Typification of cider brandy on the basis of cider used in its manufacture

A study of typification of cider brandies on the basis of the origin of the raw material used in their manufacture was conducted using chemometric techniques (principal component analysis, linear discriminant analysis, and Bayesian analysis) together with their composition in volatile compounds, as analyzed by gas chromatography with flame ionization to detect the major volatiles and by mass spectrometric to detect the minor ones. Significant principal components computed by a double cross-validation procedure allowed the structure of the database to be visualized as a function of the raw material, that is, cider made from fresh apple juice versus cider made from apple juice concentrate. Feasible and robust discriminant rules were computed and validated by a cross-validation procedure that allowed the authors to classify fresh and concentrate cider brandies, obtaining classification hits of >92%. The most discriminating variables for typifying cider brandies according to their raw material were 1-butanol and ethyl hexanoate.     

Influence of distillation system,oak wood type,and aging time on volatile compounds of cider brandy

A study of the influence of distillation system, oak wood type, and aging time on volatile compounds of cider brandy was carried out. Acetaldehyde and acetaldehyde diethyl acetal were influenced by distillation technology, oak wood type, and maturation time. The majority ester, ethyl ethanoate, increased during aging, the highest level of this ester being detected in spirits distilled by double distillation. The alcohols of higher molecular weight were better recovered in the rectification column than in the double distillation system. Ethanoate esters decreased throughout aging of the spirits, and their degradation velocity was lower in distillates obtained from double distillation. Fatty acids and their ethyl esters presented the opposite evolution during aging, detecting an increase in ethyl esters and a decrease in their corresponding fatty acids. An increase of 1,1,3-triethoxypropane was detected during aging. French oak contributes the trans isomer of beta-methyl-gamma-octalactone and American oak contributes the cis isomer.     

Extraction, detection, and quantification of flavano-ellagitannins and ethylvescalagin in a Bordeaux red wine aged in oak barrels

An extraction procedure and an analytical method have been developed to detect and quantify for the first time a series of ellagitannin derivatives formed in wine during aging in oak barrels. The method involves a preliminary purification step on XAD7 HP resin followed by a second purification step on TSK 40 HW gel. The resulting extract is analyzed for compound identification and quantitative determination by high-performance liquid chromatography-electrospray ionization-mass spectrometry in single ion recording mode. Reference compounds, which are accessible through hemisynthesis from the oak C-glycosidic ellagitannin vescalagin, were used to build calibration curves, and chlorogenic acid was selected as an internal standard. This method enabled us to estimate the content of four flavano-ellagitannins and that of another newly identified wine polyphenol, beta-1-O-ethylvescalagin, in a Bordeaux red wine aged for 18 months in oak barrels. All five ellagitannin derivatives are derived from the nucleophilic substitution reaction of vescalagin with the grape flavan-3-ols catechin and epicatechin or ethanol.     

Influence of distillation system, oak wood type, and aging time on composition of cider brandy in phenolic and furanic compounds

A control of phenolic and furanic compounds in cider brandy was carried out during maturation in oak casks, studying three technological factors: distillation (rectification column vs double distillation), oak wood type (French vs American), and aging time (32 months). Gallic acid and benzoic and cinnamic aldehydes significantly increased during maturation of cider brandies, the highest level of these phenolics being obtained when aging was conducted in French oak casks. Benzoic acids increased during aging, though furanic compounds were not influenced by the time factor. Distillation and wood factors significantly influenced furanic concentration; 5-hydroxymethylfurfural not was detected in fresh spirits and was extracted in the highest proportion in French oak. Volatile furanics, such as 5-methylfurfural, furfural, and 2-furylmethyl ketone, were influenced by the distillation factor, with the use of the double distillation system producing a higher level of these compounds. Scopoletin was the majority coumarin detected in cider brandies, the highest yield of which was obtained with the use of American oak.     

