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…

Effect of regulated deficit irrigation regime on amino acids content of Monastrell (Vitis vinifera L.) grapes

Irrigation is an important practice to influence vine quality, especially in Mediterranean regions, characterized by hot summers and severe droughts during the growing season. This study focused on deficit irrigation regime influence on amino acids composition of Monastrell grapevines under semiarid conditions (Albacete, Southeastern of Spain). In 2019, two treatments were applied: non-irrigation (NI) and regulated deficit irrigation (RDI), watered at 30% of the estimated crop evapotranspiration from fruit set to onset of veraison. Grape amino acids content was analyzed by HPLC. Berries from non-irrigated vines showed higher concentration of several amino acids, such as tryptophan (73%), arginine (70%), lysine (36%), isoleucine (27%), and leucine (21%), compared to RDI grapes. Arginine is, together with ammonium ion, the principal nitrogen source for yeasts during the alcoholic fermentation; while isoleucine, tryptophan, and leucine are precursors of fermentative volatile compounds, key compounds for wine quality. Moreover, NI treatment increased in a 14% the total amino acids content in grapes compared to RDI treatment. The reported effects might be because yield was 70% higher in RDI vines than in the NI ones and, therefore, the sink demand was increased in the irrigated vines. In addition, NI vines suffered more severe water stress and it is known that the amino acids synthesis and accumulation can be influenced by the plant response to stress. According to the results, the irrigation regime showed effect on amino acids concentration in Monastrell grapes under semiarid conditions. Grapes from non-irrigated vines showed a higher content of several amino acids relevant to the fermentative process and to the wine aroma compounds formation. It is demonstrated that the final content of nitrogen-related components in grapes is influenced by the irrigation regime. The convenience of the irrigation strategy to suggest will depend on the desired wine style and the target yield levels.

A better understanding of the climate effect on anthocyanin accumulation in grapes using a machine learning approach

The current climate changes are directly threatening the balance of the vineyard at harvest time. The maturation period of the grapes is shifted to the middle of the summer, at a time when radiation and air temperature are at their maximum. In this context, the implementation of corrective practices becomes problematic. Unfortunately, our knowledge of the climate effect on the quality of different grape varieties remains very incomplete to guide these choices. During the Innovine project, original experiments were carried out on Syrah to study the combined effects of normal or high air temperature and varying degrees of exposure of the berries to the sun. Berries subjected to these different conditions were sampled and analyzed throughout the maturation period. Several quality characteristics were determined, including anthocyanin content. The objective of the experiments was to investigate which climatic determinants were most important for anthocyanin accumulation in the berries. Temperature and irradiance data, observed over time with a very thin discretization step, are called functional data in statistics. We developed the procedure SpiceFP (Sparse and Structured Procedure to Identify Combined Effects of Functional Predictors) to explain the variations of a scalar response variable (a grape berry quality variable for example) by two or three functional predictors (as temperature and irradiance) in a context of joint influence of these predictors. Particular attention was paid to the interpretability of the results. Analysis of the data using SpiceFP identified a negative impact of morning combinations of low irradiance (lower than about 100 μmol m−2 s−1 or 45 μmol m−2 s−1 depending on the advanced-delayed state of the berries) and high temperature (higher than 25oC). A slight difference associated with overnight temperature occurred between these effects identified in the morning.

Downscaling of remote sensing time series: thermal zone classification approach in Gironde region

In viticulture, the challenges of local climate modelling are multiple: taking into account the local environment, fine temporal and spatial scales, reliable time series of climate data, ease of implementation and reproducibility of the method. At the local scale, recent studies have demonstrated the contribution of spatialization methods for ground-based climate observation data considering topographic factors such as altitude, slope, aspect, and geographic coordinates (Le Roux et al, 2017; De Rességuier et al, 2020). However, these studies have shown questions in terms of the reproducibility and sustainability of this type of climate study. In this context, we evaluated the potential of MODIS thermal satellite images validated with ground-based climate data (Morin et al, 2020). Previous studies have been encouraging, but questions remain to be explored at the regional scale, particularly in the dynamics of the massive use of bioclimatic indices to classify the climate of wine regions. The results at the local scale were encouraging, but this approach was tested in the current study at the regional scale. Several objectives were set: 1) to evaluate the downscaling method for land surface temperature time series, 2) to identify regional thermal structure variations. We used weekly minimum and maximum surface temperature time series acquired by MODIS satellites at a spatial resolution of 1000 m and downscaled at 500 m using topographical variables. Two types of analyses were performed:

