Macrowine 2021
IVES 9 IVES Conference Series 9 Kinetic investigations of the sulfite addition on flavanols

Kinetic investigations of the sulfite addition on flavanols

Abstract

Sulfonated monomeric and dimeric flavan-3-ols are recently discovered in wine and proved to have great importance in understanding wine chemistry and quality [1, 2]. Since the mechanism of their formation is still unknown, the aim of this work was to investigate the behaviour of wine monomeric and oligomeric and polymeric flavanols in the presence of SO2, through the evaluation of the kinetic parameters of the monomeric and dimeric flavanols sulfonation at the wine pH.The experimental design considered two different pH (3 and 4) and at five different temperature values (23, 30, 40, 50 and 60 oC), in order to study the reaction products obtained by SO2 addition to both monomeric (epicatechin and catechin) and dimeric flavanols (procyanidin B2 and procyanidin B3). The quantitative measurements were carried out by using a UHPLC-QTOF-MS instrument. The results demonstrated that [3]:a) the major sulfonation route that leads quickly and in good yields to monomeric 4β-sulfonated derivatives passes through the acid-catalysed depolymerisation of proanthocyanidins; b) monomeric flavanols lead with a significantly slower process to the same 4β-sulfonated products; c) kinetic data in our hands, in particular the temperature dependence of the observed rates, suggest the involvement of two completely different reaction mechanisms for the SO2 addition to dimeric and monomeric flavanol substrates; d) the direct sulfonation of epicatechin is slightly faster with respect to catechin.In conclusion, this new knowledge provides essential information in order to better understand tannin chemistry in food and predict or model the chemical/sensorial behaviour of wine or other food rich in proanthocyanidins.

DOI:

Publication date: September 10, 2021

Issue: Macrowine 2021

Type: Article

Authors

Panagiotis Arapitsas 1, Federico BONALDO 2, Fulvio MATTIVI 2, Graziano GUELLA 2

1 Fondazione Edmund Mach, San Michele all’Adige, Italy.
2 University of Trento, Trento, Italy.

Contact the author

Keywords

proanthocyanidins; tannins; sulfonation

Citation

Related articles…

Evaluation of climate change impacts at the Portuguese Dão terroir over the last decades: observed effects on bioclimatic indices and grapevine phenology

In the last decades the growers of the Portuguese Dão winegrowing region (center of Portugal) are experiencing changes in climate that are influencing either grape phenology berry health and ripening. Aiming to study the relationships between climate indices (CI), seasonal weather and grapevine phenology, in this work long-term climate and phenological data collected at the experimental vineyard of the Portuguese Dão research centre between 1958 and 2019 (61 years) for the red variety Touriga Nacional, was analyzed. The trends over time for the classical temperature-based indices (Growing Season Temperature – GST -, Growing Degree Days – GDD, Huglin Index – HI and Cool Night Index – CI) presented a significantly positive slope while the Dryness Index (DI) showed a negative trend over the last 61 years. Regarding grapevine phenology, an average advance of 4.5 days per decade in the harvest day was observed throughout the last 61 years. Consequently, the weather conditions during the ripening period have changed, showing an increasing trend over time in the average temperature (higher magnitude in the maximum than in the minimum temperature) and a decrease in the accumulated rainfall. A regression analysis showed that ~50% of harvest date variability over years was explained by the temperature-based indices variability. These observed effects of climate change on bioclimatic indices and corresponding anticipation of harvest date can still be considered advantageous for the Dão terroir as it allows to achieve an optimal berry ripening before the common equinox rains and, therefore, avoid the potential negative impacts of the rainfall on berry health and composition.

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).

Current climate change in the Oplenac wine-growing district (Serbia)

Serbian autochthonous vine varieties Smederevka (for white wines) and Prokupac (for rosé and red wines) are the primary representatives of typical characteristics of wines and terroir of numerous wine-growing areas in Serbia. In the past, these varieties were the leading vine varieties, however, as the result of globalization of winemaking and the trend of consumption of wines from widely prevalent vine varieties, they were replaced by introduced international varieties. Smederevka and Prokupac vine varieties are characterized by later time of grape ripening, and relative sensitivity to low temperatures. Climate conditions can be a restrictive factor for production of high-quality grapes and wine and for the spatial spreading of these varieties in hilly continental wine-growing areas.
This paper focuses on the spatial analysis of changes of main climate parameters, in particular, analysis of viticultural bioclimatic indices that were determined for the purposes of viticulture zoning of wine-growing areas in the period 1961-2010, and those same parameters determined for the current, that is, referential climate period (1988-2017). Results of the research, that is, analysis of climate changes indicate that the majority of examined climate parameters in the Oplenac wine-growing district improved from the perspective of Smederevka and Prokupac vine varieties. These studies of climate conditions indicate that changes of analyzed climate parameters, that is, bioclimatic indices will be favorable for cultivation of varieties with later grape ripening times and those more sensitive to low temperatures, such as the autochthonous vine varieties Smederevka and Prokupac, therefore, it is recommended to producers to more actively plant vineyards with these varieties in the territory of the Oplenac wine-growing district.

