wines like Sauvignon blanc, or negative when related to off-flavours caused by H2S. Recently, H2S formation from degradation of polysulfides has gained interest in the wine sector as it could potentially lead to wine defects or quality reduction (1). It has been proposed that polysulfides can be formed upon oxidation of thiol compounds (for example glutathione and cysteine) with Cu2+ or elemental sulfur and could form a reservoir for H2S release post-bottling (2,3,4). Polysulfide formation has been demonstrated in several matrices including real wines (5,6,7), but the exact reaction mechanisms have not been proven yet. It has been suggested that both chemical and biochemical activities can play a role (8), which is a topic that is still under investigation.
In the present work we investigated the possible technological factors that could influence the formation of polysulfides. Furthermore, we proposed a new method using both liquid chromatography with mass spectrometry and parallel ion chromatography in order to study the degradation of single polysulfides and the formation of H2S, respectively.

METHODS
For the study we used ultra-high-performance liquid chromatography (UHPLC) coupled to hybrid quadrupole/high-resolution mass spectrometry (HRMS, Q-Orbitrap) for the detection, characterisation and accumulation of polysulfides. For the study of polysulfide degradation UHPLC was used with an on-line fraction collector (UHPLC-FC) in order to isolate the single compounds. After collection the sampled compound was kept at 30°C to promote degradation and injections were performed until complete degradation. For the detection of H2S Ion Chromatography (IC) was used. For the technological studies, wines fortified with varietal thiols were treated with Cu2+ or Ag+ and subjected to accelerated aging and different musts were fermented with different oenological yeasts in single vinifications.

RESULTS
Using UHPLC-FC and subsequent UHPLC-HRMS it was possible to follow single polysulfide degradation in time. The technological studies revealed treatment effects of post-fermentation treatments with Cu2+ and Ag+ and significant differences were found in polysulfide profiles of wines fermented with different oenological yeasts. These studies gave new insides in the formation and degradation mechanisms of polysulfides, which is considered relevant with regard to potential alterations of wine quality

DOI:

Publication date: June 22, 2022

Issue: IVAS 2022

Type: Article

Authors

Dekker Susanne¹*, Nardin Tiziana¹, Fedrizzi Bruno², Van Leeuwen Katryna², Roman Tomas¹ and Larcher Roberto¹

¹FEM-IASMA Fondazione Edmund Mach, Via Edmund Mach, 1, 38098 San Michele All’adige TN
²School of Chemical Sciences, The University of Auckland, 23 Symonds Street, Auckland, 1142, New Zealand

Contact the author

Keywords

polysulfides, oxidation, UHPLC-HRMS, reductive odours

 

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Upscaling the integrated terroir zoning through digital soil mapping: a case study in the Designation of Origin Campo de Borja

homogeneous zones by intersecting several partial zonings of major factors that influence vineyard growth. Each of them follows specific process from their corresponding disciplines. Soil zoning specifically refers to a Soil Resource Inventory map that has traditionally been generated by conventional soil mapping methods. These methods have shortcomings in reaching fine cartographic and categorical details and involve significant expenses, which undermines their applicability. A new framework named Digital Soil Mapping has introduced quantitative models by statistical techniques to establish soil-landscape relationships and is able to provide intensive scale cartography.

In the present study, a microzoning at 1:10.000 scale is generated from an initial zoning, where the conventional soil map with polytaxic map units is replaced by a new one from digital techniques that disaggregates them. The comparison between the zonings considers a quantitative evaluation of capability for each Homogeneous Terroir Unit by means of the Viticultural Quality Index and its categorization based on its distribution by map. The spatial intersection of both maps gives rise to a confusion matrix in which the flows of class variations after the substitution are assessed.

The results show a five-fold increase in the number of Homogeneous Terroir Units identified and a larger differentiation among them, evidenced by a wider range in the capability index distribution. Both elements are accompanied by an increase in the detection of areas of higher potential within previously undervalued uniform zones.These features are a direct effect of the improvements brought by Digital Soil Mapping techniques and would verify the advantages of their implementation in the Integrated Terroir zoning. Eventually, such new highly detailed terroir units would benefit precision viticulture and sustainable management practices.

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.

