Macrowine 2021
IVES 9 IVES Conference Series 9 Determination of quality related polyphenols in chilean wines by absorbance-transmission and fluorescence excitation emission matrix (a-teem) analyses

Determination of quality related polyphenols in chilean wines by absorbance-transmission and fluorescence excitation emission matrix (a-teem) analyses

Abstract

Phenolic composition is essential to wine quality (Cleary et al., 2015; Bindon et al., 2020; Niimi et al., 2020) and its assessment is a strong industrial need to quality management. Objective of this work was to develop a rapid analysis method using the Absorbance-Transmission and fluorescence Excitation-Emission Matrix (A-TEEM) technique. Polyphenols exhibit characteristic and high fluorescence quantum yields, which makes them highly suitable for this technique. The method’s automatic real-time Inner Filter Effect (IFE) correction allows the quantification of minor compounds (Gilmore et al., 2016). IFE-corrected fluorescence EEM data and the absorbance data were combined, and the spectral data were regressed against the concentrations of 34 anthocyanins, flavan-3-ols, tannins, polymeric pigments, flavonols and hydroxycinnamic acids measured independently by HPLC-DAD and UV-vis. The study focused on comparing Partial Least Squares Regression (PLSR) and Extreme Gradient Boost Regression (XGBR) for the single- (fluorescence EEM or absorbance) and multi- (combined) block data. The calibration set comprised 1133 files acquired from 126 diverse experimental and commercial wines. Validation was carried out on two data sets, first by a 14% randomized sample split from the calibration data keeping instrument replicates together, and thereafter by another independent set of 96 files from 16 wines. As a general trend, validation of the multi-block data models with independent data using XGBR, compared to PLSR, yielded higher prediction correlation coefficients (R2P) and lower Root Mean Square Errors for Prediction (RMSEP). Considering all 34 compound fits, mean R2P of 0.947 with XGBR and of 0.899 with PLSR were obtained. The highest fits were obtained for compounds of the anthocyanin family with mean R2P of 0.974 (XGBR) and 0.954 (PLSR), respectively, while lower fits were found for flavan-3-oles with R2P of 0.878 (XGBR) and 0.771 (PLSR), indicating compound effects due to extraction and chromatographic and spectral analysis methods affecting repeatability and quantification limits. In general, precise model fits were found for compounds > 10 mg/L with R2P between 0.929 and 0.992 (XGBR) and between 0.875 and 0.992 (PLSR). Supplementary, all individual compounds could be identified according to their family by spectral fingerprints. However, these multi-block data sets were also associated with significantly higher R2P (and lower RMSEP) compared to a single block evaluation of the fluorescence EEM or absorbance data only. By using mean-centering and an Extended Mixture Model filter the multi-block data sets fit robustly using both XGBR and PLSR without the need to apply secondary variable selection algorithms. We conclude that analyzing the A-TEEM data using the multi-block organization and the XGBR algorithm facilitates a robust prediction of the key phenolic compound concentrations that strongly influence the Chilean wine quality.

DOI:

Publication date: September 7, 2021

Issue: Macrowine 2021

Type: Article

Authors

Doreen Schober

Center for Research and Innovation, Viña Concha y Toro, Ruta k-650 km 10, Pencahue, Región de Maule, Chile,Adam Gilmore, HORIBA Instruments Inc. 20 Knightsbridge Rd., Piscataway, NJ 08854, USA Jorge Zincker, Center for Research and Innovation, Viña Concha y Toro, Ruta k-650 km 10, Pencahue, Región de Maule, Chile Alvaro Gonzalez, Center for Research and Innovation, Viña Concha y Toro, Ruta k-650 km 10, Pencahue, Región de Maule, Chile

Contact the author

Keywords

quality, polyphenols, spectroscopy, a-teem, wine, machine learning

Citation

Related articles…

Grape berry size is a key factor in determining New Zealand Pinot noir wine composition

Making high quality but affordable Pinot noir (PN) wine is challenging in most terroirs and New Zealand’s (NZ) situation is no exception. To increase the probability of making highly typical PN wines producers choose to grow grapes in cool climates on lower fertility soils while adopting labour intensive practices. Stringent yield targets and higher input costs necessarily mean that PN wine cost is high, and profitability lower, in line-priced varietal wine ranges. To understand the reasons why higher yielding vines are perceived to produce wines of lower quality we have undertaken an extensive study of PN in NZ. Since 2018, we established a network of twelve trial sites in three NZ regions to find individual vines that produced acceptable commercial yields (above 2.5kg per vine) and wines of composition comparable to “Icon” labels. Approximately 20% of 660 grape lots (N = 135) were selected from within a narrow juice Total Soluble Solids (TSS) range and made into single vine wines under controlled conditions. Principal Component Analysis of the vine, berry, juice and wine parameters from three vintages found grape berry mass to be most effective clustering variable. As berry mass category decreased there was a systematic increase in the probability of higher berry red colour and total phenolics with a parallel increase in wine phenolics, changed aroma fraction and decreased juice amino acids. The influence of berry size on wine composition would appear stronger than the individual effects of vintage, region, vineyard or vine yield. Our observations support the hypothesis that it is possible to produce PN wines that fall within an “Icon” benchmark composition range at yields above 2.5kg per vine provided that the Leaf Area:Fruit Weight ratio is above 12cm2 per g, mean berry mass is below 1.2g and juice TSS is above 22°Brix.

What are the optimal ranges and thresholds for berry solar radiation for flavonoid biosynthesis?

