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…

The use of rootstock as a lever in the face of climate change and dieback of vineyard

As viticulture faces challenges such as climate change or vineyard dieback, the choice of the variety and rootstock becomes more and more crucial. To study rootstock levers in the Bordeaux region, a parcel of Cabernet Sauvignon (CS) was planted with four rootstocks in 2014. Twenty repetitions of each of the following four rootstocks were set up: 101-14 MGt, Nemadex AB, 420A MGt and Gravesac. The number of bunches, yields and pruning weights of the vine shoots were measured individually on 240 vines from 2017 to 2021. Since 2020, nitrogen status assessed by assimilable nitrogen level, hydric status assessed by δ13C and berry maturity were measured on 80 samples taken from 20 repetitions of the four rootstocks. A lower yield was measured for CS grafted onto Nemadex AB due to the lower number of bunches and the lower weight of berries. The differences between the other three rootstocks are small, but CS grafted onto 420A MGt was the most productive. The CS grafted onto Nemadex AB had the lowest pruning weight while 101-14 MGt had the highest. In 2020, δ13C showed a more moderate water stress with 101-14 MGt and 420A MGt than with Nemadex AB. Surprisingly, the Gravesac was under more stress than the 101-14 MGt. The nitrogen status in the berries was better for Nemadex AB but this was perhaps due to the significantly lower weight of the berries.Rootstock 101-14 MGt attained the highest accumulation of sugars in the berries while 420A MGt allows to preserve higher acidity. The parcel is still young which may explain some of the results. These measures must therefore be continued over the next several years to fully assess the effects of these rootstocks on the development of the vines and the quality of the production under new climatic conditions.

Copper contamination in vineyard soils of Bordeaux: spatial risk assessment for the replanting of vines and crops

Copper (Cu) is widely and historically used in viticulture as a fungicide against mildew. Cu has a strong affinity for soil organic matter and accumulates in topsoil horizons. Thus, Cu may negatively affect soil organisms and plants, consequently reducing soil fertility and productivity. The Bordeaux vineyards have the largest vineyard surfaces (26%) within French controlled appellation and a great proportion of French wine production (around 5 million hl per year). Considering the local context of vineyard surfaces decreasing (vine uprooting) and possible new crop plantation, the issue of Cu potential toxicity rises. Therefore, the aims of this work are firstly to evaluate the Cu contamination in vineyard soils of Bordeaux, secondly to produce a risk assessment map for new vine or crop plantation. We used soil analyses from several local studies to build a database with 4496 soil horizon samples. The database was enhanced by means of pedotransfer functions in order to estimate the bioaccessible (EDTA-extractable) Cu in soils of samples without measurements. From this database, 1797 georeferenced samples with CuEDTA concentrations in the topsoil (0-50 cm depth) were used for kriging interpolation in order to produce the spatial distribution map of CuEDTA in vineyard soils. Then, the spatial distribution of Cu was crossed with vine uprooting surfaces and municipality boundaries. CuEDTAconcentrations ranged from 0.52 to 459 mg/kg and showed clear anomalies. Our results from spatial analysis showed that almost 50% of vineyard soil surfaces have CuEDTA concentrations higher than 30 mg/kg (moderate risk for new plantation) and 20% with concentrations higher than 50 mg/kg (high risk for new plantation). A decision-support map based on municipalities was realised to provide a simple tool to stakeholders concerned by land use management.

Ecophysiological performance of Vitis rootstocks under water stress

The use of rootstocks tolerant to soil water deficit is an interesting strategy to cope with limited water availability. Currently, several nurseries are breeding new genotypes, but the physiological basis of its responses under water stress are largely unknown. To this end, an ecophysiological assessment of the conventional 110-Richter (110R) and SO4, and the new M1 and M4 rootstocks was carried out in potted ungrafted plants. During one season, these Vitis genotypes were grown under greenhouse conditions and subjected to two water regimes, well-watered and water deficit. Water potentials of plants under water deficit down to < -1.4 MPa, and net photosynthesis (AN) <5 μmol m-2 s-1 did not cause leaf oxidative stress damage compared to well-watered conditions in any of the genotypes. The antioxidant capacity was sufficient to neutralize the mild oxidative stress suffered. Under both treatments, gravimetric differences in daily water use were observed among genotypes, leading to differences in the biomass of root, shoot and leaf. Under well-watered conditions, SO4 and 110R were the most vigorous and M1 and M4 the least. However, under water stress, SO4 exhibited the greatest reduction in biomass while M4 showed the lowest. Remarkably, under these conditions, SO4 reached the least negative stem water potential (Ψstem), while M1 reduced stomatal conductance (gs) and AN the most. In addition, SO4 and M1 genotypes also showed the highest and lowest hydraulic conductance values, respectively. Our results suggest that there are differences in water use regulation among genotypes, not only attributed to differences in stomatal regulation or intrinsic water use efficiency at the leaf level. Therefore, because no differences in canopy-to-root ratio were achieved, it is hypothesized that xylem vessel anatomical differences may be driving the reported differences among rootstocks performance. Results demonstrate that each Vitis rootstock differs in its ecophysiological responses under water stress.

