First Approach to the Aroma Characterization of Monovarietal Red Wines Produced from Varieties Better Adapted to Abiotic Stresses.

Adaptation strategies in the wine sector consist of the use of cultural techniques to limit damages caused by climate change, using, among other resources, varieties better adapted to the scenarios of abiotic stress exacerbation, namely water and thermal stress, as well as those more tolerant to heatwaves. With the intention to determine the aromatic characterization of ten monovarietal wines produced from cultivars with high productive performance in a global warming scenario ('Petit Verdot', 'Marselan', 'Merlot', 'Touriga Franca', 'Syrah', 'Vinhão', 'Bobal', 'Preto Martinho', 'Trincadeira', and 'Alicante Bouschet'), grown in Esporão vineyard (Alentejo, Portugal) and submitted to deficit irrigation (Ks ± 0.5), their aromatic character has been analyzed. Each grape variety was vinified at a small scale, in duplicate, and the wines were evaluated by a sensory panel, which rated several sensory attributes (visual, olfactory, and gustatory). Sensory analysis revealed a discrete appreciation for the monovarietal wines tasted, showing a differentiation at the olfactory level that was not too marked, although present, between the samples. The free volatile compounds were analysed using gas chromatography-olfactometry (GC-O), identified using a gas chromatography-mass spectrometry (GC-MS) technique and semi-quantified using the gas chromatography-flame ionization detector (GC-FID) technique. Based on the interpolation of the results of the various statistical analyses carried out, 49 probable odor active compounds (pOACs) were identified and based on the odor activity values (OAVs), 24 of them were recognized as odor active compounds (OACs) originated mainly during the fermentation processes. An aromatic characterization of the varieties has been proposed.

Shedding Light on Metals Release from Chestnut Wood to Wine Spirit Using ICP-MS.

Possible effects caused by mineral elements during wine spirit ageing are diverse. In this study, the evolution of the mineral composition of wine spirit during ageing with chestnut (Castanea sativa Mill.) wood was investigated. A wine distillate was aged in 250 L wooden barrels (traditional ageing) and in 50 L glass demijohns with wood staves and micro-oxygenation (alternative ageing). Sampling was performed after 21, 60, 180, 270, and 365 days of ageing. The elemental composition of the wine spirits, including alkaline, alkaline earth metals, and heavy metals, was assessed by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). For most of the elements, no significant differences between wine spirits from distinct ageing modalities were observed. Ageing time had significant effect on most of them, with different trends and distinct magnitude of changes, depending on each specific element. The concentrations of the mineral elements found in the wine spirits were very low, especially those of heavy metals, which is quite positive in terms of quality and food safety. Novel information on metals released from chestnut wood to wine spirits confirms its appropriateness for ageing this beverage.

Saccharomyces cerevisiae Diversity in Arbutus unedo L. Fermentations in Association with the Volatile and Sensory Similarities of the Distillates.

The fermentation of Arbutus unedo L. fruit is traditionally carried out in the production of spirits. The present study followed the spontaneous fermentation of A. unedo fruit harvested in October and December 2019 by two producers from the central region of Portugal. The microbiota was studied, and although a great diversity of indigenous yeasts was found, S. cerevisiae isolates could still be grouped into eight clusters, and a good separation between producers was achieved. Based on the results of a multivariate analysis of the physical-chemical and volatile composition of the distillates, a distinction between the distillates from the two producers was determined. Moreover, these findings are corroborated by the similarities in flavor that were found. Along with the variability found in the distillates, S. cerevisiae isolates could be clustered and associated with each producer. On the other hand, the differentiation of the harvesting period was not so clear. The characterization of the indigenous yeasts associated with the fermentation process of Arbutus unedo L. fruit can serve as an important contribution to the preservation of the specific characteristics of its distillates.

Identification of gallotannins and ellagitannins in aged wine spirits: A new perspective using alternative ageing technology and high-resolution mass spectrometry.

