Evolution of the aroma profile of sherry wine vinegars during an experimental aging in wood

Changes in the aroma profile of five Sherry wine vinegars submitted to an experimental static aging in wood were followed along 24 months. Eighteen volatile compounds were determined by GC-FID. The results were subjected to multivariate analyses: principal component analysis and linear discriminant analysis. The aroma profile of vinegar can be useful to discriminate vinegars produced from different substrates or with different aging times. During the experimental aging, volatile compounds such as methyl acetate, methanol, diacetyl, and gamma-butyrolactone underwent significant concentration increases. Moreover, the initial ethanol content of vinegars is a factor in the final aromatic richness. The formation of ethyl acetate stood out in samples with an initial ethanol content of approximately 2 alcoholic degrees.     

Physicochemical model to interpret the kinetics of aroma extraction during wine aging in wood. Model limitations suggest the necessary existence of biochemical processes

A model based on physicochemical parameters has been developed and applied to the study of the kinetics of extraction of aroma compounds from oak casks having been used a variable number of times. Two major deviations from the model can be observed: a strong seasonal dependence of extraction (unexpected in a thermostated cellar); and higher yields with a smaller number of longer extractions. 4-Propylguaiacol follows both behaviors, and its levels have been found to be closely related to those of 4-ethylguaiacol and to the number of uses of the barrel, which suggests that this compound may be formed by the same microorganisms forming ethylphenols from a precursor found in wood. Although the extraction kinetics of all aroma compounds appear to be more or less mediated by the action of microorganisms, those of whiskeylactones, eugenol, and 4-allyl-2,6-dimethoxyphenol are more in accordance with the physicochemical model, whereas those of vanillin, syringaldehyde, furfuryl alcohol, and, of course, 4-propylguaiacol are much more coherent with a microbiological extraction/formation.     

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.     

Effect of oak extract application to Verdejo grapevines on grape and wine aroma

Volatile compounds from a commercial aqueous oak extract application to white Verdejo grapevines at veraison have been studied. Treated grapes under two types of formulation (25% and 100%) have been analyzed at the optimum maturation time, and winemaking was then subsequently carried out. The volatile compounds were analyzed by stir bar sorptive extraction-gas chromatography-mass spectrometry. The results suggest that after the grapevine treatments, grapes store the volatiles in the form of nonvolatile precursors, and some of the volatiles are released during the winemaking process, especially six months after the alcoholic fermentation. The sensory analysis shows that wines maintain the typical aroma properties of Verdejo wines at the end of fermentation; but after six months, the wine color is greener and more astringent, and, in terms of aroma, it has wooden notes as if the wine has been aged in oak barrels.     

Changes in the aroma compounds of sake during aging

Changes in the aroma of sake during aging were investigated by aroma extract dilution analysis (AEDA) and quantitative analysis using the stir bar sorptive extraction method. In AEDA, more odor zones were detected in aged sake than in fresh sake. The dilution factors of aldehydes, polysulfides, and some esters were greater in the aged sake, and their increase during aging was confirmed through a quantitative analysis of sake stored for 0-35 years. Among these compounds, 3-methylbutanal, methional, and dimethyltrisulfide (DMTS) were present in aged sake at concentrations exceeding their odor thresholds, and the highest odor active value was observed for DMTS. Sensory tests showed that supplementation with DMTS contributed to both the total odor intensity and the sulfury odor of aged sake aroma.     

Approaches to wine aroma: release of aroma compounds from reactions between cysteine and carbonyl compounds in wine

Under conditions close to those of wine, that is, low pH, aqueous medium, and low temperatures, this work examines the role of carbonyl (acetoin and acetol) and dicarbonyl (glyoxal, methylglyoxal, diacetyl, and pentane-2,3-dione) compounds associated with cysteine in the formation of odorous products. In particular, thiazole, 4-methylthiazole, 2-acetylthiazole, and trimethyloxazole and two sulfur and oxygenated heterocyclic compounds, 2-furanmethanethiol and thiophene-2-thiol, are examined. For thiophene-2-thiol, the reactional mechanism is proposed. Attempts were made to detect these compounds in wines from various origins. Certain molecules were identified for the first time in wine.     

