IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 New insight the pinking phenomena of white wine

New insight the pinking phenomena of white wine

Abstract

Pinking of white wine is an undesired change potentially occurring over storage, leading to the turning of color from yellow into salmon-red hue. Recently, the appearance of pink color was associated to small concentrations of malvidin-3-O-glucoside (∼ 0.3mg/L) present in white wines produced under reducing conditions from Síria grape variety [1]. Other suggested mechanisms were the polymerization of anthocyanins under oxidative condition, the combination of more than ten different monomers and polymeric compounds, the formation of a derivative from 2-S-glutathionyl-caftaric acid [2]. However, this color modification has been not fully understood. This study aimed to clarify the molecular mechanisms and the compound(s) involved in the pinking of white wine. 
The appearance of pinking was evaluated in model wine added with increasing concentrations of sulfur-containing compounds (i.e. glutathione, cysteine, mercaptoethanol), and fixed amounts of the phenolics (i.e. catechin and caffeic acid), singularly or in combination. An assay with copper, with and without phenolics, was also carried out. The oxidation was generated by adding p-benzoquinone in both oxic and anoxic conditions. The intensity of pink color was measured at 520 nm. A major compound associated to pinking was detected by UPLC-UV and its molecular weight and structure were investigated by High Resolution Mass Spectrometry (HRMS) and Nuclear Magnetic Resonance (NMR), respectively.
In most of the tested conditions, the pink color appeared and resulted more intense with catechin. On the contrary, the color was yellow-brownish in the absence of phenolics notwithstanding the presence of copper. Considering the single addition of the thiol compounds, the major pink intensity and the fastest appearance were due to cysteine. The pinking intensity was lower with glutathione and it was not detected with mercaptoethanol. Catechin was the phenolic mainly involved into the pinking. The rate of pinking formation was dependent on both the thiol/p-benzoquinone and catechin/p-benzoquinone molar ratios with the former playing a paramount role. Copper was also involved in this phenomenon The major formation rate was observed when thiol/p-benzoquinone molar ratio was about 0.7. The compound associated to the pink color showed a maximum adsorption at 505 nm, characteristic of anthocyanin-like moieties and its accurate mass ([M+H]+) was 450.0635 Da. NMR analysis evidenced three molecular forms in equilibrium. The estimated conversion yield was 5%.These data suggest that pinking phenomena, in our experimental conditions, is due to the oxidation of catechin with the aid of sulphur-containing compounds, the latter with a crucial role for this color change.

References

[1] Andrea-Silva J., Cosme F., Ribeiro L. F., Moreira A. S. P., Malheiro A. C., Coimbra M. A., Domingues M. R. M., & Nunes F. M. (2014). Origin of the pinking phenomenon of white wines. Journal of Agriculture and Food Chemistry, 62(24), 5651–5659. https://doi.org/10.1021/jf500825h.
[2] Gabrielli M., Fracassetti D., Romanini E., Colangelo D., Tirelli A., Lambri, M. (2021). Oxygen-induced faults in bottled white wine: A review of technological and chemical characteristics. Food Chemistry, 348, 128922. https://doi.org/10.1016/j.foodchem.2020.128922.

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Ragg Enzio1, De Noni Ivano1 and Tirelli Antonio1

1Department of Food, Environmental and Nutritional Sciences (DeFENS), Università degli Studi di Milano, Via G. Celoria 2, 20133 Milan, Italy

Contact the author

Keywords

Pinking, Oxidation, Quinones, Cysteine, Catechin

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

1H-NMR-based Metabolomics to assess the impact of soil type on the chemical composition of Mediterranean red wines

The aim of this study was to evaluate the effects of different soil types on the chemical composition of Mediterranean red wines, through untargeted and targeted 1H-NMR metabolomics. One milliliter of raw wine was analyzed by means of a Bruker Avance II 400 spectrometer operating at 400.15 MHz. The spectra were recorded by applying the NOESYGPPS1D pulse sequency, to achieve water and ethanol signals suppression. No modification of the pH was performed to avoid any chemical alteration of the matrix. The generation of input variables for untargeted analysis was done via bucketing the spectra. The resulting dataset was preprocessed prior to perform unsupervised PCA, by means of MetaboAnalyst web-based tool suite. The identification of compounds for the targeted analysis was performed by comparison to pure compounds spectra by means of SMA plug-in of MNova 14.2.3 software. The dataset containing the concentrations (%) of identified compounds was subjected to one-way analysis of variance (ANOVA) to highlight significant differences among the wines. The untargeted analysis, carried out through the PCA, revealed a clear differentiation among the wines. The fragments of the spectra contributing mostly to the separation were attributed to flavonoids, aroma compounds and amino acids. The targeted analysis leaded to the identification of 68 compounds, whose concentrations were significant different among the wines. The results were related to soils physical-chemical analysis and showed that: 1) high concentrations of flavan-3-ols and flavonols are correlated with high clay content in soils; 2) high concentrations of anthocyanins, amino acids, and aroma compounds are correlated with neutral and moderately alkaline soil pH; 3) low concentrations of flavonoids and aroma compounds are correlated with high soil organic matter content and acidic pH. The 1H-NMR metabolomic analysis proved to be an excellent tool to discriminate between wines originating from grapes grown on different soil types and revealed that soils in the Mediterranean area exert a strong impact on the chemical composition of the wines.