This research was focused on identifying gallotannins and ellagitannins degradation pathways to better understand their behavior in complex media such as wine spirits (WS). A WS was aged with chestnut wood staves with three levels of micro-oxygenation, nitrogen, and using wooden barrels. Gallotannins and ellagitannins were identified by LC-ESI-HRMS/MS using a Q-TOF in samples collected at 8, 21, 60, 180, 270, and 365 days of ageing, allowed comparing their relative abundances according to the ageing technology. It was established for the first time, the importance of oxygen in gallotannins and ellagitannins formation/degradation pathways in WS and shading light into the explanation for the steady increase of gallic and ellagic acid contents on WS during ageing. The results also highlighted the presence of penta-O-galloyl-ß-d-glucose, tetra-O-galloyl-ß-d-glucose, tri-O-galloyl-ß-d-glucose, di-O-galloyl-ß-d-glucose, and mono-O-galloyl-ß-d-glucose, 2,3-(S)-hexahydroxydiphenoyl-ß-d-glucose, pedunculagin, isomers vescalagin/castalagin and two products stemming from ethanol-promoted oxidation of castalagin/vescalagin and vescalin/castalin, in the composition WS aged with chestnut wood.

Influence of the Storage in Bottle on the Antioxidant Activities and Related Chemical Characteristics of Wine Spirits Aged with Chestnut Staves and Micro-Oxygenation.

Different ageing technology of wine spirits (WSs) has been investigated, but little has been published on the chemical evolution of aged WS during storage in bottle. The purpose of this study was to examine how 12 months of storage in bottle affected the evolution of antioxidant activity (DPPH, FRAP and ABTS assays), total phenolic index (TPI) and low molecular weight (LMW) compounds content of the WSs aged through alternative technology using three micro-oxygenation levels (MOX) and nitrogen control (N). Results revealed the ability of phenolic compounds from aged WSs to scavenge free radicals during storage in bottle. Among the in vitro antioxidant-activity methods, FRAP assay was the more effective to differentiate WSs according to the ageing technology. Concerning the overall influence of storage in bottle on antioxidant activity, and TPI and LMW compounds content, the higher results were obtained for the MOX modalities (O15, O30 and O60), which showed a similar evolution. In summary, this study provides innovative information, demonstrating that the differences between the aged WSs imparted throughout the ageing process (resulting from different MOX levels) were mostly retained, and only slight modifications during storage in bottle were found.

PLS-R Calibration Models for Wine Spirit Volatile Phenols Prediction by Near-Infrared Spectroscopy.

Near-infrared spectroscopic (NIR) technique was used, for the first time, to predict volatile phenols content, namely guaiacol, 4-methyl-guaiacol, eugenol, syringol, 4-methyl-syringol and 4-allyl-syringol, of aged wine spirits (AWS). This study aimed to develop calibration models for the volatile phenol's quantification in AWS, by NIR, faster and without sample preparation. Partial least square regression (PLS-R) models were developed with NIR spectra in the near-IR region (12,500-4000 cm-1) and those obtained from GC-FID quantification after liquid-liquid extraction. In the PLS-R developed method, cross-validation with 50% of the samples along a validation test set with 50% of the remaining samples. The final calibration was performed with 100% of the data. PLS-R models with a good accuracy were obtained for guaiacol (r2 = 96.34; RPD = 5.23), 4-methyl-guaiacol (r2 = 96.1; RPD = 5.07), eugenol (r2 = 96.06; RPD = 5.04), syringol (r2 = 97.32; RPD = 6.11), 4-methyl-syringol (r2 = 95.79; RPD = 4.88) and 4-allyl-syringol (r2 = 95.97; RPD = 4.98). These results reveal that NIR is a valuable technique for the quality control of wine spirits and to predict the volatile phenols content, which contributes to the sensory quality of the spirit beverages.

Behaviour of Low Molecular Weight Compounds, Iron and Copper of Wine Spirit Aged with Chestnut Staves under Different Levels of Micro-Oxygenation.