Effects of organic mulches on the soil environment and yield of grapevine

Farming management practices aiming at conserving soil moisture have been developed in arid and semiarid-areas facing water scarcity problems. Organic mulching is an effective method to manipulate the crop-growing microclimate increasing crop yield by controlling soil temperature, and retaining soil moisture by reducing soil evaporation. In this sense, the effectiveness of different organic mulching materials (straw mulch and grapevine pruning debris) applied within the row of a vineyard was evaluated on the soil and on the vine in a Tempranillo vineyard located in La Rioja (Spain). Organic mulches were compared with a traditional bare soil management technique (based on the use of herbicides to avoid weed incidence). Mulching coverages favourably influenced the soil water retention throughout all the grapevine vegetative cycle. However, the soil-moisture variation was not the same under different mulching materials, being the straw mulch (SM) the one that retained more water in comparison with grapevine pruning debris (GPD) based-cover. The changes of soil moisture in the upper surface layer (0–10 cm) were highly dynamic, probably due to water vapour fluxes across the soil-atmospheric interface. However, both, SM and GPD reduced these fluctuations as compared with bare soils. A similar trend occurred with soil temperature. Both organic mulches altered soil temperature in comparison with bare soil by reducing soil temperature in summer and raising it in winter. Moreover, the same buffering effect for the temperature on the covered soil also remains in the deeper layers. To conclude, we could see that organic mulching had a positive impact on soil-moisture storage and soil temperature and the extent of this effect depends on the type of mulching materials. These changes led to higher rates of photosynthesis and stomatal conductivity compared to bare soils, also favouring crop growth and grape yields.

Use of multispectral satellite for monitoring vine water status in mediterranean areas

The development of new generations of multispectral satellites such as Sentinel-2 opens possibilities as to vine water status assessment (Cohen et al., 2019). Based on a three years field campaign, a model of Stem Water Potential (SWP) estimation on vine using four satellite bands in Red, Red-Edge, NIR and SWIR domains was developed (Laroche-Pinel et al., 2021). The model relies on SWP field measures done using a pressure chamber (Scholander et al., 1965), which is a common, robust and precise method to assess vine water status (Acevedo-Opazo et al., 2008). The model was mainly developed from from SWP measures on Syrah N (Laroche Pinel E., 2021).

A large scale monitoring was organized in different vineyards in the Mediterranean region in 2021. 10 varieties amongst the most represented in this area were monitored (Cabernet sauvignon N, Chardonnay B, Cinsault N, Grenache N, Merlot N, Mourvèdre N, Sauvignon B, Syrah N, Vermentino B, Viognier B). The model was used to produce water status maps from Sentinel-2 images, starting from the beginning of June (fruit set) up to September (harvest). The average estimated SWP for each vine was compared to actual field SWP measures done by wine growers or technicians during usual monitoring of irrigation programs. The correlations between mean estimated SWP and mean measured SWP were at the same level than expected by the model. (Laroche Pinel, 2021) The general SWP kinetics were comparable. The estimated SWP would have led to same irrigation decisions concerning the date of first irrigation in comparison with measured SWP.

Acevedo-Opazo, C., Tisseyre, B., Ojeda, H., Ortega-Farias, S., Guillaume, S. (2008). Is it possible to assess the spatial variability of vine water status? OENO One, 42(4), 203.
Cohen, Y., Gogumalla, P., Bahat, I., Netzer, Y., Ben-Gal, A., Lenski, I., … Helman, D. (2019). Can time series of multispectral satellite images be used to estimate stem water potential in vineyards? In Precision agriculture ’19, The Netherlands: Wageningen Academic Publishers, pp. 445–451.
Laroche-Pinel, E., Duthoit, S., Albughdadi, M., Costard, A. D., Rousseau, J., Chéret, V., & Clenet, H. (2021). Towards vine water status monitoring on a large scale using sentinel-2 images. remote sensing, 13(9), 1837.
Laroche-Pinel,E. (2021). Suivi du statut hydrique de la vigne par télédétection hyper et multispectrale. Thèse INP Toulouse, France.
Scholander, P.F., Bradstreet, E.D., Hemmingsen, E.A., & Hammel, H.T. (1965). Sap pressure in vascular plants: Negative hydrostatic pressure can be measured in plants. Science, 148(3668), 339–346.