Sorption behavior of volatile phenols at the oak wood/wine interface in a model system

The sorption in a model system of aroma compounds of enological interest (mixture of the eight derivatives from guaiacol, 4-ethylphenol, and whiskylactone) onto wood was investigated to assess the influence of wood on the concentration of these volatiles during the aging of wine. To evaluate the influence of the solubility of aroma compounds in sorption phenomena, this parameter was determined for each volatile compound in model wine at 10 and 25 degrees C. The solubility is significantly higher in the model wine than in water and remains constant in the range of temperatures studied, except for guaiacol and vanillin. Kinetic and equilibrium sorptions were investigated. Sorption kinetics showed that the sorption equilibrium for all aroma compounds was reached after 6-7 days. From the study of the individual sorption isotherms, two distinct kinds of sorption behavior were observed depending on the presence or not of an ethylenic para substituent conjugated to the phenyl ring. K(ww) partition coefficients between the wood and the model wine were determined, which exhibited an unusual positive variation with temperature.     

Evolution of phenolic compounds during an experimental aging in wood of Sherry vinegar

Changes in the physicochemical composition of wine vinegars produced by submerged culture system and aged in wood were followed. Five Sherry wine vinegars and a model vinegar solution were aged in six new American oak butts of 16.6 L capacity. A total of 24 phenolic compounds were monitored during the maturation study (24 months), along with other physicochemical parameters (total extract, acidity, residual alcohol and total phenolic index). Multivariate statistical analysis was applied to the data. From the sixth month on, significant changes were produced in most of the phenolic compounds, mainly aromatic aldehydes and 5-(hydroxymethyl)-2-furaldehyde. When all the phenolic compounds were considered as variables, cluster analysis grouped samples according to the wine substrate employed in the elaboration of vinegars under study. Within each subcluster, samples are arranged according to their aging status when phenolic compounds accounting significative changes at 180 days of aging are considered. Discriminant functions were constructed from the phenolic compounds data set. The validity of these functions was tested using 13 samples of aged commercial Sherry wine vinegars and 25 unaged vinegars. A total of 97.4% of the test samples was correctly classified within its respective group.     

Impact of concentration of ellagitannins in oak wood on their levels and organoleptic influence in red wine

Some wood substances such as ellagitannins can be extracted during wine aging in oak barrels. The level of these hydrolyzable tannins in wine depends of some parameters of oak wood. Their impact on the organoleptic perception of red wine is poorly known. In our research, oak staves were classified in three different groups according to their level of ellagitannins estimated by NIRS (near infrared spectroscopy) online procedure (Oakscan). First, the ellagitannin level and composition were determine for each classified stave and an excellent correlation between the NIRS classification (low, medium and high potential level of ellagitannin) and the ellagitannin content estimated by HPLC-UV was found. Each different group of NIRS classified staves was then added to red wine during its aging in a stainless tank, and the extraction and evolution of the ellagitannins were monitored. A good correlation between the NIRS classification and the concentration of ellagitannins in red wine aging in contact with the classified staves was observed. The influence of levels of ellagitannins on the resulting wine perception was estimated by a trained judge's panel, and it reveals that the level of ellagitannins in wine has an impact on the roundness and amplitude of the red wine.     

Evaluation of aroma compounds contributing to muskmelon flavor in Porapak Q extracts by aroma extract dilution analysis

The flavor of the Miyabi variety of Japanese muskmelon was extracted according to the Porapak Q column method (PQM) and evaluated by using aroma extract dilution analysis (AEDA) method. The overall odor of the PQM extracts was perceived as having a natural muskmelon-like odor, suggesting that the PQM was able to extract volatile compounds in muskmelon fruit without degradation of original flavor. Forty-six odorant compounds [Kovats index (KI), 961 < or = KI < or = 2605] were found by GC-sniffing in PQM extracts, confirming the effectiveness of PQM in trapping a wide range of volatile compounds in muskmelon flavor. The 46 odorants could be divided into three groups on the basis of their odor attributes: fruity note (KI < 1300); green, grassy, or cucumber-like note (1300 < KI < 2020); and sweet note (KI > 2020). When the original extracts were diluted in AEDA analysis, seven odorants could still be detected by GC-sniffing at a flavor diluation (FD) factor of 128 or above: one had a fruity note (compound 3); four had a cucumber-like, green, or grassy note (compounds 12, 17, 21, and 23); and two had a sweet note (caramel-like or yakitori-like) (compounds 32 and 34).     