Alternative technologies for a more sustainable wine spirits' ageing have been studied but a lack of knowledge on the effect of oxygenation level remains. This work examined the behaviour of low molecular weight compounds, iron and copper of a wine spirit aged in 50 L demijohns with chestnut wood staves combined with three levels of micro-oxygenation or nitrogen. Compounds and mineral elements were quantified by HPLC and FAAS, respectively, in samples collected at 8, 21, 60, 180, 270 and 365 days of ageing. Results showed that most of the compounds underwent significant changes in their content over time and behave differently depending on the wine spirit's oxygenation level: higher contents of gallic acid, syringic acid and vanillin were associated with lower micro-oxygenation level while higher contents of ellagic acid, syringaldehyde, coniferaldehyde and sinapaldehyde resulted from higher one; lowest contents of these compounds were found in the nitrogen modality. Weak correlation between copper and the studied compounds was evidenced whereas closer relationship between iron, vanillin, gallic, syringic and ellagic acids at end of ageing was observed. This study provides innovative information on the role of oxygen in wine spirit's ageing, and on chestnut wood effect on wine spirit's mineral composition.

Chemical composition and sensory properties of Albariño wine: Fertigation effects.

Interannual climate variability and management practices, including fertigation, can alter volatile compound concentrations in wines from a given grapevine cultivar. These compounds are highly relevant for wine aroma. The current study aimed to assess the effect of two levels of fertigation on the volatile composition and sensory properties of wines from Albariño grown in two vineyards in NW Spain over three years. Treatments were fertigation to 60% (F-60) and 100% (F-100) of crop needs since budbreak, and a rain-fed control (F-0). Volatile compounds were determined through gas chromatography and mass spectrometry (GC-MS) and wine sensory evaluation was performed by nine experts using quantitative descriptive analysis. General chemical parameters of wines were similar among treatments; however, F-60 and F-0 slightly reduced volatile total concentrations in both vineyards. Wines from the fertigation treatments had greater concentrations of volatile fatty acids, ethyl esters, acetates and C6 compounds. However, terpene concentrations slightly decreased when fertigation was applied. Higher alcohols showed a different behavior between vineyards, mainly related with grapevine water status during the growing season. Seven sensory descriptors differed significantly between vineyards. This study indicates that fertigation could be a tool for modulating wine chemical and sensory characteristics.

Effect of innovative technology using staves and micro-oxygenation on the odorant and sensory profile of aged wine spirit.

The aged wine spirit is a beverage with great aromatic complexity. Their volatile compounds with odorant power coming from the distillate and from the wood used in its ageing, and the interactions that take place in the process, enhanced by oxygen, all contribute to this complexity. Due to time and cost inherent of ageing wine spirits in wooden barrels, research has sought to develop more sustainable alternatives to do it. In this context, the present study compares, the effect of traditional (wooden barrel) and alternative system (stainless steel tank with dipped staves and micro-oxygenation), on the odorant and sensory profile of a wine spirit, using Limousin oak and chestnut wood, after 12 months of ageing. The results suggest that the ageing process is accelerated by the alternative ageing technology and the chestnut wood, and the corresponding wine spirits presented characteristics of greater sensory evolution and strong wood compounds extraction.

FT-RAMAN methodology for the monitoring of honeys' spirit distillation process.

Honey spirit is an alcoholic beverage produced by fermentation followed by distillation of the honey must, which has distinct organoleptic characteristics derived mostly from the raw material used. In order to accurately monitor the quality of the product throughout the distillation process (head, heart and tail stages), FT-RAMAN spectroscopy was applied. Dark honey, light honey and honey obtained following waxes' wash was used to produce honey spirit. The pH, alcoholic strength, methanol content, acetaldehyde content, ethyl acetate content and higher alcohols content were evaluated during the distillation process. The FT-RAMAN technique was used to obtain spectral information for all fractions collected during beverage production. The results suggest that the honey spirit had good quality concerning the volatile composition and methanol was not detected in any sample. FT-RAMAN is promising for the online monitoring of the distillation process in order to improve the final quality of this beverage.

Development of blueberry liquor: influence of distillate, sweetener and fruit quantity.

