FT-Raman Methodology Applied to Study the Effect of Time and Type of Seasoning in the Crafting of Sherry Casks® Used in the Aging of Brandy De Jerez.

Brandy de Jerez is a grape-derived spirit produced in Southern Spain with specific characteristics that come from the casks where it is produced, which must have previously contained some type of Sherry wine for at least 12 months. These casks are known as Sherry Cask®. In this work, Brandies de Jerez aged for different aging times (0, 3, 6 and 12 months) in casks seasoned with three different types of Sherry wines (Fino, Oloroso and Amontillado) have been studied. The samples have been analyzed using FT-Raman spectroscopy, and their chemical characterization has also been realized by studying their total content of organic acid, volatile compounds, and phenolic and furanic compounds. Their chemical study showed that the main differences between the studied samples were due to the duration and the type of seasoning performed. However, the spectra obtained through FT-Raman presented noticeable differences according to cask seasoning time and the Sherry wine used for the process. A PCA (Principal Component Analysis) confirmed that the Brandies de Jerez presented significant differences depending on the seasoning time and type that the casks were subjected to. A PLS-R (Partial Least Squares Regression) study enabled establishing a close correlation between specific regions of the FT-Raman spectra and cask seasoning time.

Fatty Acid and Tocopherol Composition of Pomace and Seed Oil from Five Grape Varieties Southern Spain.

Grape pomace and seeds are important winemaking by-products. Their oils are rich in bioactive compounds such as fatty acids and tocopherols. We have characterized oils from both by-products from five Spanish grape varieties (Palomino Fino, Pedro Ximénez, Muscat of Alexandria, Tempranillo and Tintilla de Rota). A high content of UFAs was found in all the analyzed samples. Grape pomace oils generally had the same oleic acid (PUFAω-6) content as seed oils, and lower PUFA contents; they also had a markedly higher linolenic acid (PUFAω-3) content, improving the PUFAω-6/PUFAω-3 ratio. All the oil studied show good indicators of nutritional quality: low values of the atherogenicity (0.112-0.157 for pomace, 0.097-0.112 for seed) and thrombogenicity indices (0.30-0.35 for pomace, 0.28-0.31 for seed) and high values of the relationship between hypo- and hypercholesterolemic fatty acids (6.93-9.45 for pomace, 9.11-10.54 for seed). Three tocopherols were determined: α-, γ- and δ-tocopherol. Pomace oils have higher relative contents of α- and δ-tocopherol, whereas seed oils have higher relative contents of γ-tocopherol. A significantly higher content of total tocopherols has been found in pomace oil; it is higher in the oils from red varieties of pomace (628.2 and 706.6 mg/kg by-product), and in the oils from pomace containing stems (1686.4 mg/kg by-product). All the oils obtained can be considered as a source of vitamin E, and their consumption is beneficial for health.

Effect of the type of wood used for ageing on the volatile composition of Pedro Ximénez sweet wine.

BACKGROUND: The present study investigated the volatile composition of a Pedro Ximénez sweet wine that had been aged in barrels made of different types of wood (Spanish oak, French oak, American oak and chestnut) and subjected to different degrees of toasting (medium toasting and intense toasting). The analyses were carried out using stir bar sorptive extraction gas chromatography-mass spectrometry after validation of the matrix in this case. RESULTS: Good values of linearity, precision, limits of detection and limits of quantification were obtained for the 36 compounds studied, six of which were identified for the first time in Pedro Ximénez (propyl acetate, cis-3-hexenyl acetate, benzyl acetate, guaiacol, trans-whiskeylactone and 4-ethylguaiacol). The volatile composition of the samples varied as the ageing process progressed, and higher volatile concentrations were obtained in samples aged in barrels that had been intensely toasted compared to in those with medium toasting. A multivariate statistical study allowed the samples to be correctly classified according to ageing time, wood toasting and the type of wood used for ageing. CONCLUSION: The organoleptic analysis performed on the Pedro Ximénez sweet wine samples resulted in differences between the wines aged in the different types of wood during the early weeks of ageing, and scarce differences towards the end of the study period. At the end of the process, all of the wines were better valued and wines aged in medium toasted barrels were the best rated by the panel of judges for all four woods under investigation. This fact could indicate the suitability of alternative woods for the ageing of Pedro Ximénez sweet wines. © 2020 Society of Chemical Industry.

Effect of Drying on the Phenolic Content and Antioxidant Activity of Red Grape Pomace.

Winemaking by-products are considered to be a rich source of bioactive compounds. Grape pomace is susceptible to microbial degradation due to the degree of residual moisture, so the drying of this pomace for conservation is considered to be an essential first step. Previous studies concerning the way in which drying affects winery by-products have produced contradictory results. In this study, a new methodology for drying grape pomace in a climatic chamber has been evaluated. Five red grape pomace varieties were dried in a climatic chamber at 40 °C and 10% relative humidity and the phenolic content and antioxidant activity of the dried and wet pomace samples were compared. The results indicate that this drying process is both feasible and beneficial because significant increases in the extractability of phenolic compounds and antioxidant activity were achieved.

