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.     

Evolution of sugars in cider brandy aged in oak barrels: a contribution to its characterization

A chemometric study was carried out to typify cider brandies according to the type of wood employed in the maturation process and their aging time. Monosaccharides, previously derivatized with p-aminobenzoic ethyl ester, were analyzed using a reversed-phase high-performance liquid chromatographic method. Univariate data treatment was not sufficient to enable differentiation of the classes of cider brandies on the basis of wood type and maturation time. Two linear combinations of original variables, ascertained by principal components analysis, provided an adequate data structurization. A mathematical decision rule was established to classify cider brandies with prediction capacities of 92 and 97% using an LDA method and Bayesian analysis, respectively. The use of the PLS algorithm allowed the authors to differentiate cider brandies according to the age and type of oak used in the aging process.     

Monitoring toasting intensity of barrels by chromatographic analysis of volatile compounds from toasted oak wood.

Toasting changes both the quantity and the quality of the extractable substances in the oak wood of barrels used for the aging of fine wines and spirits. Mastery and repeatability of toasting are vital in the production of quality barrels to be used for the aging of wines and spirits. In this study, we show that it is possible for a given cooperage to differentiate barrel toasting levels by analyzing a certain number of volatile and semivolatile compounds resulting from the thermal degradation of oak. Toasted wood components, which can be extracted by the wines or spirits during the aging process, are normally analyzed after the wood has soaked in standard alcoholic solutions and can be used to control the intensity of the wood toasting. The results of the comparative analysis presented in this work show that headspace analysis with a microextractive method using a stationary polydimethylsiloxane type phase is a promising technique for analyzing toasted oak wood from barrels. It is easier to use than the traditional maceration and extraction method and provides similar information.     

Formation pathways of ethyl esters of branched short-chain fatty acids during wine aging

The particular behavior during wine aging of fermentative branched fatty acid ethyl esters, related to yeast nitrogen metabolism, compared that of their straight-chain analogues, related to yeast lipid metabolism, was first checked in 1-5 year aged Muscadet wines. Quantitative SIDA measurements showed that the levels of the former increased, whereas those of the latter decreased. Then, three hypothetical pathways suggested in the literature to explain these variations of branched esters were investigated. Two Muscadet and Sylvaner wines were spiked with levels of deuterated isobutanoic acid and its ethyl ester, similar to those of their natural analogues, then they were submitted to model aging. Quantitative SIDA measurements on the formation of these natural and labeled ethyl esters from the corresponding acids revealed that the behavior of the natural and labeled compounds were similar. The acid levels were much higher than the ester levels in the initial young wine, and a significant upward trend of their esterification ratios to those of the acid-ester equilibrium was observed with aging. Thus, this equilibrium proved to be the most effective in generating the branched fatty acid ethyl esters during wine aging. In contrast, the formation of these acids by Strecker-type degradation of wine amino acids in the conditions of the model aging or by hydrolysis of their glycoconjugates proved to be ineffective.     

Using electronic odor sensors to discriminate among oak barrel toasting levels.

Toasting changes both the quantity and the quality of the extractable substances in oak wood of barrels used for the aging of fine wines and spirits. Mastery and repeatability of toasting are vital in the production of quality barrels to be used for aging wines and spirits. Toasted wood components, which can be extracted by the wines or spirits during the aging process, are normally analyzed by maceration in standard alcohol solutions at concentrations adapted to the various products and can be used to control the intensity of the wood toasting. These kinds of analyses are accurate but time-consuming and need specialized laboratories. In this work, the feasibility of monitoring barrel toasting levels using an electronic nose with a metal oxide odor sensor array (MOS) was studied. The results of oak toasting level differentiation obtained via the MOS network were identical to those obtained by analyzing extractable compounds in liquid or gas phase as described in a previous paper. The results presented in this work at the laboratory scale could be used to implement a nondestructive monitoring system based on the analysis of headspace of barrels under industrial conditions.     