VINIoT: Precision viticulture service for SMEs based on IoT sensors network

The main innovation in the VINIoT service is the joint use of two technologies that are currently used separately: vineyard monitoring using multispectral imaging and deployed terrain sensors. One part of the system is based on the development of artificial intelligence algorithms that are feed on the images of the multispectral camera and IoT sensors, high-level information on water stress, grape ripening status and the presence of diseases. In order to obtain algorithms to determine the state of ripening of the grapes and avoid losing information due to the diversity of the grape berries, it was decided to work along the first year 2020 at berry scale in the laboratory, during the second year at the cluster scale and on the last year at plot scale. Different varieties of white and red grapes were used; in the case of Galicia we worked with the white grape variety Treixadura and the red variety Mencía. During the 2020 and 2021 campaigns, multispectral images were taken in the visible and infrared range of: 1) sets of 100 grapes classifying them by means of densimetric baths, 2) individual bunches. The images taken with the laboratory analysis of the ripening stage were correlated. Technological maturity, pH, probable degree, malic acid content, tartaric acid content and parameters for assessing phenolic maturity, IPT, anthocyanin content were determined. It has been calculated for each single image the mean value of each spectral band (only taking into account the pixels of interest) and a correlation study of these values with laboratory data has been carried out. These studies are still provisional and it will be necessary to continue with them, jointly with the training of the machine learning algorithms. Processed data will allow to determine the sensitivity of the multispectral images and select bands of interest in maturation.

Characterization of variety-specific changes in bulk stomatal conductance in response to changes in atmospheric demand and drought stress

In wine growing regions around the world, climate change has the potential to affect vine transpiration and overall vineyard water use due to related changes in atmospheric demand and soil water deficits. Grapevines control their transpiration in response to a changing environment by regulating conductance of water through the soil-plant-atmosphere continuum. Most vineyard water use models currently estimate vine transpiration by applying generic crop coefficients to estimates of reference evapotranspiration, but this does not account for changes in vine conductance associated with water stress, nor differences thought to exist between varieties. The response of bulk stomatal conductance to daily weather variability and seasonal drought stress was studied on Cabernet-Sauvignon, Merlot, Tempranillo, Ugni blanc, and Semillon vines in a non-irrigated vineyard in Bordeaux France. Whole vine sap flow, temperature and humidity in the vine canopy, and net radiation absorbed by the vine canopy were measured on 15-minute intervals from early July through mid-September 2020, together with periodic measurement of leaf area, canopy porosity, and predawn leaf water potential. From this data, bulk stomatal conductance was calculated on 15-minute intervals, and multiple regression analysis was performed to identify key variables and their relative effect on conductance. Attention was focused on addressing multicollinearity and time-dependency in the explanatory variables and developing regression models that were readily interpretable. Variability of vapor pressure deficit over the day, and predawn water potential over the season explained much of the variability in conductance, with relative differences in response coefficients observed across the five varieties. By characterizing this conductance response, the dynamics of vine transpiration can be better parameterized in vineyard water use modeling of current and future climate scenarios.

austrianvineyards.com: online viewer of all designations of Austrian wine

To digitally record and present all the origins of Austrian wines in the same perfect and clear way was the motivation for the Austrian Wine Marketing Board (Austrian Wine) to start with the project in 2018. In June 2021 the results were presented to the public in an online viewer showing all the designations of Austrian wine, available at https://austrianvineyards.com in a largely barrier-free manner. The online viewer provides tailored individual maps fitted to the respective zoom level. The smallest unit of wine-origins in Austria is called Ried and is displayed in a plot-specific manner highlighting areas under vine. Information on the Ried include administrative district, winegrowing municipality, cadastral municipality, large collective vineyard site, specific winegrowing region, generic winegrowing region, winegrowing area and, in many cases, an illustrative picture. Complementary data on the size, elevation (minimum-maximum), orientation (in 8 sectors plus flat) and gradient (minimum, maximum, average) are based on the area under vine according to the EU’s Integrated Administration and Control System. Additional information covers climate data. The diagrams are taken from the monthly breakdown of data in the annals of the Central Institute for Meteorology and Geodynamics, Austria provide a display of values for air temperature, precipitation, and sunshine hours for the reference year and the long-term average. Seasonal aggregated data on temperature, precipitation, and sunshine hours complete the display. Short descriptions with emphasis on geology and soil, field name in historical maps, etymology of the denomination, and main planted variety complements the available information for the main designations in the online viewer. These descriptions are compiled by winegrowers, geologists, historians, and journalists. All the information and data can be extracted to a pdf-file. Printed vineyard maps are also available. Missing content regarding wine origins in Styria will be completed in winter 2021/22.