Volatile compounds in a spanish red wine aged in barrels made of Spanish, French, and American oak wood

A red Rioja wine was aged in barrels made of Spanish oak wood (Quercus robur, Quercus petraea,Quercus pyrenaica, and Quercus faginea) during 21 months. The concentrations of some volatile compounds [syringaldehyde, vanillin, eugenol, maltol, guaiacol, 4-ethylphenol, cis and trans isomers of beta-methyl-gamma-octalactone, 2-furfuraldehyde, 5-methyl-2-furfuraldehyde, 5-(hydroxymethyl)-2-furfuraldehyde, and furfuryl alcohol] were studied in these wines and compared with those of the same wine aged in barrels made from French oak of Q. robur (Limousin, France) and Q. petraea (Allier, France) and American oak of Quercus alba (Missouri). Similar concentrations of these compounds were found in wines aged in Spanish and French oak wood barrels, and significantly different concentrations were found with respect to wines aged in barrels made of American oak wood, indicating a different behavior. Thus, wines with different characteristics were obtained, depending on the kind of wood. Also, the kind of wood had an important influence on sensory characteristics of wine during the aging process. Spanish oak wood from Q. robur, Q. petraea, and Q. pyrenaica can be considered to be suitable for barrel production for quality wines, because a wine aged in barrels made of these Spanish oak woods showed similar and intermediate characteristics to those of the same wine aged in French and American oak woods usually used in cooperage.     

Determination of ellagitannins in extracts of oak wood and in distilled beverages matured in oak barrels

A method is described for determination of ellagitannins in ethanol-water extracts of oak wood and in distilled alcoholic beverages matured in oak barrels. It is based on the combined ellagic acid content according to ellagitannin structure. Hydrolysis was carried out in the presence of hydrochloric acid under reflux in a 100 degrees C oil bath for 3 h. Total ellagic acid was thus determined by liquid chromatography (LC), and the free ellagic acid content present in the ethanol-water media was subtracted, the difference being the combined ellagic acid content corresponding to ellagitannins. A 5 micron C18 column was used with detection at 254 nm. The method is specific for ellagitannins, which is an advantage over other analytical techniques for overall evaluation of these substances extracted from wood. Results for spirits distilled from wine, grain, and sugarcane were highly variable.     

Volatile compounds and sensorial characterization of wines from four Spanish denominations of origin, aged in Spanish Rebollo (Quercus pyrenaica Willd.) oak wood barrels

The evolution of almost 40 oak-related volatile compounds and the sensorial characteristics of red wines from four Spanish denominations of origin (DOs) (Bierzo, Toro, Ribera de Duero, and Rioja) during aging in barrels made of Rebollo oak wood, Quercus pyrenaica, were studied and compared to the same wines aged in American and French oak barrels. Each oak wood added unique and special characteristics to the wine, and in addition, each wine showed a different ability to extract the compounds, which result in these characteristics from the oak wood. In general, wines aged in Q. pyrenaica wood were characterized by high levels of eugenol, guaiacol, and other volatile phenols. In regards to compounds like cis-whiskylactone or maltol, the behavior of this wood is very similar to that of American oaks. When considering phenolic aldehydes and ketones, the levels of these compounds are intermediate between those of French and American woods and depend greatly on the type of wine. The type of oak, on the other hand, does not affect the chromatic characteristics of the wines. In sensory analysis, the biggest differences are found in the olfactory phase. Among the four DOs studied, wine aged in Q. pyrenaica presented the highest notes of wood, with more aromas of roasting, toasting, milky coffee, spices, or wine-wood interactions. The wines aged in barrels made of Q. pyrenaica wood were highly regarded, and preference was shown for them over those same wines when they had been aged in barrels of American or French oak.     

Behavior of monosaccharides, phenolic compounds, and color of red wines aged in used oak barrels and in the bottle

A red wine with appropriate basic quality characteristics for aging was stored in oak barrels for 12 months and then bottled and aged for a further 6 months. The same ambient conditions of temperature and humidity were maintained throughout the entire aging process. The barrels used were made from three different species of oak by four different cooperages and had been used for at least two years. Analysis of variance and principal component analysis were run on the values for hexoses, pentoses, total anthocyanins, ortho-diphenols, low- and high-polymer polyphenols, and color parameters to study the behavior of the monosaccharides and polyphenols in response to the factors of aging time, the oak variety employed, and the source cooperage where the barrels had been made. Time trends for all the phenolic components were directly related to aging time, with low-polymeric polyphenols (LPPs) being the most affected by wood type and source cooperage. Wine color was defined by a basic red color which decreased with aging time in the barrel and was altered by yellowish pigment components differing for each of the barrels in which oxidative aging took place and by increased stability of the blue copigments. Principal component analysis showed that samples of the same source wine aged in different barrels tended to be grouped together according to each of the aging intervals considered.     

