OENO IVAS 2019 banner
IVES 9 IVES Conference Series 9 OENO IVAS 9 OENO IVAS 2019 9 Analysis and composition of grapes, wines, wine spirits 9 The fundamental role of pH in the anthocyanins chemical behavior and in their extractability during winemaking

The fundamental role of pH in the anthocyanins chemical behavior and in their extractability during winemaking

Abstract

The chemical behavior of anthocyanins is considerably affected even by slight pH variations with impor-tant implications for the winemaking as well as for the wine conservation. Considering that this is a cen-tral issue to the enological sector, we decided to better investigate the influence of pH on the anthocyanin chemistry.

Initially, by chromatographic and advanced NMR techniques the chemical behavior of malvi-din- 3-O-glucoside was studied in wine-like solutions with pH values ranging from 3 to 4. First, the already composite aqueous equilibrium of malvidin-3-O-glucoside turned out to be even more complex than so far thought, as a new hydration product of the anthocyanin was detected and characterized in solution.

More importantly on account of its technological implications, the anthocyanin solubility appeared to decrease remarkably as the pH value of the wine-like solutions increased. A dramatic drop in terms of anthocyanin solubility was observed at pH 3.32, where the measured molecule concentration was reduced to almost 25% the expected one. Also, at such pH level the anthocyanin self-association appeared significantly affected.

In more detail,the flavylium ion self-association predominant at lower pH levels was altered and found to co-occur with a preferential co-pigmentation involving flavylium ion species and the trans-chalcone form of malvidin-3-O-glucoside. At higher pH values, this latter association was the only one detected in so-lution. In the light of these results, we set up an experimental protocol with the purpose of analyzing the pH influence on the anthocyanin chemistry and extractability in real wines produced by varying their pH levels during the maceration-fermentation phases.

Preliminary chemical analysis of such wines provided data consistent with those obtained in wine-like solutions. Indeed, the extraction of malvidin-3-O-gluco-side and that of anthocyanins in general was more contained as the pH value increased.

Additionally, other molecules of enological interest, including catechins, cinnamates, syringic acid and terpenoids, turned out to be affected by the wine pH. These analytical data highlight the fundamental role of pH during the wine-making and the importance of regulating its level to obtain wines with the desired polyphenolic structure.

Boulton. American journal of enology and viticulture, 52(2), 67-87 (2001). Forino, M., Gambuti, A., Luciano, P., Moio, L. J. Agric. Food Chem. (2019) doi:10.1021/acs.jafc.8b05895 

DOI:

Publication date: June 11, 2020

Issue: OENO IVAS 2019

Type: Article

Authors

Martino Forino, Angelita Gambuti, Luigi Picariello, Luigi Moio

Department of Agricultural Sciences, University of Napoli “Federico II”−Oenology Sciences Section Viale Italia, 83100 Avellino, Italy

Contact the author

Keywords

Anthocyanin , pH, pigmentation, anthocyanin solubility

Tags

IVES Conference Series | OENO IVAS 2019

Citation

Related articles…

The concept of terroir: what place for microbiota?

Microbes play key roles on crop nutrient availability via biogeochemical cycles, rhizosphere interactions with roots as well as on plant growth and health. Recent advances in technologies, such as High Throughput Sequencing Techniques, allowed to gain deeper insight on the structure of bacterial and fungal communities associated with soil, rhizosphere and plant phyllosphere. Over the past 10 years, numerous scientific studies have been carried out on the microbial component of the vineyard. Whether the soil or grape compartments have been taken into account, many studies agree on the evidence of regional delineations of microbial communities, that may contribute to regional wine characteristics and typicity. Some authors proposed the term “microbial terroir” including “yeast terroir” for grapes to describe the connection between microbial biogeography and regional wine characteristics. Many factors are involved in terroir including climate, soil, cultivar and human practices as well as their interactions. Studies considering “microbial terroir” greatly contributed to improve our knowledge on factors that shape the vineyard microbial structure and diversity. However, the potential impact of “microbial terroir” on wine composition has yet not received strong scientific evidence and many questions remain to be addressed, related to the functional characterization of the microbial community and its impact on plant physiology and grape composition, the origins and interannual stability of vineyard microbiota, as well as their impact on wine sensorial attributes. The presentation will give an overview on the role of microbiota as a terroir component and will highlight future perspectives and challenges on this key subject for the wine industry.

VINIoT – Precision viticulture service

The project VINIoT pursues the creation of a new technological vineyard monitoring service, which will allow companies in the wine sector in the SUDOE space to monitor plantations in real time and remotely at various levels of precision. The system is based on spectral images and an IoT architecture that allows assessing parameters of interest viticulture and the collection of data at a precise scale (level of grape, plant, plot or vineyard) will be designed. In France, three subjects were specifically developed: evaluation of maturity, of water stress, and detection of flavescence dorée. For the evaluation of maturity, it has been decided first to work at the berry scale in the laboratory, then at the bunch scale and finally in the vineyard. The acquisition of the spectral hyperstal image as well as the reference analyzes to measure the maturity, were carried out in the laboratory after harvesting the berries in a maturity monitoring context. This work focuses on a case study to predict sugar content of three different grape varieties: Syrah, Fer Servadou and Mauzac. A robust method called Roboost-PLSR, developed in the framework of this work (Courand et al., 2022), to improve prediction model performance was applied on spectra after the acquirement of hyperspectral images. Regarding the evaluation of water stress, to work with a significant variability in terms of water status, it has been worked first with potted plants under 2 different water regimes. The facilities have allowed the supervision of irrigation and micro-climatic conditions. The regression models on agronomic variables (stomatal conductance, water potential, …) are studied. To detect flavescence dorée, the experimental plan has consisted of work at leaf scale in the laboratory first, and then in the field. To detect the disease from hyper-spectral imaging, a combination of multivariate curve resolution-alternating least squares (MCR-ALS) and factorial discriminant analysis (FDA) was proposed. This strategy proved the potential towards the discrimination of healthy and infected leaves by flavescence dorée based on the use of hyperspectral images (Mas Garcia et al., 2021).