BACKGROUND: In this work different formulations of blueberry liquor were tested and characterised based on their physico-chemical and sensory characteristics. RESULTS: Three factors were evaluated: the distillate used to produce the liquor (wine spirit or grape marc spirit); the sweetener (white sugar or honey) and the fruit quantity (two doses). For each liquor, pH, total acidity, dry soluble solids content, dry extract, alcoholic strength, reducing sugars, colour intensity, methanol content, acetaldehyde and fusel alcohols were determined. Sensory tests were carried out with a trained panel. CONCLUSION: The three factors studied significantly influenced the physico-chemical features of the liquors, being the quantity of fruit the most discriminating factor, except for the volatile compounds which were mainly influenced by the distillate. As regards the sensory analysis, it was found that the most appreciated liquor was that prepared with wine spirit, sugar and a lower dose of blueberry, and the less appreciated formulation was the one made with grape marc spirit, honey and a lower quantity of blueberry. © 2017 Society of Chemical Industry.

Physicochemical and Sensorial Characterization of Honey Spirits.

Distilled spirits are usually made from fermented sugar-based materials, such as wines or fermented fruits, but other products can be used, namely berries or honey. In this work, an evaluation of honey spirits is done based on its physicochemical and sensory characteristics. Fourteen honey spirit samples of different brands of honey spirit were purchased at the market and from artisan Portuguese producers. Several analytical determinations, namely alcoholic strength, dry matter, density, total acidity, chromatic characteristics, methanol, acetaldehyde, ethyl acetate and higher alcohols were done to characterize all samples. The results pointed out several differences in physicochemical composition of samples. In general, these drinks are characterized by an alcohol strength between 37.4% and 53.0% and a low methanol content, quite null for most samples. Samples with higher ethanol content corresponded to the artisanal samples. Significant differences (p < 0.05) were also observed in the volatile composition and chromatic characteristics suggesting different production technologies. A first list of sensory attributes was obtained for this beverage. Therefore, further research must be done in order to characterize this spirit drink, which has gained market value.

Kinetics of odorant compounds in wine brandies aged in different systems.

The odorants compounds of aged wine brandies comprise compounds deriving from the wood, from the distillate and from the reactions that occur inside the barrel. The aim of this work was to study the kinetics of the odorant compounds of a wine brandy during two years of ageing in two ageing systems. The odorant compounds in the analysed brandies changed significantly over the time, but with different evolution patterns. The wood related compounds increased over time, with the highest increase in the first months of ageing. The kinetics of cis, trans-ß-methyl-γ-octalactone, acetovanillone and of seven volatile phenols are established for the first time in brandies. Moreover, a significant effect of the ageing system was found on the kinetics of the wood related compounds. These results pointed out the interest of these compounds as a tool to discriminate different ageing technologies.

FTIR-ATR spectroscopy applied to quality control of grape-derived spirits.

The Fourier transform infrared (FTIR) spectroscopic method with attenuated total reflectance (ATR) was used for predicting the alcoholic strength, the methanol, acetaldehyde and fusel alcohols content of grape-derived spirits. FTIR-ATR spectrum in the mid-IR region (4000-400 cm(-1)) was used for the quantitative estimation by applying partial least square (PLS) regression models and the results were correlated with those obtained from reference methods. In the developed method, a cross-validation with 50% of the samples was used for PLS analysis along with a validation test set with 50% of the remaining samples. Good correlation models with a great accuracy were obtained for methanol (r(2)=99.4; RPD=12.8), alcoholic strength (r(2)=97.2; RPD=6.0), acetaldehyde (r(2)=98.2; RPD=7.5) and fusel alcohols (r(2) from 97.4 to 94.1; RPD from 6.2 to 4.1). These results corroborate the hypothesis that FTIR-ATR is a useful technique for the quality control of grape-derived spirits, whose practical application may improve the efficiency and quickness of the current laboratory analysis.

Extraction/oxidation kinetics of low molecular weight compounds in wine brandy resulting from different ageing technologies.