Changes in amine concentrations during aging of red wine in oak barrels

This investigation studied the evolution of amines in red wines made with Merlot variety, during aging in American oak barrels (Quercus alba) and in French oak barrels (Quercus sessilis) from the Allier and Nevers regions. From the results obtained it was observed that the evolutions of the amines were similar in all three types of oak woods. Histamine and tyramine were produced at the beginning of the aging process, although they were not accumulated in the wines, probably due to their degradation. Putrescine was the most abundant amine in the wines; its concentration increased to an important extent during aging as it did not undergo degradation. The concentration of cadaverine increased slightly at the first stage of aging and, like putrescine, did not degrade at all. The volatile amines showed slight variations during aging, although in no cases were high accumulations observed in the wines. Dimethylamine and isobutylamine were degraded during storage in the barrels.     

Impact of toasting oak barrels on the presence of polycyclic aromatic hydrocarbons in wine

Toasting Quercus sp. oak wood is one of the key stages in manufacturing barrels intended for aging wines and spirits. During this operation, the increase in temperature causes variable modifications in the physical structure and, more importantly, the chemical composition of the wood. Polycyclic aromatic hydrocarbons (PAH) are high-risk molecules likely to be formed during toasting of the wood and later extracted by wine or spirits in direct contact with the barrel. In the context of an analysis of all potential sources of risk associated with the manufacture of barrels for winery use [prevention policy defined using a Hazard Analysis Critical Control Point (HACCP) approach], we carried out a preliminary study to provide a more accurate assessment of potential risks related to the presence of PAH in cooperage and winemaking. Wood toasted to different levels under different conditions, as well as wines aged in barrels made using different methods, was analyzed by gas chromatography and mass spectrometry (GC-MS) for the identification of the main PAH present, quantification of each of the molecules extracted, and estimation of any possible toxicological risks, via a comparison of values with those measured in other types of food. The results clearly showed that the heating processes associated with barrel production actually resulted in the formation of various molecules in the PAH family. However, only a minority of the target PAH presented high toxicity, particularly carcinogenic potential. Because of the specific toasting process used, benzo[a]pyrene, the best-known, and one of the most dangerous, contaminants, was not significantly present in toasted barrel wood. In view of the PAH concentrations in wood and the low solubility of these compounds, their extraction in wine is apparently relatively slow and limited. Finally, comparing the overall PAH concentrations, and particularly those of the most toxic compounds, with estimated absorption from food or the environment, we found it was obvious that the contribution of toasted barrels to the total amount was extremely low and should not, therefore, be considered a major health concern.     

Cider proteins and foam characteristics: a contribution to their characterization

A capillary sieving electrophoretic method for protein analysis and molecular weight determination was used to characterize ciders from Asturias, northern Spain. The total protein content (Bradford method) and the foam parameters (Bikerman method) were also analyzed to complete this characterization. The polypeptide profile, based on the molecular weight, together with exploratory and classification techniques, that is, principal component analysis (PCA) or linear discriminant analysis (LDA), allowed ciders to be differentiated on the basis of their foam assessment and the apple juice extraction technology used in the cidermaking process. In addition, the application of correlation analysis, that is, canonical correlations (CCA) or partial least-squares (PLS), revealed that the proteins with higher molecular weight were more relevant with respect to cider foamability. PLS analysis also provided a mathematical equation that is able to predict the stabilization time of foam from the polypeptide profile of the cider, because this is the foam parameter most influenced by these compounds.     