Spatiotemporal patterns of chemical attributes in Vitis vinifera L. cv. Cabernet Sauvignon vineyards in Central California

Spatial variability of vine productivity in winegrapes is important to characterise as both yield and quality are relevant for the production of different wine styles and products. The objectives were to understand how patterns of variability of Cabernet Sauvignon fruit composition changed over time and space, how these patterns could be characterised with indirect measurements, and how spatial patterns of the variation in fruit compositional attributes can aid in improving management. Prior to the 2017 vintage, 125 data vines were distributed across each of four vineyards in the Lodi American Viticultural Area (AVA) of California. Each data vine was sampled at commercial harvest in 2017, 2018, and 2019. Yield components and fruit composition were measured at harvest for each data vine, and maps of yield and fruit composition were produced for eight ‘objective measures of fruit quality’: total anthocyanins, polymeric tannins, quercetin glycosides, malic acid, yeast assimilable nitrogen, β-damascenone, C6 alcohols and aldehydes, and 3-isobutyl-2-methoxypyrazine. Patterns of variation in anthocyanins and phenolic compounds were found to be most stable over time. Given this relative stability, management decisions focused on fruit quality could be based on zonal descriptions of anthocyanins or phenolics to increase profitability in some vineyards. In each vineyard, dormant season pruning weights and soil cores were collected at each location, elevation and soil apparent electrical conductivity surveys were completed, and remotely sensed imagery was captured by fixed wing aircraft and two satellite platforms at major phenological stages. The data collected were used to develop relationships among biophysical data, soil, imagery, and fruit composition. The standardised and aggregated samples from four vineyards over three seasons were included in the estimation of ‘common variograms’ to assess how this technique could aid growers in producing geostatistically rigorous maps of fruit composition variability without cumbersome, single season sampling efforts.

How distinctive are single vineyard Gewürztraminer musts and wines from Alto Adige (Italy) based on untargeted analysis, sensory profiling, and chemometric elaboration?

Vitis vinifera L. ‘Gewürztraminer’ is a historical grape variety of Alto Adige (Südtirol), Italy, which is widely grown in the area of Tramin an der Weinstraße, but is also grown globally. It produces highly aromatic wines that are strongly influenced by the terroir of the vineyard sites where they are grown. This study looked at musts and young wines from ‘Gewürztraminer’ grapes harvested in seven distinct vineyards near Tramin and then processed at Cantina di Termeno, minimizing winemaking protocol variability. Samples were profiled using bidimensional gas chromatography–time-of-flight mass spectrometry, liquid chromatography coupled to electrochemical detection, and near-IR spectrometry. The data were subjected to Principle Component Analysis and Hierarchical Clustering Analysis. Sensory discriminant testing was undertaken using the sorting method with a semi-trained panel, and the data were processed using Multidimensional Scaling. Seven must/wine pairs could be distinguished based on their untargeted volatilome profiles and on sensory evaluation. As expected, there were greater differences in the volatile compounds between the wines than between the musts. The wines from vineyards 4 and 5 were nonetheless quite homogenous in terms of chemical and sensory analyses, as were the wines from vineyards 1 and 3. For the phenolic profile, differences were noted between the musts and wines of vineyards 2, 3, and 4, but the musts from vineyards 5 and 7 were similar. Sensory analysis showed the wines from vineyards 6 and 7 to be distinct from the rest. These results reinforce that the composition of ‘Gewürztraminer’ musts and wines is strongly determined by vineyard site, even in a small geographic area with high variability of the terroir (soil and microclimate), and that these differences are apparent in the flavours and aromas of the finished wines. Further confirmation would require a larger sample of wines, preferably from several vintages.

VINIoT: Precision viticulture service for SMEs based on IoT sensors network

The main innovation in the VINIoT service is the joint use of two technologies that are currently used separately: vineyard monitoring using multispectral imaging and deployed terrain sensors. One part of the system is based on the development of artificial intelligence algorithms that are feed on the images of the multispectral camera and IoT sensors, high-level information on water stress, grape ripening status and the presence of diseases. In order to obtain algorithms to determine the state of ripening of the grapes and avoid losing information due to the diversity of the grape berries, it was decided to work along the first year 2020 at berry scale in the laboratory, during the second year at the cluster scale and on the last year at plot scale. Different varieties of white and red grapes were used; in the case of Galicia we worked with the white grape variety Treixadura and the red variety Mencía. During the 2020 and 2021 campaigns, multispectral images were taken in the visible and infrared range of: 1) sets of 100 grapes classifying them by means of densimetric baths, 2) individual bunches. The images taken with the laboratory analysis of the ripening stage were correlated. Technological maturity, pH, probable degree, malic acid content, tartaric acid content and parameters for assessing phenolic maturity, IPT, anthocyanin content were determined. It has been calculated for each single image the mean value of each spectral band (only taking into account the pixels of interest) and a correlation study of these values with laboratory data has been carried out. These studies are still provisional and it will be necessary to continue with them, jointly with the training of the machine learning algorithms. Processed data will allow to determine the sensitivity of the multispectral images and select bands of interest in maturation.