Influence of Oak Species, Toasting Degree, and Aging Time on the Differentiation of Brandies Using a Chemometrics Approach Based on Phenolic Compound UHPLC Fingerprints.

Oak wood is the main material used by coopers to manufacture casks for the aging of spirits or wines. Phenolic compounds are the main components extracted from the wood during spirit aging. In the present study, a chemometric approach based on unsupervised (PCA) and supervised (PLS-DA) pattern recognition techniques has been applied to the chromatographic instrumental fingerprints, obtained by ultra-high-performance liquid chromatography (UHPLC) at 280 nm, of the phenolic profiles of brandies aged in casks made of different oak wood species. The resulting natural data groupings and the PLS-DA models have revealed that the oak wood species, the toasting level, and the aging time are the most influential factors on the phenolic profile of the final products. Fingerprinting should be considered as a very useful feature, as it represents a considerable advantage, in terms of internal and quality control, for brandy producers.

Influence of the use of sulfur dioxide, the distillation method, the oak wood type and the aging time on the production of brandies.

Brandies are spirits produced from wine spirit and wine distillates. The original wines selected to be distilled to produce the wine spirits as well as the distillation method used determine, to a large extent, the organoleptic characteristics of the final products. The young wine spirits evolve during their aging in oak casks, this being another key stage that affects the chemical and sensorial characteristics of the final brandy. In this work, seven different brandies have been studied. They were obtained from wine produced with and without the addition of sulfur dioxide, during their fermentation, using different distillation methods (single, double or serial distillation using pot stills and continuous column distillation) and aged for 14 or 28 months in three different types of oak wood (Quercus alba, Quercus robur and Quercus petraea) previously toasted to two different grades (medium or light). The use of unsupervised pattern recognition methods (HCA and FA) determined that the addition of sulfur dioxide during the fermentation of the base wine has a major influence on the aromatic and phenolic profile of the aged distillates. On the other hand, by means of supervised pattern recognition methods such as LDA and ANNs, the most significant variables that would allow to discriminate between the classes of brandies identified in the study were evaluated. Thus, the results obtained should cast some light on the most significant variables to be taken into account regarding Brandy production processes if a better control over these production processes is to be achieved, so that more exclusive and better quality products are obtained.

Study of the Cluster Thinning Grape as a Source of Phenolic Compounds and Evaluation of Its Antioxidant Potential.

Thinning is a common viticulture practice in warm climates, and it is applied to increase the quality of the harvest. Thinning clusters are usually discarded, and they are considered another oenological industry waste. To valorize this by-product, the phenolic content and antioxidant activity of three red varieties (Tempranillo, Cabernet Sauvignon, and Syrah), thinned at three different times between veraison and harvest, were studied: the first at the beginning of the veraison stage, in a low ripening stage; the second in an intermediate ripening stage; and, finally, the third sampling in the highest ripening stage. These by-products showed high values of total phenolic contents (10.66-11.75 mg gallic acid equivalent/g), which is of the same order as or even higher than that found in grape pomace. In thinned grape were identified 24 phenolic compounds, being the flavan-3-ols (catechin and epicatechin) of particular interest, with mean contents ranging from 105.1 to 516.4 mg/kg of thinned grape. Antioxidant activity similar to that of the vintage grape was found. It is concluded that thinned grape is a good source of phenolic compounds. Its content does not depend mainly on the grape variety; however, it has been possible to establish differences based on the maturity stage of the thinning grapes: the intermediate ripeness stage, with a Brix degree in the range of 15-16 for this area, would be the optimum collection time for cluster thinning. In this intermediate ripeness stage, thinning grapes present a higher antioxidant activity and there is also appreciable anthocyanin content, which is not found for the lowest ripeness stage, since these samples present an intermediate composition in all the families of determined phenolic compounds: anthocyanins, flavonols, flavan-3-ols, cinnamic acids, and benzoic acids. It is important to note that the experiments in this study have been carried out with whole tinned grapes, without separating the skin or the seeds.

Comparative Evaluation of Brandy de Jerez Aged in American Oak Barrels with Different Times of Use.