Maturing wines in oak barrels. Effects of origin,volume, and age of the barrel on the wine volatile composition

The influence of the oak origin, volume, and age of the barrel on the volatile composition of a red wine after six months of maturation have been studied. Major volatile compounds in wine were determined using liquid-liquid extraction with dichloromethane, and those volatiles being due to the oak were determined by extraction with pentane-ether using deuterated analogues as internal standards. The results show that there is little difference between the volatile composition of wines matured in French oak barrels and those matured in American oak barrels. The concentration of cis-oak lactone was the most significant difference. The greatest instrumental and sensory differences were found between new and used barrels, with important decreases in lactones and vanillin concentration in used barrels. When studying the effect of the volume of the barrel, the characteristics of the wine matured in 220-L new barrels versus those matured in 1000-L new barrels were very different. In new barrels, the larger the volume of the barrel, the lower the concentrations of those compounds responsible for the oaky aroma. These differences were less evident when comparing wines matured in used barrels with different capacities.     

Evolution of phenolic composition of red wine during vinification and storage and its contribution to wine sensory properties and antioxidant activity

The objective of this work was to study the evolution of the phenolic composition of red wine during vinification and storage and its relationship with some sensory properties (astringency and bitterness) and antioxidant activities. Thus, red wine was made by a classic vinification method with Castela?o and Tinta Miu?da grapes (Vitis vinifera L.) harvested at maturity (3:2; w/w). Samples were taken at 2 and 7 days of maceration, at second racking, at the time of bottling and at 6 and 14 months after bottling. The total polyphenols extract (TPx) in each sample was isolated by column chromatography. The phenolic composition (anthocyanins and proanthocyanidins), in vitro antioxidant activity, and sensory property (astringency, bitterness) of the isolated TPx from different winemaking stages were evaluated through high-performance liquid chromatography-diode array detection, 1,1-diphenyl-2-picrylhidrazyl radical test, ferric reducing antioxidant power assay, total phenolic index, MWI (polyphenol molecular weight index), TSA (tannin specific activity), and sensory panel tasting. The results showed that the phenolic composition of red wine varied significantly during winemaking. The intensity of astringency (IA) and the intensity bitterness (IB) of the isolated TPx from different winemaking stages increased from 2 days of maceration until second racking and then decreased. Furthermore, MWI and TSA are positively correlated with IA and IB. The in vitro antioxidant activity of the isolated TPx from different winemaking stages maintained unchanged after alcoholic fermentation, which was independent of the variation of phenolic composition and sensory properties.     

Comparative changes in color features and pigment composition of red wines aged in oak and cherry wood casks

The color features and the evolution of both the monomeric and the derived pigments of red wines aged in oak and cherry 225 L barriques have been investigated during a four months period. For cherry wood, the utilization of 1000 L casks was tested as well. The use of cherry casks resulted in a faster evolution of pigments with a rapid decline of monomeric anthocyanins and a quick augmentation formation of derived and polymeric compounds. At the end of the aging, wines stored in oak and cherry barriques lost, respectively, about 20% and 80% of the initial pigment amount, while in the 1000 L cherry casks, the same compounds diminished by about 60%. Ethyl-bridged adducts and vitisins were the main class of derivatives formed, representing up to 25% of the total pigment amount in the cherry aged samples. Color density augmented in both the oak and cherry wood aged samples, but the latter had the highest values of this parameter. Because of the highly oxidative behavior of the cherry barriques, the use of larger casks (e.g., 1000 L) is proposed in the case of prolonged aging times.     

Validation of a mass spectrometry method to quantify oak ellagitannins in wine samples

Detection and individual quantification of oak wood ellagitannins in oak barrel aged red wine samples are difficult mainly due to their low levels and the similarity between their structures. In this work, a quantification method using mass spectrometry has been developed and validated to quantify wine ellagitannins after sample fractionation with a previously reported method. The use of an internal standard is a requirement to correct mass signal variability. (-)-Gallocatechin, among the different tested compounds, was the only one that proved to be a suitable internal standard making possible the accurate and individual quantification of the main oak wood ellagitannins. The developed methodology has been used to detect and quantify these ellagitannins in different Spanish commercial wines, proving its usefulness.     