Liquid chromatographic determination of scopoletin in hydroalcoholic extract of oak wood and in matured distilled alcoholic beverages

A liquid chromatographic (LC) method is described for determination of the coumarins esculin, umbelliferone, scopoletin, and 4-methyl umbelliferone in hydroalcoholic extracts of oak wood and in matured distilled alcoholic beverages. Samples were injected directly into the LC column (30 cm, 5 micron C18) and detected by fluorescence detector. Under these experimental conditions, only scopoletin (detection limit, 200 pg) was found in hydroalcoholic oak wood extracts and in spirits matured in oak wood. Applications of this method to spirits distilled from wine, grain, and sugar cane aged in oak barrels showed that amounts varied from 0.026 to 1.57 ppm.     

Fermentation of white wines in the presence of wood chips of American and French oak

Must obtained from Airén grapes was fermented in the presence of wood chips (4 and 7 g/L) of either French oak (from Vosges, central France, and Allier zones) or American oak. Fermentation yields were higher than in the control fermentations carried out in the absence of wood, and production of volatile substances during fermentation (alcohols, esters, and acetates) was also higher. The volatile substances that leached out of the wood were analyzed by GC-MS-SIR. The results showed that their concentrations depended on the type and amount of the oak; some of these substances were consumed in part by the yeasts during fermentation. A taste panel favorably assessed the wines produced by fermentation in the presence of oak chips, which retained part of the must original fruity aroma.     

Biosynthesis of strawberry aroma compounds through amino acid metabolism

The fate of amino acids in relation to aroma biogenesis was studied in strawberries using the in vitro growth approach. This fruit presented differences in the level of metabolization for different amino acids. Incubations of strawberries with L-isoleucine gave rise to an increase of fourteen compounds in this fruit aroma, either not detected previously or constituents of strawberry aroma. However, L-valine incubations did not provide a significant change in this fruit aroma. Strawberry feeding with L-isoleucine resulted in a 7-fold increase in the sum of 2-methylbutanoate esters, and a double production of 2-methylbutyl esters compared to those of control fruits. Around 94% of the ester increase corresponded to 2-methylbutanoates, with ethyl 2-methylbutanoate being the most representative compound (92%). On the other hand, among the 2-methylbutyl esters, comprising around 6% of total aroma volatiles increase, 2-methylbutyl acetate was the major compound (95%) arising from L-isoleucine strawberry feeding. The role of enzymatic activities within the amino acid metabolic pathway in strawberry fruits is discussed.     

Identifying new volatile compounds in toasted oak

Toasting wood to be used in barrels for aging wine produces a great number of volatile and odiferous compounds. Three new volatile odorous compounds in toasted oak were identified. Analysis by high-performance gas chromatography of toasted oak extracts, combined with olfactory detection, enabled various chromatographic peaks with these specific aromas to be isolated. These same odors were simultaneously studied by heating glucose both with and without proline and phenylalanine. Aromatic compounds of interest were identified thanks to a combination of gas chromatography and both mass and infrared spectrometry. An analysis RMN was also used. Hydroxymaltol, 2,5-furanedicarbaldehyde, and furylhydroxymethyl ketone have been detected in extract of toasted oak wood. These molecules may be formed by direct pyrolysis of sugar or Maillard reactions. The acetylformoine was not detected in extract of toasted oak wood, whereas it was detected in heated extracts of various sugars and sugars mixtures with amino acids.     

Quantitative ester analysis in cachaca and distilled spirits by gas chromatography-mass spectrometry (GC-MS)

An analytical procedure for the separation and quantification of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl laurate in cachaca, rum, and whisky by direct injection gas chromatography-mass spectrometry was developed. The analytical method is simple, selective, and appropriated for the determination of esters in distilled spirits. The limit of detection ranged from 29 (ethyl hexanoate) to 530 (ethyl acetate) microg L(-1), whereas the standard deviation for repeatability was between 0.774% (ethyl hexanoate) and 5.05% (isoamyl octanoate). Relative standard deviation values for accuracy vary from 90.3 to 98.5% for ethyl butyrate and ethyl acetate, respectively. Ethyl acetate was shown to be the major ester in cachaca (median content of 22.6 mg 100 mL(-1) anhydrous alcohol), followed by ethyl lactate (median content of 8.32 mg 100 mL(-1) anhydrous alcohol). Cachaca produced in copper and hybrid alembic present a higher content of ethyl acetate and ethyl lactate than those produced in a stainless-steel column, whereas cachaca produced by distillation in a stainless-steel column present a higher content of ethyl octanoate, ethyl decanoate, and ethyl laurate. As expected, ethyl acetate is the major ester in whiskey and rum, followed by ethyl lactate for samples of rum. Nevertheless, whiskey samples exhibit ethyl lactate at contents lower or at the same order of magnitude of the fatty esters.     