This study provides innovative information on the influence of new technologies of ageing (stainless steel tanks with wood staves or wood tablets of chestnut or Limousin oak), in comparison with traditional technology (oak wooden barrels), on the extraction/oxidation kinetics of low molecular weight compounds of wine brandy. The brandy was sampled and analysed by HPLC during the first year of ageing. The results show that most of the compounds tend to increase over the time, but their extraction/oxidation kinetics depend on the ageing technology. The wooden barrels promote greater enrichment in the majority of the compounds. However, gallic acid, ellagic acid and syringaldehyde, and vanillin and 5-methylfurfural, which are strong antioxidants and key-odourant compounds, respectively, present higher contents in the brandy aged with the alternative technologies. Chestnut proves to be a suitable alternative to Limousin oak for the ageing of brandy in all the studied technologies, inducing faster evolution and high quality.

Reactivity of polymeric proanthocyanidins toward salivary proteins and their contribution to young red wine astringency.

Recent studies have indicated the presence of significant amount of highly polymerized and soluble proanthocyanidins in red wine and such compounds interacted readily with proteins, suggesting that they might be particularly astringent. Thus, the objective of this work was to verify the astringency of polymeric proanthocyanidins and their contribution to red wine astringency. The precipitation reactions of the purified oligomeric procyanidins (degree of polymerization ranging from 2 to 12-15) and polymeric procyanidins (degree of polymerization ranging from 12-15 to 32-34) with human salivary proteins were studied; salivary proteins composition changes before and after the reaction was verified by SDS-PAGE and procyanidins composition changes by spectrometric, direct HPLC and thiolysis-HPLC methods. The astringency intensity of these two procyanidin fractions was evaluated by a sensory analysis panel. For verifying the correlation between polymeric proanthocyanidins and young red wine astringency, the levels of total oligomeric and total polymeric proanthocyanidins and other phenolic composition in various young red wines were quantified and the astringency intensities of these wines were evaluated by a sensory panel. The results showed that polymeric proanthocyanidins had much higher reactivity toward human salivary proteins and higher astringency intensity than the oligomeric ones. Furthermore, young red wine astringency intensities were highly correlated to levels of polymeric proanthocyanidins, particularly at low concentration range (correlation coefficient r = 0.9840) but not significant correlated to total polyphenols (r = 0.2343) or other individual phenolic compounds (generally r < 0.3). These results indicate the important contribution of polymeric proanthocyanidins to red wine astringency and the levels of polymeric polyphenols in red wines may be used as an indicator for its astringency.

Sensory and chemical modifications of wine-brandy aged with chestnut and oak wood fragments in comparison to wooden barrels.

Wooden barrels are used in the ageing or maturation of many alcoholic beverages, namely brandies and wines. However, the high costs related to ageing in wooden barrels have led to a search for alternative technologies. In this study we examined the application of wood fragments to the beverage in order to promote an accelerated ageing. We evaluated the sensory and chemical modifications in brandy aged in presence of two types of wood fragments, from two different woods (Limousin oak wood and Portuguese chestnut wood), and compared those with a brandy aged in wooden barrels. The results of the analysis of variance revealed more significant effects of wood botanical species than the ageing system on the sensory attributes. Concerning the ageing system, significant differences in brandy colour attributes were found, namely golden, topaz and greenish; olfactory attributes such as alcoholic, toasted and coffee; and the gustatory attribute, bitter. The brandies aged in the presence of wood tablets presented the highest intensities of topaz and greenish colour, toasted and coffee odours, while the brandies aged in wooden barrels presented the highest intensities of golden colour, alcohol odour and bitter taste. However, the overall quality of the brandies was similar. The analysis of odourant compounds showed a great discrimination of the brandies based on the ageing system. The brandies aged in wooden barrels presented the highest levels of several ethyl esters, acids, furanic aldehydes and the lowest levels of volatile phenols. Thus, considering the overall quality of the brandies, these results suggest the use of wood fragments to be an interesting alternative technology. On the other hand, the chemical analysis of the brandies showed the possibility of discriminating the ageing technologies based on odourant compound levels.