Hydrogen isotopic profile in the characterization of sugars. Influence of the metabolic pathway

The site-specific natural hydrogen isotope ratios of plant metabolites determined by 2H nuclear magnetic resonance (SNIF-NMR method) can provide powerful criteria for inferring mechanistic and environmental effects on biosynthetic pathways. This work examines the potential of isotopic profiles for the main constituents of carbohydrates, glucose and fructose, to distinguish different photosynthetic pathways. An appropriate analytical strategy, involving three suitable isotopic probes, has been elaborated with a view to measuring simultaneously, in conditions devoid of isotopic perturbations, all (or nearly all) of the carbon-bound hydrogen isotope ratios. It is shown that the type of photosynthetic metabolism, either C3 (sugar beet, orange, and grape), C4 (maize and sugar cane), or CAM (pineapple), and the physiological status of the precursor plant exert strong influences on the deuterium distribution in the sugar molecules. Consequently, this isotopic fingerprint may be a rich source of information for the comparison of mechanisms in metabolic pathways. In addition, it can provide complementary criteria to ethanol as a probe for the origin of sugars.     

Analysis of polysaccharides in cider: their effect on sensory foaming properties

A feasible spectrophotometric method for determining acidic and neutral polysaccharides in cider is described, and the advantages of this method are examined with respect to precision, accuracy, and detection and quantitation limits. The concentration of nonvolatile and volatile components in cider, together with chemometric techniques such as principal component analysis (PCA), soft independent modeling of class analogy (SIMCA), and partial least squares (PLS), allowed us to typify the ciders on the basis of their foaming properties. Acidic polysaccharide and 1-propanol were the most relevant variables for this purpose.     

Evolution of the taste of a bitter Camembert cheese during ripening: characterization of a matrix effect.

The objective of this study was to characterize the effect of ripening on the taste of a typically bitter Camembert cheese. The first step was to select a typically bitter cheese among several products obtained by different processes supposed to enhance this taste defect. Second, the evolution of cheese taste during ripening was characterized from a sensory point of view. Finally, the relative impact of fat, proteins, and water-soluble molecules on cheese taste was determined by using omission tests performed on a reconstituted cheese. These omission tests showed that cheese taste resulted mainly from the gustatory properties of water-soluble molecules but was modulated by a matrix effect due to fat, proteins, and cheese structure. The evolution of this matrix effect during ripening was discussed for each taste characteristic.     

A contribution to environmental control in a glasshouse by a computer

The environmental conditions of plants grown in a glasshouse were controlled by a minicomputer (IBM-Series 1). The simulation model thus developed provides better analyses of the relationship between yield increase and control of environmental factors.The glasshouse used was in several sections, with all the necessary devices for controlling environmental conditions. Two different climatic regimes were stimulated in order to find a better agreement of simulated values with experimental data.The computer used can be applied to a system comprising several glasshouses where different crops are grown.     

Evolution of ellagitannins in Spanish, French, and American oak woods during natural seasoning and toasting

The evolution of tannins in Spanish oak heartwood of Quercus robur L., Quercus petraea Liebl.,Quercus pyrenaica Wild., and Quercus faginea Lam. was studied in relation to the processing of wood in barrel cooperage. Their evolution was compared with that of French oak of Q. robur (Limousin, France) and Q. petraea (Allier, France) and American oak of Quercus alba L. (Missouri), which are habitually used in cooperage. Two stages of process were researched: the seasoning of woods during 3 years in natural conditions and toasting. Total phenol and total ellagitannin contents and optical density at 420 nm of wood extracts were determined. The ellagitannins roburins A-E, grandinin, vescalagin, and castalagin were identified and quantified by HPLC, and the molecular weight distribution of ellagitannins was calculated by GPC. During the seasoning process the different ellagitannin concentrations decreased according to the duration of this process and in the same way as those in French and American woods. The toasting process also had an important influence on the ellagitannin composition of wood. Roburins A-E, grandinin, vescalagin, and castalagin decreased during this process in the Spanish wood species, in the same proportion as in the French and American ones. Also, the seasoning and toasting processes lead to qualitative variations in the structure of ellagitannins, especially in the molecular weight distribution, as was evidenced by GPC analysis of their acetylated derivatives.