In wine grape production, canopy management practices are applied to control the source-sink balance and improve the cluster microclimate to enhance berry composition. The aim of this study was to identify the optimal ranges of berry solar radiation exposure (exposure) for upregulation of flavonoid biosynthesis and thresholds for their degradation, to evaluate how canopy management practices such as leaf removal, shoot thinning, and a combination of both affect the grapevine (Vitis vinifera L. cv. Cabernet Sauvignon) yield components, berry composition, and flavonoid profile under context of climate change. First experiment assessed changes in the grape flavonoid content driven by four degrees of exposure. In the second experiment, individual grape berries subjected to different exposures were collected from two cultivars (Cabernet Sauvignon and Petit Verdot). The third experiment consisted of an experiment with three canopy management treatments (i) LR (removal of 5 to 6 basal leaves), (ii) ST (thinned to 24 shoots per vine), and (iii) LRST (a combination of LR and ST) and an untreated control (UNT). Berry composition, flavonoid content and profiles, and 3-isobutyl 2-methoxypyrazine were monitored during berry ripening. Although increasing canopy porosity through canopy management practices can be helpful for other purposes, this may not be the case of flavonoid compounds when a certain proportion of kaempferol was achieved. Our results revealed different sensitivities to degradation within the flavonoid groups, flavonols being the only monitored group that was upregulated by solar radiation. Within different canopy management practices, the main effects were due to the ST. Under environmental conditions given in this trial, ST and LRST hastened fruit maturity; however, a clear improvement of the flavonoid compounds (i.e., greater anthocyanin) was not observed at harvest. Methoxypyrazine berry content decreased with canopy management practices studied. Although some berry traits were improved (i.e. 2.5° Brix increase in berry total soluble solids) due to canopy management practices (ST), this resulted in a four-fold increase in labor operations cost, two-fold decrease in yield with a 10-fold increase in anthocyanin production cost per hectare that should be assessed together as the climate continues to get hot.

Modelling vine water stress during a critical period and potential yield reduction rate in European wine regions: a retrospective analysis

Most European vineyards are managed under rainfed conditions, where seasonal water deficit has become increasingly important. The flowering-veraison phenophase represents an important period for vine response to water stress, which is seldomly thoroughly evaluated. Therefore, we aim to quantify the flowering-veraison water stress levels using Crop Water Stress Indicator (CWSI) over 1986–2015 for important European wine regions, and to assess the respective potential Yield Lose Rate (YLR). Additionally, we also investigate whether an advanced flowering-veraison phase may help alleviating the water stress with improved yield. A process-based grapevine model STICS is employed, which has been extensively calibrated for flowering and veraison stages using observed data at 38 locations with 10 different grapevine varieties. Subsequently, the model is being implemented at the regional level, considering site-specific calibration results and gridded climate and soil datasets. The findings suggest wine regions with stronger flowering-veraison CWSI tend to have higher potential YLR. However, contrasting patterns are found between wine regions in France-Germany-Luxembourg and Italy-Portugal-Spain. The former tends to have slight-to-moderate drought conditions (CWSI<0.5) and a negligible-to-moderate YLR (<30%), whereas the latter possesses severe-to-extreme CWSI (>0.5) and substantial YLR (>40%). Wine regions prone to a high drought risk (CWSI>0.75) are also identified, which are concentrated in southern Mediterranean Europe. An advanced flowering-veraison phase may have benefited from cooler temperatures and a higher fraction of spring precipitation in wine regions of Italy-Portugal-Spain, resulting in alleviated CWSI and moderate reductions of YLR. For those of France-Germany-Luxembourg, this can have reduced flowering-veraison precipitation, but prevalent alleviations of YLR are also found, possibly because of shifted phase towards a cooler growing season with reduced evaporative demands. Overall, such a retrospective analysis might provide new insights towards better management of seasonal water deficit for conventionally vulnerable Mediterranean wine regions, but also for relatively cooler and wetter Central European regions.

Mechanisms involved in the heating of the environment by the aerodynamic action of a wind machine to protect a vineyard against spring frost

One of the main consequences of global warming is the rise of the mean temperature. Thus, the heat summation by the plants begins sooner in the early spring, and by cumulating growing degree-days, phenological development tends to happen earlier. However, spring frost is still a recurrent phenomenon causing serious damages to buds and therefore, threatening the harvests of the winegrowers. The wind machine is a solution to protect fruit crops against spring frost that is increasingly used. It is composed of a 10-m mast with a blowing fan at its peak. By tapping into the strength of the nocturnal thermal inversion, it sweeps the crop by propelling warm air above to the ground. Thus, stratification is momentarily suppressed. Furthermore, the continuous action of the machine, alone or in synergy, or the addition of a heater allow the bud to be bathed in a warmer environment. Also, the punctual action of the tower’s warm gust reaches the bud directly at each rotation period. All these actions allow the bud to continuously warm up, but with different intensities and over a different period. Although there is evidence of the effectiveness of the wind machines, the thermal transfers involved in those mechanisms raise questions about their true nature. Field measurements based on ultrasonic anemometers and fast responding thermocouples complemented by laboratory measurements on a reduced scale model allow to characterize both the airflow produced by the wind machine and the local temperature in its vicinity. Those experiments were realized in the vineyard of Quincy, in the framework of the SICTAG project. In the future paper, we will detail the aeraulic characterization of the wind machine and the thermal effects resulting from it and we will focus on how the wind machine warms up the local atmosphere and enables to reduce the freezing risk.

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.