OENO IVAS 2019 banner
IVES 9 IVES Conference Series 9 OENO IVAS 9 OENO IVAS 2019 9 Chemical and Biochemical reactions, including grape and wines microorganisms impact 9 Are dicysteinyl polysulfanes responsible for post-bottling release of hydrogen sulfide?

Are dicysteinyl polysulfanes responsible for post-bottling release of hydrogen sulfide?

Abstract

Hydrogen sulfide (H2S) has a significant impact on wine aroma attributes and wine quality when present at concentrations above its aroma threshold of 1.1 to 1.6 μg/L. Therefore, the management of H2S concentrations in wines, whether from fermentation or “other” origins, is an important consideration for winemakers. The main techniques used for H2S removal are oxidative handling and/or copper fining; however, the effectiveness of these treatments may be temporary, as H2S can often reappear post-bottling along with other volatile sulfur compounds (VSCs) when reductive conditions are re-established. Moreover, it is proposed that oxidative treatments applied in the presence of copper may produce compounds such as disulfides and diorganopolysulfanes, which might initially appear stable but are susceptible to reductive cleavage, thereby potentially acting as latent sources of H2S. 

The aim of this study was to determine whether putative polysulfanes could act as latent sources of H2S during post-bottling storage. Experiments conducted in model wine enabled identification of four dicysteinyl polysulfanes when H2S was oxidised in the presence of cysteine, copper and iron. The stability of the dicysteinyl polysulfanes formed in-situ was evaluated and conditions impacting the release of H2S from the polysulfanes were also determined, which provided some understanding of the possible mechanisms of release. 

The results of this study showed that the stability of the dicysteinyl polysulfanes decreased as sulfur chain length increased, which accorded with the relative proportions of polysulfanes initially formed. 

Notably, H2S was released over time, with the greatest decline in polysulfane relative abundance and largest release of H2S (up to 212 μg/L) being associated with the addition of commonly used reducing agents, especially sulfur dioxide, to the model wines containing the polysulfanes. Desulfurisation of cysteine could account for only minor quantities of H2S. In addition, Cysteine-S-sulfonates were tentatively identified by mass spectrometry after six months of storage, and similarly to the parent polysulfanes, their relative concentrations decreased with increasing number of linking sulfur atoms. These results shed light on the potential pathways for reformation of VSCs in bottled wine and demonstrate that dicysteinyl polysulfanes may have the potential to act as latent sources of H2S in wine post-bottling, potentially via a sulfitolysis mechanism.

DOI:

Publication date: June 11, 2020

Issue: OENO IVAS 2019

Type: Article

Authors

Marlize Bekker , David Jeffery, Gal Kreitman, John Danilewicz

The Australian Wine Research Institute PO Box 197 – Glen Osmond SA 5064 – Australia

Contact the author

Keywords

Polysulfanes, S-sulfonate, Copper, Sulfur dioxide 

Tags

IVES Conference Series | OENO IVAS 2019

Citation

Related articles…

Vineyards and clay minerals: multi-technique analytical approach and correlations with soil properties

Purpose of this research is to quantitatively assess the mineral component of vineyard soils, with particular attention to the mineralogical analysis of clays, which represent an element of high importance in the vineyard culture as well as in general agriculture. An X-ray diffraction (XRD) / thermogravimetric (TG) multi-technique analytical approach was developed, tested on soil samples taken from vineyards around the world. This codified analytical procedure was necessary to obtain precise qualitative and quantitative mineralogical data, globally comparable to distinguish the geopedological identity of the vineyards. Soil samples from vineyards of various locations were analysed, in very different geological conditions. The bulk-rock quantitative phase analysis (QPA) was obtained by the Rietveld method while the detailed composition of the clay-sized fraction was determined by modelling of the oriented X-ray diffraction patterns. The research provided a precise classification of the mineral component of soils, distinguishing the mineral phases of the clays and the so-called mixed-layer clay minerals. We found that the content in mixed layers can be directly correlated with the water retention and the cation exchange capacity ​​of the soil, while the presence of other clayey minerals and phyllosilicates in this research did not affect this CEC parameter, which codes the fertility level of the soils. The study demonstrates that terroir, in particular soils formed in complex or very different geological conditions, can only be effectively interpreted by properly analysing its mineral phases, in particular the mixed-layer clay component. These are characteristic abiotic ecological indicators, which may have specific eco-physiological influences on the plant.

Amino nitrogen content in grapes: the impact of crop limitation

As an essential element for grapevine development and yield, nitrogen is also involved in the winemaking process and largely affects wine composition. Grape must amino nitrogen deficiency affects the alcoholic fermentation kinetics and alters the development of wine aroma precursors. It is therefore essential to control and optimize nitrogen use efficiency by the plant to guarantee suitable grape nitrogen composition at harvest. Understanding the impact of environmental conditions and cultural practices on the plant nitrogen metabolism would allow us to better orientate our technical choices with the objective of quality and sustainability (less inputs, higher efficiency). This trial focuses on the impact of crop limitation – that is a common practice in European viticulture – on nitrogen distribution in the plant and particularly on grape nitrogen composition. A wide gradient of crop load was set up in a homogeneous plot of Chasselas (Vitis vinifera) in the experimental vineyard of Agroscope, Switzerland. Dry weight and nitrogen dynamics were monitored in the roots, trunk, canopy and grapes, during two consecutive years, using a 15N-labeling method. Grape amino nitrogen content was assessed in both years, at veraison and at harvest. The close relationship between fruits and roots in the maintenance of plant nitrogen balance was highlighted. Interestingly, grape nitrogen concentration remained unchanged regardless of crop load to the detriment of the growth and nitrogen content of the roots. Meanwhile, the size and the nitrogen concentration of the canopy were not affected. Leaf gas exchange rates were reduced in response to lower yield conditions, reducing carbon and nitrogen assimilation and increasing intrinsic water use efficiency. The must amino nitrogen profiles could be discriminated as a function of crop load. These findings demonstrate the impact of plant balance on grape nitrogen composition and contribute to the improvement of predictive models and sustainable cultural practices in perennial crops.

