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…

Updating the Winkler index: An analysis of Cabernet sauvignon in Napa Valley’s varied and changing climate

This study aims to create an updated, agile viticultural climate index (similar to the Winkler Index) by performing in-depth analyses of current and historical data from industry partners in several major winegrowing regions. The Winkler Index was developed in the early twentieth century based on analysis of various grape-growing regions in California. The index uses heat accumulation (i.e. Growing Degree Days) throughout the growing season to determine which grape varieties are best suited to each region. As viticultural regions are increasingly subject to the complexity and uncertainty of a changing climate, a more rigorous, agile model is needed to aid grape growers in determining which cultivars to plant where. For the first phase of this study, 21 industry partners throughout Napa Valley shared historical phenology, harvest, viticultural practice, and weather data related to their Cabernet sauvignon vineyard blocks. To complement this data, berry samples were collected throughout the 2021 growing season from 50 vineyard blocks located throughout 16 American Viticultural Areas that were then analyzed for basic berry chemistry and phenolics. These blocks have been mapped using a Geographic Information System (GIS), enabling analysis of altitude, vineyard row orientation, slope, and remotely sensed climate data. Sampling sites were also chosen based on their proximity to a weather station. By analyzing historical data from industry partners and data specifically collected for this study, it is possible to identify key parameters for further analysis. Initial results indicate extreme variability at a high spatial resolution not currently accounted for in modern viticultural climate indices and suggest that viticultural practices play a major role. Using the structure of data collection and analyses developed for the first phase, this project will soon be expanded to other wine regions globally, while continuing data collection in Napa Valley.

Modeling the suitability of Pinot Noir in Oregon’s Willamette Valley in a changing climate

Air temperature is the key driver of grapevine phenology and a significant environmental factor impacting yield and quality for a winegrape growing region. In this study the optimal downscaled CMIP5 ensemble for computing thegrowing season average temperature (GST) viticulture climate classification index was determined to spatially compute on a decadal basis predictions of the GST climate index and the grapevine sugar ripeness (GSR) model for Pinot Noir throughout the Willamette Valley (WV) American Viticultural Area (AVA). Forecasts for average temperature and a 220 g/L target sugar concentration level were computed using daily Localized Constructed Analogs (LOCA) downscaled CMIP5 historic and Representative Concentration Pathways (RCP) future climate projections of minimum and maximum daily temperature. We explore spatiotemporal trends of the GST climate classification index and Pinot Noir specific applications of the GSR phenology model for the WV AVA. Spatiotemporal computations of the GST climate index and Pinot Noir specific applications of the GSR model enable the opportunity to explore relationships between their computed values with one intent being to provide updated GST ranges that better align with current temperature-based modeling understanding of Pinot Noir grapevine phenology and the viticultural application of LOCA CMIP5 climate projections for the WV AVA. The Pinot Noir specific applications of the GSR model or the GST index with updated bounds indicate that the percent of the WV AVA area suitable for Pinot Noir production is currently at or near its peak value in the upper 80s to lower 90s of this century.

Use of a new, miniaturized, low-cost spectral sensor to estimate and map the vineyard water status from a mobile 

Optimizing the use of water and improving irrigation strategies has become increasingly important in most winegrowing countries due to the consequences of climate change, which are leading to more frequent droughts, heat waves, or alteration of precipitation patterns. Optimized irrigation scheduling can only be based on a reliable knowledge of the vineyard water status.

In this context, this work aims at the development of a novel methodology, using a contactless, miniaturized, low-cost NIR spectral tool to monitor (on-the-go) the vineyard water status variability. On-the-go spectral measurements were acquired in the vineyard using a NIR micro spectrometer, operating in the 900–1900 nm spectral range, from a ground vehicle moving at 3 km/h. Spectral measurements were collected on the northeast side of the canopy across four different dates (July 8th, 14th, 21st and August 12th) during 2021 season in a commercial vineyard (3 ha). Grapevines of Vitis vinifera L. Graciano planted on a VSP trellis were monitored at solar noon using stem water potential (Ψs) as reference indicators of plant water status. In total, 108 measurements of Ψs were taken (27 vines per date).