Concurrent phenomena contributing to the formation of the aroma of wine during aging in oak wood: an analytical study

Red wine was stored in different oak barrels or in stainless steel, and samples were taken for two years to determine 79 aroma compounds. Aging in oak affects 41 compounds. The type of wood affects 11 compounds. At least seven different processes seem to take place concurrently in aroma evolution, and five such processes, affecting 37 compounds, are linked to the oak cask. These are extraction from the wood, oxidation of wine alcohols and amino acids, microbiological formation of ethyl phenols, sorption processes, and condensation of acetaldehyde with polyphenols. The wood can release linear gamma- and delta-lactones, beta-damascenone, and ionones. Some compounds are released very fast from wood, which suggests they lie in the external part of the wood. Some extraction profiles are too complex to be explained by physical processes. Finally, the levels of 2,5-dimethyl-4-hydroxy-3(2H)-furanone and 2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone increase even in the reference wine, which suggests the presence of a precursor.     

Generation of saffron volatiles by thermal carotenoid degradation

Generation of volatiles by thermal treatments has been studied in saffron spice for two reasons: (a) to determine volatile profile changes during simulated aging processes and (b) to study the volatile generation pathway. During the aging process, while the amounts of C10 compounds such as safranal and HTCC increase, the amounts of C9 compounds such as isophorone and 2,6,6-trimethylcyclohexane-1,4-dione decrease. A new compound tentatively identified as 4,5,6,7-tetrahydro-7,7-dimethyl-5-oxo-3H-isobenzofuranone seems to play a very important role in the aging process. The importance of this compound, structurally similar to dihydroactindiolide, was also confirmed when the saffron volatile fraction was analyzed via the degradation of the linear chain of crocetin and crocetin esters and is reported for the first time in this paper. Thermal degradation studies of zeaxanthin, crocetin, and trans and cis crocetin esters isomers allowed us to propose different mechanisms which explain saffron volatile generation depending on the crocetin ester isomer structure.     

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.     

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.     

Isolation and structure of whiskey polyphenols produced by oxidation of oak wood ellagitannins

Three new phenolic compounds named whiskey tannins A and B and carboxyl ellagic acid were isolated from commercial Japanese whiskey, along with gallic acid, ellagic acid, brevifolin carboxylic acid, three galloyl glucoses, a galloyl ester of phenolic glucoside, 2,3-(S)-hexahydroxydiphenoylglucose, and castacrenin B. Whiskey tannins A and B were oxidation products of a major oak wood ellagitannin, castalagin, in which the pyrogallol ring at the glucose C-1 position of castalagin was oxidized to a cyclopentenone moiety. These tannins originated from ellagitannins contained in the oak wood used for barrel production; however, the original oak wood ellagitannins were not detected in the whiskey. To examine whether the whiskey tannins were produced during the charring process of barrel production, pyrolysis products of castalagin were investigated. Dehydrocastalagin and a new phenolcarboxylic acid trislactone having an isocoumarin structure were isolated, along with castacrenin F and ellagic acid. However, whiskey tannins were not detected in the products.     