Grapevine yield estimation in a context of climate change: the GraY model

Grapevine yield is a key indicator to assess the impacts of climate change and the relevance of adaptation strategies in a vineyard landscape. At this scale, a yield model should use a number of parameters and input data in relation to the information available and be able to reproduce vineyard management decisions (e.g. soil and canopy management, irrigation). In this study, we used data from six experimental sites in Southern France (cv. Syrah) to calibrate a model of grapevine yield limited by water constraint (GraY). Each yield component (bud fertility, number of berries per bunch, berry weight) was calculated as a function of the soil water availability simulated by the WaLIS water balance model at critical phenological phases. The model was then evaluated in 10 grapegrowers’ plots, covering a diversity of biophysical and technical contexts (soil type, canopy size, irrigation, cover crop). We identified three critical periods for yield formation: after flowering on the previous year for the number of bunches and berries, around pre-veraison and post-veraison of the same year for mean berry weight. Yields were simulated with a model efficiency (EF) of 0.62 (NRMSE = 0.28). Bud fertility and number of berries per bunch were more accurately simulated (EF = 0.90 and 0.77, NRMSE = 0.06 and 0.10, respectively) than berry weight (EF = -0.31, NRMSE = 0.17). Model efficiency on the on-farm plots reached 0.71 (NRMSE = 0.37) simulating yields from 1 to 8 kg/plant. The GraY model is an original model estimating grapevine yield evolution on the basis of water availability under future climatic conditions.  It allows to evaluate the effects of various adaptation levers such as planting density, cover crop management, fruit/leaf ratio, shading and irrigation, in various production contexts.

Second pruning as a strategy to delay maturation in cv. ‘Touriga nacional’ in the Portuguese Douro region

The advance in maturation of wine grapes is an important climate change risk related effect that could affect warm regions like Portuguese Douro Wine Region. Indeed, the climate analysis over the past years registered a decrease in the precipitation, significant higher average temperatures, and a more frequent occurrence of extreme weather events, including heat waves. In these conditions the length from anthesis until maturation is shortened and the uncoupling of technical and phenolic maturity results in berries with higher sugar concentration (and lower acidity), but lower anthocyanins, tannins, and total phenolic concentration, which produce unbalanced wines.
In this work, an innovative strategy of crop forcing, based on forcing vine regrowth after a second pruning of green shoots, was tested, aimed at delaying ripening until the temperature becomes lower and, therefore, preventing acidity loss and increasing anthocyanin-to-sugar ratio. The experiments were conducted in 2019 and 2020 in a commercial vineyard of ‘Touriga Nacional’ located in the Douro Region. Crop forcing was conducted 15 (CF1) to 30 (CF2) days after fruit set. Vines pruned with conventional methods were used as control (CF0). Results confirmed that fruit ripening was shifted from the hot season (August/September), until a cooler period (October through early-November). At harvest, grapevine berries from CF1 and CF2 presented lower pH and higher acidity, than control, with no significant differences in colour intensity and phenolic levels composition. Sugar content was lower in CF2-treated vines in both seasons. However, in CF-treated vines the number and size of clusters were significantly lower (up to 88% reduction) than in control plants. A metabolomics analysis of mature berries from CF-treated vines and control is underway. Crop forcing was indeed effective in producing a more balance berry composition but severely reduced grapevine yield,

Modeling island and coastal vineyards potential in the context of climate change

Climate change impacts regional and local climates, which in turn affects the world’s wine regions. In the short term, these modifications rises issues about maintaining quality and style of wine, and in a longer term about the suitability of grape varieties and the sustainability of traditional wine regions. Thus, adaptation to climate change represents a major challenge for viticulture. In this context, island and coastal vineyards could become coveted areas due to their specific climatic conditions. In regions subject to warming, the proximity of the sea can moderate extremes temperatures, which could be an advantage for wine. However, coastal and island areas are particular prized spaces and subject to multiple pressures that make the establishment or extension of viticulture complex.
In this perspective, it seems relevant to assess the potentialities of coastal and island areas for viticulture. This contribution will present a spatial optimization model that tends to characterize most suitable agroclimatic patterns in historical or emerging vineyards according to different scenarios. Thanks to an in-depth bibliography a global inventory of coastal and insular vineyards on a worldwide scale has been realized. Relevant criteria have been identified to describe the specificities of these vineyards. They are used as input data in the optimization process, which will optimize some objectives and spatial aspects. According to a predefined scenario, the objectives are set in three main categories associated with climatic characteristics, vineyards characteristics and management strategies. At the end of this optimization process, a series of maps presents the different spatial configurations that maximize the scenario objectives.