Pruned vine biomass exclusion from a clay loam vineyard soil – examining the impact on physical/chemical properties

The wine industry worldwide faces increasing challenges to achieve sustainable levels of carbon emission mitigation. This project seeks to establish the feasibility of harvesting winter pruned vineyard biomass (PVB) for potential use in carbon footprint reduction, through its use as a renewable biofuel for energy production. In order to make this recommendation, technical issues such as the potential environmental impact, chemical composition and fuel suitability, and logistical challenges of harvesting biomass needs to be understood to compare with the results from similar studies. Of particular interest is the role PVB plays as a carbon source in vineyard soils and what effect annual removal might have on soil carbon sequestration. A preliminary trial was established in the Waite Campus vineyard (University of Adelaide) to test current management strategies. Vines are grown in a Eutrophic, Red Dermosol clay loam soil with well managed midrow swards. A comparison was undertaken of mid-row treatments in two 0.25 Ha blocks (Shiraz and Semillon), including annual cultivation for seed bed preparation, the deliberate exclusion of PVB (25 years) and incorporation of PVB (13 years) at an average of 3.4 and 5.5 Mg/Ha-1 for Shiraz and Semillon respectively. In both 0-10cm and 10-30cm soil core sample depths, combined soil carbon % measures in the desired range of 1.80 to 3.50, were not significantly different between treatments or cultivars and yielded an estimated 42 Mg/ha-1 of sequestered soil carbon. Other key physical and chemical measures were likewise not significantly different between treatments. Preliminary results suggest that in a temperate zone vineyard, managed such as the one used in this study, there is no long term negative impact on soil carbon sequestration through removing PVB. This implies that growers could confidently harvest PVB for use in several end fates including as a bio fuel.

Climate change impacts on Douro Region viticulture and adaptation measures

Climate has a significant impact in the success of any agricultural system, with a direct influence on the crops suitability to a given region, interfering on yield and quality and also with the economic sustainability of the productive activity. In the Douro Demarcated Region (RDD), as in most regions of the Mediterranean climate, the scarce precipitation (33% has less than 600 mm per year), and your high variability, associated with high rates of evapotranspiration during the summer, is usually one of the fundamental factors that limit the grapevine development, as well as the production and quality of the harvest. Thus, facing the scenario in temperature changes for the next decades (1.5-2.5°C) and confirming the predictions of precipitation decreases and/or great variability in the occurrence of heat waves and intense rainfall, the consequences for slope stability in mountain viticulture and sustainability of all operations involved, are risks to be taken into account. In this way, a deepest and sustained knowledge regarding the adaptation measures to adverse environmental conditions is of a crucial importance, enabling a more efficient adaptation of plant growth conditions and the optimization of production and quality of the grapevines. The development of this work, carried out in two commercial vineyards, one located in Soutelo do Douro, São João da Pesqueira, Cima Corgo sub-region, and another located in Numão, Vila Nova de Foz Côa, Douro Superior sub-region, it seeks to establish a relationship between climatic elements and physiological, productive and qualitative parameters, as well as to evaluate the effectiveness of adaptation measures, including different types of deficit irrigation (2002-2019) and the application of shading nets (2019-2020) in the physiological, viticultural and oenological behavior in the Touriga Nacional and Moscatel Galego Branco varieties, respectively. The results showed that the application of deficit irrigation allowed to significantly reduce the impact of the adverse weather conditions at key moments in the development of the grapevine, particularly in the period immediately before veráison and maturation, reducing the negative effects on the physiological processes and productivity, without compromise the must quality parameters. On the other hand, the application of shading nets significantly reduced de leaves temperature, allowing to increase the water potential, stomatal conductance and photosynthetic rate of grapes, which was reflected in the yield increase in the 2nd year of the study. For the maturation indicators, higher levels of total acidity, malic acid and assimilable nitrogen were obtained. The last measure presents a huge potential, being essential to carry out more years of trials to obtain stronger conclusions in terms of production parameters, but also in characteristics as important as the grape ripening components and the organoleptic characteristics of wines.