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…

A spatial explicit inventory of EU wine protected designation of origin to support decision making in a changing climate

Winemaking areas recognized as protected designations of origin (PDOs) shape important economic, environmental and cultural values that are tied to closely defined geographic locations. To preserve wine products and wine-growing practices adopted in different PDOs these areas are strictly regulated by legal specifications. However, quality viticulture is increasingly under pressure from climate change, which is altering the local conditions of many winegrowing areas. Therefore, maintaining traditional wine products will require the adoption of tailored adaptation strategies, including possible changes in the legal regulation of protected wines. To this end, it is necessary to have a comprehensive knowledge on PDOs including their extension, products and allowed practices. While there have been efforts to build databases that summarize the characteristics for individual wine PDO areas and to quantify the related effects of climate change, much information is still included only in the official documentation of the EU geographical indication register and has never been collected in a comprehensive manner. With this study we aim at filling this gap by building a spatial inventory of European wine PDOs that supports decision making in viticulture in the context of climate change. To map and characterize European wine PDOs, we analysed their legal documents and extracted relevant information useful for climate change adaptation. The output consists of a comprehensive geographical dataset that identifies the boundaries of all 1200 European wine PDOs at unprecedented spatial resolution and includes a set of legally binding regulations, such as authorized vine varieties, maximum yields and planting density. The inventory will allow researchers to analyse the impacts of climate change on European wine PDOs and support decision makers in developing tailored adaptation strategies. This includes, among others, the evaluation of new vineyard site selection, the expansion of cultivated varieties or the authorization of irrigation in vineyards.

Climate change projections to support the transition to climate-smart viticulture

The Earth’s system is undergoing major changes through a wide range of spatial and temporal scales as a response to growing anthropogenic radiative forcing, which is pushing the whole system far beyond its natural variability. Sources of greenhouse gases largely exceed their sinks, thus leading to a strengthened greenhouse effect. More energy is thereby being supplied to the system, with inevitable shifts in climatic patterns and weather regimes. Over the last decades, these modifications have been manifested in the full statistical distributions of the atmospheric variables, with dramatic changes in the frequency and intensity of extremes. Natural hazards, such as severe droughts, floods, forest fires, or heatwaves, are being triggered by extreme atmospheric events worldwide, thus threatening human activities. Viticultculture is not only exposed to changing climates but is also highly vulnerable, as grapevine phenology and physiological development are strongly controlled by atmospheric conditions. Therefore, the assessment of climate change projections for a given region is critical for climate change adaptation and risk reduction in viticulture. By adopting timely and suitable measures, the future sustainability and resiliency of the sector can be fostered. Climate-grapevine chain modelling is an essential tool for better planning and management. However, the accuracy of the resulting projections is limited by many uncertainties that must be duly taken into account when transferring knowledge to stakeholders and decision-makers. Climate-smart viticulture will comprise ensembles of locally tuned strategies, envisioning both adaptation and mitigation, assisted by emerging technologies and decision-support systems.

Low-cost sensors as a support tool to monitor soil-plant heat exchanges in a Mediterranean vineyard

Mediterranean viticulture is increasingly exposed to more frequent extreme conditions such as heat waves. These extreme events co-occur with low soil water content, high air vapor pressure deficit and high solar radiant energy fluxes and result in leaf and berry sunburn, lower yield, and berry quality, which is a major constraint for the sustainability of the sector. Grape growers must find ways to proper and effectively manage heat waves and extreme canopy and berry temperatures. Irrigation to keep soil moisture levels and enable adequate plant turgor, and convective and evaporative cooling emerged as a key tool to overcome this major challenge. The effects of irrigation on soil and plant water status are easily quantifiable but the impact of irrigation on soil and canopy temperature and on heat convection from soil to cluster zone remain less characterized. Therefore, a more detailed quantification of vineyard heat fluxes is highly relevant to better understand and implement strategies to limit the effects of extreme weather events on grapevine leaf and berry physiology and vineyards performance. Low-cost sensor technologies emerge as an opportunity to improve monitoring and support decision making in viticulture. However, validation of low-cost sensors is mandatory for practical applicability. A two-year study was carried in a vineyard in Alentejo, south of Portugal, using low-cost thermal cameras (FLIR One, 80×60 pixels and FLIR C5, 160×120 pixels, 8-14 µm, FLIR systems, USA) and pocket thermohygrometers (Extech RHT30, EXTECH instruments, USA) to monitor grapevine and soil temperatures. Preliminary results show that low-cost cameras can detect severe water stress and support the evaluation of vertical canopy temperature variability, providing information on soil surface temperature. All these thermal parameters can be relevant for soil and crop management and be used in decision support systems.

Comparison of imputation methods in long and varied phenological series. Application to the Conegliano dataset, including observations from 1964 over 400 grape varieties

A large varietal collection including over 1700 varieties was maintained in Conegliano, ITA, since the 1950s. Phenological data on a subset of 400 grape varieties including wine grapes, table grapes, and raisins were acquired at bud break, flowering, veraison, and ripening since 1964. Despite the efforts in maintaining and acquiring data over such an extensive collection, the data set has varying degrees of missing cases depending on the variety and the year. This is ubiquitous in phenology datasets with significant size and length. In this work, we evaluated four state-of-the-art methods to estimate missing values in this phenological series: k-Nearest Neighbour (kNN), Multivariate Imputation by Chained Equations (mice), MissForest, and Bidirectional Recurrent Imputation for Time Series (BRITS). For each phenological stage, we evaluated the performance of the methods in two ways. 1) On the full dataset, we randomly hold-out 10% of the true values for use as a test set and repeated the process 1000 times (Monte Carlo cross-validation). 2) On a reduced and almost complete subset of varieties, we varied the percentage of missing values from 10% to 70% by random deletion. In all cases, we evaluated the performance on the original values using normalized root mean squared error. For the full dataset we also obtained performance statistics by variety and by year. MissForest provided average errors of 17% (3 days) at budbreak, 14% (4 days) at flowering, 14.5% (7 days) at veraison, and 17% (3 days) at maturity. We completed the imputations of the Conegliano dataset, one of the world’s most extensive and varied phenological time series and a steppingstone for future climate change studies in grapes. The dataset is now ready for further analysis, and a rigorous evaluation of imputation errors is included.

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