From wine to pepper: rotundone, an obscure sesquiterpene, is a potent spicy aroma compound

An obscure sesquiterpene, rotundone, has been identified as a hitherto unrecognized important aroma impact compound with a strong spicy, peppercorn aroma. Excellent correlations were observed between the concentration of rotundone and the mean 'black pepper' aroma intensity rated by sensory panels for both grape and wine samples, indicating that rotundone is a major contributor to peppery characters in Shiraz grapes and wine (and to a lesser extent in wine of other varieties). Approximately 80% of a sensory panel were very sensitive to the aroma of rotundone (aroma detection threshold levels of 16 ng/L in red wine and 8 ng/L in water). Above these concentrations, these panelists described the spiked samples as more 'peppery' and 'spicy'. However, approximately 20% of panelists could not detect this compound at the highest concentration tested (4000 ng/L), even in water. Thus, the sensory experiences of two consumers enjoying the same glass of Shiraz wine might be very different. Rotundone was found in much higher amounts in other common herbs and spices, especially black and white peppercorns, where it was present at approximately 10000 times the level found in very 'peppery' wine. Rotundone is the first compound found in black or white peppercorns that has a distinctive peppery aroma. Rotundone has an odor activity value in pepper on the order of 50000-250000 and is, on this criterion, by far the most powerful aroma compound yet found in that most important spice.     

Metabolic profiling: a new tool in the study of wood formation

In the realm of plant genomics, metabolic profiling has become a valuable tool with which to assess the effect of genetic and/or environmental factors on plant development. This paper reports the first application of metabolic profiling on differentiating xylem tissue of loblolly pine. A protocol is presented for the analysis of loblolly pine xylem tissue. The effects of sample preparation, extraction, and derivatization on the corresponding metabolite profiles and yields have been investigated and are reported. Gas chromatography-mass spectroscopy has been used to quantify >60 polar and lipophilic metabolites from wood-forming tissue. It was possible to assign chemical structures to approximately half of these compounds. Comparison of six loblolly pine genotypes, three high cellulose (50-52%) and three medium (45-48%) cellulose, showed distinct metabolic profiles. Principal component analysis enabled the assignment of metabolic phenotypes using these large data sets. Metabolic phenotype clustering occurred in which the three high-cellulose genotypes were segregated from the medium-cellulose genotypes. These results demonstrate the use of metabolic profiling for the study of wood-forming tissue and as a tool in functional genomics.     

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.     

Stereoselective formation of the varietal aroma compound rose oxide during alcoholic fermentation

The potent aroma compound rose oxide was quantified in several white wines by a headspace solid-phase microextration stable isotope dilution assay (HS-SPME-SIDA) and the enantiomeric ratios of the cis diastereomers were determined by enantioselective capillary GC. The most odor-active stereoisomer (23)-cis-rose oxide was detectable in all investigated white wines ranging from 0.2 to 12 microg/L. However, its contribution to the overall aroma in some white wine varieties can be neglected as indicated by a low odor activity value (OAV). The highest concentrations were found in Gewürztraminer wines, confirming the importance of rose oxide as a varietal aroma compound in this variety. Surprisingly, the enantiomeric ratio of cis-rose oxide in all investigated wines was substantially lower than in nonfermented musts and in some wines almost racemic cis-rose oxide was detected. Fermentation studies with a model must that contained deuterated water revealed that yeast is capable of reducing the precursor 3,7-dimethyl octa-2,5-dien-1,7-diol (geranyl diol I) yielding 3,7-dimethyl-5-octen-1,7-diol (citronellyl diol I) that gives rise to cis- and trans-rose oxide after acid catalyzed cylization. The deuterium labeling pattern of the resulting rose oxide stereoisomers and a clearly detectable kinetic isotope effect indicate that at least two different reductive pathways in yeast exist that yield cis-rose oxide with different enantiomeric ratios altering the genuine enantiomeric ratio in grape musts. The presence of (+)-cis-rose oxides in wines can therefore be attributed to the reductive yeast metabolism during fermentation. This observation corroborates recent findings that the modification of terpene derived varietal aroma is an integral part of yeast metabolism and not only a simple hydrolytical process.     

