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…

Different soil types and relief influence the quality of Merlot grapes in a relatively small area in the Vipava Valley (Slovenia) in relation to the vine water status

Besides location and microclimatic conditions, soil plays an important role in the quality of grapes and wine. Soil properties influence…

The plantation frame as a measure of adaptation to climate change

The mechanization of vineyard work originally led to a reduction in planting densities due to the lack of machinery adapted to the vineyard. The current availability of specific machinery makes it possible to establish higher planting densities. In this work, three planting densities (1.40×0.80 m, 1.80×1 m and 2.20×1.20 m, corresponding to 8928, 5555 and 3787 plants/ha respectively) were studied with four varieties autochthonous of Galicia (northwestern Spain): Albariño and Treixadura (white), Sousón and Mencía (red). The vines were trained in a vertical shoot positioning system using a single Royat cordon, and pruned to spurs with two buds each. Agronomic data (yield, pruning wood weight, Ravaz index) and oenological data in must were collected. The higher planting density (1.40×0.80 m) had no significant effect on grape yield per vine in white varieties, although production per hectare was much higher due to the greater number of plants. In red varieties, this planting density resulted in a significantly lower production per vine, compensated by the greater number of plants. In addition, it significantly reduced the Brix degree in the must of the Albariño, Treixadura and Sousón varieties, and increased the total acidity in the latter two and Mencía. It also caused an increase in extractable and total anthocyanins and IPT in red grapes. The effects of high planting density on grapes are of great interest for the adaptation of varieties in the context of climate change. In the future, it could be advisable to modify the limits imposed by the appellations of origin on the planting density of these varieties in order to obtain more balanced wines.

Towards adaptation to climate change in Rioja: Quality evaluation of wines obtained from Grenache x Tempranillo selections

The wine sector is of great relevance and tradition in Mediterranean countries, however, it may be most susceptible to climate change. In recent years, wine production is facing changes worldwide, both at environmental as well as commercial levels, due to global warming and the shift in consumers’ preferences. Wine growers and wine makers are in search of solutions that allow to face these new challenges. One of the most promising initiatives in the long term is the introduction of new plant materials, specifically intraspecific hybridizations between premium varieties that may improve traditional germplasm in its adaptation to climate change. These inter-varietal crosses have the potential to generate quality wines, whilst maintaining the regional typicity, and constitute an attractive alternative for the consumer due to their sensory attributes. In this study, we have evaluated wines from 29 intraspecific Garnacha x Tempranillo hybrids in two different locations, with the aim to assess their oenological potential and sensory attributes. Thirteen of the selections were white and 16 were red. Microvinifications were conducted with two or three replications depending on grape availability. Conventional oenological parameters were determined for all wines. The sensory evaluation and hedonic scores were given by five experts. Red selections obtained higher quality scores than white ones. Among the white selections with higher quality scores, GT-41 Varea and GT-159 Varea outstand, due to their high total acidity and high malic acid content. Regarding red selections, GT-57 Varea and GT-57 UR were perceived as higher in quality, highlighted for their moderate alcoholic and high anthocyanin content. Our results indicate that intraspecific hybridization may be a powerful tool for adapting traditional cultivars to climate change in Rioja.

Geospatial trends of bioclimatic indexes in the topographically complex region of Barolo DOCG

Barolo DOCG is an economically important wine producing region in Northwest Italy. It is a small region of approximately 70 km2 gross area. The topography is very complex with steep sloped hills ranging in elevation from below 200 m to 550 m. Barolo DOCG wine is made exclusively from the Nebbiolo grape. Bioclimatic indexes are often used in viticulture to gain a better understanding of broader climate trends which can be compared temporally and geographically. These indexes are also used for identifying potential phenological timing, growing region suitability, and potential risks associated with expected climatic changes. Understanding how topography influences bioclimatic indexes can help with understanding of mesoscale climate behaviour leading to improved decision making and risk management strategies. The average monthly maximum and minimum temperatures, the Cool Night Index, the Huglin Index, and the monthly diurnal range (from July to October) were calculated using data from 45 weather stations within a 40 km radius of the Barolo DOCG growing area between the years 1996 and 2019. Linear and multiple regression models were developed using independent variables (elevation, aspect, slope) extracted from a digital elevation model to identify significant relationships. Bioclimatic indexes were then kriged with external drift using independent variables that showed significant relationships with the bioclimatic index using a 100 m resolution grid. The maximum monthly temperatures and the Huglin Index showed consistent significant negative relationships with elevation in all years. The minimum monthly temperatures showed no relationship with elevation but in some months a small but significant relationship was observed with aspect. Due to the lack of a relationship between minimum monthly temperatures and elevation compared to the significant relationship between maximum monthly temperatures and elevation, monthly diurnal range had a negative relationship with elevation.

Climate change impacts: a multi-stress issue

With the aim of producing premium wines, it is admitted that moderate environmental stresses may contribute to the accumulation of compounds of interest in grapes. However the ongoing climate change, with the appearance of more limiting conditions of production is a major concern for the wine industry economic. Will it be possible to maintain the vineyards in place, to preserve the current grape varieties and how should we anticipate the adaptation measures to ensure the sustainability of vineyards? In this context, the question of the responses and adaptation of grapevine to abiotic stresses becomes a major scientific issue to tackle. An abiotic stress can be defined as the effect of a specific factor of the physico-chemical environment of the plants (temperature, availability of water and minerals, light, etc.) which reduces growth, and for a crop such as the vine, the yield, the composition of the fruits and the sustainability of the plants. Water stress is in many minds, but a systemic vision is essential for at least two reasons. The first reason is that in natural environments, a single factor is rarely limiting, and plants have to deal with a combination of constraints, as for example heat and drought, both in time and at a given time. The second reason is that plants, including grapevine, have central mechanisms of stress responses, as redox regulatory pathways, that play an important role in adaptation and survival. Here we will review the most recent studies dealing with this issue to provide a better understanding of the grapevine responses to a combination of environmental constraints and of the underlying regulatory pathways, which may be very helpful to design more adapted solutions to cope with climate change.