Brandy de Jerez is a European Geographical Indication for grape-derived spirits aged in oak casks that have previously contained any kind of Sherry wine and, therefore, are known as Sherry Casks®. Wood compounds have a substantial influence in the quality of the brandies that are aged in the barrels. In the cellar, the barrels that have been used for many years to keep Sherry wine or other wine spirits are often used for this purpose. When wooden barrels are used for the first time, they release a large amount of compounds into the liquid contained in them. Such amount decreases over time but casks life cycle has remained unexplored until now. The present work has the aim to study the brandies obtained from the same wine spirit after two years ageing in three differently oak casks: namely new, 7 years of use (4 years containing Oloroso wine and 3 years containing wine spirits) and 32 years of use (8 years containing Oloroso wine and 24 years containing wine spirits). According to the results from our experiments, even after 32 years of use, the wood barrels still contribute to modify the organoleptic characteristics of brandy. Moreover, the brandies aged in used barrels were judged more balanced than those aged in new barrels.

Characterization of the Aromatic and Phenolic Profile of Five Different Wood Chips Used for Ageing Spirits and Wines.

Wooden barrels and wood chips are usually used in the ageing of spirits and wines to improve their sensorial profile. Oak wood is the most popular material used in cooperage, but there are other interesting woods, such as cherry or chestnut, that could be considered for this purpose. In this study, a novel method for the determination of the aromatic profile of wood powder by Direct Thermal Desorption-Gas Chromatography-Mass Spectrometry (DTD-GC-MS) was optimized by experimental design. The volatile composition of five different types of wood chips was determined by direct analysis of wood powder by DTD-GC-MS method developed. Thirty-one compounds from wood were identified through this analysis, allowing the differentiation between woods. The aromatic and phenolic compound profile of the 50% hydroalcoholic extract of each type of wood studied was analyzed by Stir-bar Sorptive Extraction-Gas Chromatography-Mass Spectrometry (SBSE-GC-MS) and Ultra-High-Performance Liquid Chromatography (UHPLC) to determine which wood compounds are transferred to spirits and wine after ageing. Different phenolic profiles were found by UHPLC in each wood extract, allowing their differentiation. However, results obtained by SBSE-GC-MS did not allow distinguishing between wood extracts. The analysis of wood in solid state, without any type of previous treatment except grinding, by DTD-GC-MS does not imply any loss of information of the aromatic compounds present in wood as other techniques. This is a potential method to identify aromas in wood that, in addition, allows different types of wood to be differentiated.

Use of Alternative Wood for the Ageing of Brandy de Jerez.

The use of alternative types of wood has arisen for the aging of the Brandy de Jerez, on a pilot plant level. In particular, besides the use of American oak, two more types of oak have been studied, French oak and Spanish oak, allowed by the Technical File for the ID Brandy de Jerez, and chestnut, which, though it is not officially allowed, is a type of wood which had been traditionally used in the area for the aging of wines and distillates. All of them have been studied with different toasting levels: Intense toasting and medium toasting. The study of the total phenolic composition (TPI), chromatic characteristics, organic acids, and sensory analysis have proven that chestnut leads to distillates with a higher amount of phenolic compounds and coloring intensity than oak. This behavior is the opposite as regards the toasting of the wood. Among the different types of oak, Spanish oak produces aged distillates with a higher phenolic composition and a higher color intensity. Regarding tasting, the best-assessed samples were those aged with chestnut, French oak, and American oak, and the assessors preferred those who had used a medium toasting level to those with an intense level.

Comparison of the evolution of low molecular weight phenolic compounds in typical Sherry wines: Fino, Amontillado, and Oloroso.

Changes in the content of low molecular weight phenolic compounds (hydroxybenzoic and hydroxycinnamic acids, aldehydes, and their esterified derivatives, tyrosol and 5-(hydroxymethyl)-2-furaldehyde) during the aging of three different classes of Sherry wine, Fino, Oloroso, and Amontillado, have been studied. The samples studied were taken from each of the scales of the particular aging system applied to the three classes of wine. Clear differences were observed in the behavior of the low molecular weight phenolic in the three classes of wine. The wines subjected to oxidative aging presented a higher phenolic content overall, with the exception of the esterified derivatives of phenolic compounds that are mainly found in the samples that have not undergone any process of oxidation. MANOVA results confirmed that there are significant differences between all of the samples of the three types of wines. Using LDA, a classification of 100% of the samples has been made.

Simplification of the DPPH assay for estimating the antioxidant activity of wine and wine by-products.

The DPPH assay is one of the most commonly employed methods for measuring antioxidant activity. Even though this method is considered very simple and efficient, it does present various limitations which make it complicated to perform. The range of linearity between the DPPH inhibition percentage and sample concentration has been studied with a view to simplifying the method for characterising samples of wine origin. It has been concluded that all the samples are linear in a range of inhibition below 40%, which allows the analysis to be simplified. A new parameter more appropriate for the simplification, the EC20, has been proposed to express the assay results. Additionally, the reaction time was analysed with the object of avoiding the need for kinetic studies in the method. The simplifications considered offer a more functional method, without significant errors, which could be used for routine analysis.