Evaluation of the combined effects of enzymatic treatment and aging on lees on the aroma of wine from Bombino bianco grapes

In this study, two different doses of commercial beta-glucanase enzyme preparation were tested to verify their effect on wines aged on lees. These wines were compared with two samples with no enzymatic treatment. The former was aged on lees (control), and the latter was readily filtered off from the yeast cell biomass (standard). Analysis of variance (one-way ANOVA), the Tukey test, and principal component analysis (PCA) were applied to all of the samples, which were analyzed for aroma composition, along with galacturonic acid, total acidity, pH, and color. Results showed a large number of statistically significant differences among samples. In general, wines treated with beta-glucanase were characterized by higher concentration of many volatile compounds. The presence of lees and even more the exogenous enzymatic action enhanced almost all volatile compounds. Besides the high presence of ethyl esters, it is worth mentioning the behavior of hexanol and trans-3-hexenol, which are strongly enhanced by the presence of lees and by enzymatic treatments.     

Ability of possible DMS precursors to release DMS during wine aging and in the conditions of heat-alkaline treatment

The origin of dimethyl sulfide (DMS) produced during wine aging was examined through different assays. The production of DMS during the model aging of a wine and the concomitant decrease of residual potential DMS (PDMS), as DMS released by heat-alkaline treatment in 0.5 M sodium hydroxide at 100 degrees C for 1 h, were demonstrated. Then, dimethyl sulfoxide (DMSO), methionine sulfoxide (MSO), S-methylmethionine (SMM), and dimethylsulfonium propanoic acid (DMSPA), reported previously as possible DMS precursors, were investigated for their ability to be DMS precursors in wine in the conditions of this model aging and of the heat-alkaline treatment. The results showed that DMSO, MSO, and DMSPA could hardly be DMS precursors in the conditions used, whereas SMM appeared to be a good candidate. Finally, the use of [(2)H(6)]-DMSPA as an internal standard for PDMS determination was proposed, because it provided better reproducibility than [(2)H(6)]-DMS used as an external standard.     

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.     

Interactions between yeast lees and wine polyphenols during simulation of wine aging: I. Analysis of remnant polyphenolic compounds in the resulting wines

Wine aging on yeast lees is a traditional enological practice used during the manufacture of wines. This technique has increased in popularity in recent years for the aging of red wines. Although wine polyphenols interact with yeast lees to a limited extent, such interactions have a large effect on the reactivity toward oxygen of wine polyphenolic compounds and yeast lees. Various domains of the yeast cell wall are protected by wine polyphenols from the action of extracellular hydrolytic enzymatic activities. Polysaccharides released during autolysis are thought to exert a significant effect on the sensory qualities of wine. We studied the chemical composition of polyphenolic compounds remaining in solution or adsorbed on yeast lees after various contact times during the simulation of wine aging. The analysis of the remnant polyphenols in the wine indicated that wine polyphenols adsorption on yeast lees follows biphasic kinetics. An initial and rapid fixation is followed by a slow, constant, and saturating fixation that reaches its maximum after about 1 week. Only very few monomeric phenolic compounds remained adsorbed on yeast lees, and no preferential adsorption of low or high polymeric size tannins occurred. The remnant condensed tannins in the wine contained fewer epigallocatechin units than the initial tannins, indicating that polar condensed tannins were preferentially adsorbed on yeast lees. Conversely, the efficiency of anthocyanin adsorption on yeast lees was unrelated to its polarity.     

Response of the aroma fraction in sherry wines subjected to accelerated biological aging.

The effect of an acceleration assay, carried out with a periodic aeration and an increased surface/volume ratio, on various aroma compounds of "fino" Sherry wines aging under a veil of a pure culture of Saccharomyces cerevisiae race capensis G1 flor film yeast was studied. The results were subjected to multifactor analysis of variance, and the compounds simultaneously depending on acceleration conditions and aging time at p < 0.01 were subjected to principal component analysis. The first component, accounting for 86.14% of the overall variance, was mainly defined by acetaldehyde and its derivatives 1,1-diethoxyethane and acetoin. These compounds reached higher concentrations in accelerated aging wines in a shorter time than they did in control wines, and no browning problems were detected. Taking into account that these compounds can be used as indicators for biological aging of "fino" Sherry wines, the acceleration condition assayed can be applied to shorten the time of this process.