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…

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…

Variety and climatic effects on quality scores in the Western US winegrowing regions

Wine quality is strongly linked to climate. Quality scores are often driven by climate variation across different winegrowing regions and years, but also influenced by other aspects of terroir, including variety. While recent work has looked at the relationship between quality scores and climate across many European regions, less work has examined New World winegrowing regions. Here we used scores from three major rating systems (Wine Advocate, Wine Enthusiast and Wine Spectator) combined with daily climate and phenology data to understand what drives variation across wine quality scores in major regions of the Western US, including regions in California, Oregon and Washington. We examined effects of variety, region, and in what phenological period climate was most predictive of quality. As in other studies, we found climate, based mainly on growing degree day (GDD) models, was generally associated with quality—with higher GDD associated with higher scores—but variety and region also had strong effects. Effects of region were generally stronger than variety. Certain varieties received the highest scores in only some areas, while other varieties (e.g., Merlot) generally scored lower across regions. Across phenological stages, GDD during budbreak was often most strongly associated with quality. Our results support other studies that warmer periods generally drive high quality wines, but highlight how much region and variety drive variation in scores outside of climate.

The concept of terroir: what place for microbiota?

Microbes play key roles on crop nutrient availability via biogeochemical cycles, rhizosphere interactions with roots as well as on plant growth and health. Recent advances in technologies, such as High Throughput Sequencing Techniques, allowed to gain deeper insight on the structure of bacterial and fungal communities associated with soil, rhizosphere and plant phyllosphere. Over the past 10 years, numerous scientific studies have been carried out on the microbial component of the vineyard. Whether the soil or grape compartments have been taken into account, many studies agree on the evidence of regional delineations of microbial communities, that may contribute to regional wine characteristics and typicity. Some authors proposed the term “microbial terroir” including “yeast terroir” for grapes to describe the connection between microbial biogeography and regional wine characteristics. Many factors are involved in terroir including climate, soil, cultivar and human practices as well as their interactions. Studies considering “microbial terroir” greatly contributed to improve our knowledge on factors that shape the vineyard microbial structure and diversity. However, the potential impact of “microbial terroir” on wine composition has yet not received strong scientific evidence and many questions remain to be addressed, related to the functional characterization of the microbial community and its impact on plant physiology and grape composition, the origins and interannual stability of vineyard microbiota, as well as their impact on wine sensorial attributes. The presentation will give an overview on the role of microbiota as a terroir component and will highlight future perspectives and challenges on this key subject for the wine industry.

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.

The impact of leaf canopy management on eco-physiology, wood chemical properties and microbial communities in root, trunk and cordon of Riesling grapevines (Vitis vinifera L.)

In the last decades, climate change required already adaptation of vineyard management. Increase in temperature and unexpected weather events cause changes in all phenological stages requiring new management tools. For example, defoliation can be a useful tool to reduce the sugar content in the berries creating differences in the wine profiles. In a ten-year field experiment using Riesling (Vitis vinifera L, planted 1986, Geisenheim, Germany), various mechanical defoliation strategies and different intensities were trialed until 2016 before the vineyard was uprooted. Wood was sampled from the plant compartments root, trunk, cordon and shoot for analyses of physicochemical properties (e.g. lignin and element content, pH, diameter), nonstructural carbohydrates and the microbial communities. The aim of the study was to investigate the influence of reduced canopy leaf area on the sink-source allocation into different compartments and potential changes of the fungal and prokaryotic wood-inhabiting community using a metabarcoding approach. Severe summer pruning (SSP) of the canopy and mechanical defoliation (MDC) above the bunch zone decreased the leaf area by 50% compared to control (C). SSP reduced the photosynthetic capacity, which resulted in an altered source-sink allocation and carbohydrate storage. With lower leaf area, less carbohydrates are allocated. This for example resulted in a decreased trunk diameter. Further, it affected the composition of the grapevine wood microbiota. SSP and MDC management changed significantly the prokaryotic community composition in wood of the root samples, but had no effect in other compartments. In general, this study found strong compartment and less management effects of the microbial community composition and associated physicochemical properties. The highest microbial diversities were identified in the wood of the trunk, and several species were recorded the first time in grapevine.