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.

Late frost protection in Champagne

Probably one of the most counterintuitive impacts of climate change on vine is the increased frequency of late frost. Champagne, due to its septentrional position is historically and regularly affected by this meteorological hazard. Champagne has therefore developed a strong experience in frost protection with first experiments dating from the end of 19th century. Frost protection can be divided in two parts: passive and active. Passive protection includes all the methods that do not seek to modify the vine’s environment or resistance at the time of frost. The most iconic passive protection in Champagne is the establishment of the individual reserve. This reserve allows to stock a certain quantity of clear wine during a surplus year to compensate a meteorological hazard like frost during the following years. Other common passive methods are the control of planting area (walls, bushes, topography), the choice of grape variety, late pruning, or the impact of grass cover and tillage. Active frost protection is also divided in two parts. Most of the existing techniques tend to modify vine’s environment. Most of the time they provide warmth (candles, heaters, windmills, heating cables…), or stabilise bud’s temperature above a lethal threshold (water sprinkling). The other way to actively fight is to enhance the resistance of buds to frost (elicitors). The Comité Champagne evaluates frost protection methods following three main axes: the efficiency, the profitability, and the environmental impact through a lifecycle assessment. This study will present the results on both passive and active protection following these three axes.

Metabolomic discrimination of grapevine water status for Chardonnay and Pinot noir

Water status impact in viticulture has been widely explored, as it strongly affects grapevine physiology and grape chemical composition. It is considered as a key component of vitivinicultural terroir. Most of the studies concerning grapevine water status have focused on either physiological traits, or berry compounds, or traits involved in wine quality. Here, the response of grapevine to water availability during the ripening period is assessed through non-targeted metabolomics analysis of grape berries by ultra-high resolution mass spectrometry. The grapevine water status has been assessed during 2 consecutive years (2019 & 2020), through carbon isotope discrimination on juices from berries collected at maturity (21.5 brix approx.) for 2 Vitis vinifera cv. Pinot noir (PN) and Chardonnay (CH). A total of 220 grape juices were collected from 5 countries worldwide (Italy; Argentina; France; Germany; Portugal). Measured δ13C (‰) varied from -28.73 to -22.6 for PN, and from -28.79 to -21.67 for CH. These results also clearly revealed higher water stress for the 2020 vintage. The same grape juices have been analysed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Liquid Chromatography coupled to Mass Spectrometry (LC-qTOF-MS), leading to the detection of up to 4500 CHONS containing elemental compositions, and thus likely tens of thousands of individual compounds, which include fatty acids, organic acids, peptides, phenolics, also with high levels of glycosylation. Multivariate statistical analysis revealed that up to 160 elemental compositions, covering the whole range of detected masses (100 –1000 m/z), were significantly correlated to the observed gradients of water status. Examples of chemical markers, which are representative of these complex fingerprints, include various derivatives of the known abscisic acid (ABA), such as phaesic acid or abscisic acid glucose ester, which are significantly correlated with higher water stress, regardless of the variety. Cultivar-specific behaviours could also be identified from these fingerprints. Our results provide an unprecedented representation of the metabolic diversity, which is involved in the water status regulation at the grape level, and which could contribute to a better knowledge of the grapevine mitigation strategy in a climate change context.

Impact of climate variability and change on grape yield in Italy

Viticulture is entangled with weather and climate. Therefore, areas currently suitable for grape production can be challenged by climate change. Winegrowers in Italy already experiences the effect of climate change, especially in the form of warmer growing season, more frequent drought periods, and increased frequency of weather extremes.
The aim of this study is to investigate the impact of climate variability and change on grape yield in Italy to provide winegrowers the information needed to make their business more sustainable and resilient to climate change. We computed a specific range of bioclimatic indices, selected by the International Organisation of Vine and Wine (OIV), and correlated them to grape yield data. We have worked in collaboration with some wine consortiums in northern and central Italy, which provided grape yield data for our analysis.
Using climate variables from the E-OBS dataset we investigate how the bioclimatic indices changed in the past, and the impact of this change on grape productivity in the study areas. The climate impact on productivity is also investigated by using high-resolution convection-permitting models (CPMs – 2.2 horizontal resolution), with the purpose of estimating productivity in future emission scenarios. The CPMs are likely the best available option for this kind of impact studies since they allow a better representation of small-scale processes and features, explicitly resolve deep convection, and show an improved representation of extremes. In our study, we also compare CPMs with regional climate models (RCMs – 12 km horizontal resolution) to assess the added value of high-resolution models for impact studies. Further development of our study will lead to assessing the future suitability for vine cultivation and could lead to the construction of a statistical model for future projection of grape yield.