Evolution of chemical and sensory properties during aging of top-fermented beer

The aging and consequent changes in flavor molecules of a top-fermented beer were studied. Different aging conditions were imposed on freshly bottled beer. After 6 months of aging, the concentration changes were recorded for acetate esters, ethyl esters, carbonyls, Maillard compounds, dioxolanes, and furanic ethers. For some flavor compounds, the changes with time of storage were monitored at different temperatures, either with CO(2) or with air in the headspace of the bottles. For some molecules a relationship was determined between concentration changes and sensory evaluation results. A decrease in volatile esters was responsible for a reduced fruity flavor during aging. On the contrary, various carbonyl compounds, some ethyl esters, Maillard compounds, dioxolanes, and furanic ethers showed a marked increase, due to oxidative and nonoxidative reactions. A very high increase was found for furfural, 2-furanmethanol, and especially the furanic ether, 2-furfuryl ethyl ether (FEE). For FEE a flavor threshold in beer of 6 mug/L was determined. In the aged top-fermented beer, FEE concentrations multiple times the flavor threshold were observed. This was associated with the appearance of a typical solvent-like flavor. As the FEE concentration increased with time at an almost constant rate, with or without air in the headspace, FEE (and probably other furanic ethers) is proposed as a good candidate to evaluate the thermal stress imposed on beer.     

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.     

Influence of fatty acids on wine foaming

The influence of fatty acids (free and bound as ethyl esters) on wine foaming was studied in different white wines and the corresponding sparkling wines. Moreover, from three of these wines the foam formed by CO(2) injection was separated, and two fractions were then obtained: foam wine (FW) and remainder wine (RW). In these fractions and the sparkling wines produced from them, foam properties and fatty acids were also determined. The free fatty acids C8, C10, and C12 were negatively correlated with foamability (HM), whereas the ethyl esters of hexanoic, octanoic, and decanoic acids were positively related to HM. The value of HM was directly proportional to the ratio of esterified to unesterified fatty acids. This was confirmed by the changes that occur in the esterification ratio during the second fermentation and aging. No influence was observed on either the Bikerman coefficient or the stability time of foam.     

Changes in low molecular weight phenolic compounds in Spanish, French, and American oak woods during natural seasoning and toasting

The evolution of low molecular weight polyphenols in Spanish oak heartwood of Quercus robur,Quercus petraea, Quercus pyrenaica, and Quercus faginea was studied by HPLC, in relation to the processing of wood in barrel cooperage. The polyphenolic composition of Spanish woods subjected to natural seasoning for 3 years and to the toasting process was studied in relation to those of French oak of Q. robur (Limousin) and Q. petraea (Allier) and American oak of Q. alba (Missouri), which are habitually used in cooperage. The concentrations of benzoic and cinnamic acids and aldehydes of Spanish woods increased during seasoning depending on the duration of this process and in the same way as those of French and American woods. The process having the main influence on the phenolic composition of wood was the toasting. It led to high increases in the concentration of phenolic aldehydes and acids, especially cinnamic aldehydes (sinapic and coniferylic aldehydes), followed by benzoic aldehydes (syringaldehyde and vanillin) and benzoic acids (syringic and vanillic acids). This polyphenolic composition in Spanish oak species evolved during toasting as in French and American oak, but quantitative differences were found, which were especially important in American species with respect to the others.     

Influence of storage conditions on the formation of some volatile compounds in white fortified wines (Vins doux naturels) during the aging process

Sweet fortified wines, traditionally aged under strong oxidation conditions, have a characteristic aroma. An experimental study investigated the aging of white sweet fortified wines under various conditions. The development of various molecules, previously identified as characteristic of the aroma of this type of wine, was monitored by analysis. The development of these compounds during accelerated aging was affected by oxidation and the color of the wine. Aging in oak containers, variable storage temperatures, and variable modes of oxidation affect the formation of many of the volatile compounds responsible for the aging aroma of vins doux naturels (fortified wines). Furfural (1), 5-ethoxymethylfurfural (2), and sotolon (3) always reach concentrations above their perception thresholds in wood-aged wines, especially when new oak is used. The isomers of methyl-gamma-octalactone (4 and 5) are reliable indicators of aging in oak. Among the many identifiable volatile phenols, only the vanillin (7) content increases with aging, particularly if the container is made of wood and there is a high degree of oxidation. This molecule frequently reaches and even exceeds its perception threshold. We show here that vanillin and isomers of methyl-gamma-octalactone have a major impact on the aromas of fortified wines.