Calibration and prediction models were performed using Partial Least Squares (PLS) regression. The best prediction models for grapevine water status yielded a determination coefficient of cross-validation (r2cv) of 0.67 and a root mean square error of cross-validation (RMSEcv) of 0.131 MPa. This predictive model was employed to map the spatial variability of the vineyard water status and provided useful, practical information towards the implementation of appropriate irrigation strategies. The outcomes presented in this work show the great potential of this low-cost methodology to assess the vineyard stem water potential and its spatial variability in a commercial vineyard.

Estimating bulk stomatal conductance of grapevine canopies

In response to changes in their environment, grapevines regulate transpiration using various physiological mechanisms that alter conductance of water through the soil-plant-atmosphere continuum. Expressed as bulk stomatal conductance at the canopy scale, it varies diurnally in response to changes in vapor pressure deficit and net radiation, and over the season to changes in soil water deficits and hydraulic conductivity of both soil and plant. It is necessary to characterize the response of conductance to these variables to better model how vine transpiration also responds to these variables. Furthermore, to be relevant for vineyard-scale modeling, conductance is best characterized using data collected in a vineyard setting. Applying a crop canopy energy flux model developed by Shuttleworth and Wallace, bulk stomatal conductance was estimated using measurements of individual vine sap flow, temperature and humidity within the vine canopy, and estimates of net radiation absorbed by the vine canopy. These measurements were taken on several vines in a non-irrigated vineyard in Bordeaux France, using equipment that did not interfere with ongoing vineyard operations. An inverted Penman-Monteith equation was then used to calculate bulk stomatal conductance on 15-minute intervals from July to mid-September 2020. Time-series plots show significant diurnal variation and seasonal decreases in conductance, with overall values similar to those in the literature. Global sensitivity analysis using non-parametric regression found transpiration flux and vapor pressure deficit to be the most important input variables to the calculation of bulk stomatal conductance, with absorbed net radiation and bulk boundary layer conductance being much less important. Conversely, bulk stomatal conductance was one of the most important inputs when calculating vine transpiration, further emphasizing the need for characterizing its response to environmental changes for use in vineyard water use modeling.

The combined effects of climate, soils, and deficit irrigation on yield and quality of Touriga Nacional under high atmospheric demand in the Douro Region

Global warming is one of the biggest environmental, social and economic threats in several viticultural regions. In the Douro Valley, changes are expected in the coming years, namely an increase in temperature and a decrease in precipitation. These changes are likely to have consequences for the production and quality of wine.
The aim of this study was to explore the effects of different soil characteristics combined with several deficit irrigation strategies, managed throughout ETc references and predawn leaf water potentials thresholds, on physiology, yield, and qualitative attributes on the Touriga Nacional variety under years of mild to severe water and heat stress.
The studies were conducted over seven years (2015 to 2021) in two plots of a commercial vineyard located at Quinta do Ataíde (Symington Family Estates) planted in 2011 and 2014 at 170 meters elevation, growing under three water regimes: non-irrigated (NI) and two deficit irrigation strategies (30% and 60% ETc) assessed weekly by Ψpd. The site has an annual rainfall below 500 mm, with high atmospheric demand. Climate data was collected from a weather station, located on site. Berry ripening was followed weekly for fruit analysis. At harvest, yield, vigour and pruning weight per vine were determined from 90 vines by treatment. Each season at veraison the NDVI Index was accessed by a drone. The soils physic-chemistry in the experimental blocs were analysed and grouped by SWHC. Delta C-13 analyses were also performed per treatment in two years.Irrigation had a positive effect on yield per vine, mostly due to an increase in berry and cluster weight, and fertility index through the years. A significant increase in sugar content, colour and phenols was observed with deficit irrigation in some years, but vine vigour related to soil characteristics had by far the greatest impact on quality.