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…

Legacy of land-cover changes on soil erosion and microbiology in Burgundian vineyards

Soils in vineyards are recognized as complex agrosystems whose characteristics reflect complex interactions between natural factors (lithology, climate, slope, biodiversity) and human activities. To date, most of the unknown lies in an incomplete understanding of soil ecosystems, and specifically in the microbial biodiversity even though soil microbiota is involved in many key functions, such as nutrient cycling and carbon sequestration. Soil biological properties are indicative of soil quality. Therefore, understanding how soil communities are related to soil ecosystem functioning is becoming an essential issue for soil strategy conservation. Here, we propose to assess the importance of land-cover history on the present-day microbiological and physico-chemical properties. The studied area was selected in the Burgundian vineyards (Pernand-Vergelesses, Burgundy, France) where land occupation has been reconstructed over the last 40 years. Soil samples were collected in five areas reflecting various land cover history (forest, vineyards, shifting from forest to vineyards). For each area, physico-chemical parameters (pH, C, N, P, grain size) were measured and DNA was extracted to characterize the abundance and diversity of microbial communities. The obtained results show significant differences in the five areas suggesting that present-day microbial molecular biomass and bacterial taxonomic is partly inherited from past land occupation. Over longer period of time, such study of land-uses legacies may help to better assess ecosystem recovery and the impact of management practices for a better soil quality and vineyards sustainability.

Updating the Winkler index: An analysis of Cabernet sauvignon in Napa Valley’s varied and changing climate

This study aims to create an updated, agile viticultural climate index (similar to the Winkler Index) by performing in-depth analyses of current and historical data from industry partners in several major winegrowing regions. The Winkler Index was developed in the early twentieth century based on analysis of various grape-growing regions in California. The index uses heat accumulation (i.e. Growing Degree Days) throughout the growing season to determine which grape varieties are best suited to each region. As viticultural regions are increasingly subject to the complexity and uncertainty of a changing climate, a more rigorous, agile model is needed to aid grape growers in determining which cultivars to plant where. For the first phase of this study, 21 industry partners throughout Napa Valley shared historical phenology, harvest, viticultural practice, and weather data related to their Cabernet sauvignon vineyard blocks. To complement this data, berry samples were collected throughout the 2021 growing season from 50 vineyard blocks located throughout 16 American Viticultural Areas that were then analyzed for basic berry chemistry and phenolics. These blocks have been mapped using a Geographic Information System (GIS), enabling analysis of altitude, vineyard row orientation, slope, and remotely sensed climate data. Sampling sites were also chosen based on their proximity to a weather station. By analyzing historical data from industry partners and data specifically collected for this study, it is possible to identify key parameters for further analysis. Initial results indicate extreme variability at a high spatial resolution not currently accounted for in modern viticultural climate indices and suggest that viticultural practices play a major role. Using the structure of data collection and analyses developed for the first phase, this project will soon be expanded to other wine regions globally, while continuing data collection in Napa Valley.

The rootstock, the neglected player in the scion transpiration even during the night

Water is the main limiting factor for yield in viticulture. Improving drought adaptation in viticulture will be an increasingly important issue under climate change. Genetic variability of water deficit responses in grapevine partly results from the rootstocks, making them an attractive and relevant mean to achieve adaptation without changing the scion genotype. The objective of this work was to characterize the rootstock effect on the diurnal regulation of scion transpiration. A large panel of 55 commercial genotypes were grafted onto Cabernet Sauvignon. Three biological repetitions per genotype were analyzed. Potted plants were phenotyped on a greenhouse balance platform capable of assessing real-time water use and maintaining a targeted water deficit intensity. After a 10 days well-watered baseline period, an increasing water deficit was applied for 10 days, followed by a stable water deficit stress for 7 days. Pruning weight, root and aerial dry weight and transpiration were recorded and the experiment was repeated during two years. Transpiration efficiency (ratio between aerial biomass and transpiration) was calculated and δ13C was measured in leaves for the baseline and stable water deficit periods. A large genetic variability was observed within the panel. The rootstock had a significant impact on nocturnal transpiration which was also strongly and positively correlated with maximum daytime transpiration. The correlations with growth and water use efficiency related traits will be discussed. Transpiration data were also related with VPD and soil water content demonstrating the influence of environmental conditions on transpiration. These results highlighted the role of the rootstock in modulating water deficit responses and give insights for rootstock breeding programs aimed at identifying drought tolerant rootstocks. It was also helpful to better define the mechanisms on which the drought tolerance in grapevine rootstocks is based on.

Adaptation to soil and climate through the choice of plant material

Choosing the rootstock, the scion variety and the training system best suited to the local soil and climate are the key elements for an economically sustainable production of wine. The choice of the rootstock/scion variety best adapted to the characteristics of the soil is essential but, by changing climatic conditions, ongoing climate change disrupts the fine-tuned local equilibrium. Higher temperatures induce shifts in developmental stages, with on the one hand increasing fears of spring frost damages and, on the other hand, ripening during the warmest periods in summer. Expected higher water demand and longer and more frequent drought events are also major concerns. The genetic control of the phenotypes, by genomic information but also by the epigenetic control of gene expression, offers a lot of opportunities for adapting the plant material to the future. For complex traits, genomic selection is also a promising method for predicting phenotypes. However, ecophysiological modelling is necessary to better anticipate the phenotypes in unexplored climatic conditions Genetic approaches applied on parameters of ecophysiological models rather than raw observed data are more than ever the basis for finding, or building, the ideal varieties of the future.

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.