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…

Long-term drought resilience of traditional red grapevine varieties from a semi-arid region

In recent decades, the scarcity of water resources in agriculture in certain areas has been aggravated by climate change, which has caused an increase in temperatures, changes in rainfall patterns, as well as an increase in the frequency of extreme phenomena such as droughts and heat waves. Although the vine is considered a drought-tolerant specie, it has to satisfy important water requirements to complete its cycle, which coincides with the hottest and driest months. Achieving sustainable viticulture in this scenario requires high levels of efficiency in the use of water, a scarce resource whose use is expected to be severely restricted in the near future. In this regard, the use of drought-tolerant varieties that are able to maintain grape yield and quality could be an effective strategy to face this change. During three consecutive seasons (2018-2020) the behavior in rainfed regime of 13 traditional red grapevine varieties of the Spain central region was studied. These varieties were cultivated in a collection at Centro de Investigación de la Vid y el Vino de Castilla-La Mancha (IVICAM-IRIAF) located in Tomelloso (Castilla-La Mancha, Spain). Yield components (yield, mean bunch and berry weight, pruning weight), physicochemical parameters of the musts (brix degree, total acidity, pH) and some physiological parameters related with water stress during ripening period (δ13C, δ18O) were analysed. The application of different statistical techniques to the results showed the existence of significant differences between varieties in their response to stressful conditions. A few varieties highlighted for their high ability to adapt to drought, being able to maintain high yields due to their efficiency in the use of water. In addition, it was possible quantify to what extent climate can be a determinant in the δ18O of musts under severe water stress conditions.

Deconstructing the soil component of terroir: from controversy to consensus

Wine terroir describes the collectively recognized relation between a geographical area and the distinctive organoleptic characteristics of the wines produced in it. The overriding objective in terroir studies is therefore to provide scientific proof relating the properties of terroir components to wine quality and typicity. In scientific circles, the role of climate (macro-, meso- and micro-) on grape and wine characteristics is well documented and accepted as the most critical. Moreover, there has been increasing interest in recent years about new elements with possible importance in shaping wine terroir like berry/leaf/soil microbiology or even aromatic plants in proximity to the vineyard conferring flavors to the grapes. However, the actual effect of these factors is also dependent on complex interactions with plant material (variety/clone, rootstock, vine age) and with human factors.
The contribution of soil, although a fundamental component of terroir and extremely popular among wine enthusiasts, remains a much-debated issue among researchers. The role of geology is probably the one mostly associated by consumers with the notion of terroir with different parent rocks considered to give birth to different wine styles. However, the relationship between wine properties and the underlying parent material raises a lot of controversy especially regarding the actual existence of rock-derived flavors in the wine (e.g. minerality). As far as the actual soil properties are concerned, the effect of soil physical properties is generally regarded as the most significant (e.g sandy soils being associated with lighter wines while those on clay with colored and tannic ones) mostly through control of water availability which ultimately modifies berry ripening conditions either directly by triggering biosynthetic pathways, or indirectly by altering vigor and yield components. The role of soil chemistry seems to be weakly associated to wine sensory characteristic, although N, K, S and Ca, but also soil pH, are often considered important in the overall soil effect.
Recently, in the light of evidence provided by precision agriculture studies reporting a high variability of vineyard soils, the spatial scale should also be taken into consideration in the evaluation of the soil effects on wines. While it is accepted that soil effects become more significant than climate on a local level, it is not clear whether these micro-variations of vineyard soils are determining in the terroir effect. Moreover, as terroir is not a set of only natural factors, the magnitude of the contribution of human-related factors (irrigation, fertilization, soil management) to the soil effect still remains ambiguous. Lastly, a major shortcoming of the majority of works about soil effects on wine characteristics is the absence of connection with actual vine physiological processes since all soil effects on grape and wine chemistry and sensorial properties are ultimately mediated through vine responses.
This article attempts to breakdown the main soil attributes involved in the terroir effect to suggest an improved understanding about soil’s true contribution to wine sensory characteristics. It is proposed that soil parameters per se are not as significant determining factors in the terroir effect but rather their mutual interactions as well as with other natural and human factors included in the terroir concept. Consequently, similarly to bioclimatic indices, composite soil indices (i.e. soil depth, water holding capacity, fertility, temperature etc), incorporating multiple soil parameters, might provide a more accurate and quantifiable means to assess the relative weight of the soil component in the terroir effect.

Climate modeling at local scale in the Waipara winegrowing region in the climate change context

In viticulture, a warming climate can have a very significant impact on grapevine development and therefore on the quality and characteristics of wines across different spatial scales, ranging from global to local. In order to adapt wine-growing to climate change, global climate models can be used to define future scenarios, but only at the scale of major wine regions. Despite the huge progress made over the last ten years in terms of the spatial resolution of climate models (now downscaled to a few square kilometres), they are not yet sufficiently precise to account for the local climate variability associated with such parameters as local topography, in spite of these parameters being decisive for vine and wine characteristics. This study describes a method to downscale future climate scenarios to vineyard scale. Networks of data loggers have been used to collect air temperature at canopy level in the Waipara winegrowing region (New Zealand) over five growing seasons. These measurements allow the creation of fine-scale geostatistical models and maps of temperature (at 100 m resolution) for the growing season. In order to model climate change at pilot site scale, these geostatistical models have been combined with regional climate change predictions for the periods 2031-2050 and 2081-2100 based on the RCP8.5 climate change scenario. The integration of local climate variability with regionalized climate change simulations allows assessment of the impacts of climate change at the vineyard scale. The improved knowledge gained using this methodology results from the increased horizontal resolution that better addresses the concerns of winegrowers. The results provide the local winegrowers with information necessary to understand current processes, as well as historical and future viticulture trends at the scale of their site, thereby facilitating decisions about future response strategies.

Analysis of Cabernet Sauvignon and Aglianico winegrape (V. vinifera L.) responses to different pedo-climatic environments in southern Italy

Water deficit is one of the most important effects of climate change able to affect agricultural sectors. In general, it determines a reduction in biomass production, and for some plants, as in the case of grapevine, it can endorse fruit quality. The monitoring and management of plant water stress in the vineyard

Soil, vine, climate change – what is observed – what is expected

To evaluate the current and future impact of climate change on Viticulture requires an integrated view on a complex interacting system within the soil-plant-atmospheric continuum under continuous change. Aside of the globally observed increase in temperature in basically all viticulture regions for at least four decades, we observe several clear trends at the regional level in the ratio of precipitation to potential evapotranspiration. Additionally the recently published 6th assessment report of the IPCC (The physical science basis) shows case-dependent further expected shifts in climate patterns which will have substantial impacts on the way we will conduct viticulture in the decades to come.
Looking beyond climate developments, we observe rising temperatures in the upper soil layers which will have an impact on the distribution of microbial populations, the decay rate of organic matter or the storage capacity for carbon, thus affecting the emission of greenhouse gases (GHGs) and the viscosity of water in the soil-plant pathway, altering the transport of water. If the upper soil layers dry out faster due to less rainfall and/or increased evapotranspiration driven by higher temperatures, the spectral reflection properties of bare soil change and the transport of latent heat into the fruiting zone is increased putting a higher temperature load on the fruit. Interactions between micro-organisms in the rhizosphere and the grapevine root system are poorly understood but respond to environmental factors (such as increased soil temperatures) and the plant material (rootstock for instance), respectively the cultivation system (for example bio-organic versus conventional). This adds to an extremely complex system to manage in terms of increased resilience, adaptation to and even mitigation of climate change. Nevertheless, taken as a whole, effects on the individual expressions of wines with a given origin, seem highly likely to become more apparent.