Biodiversity in the vineyard agroecosystem: exploring systemic approaches

Biodiversity conservation and restoration are essential for guarantee the provision of ecosystem services associated to vineyard agroecosystem such as climate regulation trough carbon sequestration and control of pests and diseases. Most of published research dealing with the complexity of the vineyard agroecosystems emphasizes the necessity of innovative approaches, including the integration of information at different temporal and spatial scales and development of systemic analysis based on modelling. A biodiversity survey was conducted in the Franciacorta wine-growing area (Lombardy, Italy), one of the most important Italian wine-growing regions for sparkling wine production, considering a portion of the territory of 112 ha. The area was divided into several Environmental Units (EUs), defined as a whole vineyard or portion of vineyard homogenous in terms of four agronomic characteristics: planting year, planting density, cultivar, and training system. In each EU a set of compartments was identified and characterised by specific variables. The compartments are meteorology, morphology (altitude, slope, aspect, row orientation, and solar irradiance), ecological infrastructures and management. The landscape surrounding EU was also characterised in terms of land-use in a buffer zone of 500 m. For each component a specific methodology was identified and applied. Different statistical approaches were used to evaluate the method to integrate the information related to different compartments within the EU and related to the buffer zone. These approaches were also preliminarily evaluated for their ability to describe the contribution of biodiversity and landscape components to ecosystem services. This methodological exploration provides useful indication for the development of a fully systemic approach to structural and functional biodiversity in vineyard agroecosystems, contributing to promote a multifunctional perspective for the all wine-growing sector.

Diagnosis of soil quality and evaluation of the impact of viticultural practices on soil biodiversity in a vineyard in southwestern France

Viticulture is facing two major changes – climate change and agroecological transition. In both cases, soil quality is seen as a lever to move towards a more sustainable viticulture. However, soil biological quality is little considered in the implementation of viticultural practices. Gascogn’Innov (2017-2022) is an Operational Group funded by the European Innovation Partnership for Agriculture. As such, it brings together winegrowers from the south-west of France, scientists, advisors and technicians, around a project focused on viticultural soil biological functioning and the design of technical routes more respectful toward soil heritage. To achieve this, the project aims to acquire references on the impact of viticultural practices on soil biology from a dynamic way, and to test a methodology to integrate information provided by the soil bioindicators to manage farming systems. A set of indicators of soil biological quality are evaluated in the project: microorganisms (bacteria and fungi abundance and diversity), fauna (abundance and diversity of nematodes and earthworms), physico-chemical characteristics, soil structure assessment and degradation rate of organic matter. Based on a network of 13 plots that have been subject to an initial diagnosis in 2017, several agronomical practices to restore soil fertility are experimented to redesign the cropping system (for instance plant cover, organic matter inputs, reduction of herbicides, mineral fertilizers). System redesign was made in collaboration by winegrowers and an interdisciplinary group of experts (agronomists, biologists). Several indicators are measured on vine and soil at each vintage to assess vine health and productivity. At the end of the project (2021), a final diagnosis was carried out. Gascogn’Innov allowed to create a regional database on the quality of wine-growing soils, which permitted to evaluate the effect of practices according to soil types. Especially, decreasing the intensity of tillage and increasing the duration and diversity of grass coverage tends to increase the abundance of all the organisms studied. This project confirmed the value of soil biological quality indicators to drive the sustainability of practices, but also highlighted the key-role of expertise, in both agronomy and soil biology, to help winegrowers understand and appropriate their soil quality diagnoses.