Brígida Fernández de Simón

Volatile Compounds in Acacia, Chestnut, Cherry, Ash, and Oak Woods, with a View to Their Use in Cooperage

Extracts of wood from acacia, European ash, American ash, chestnut, cherry, and three oak species (Quercus pyrenaica, Quercus alba and Quercus petraea) before and after toasting in cooperage were studied by GC-MS. 110 compounds were detected, and 97 of them were identified. In general, all studied woods showed more lignin derivatives than lipid and carbohydrate derivatives, with a higher variety of compounds detected and abundance of them. The toasting led to an increase in the concentrations of most of these compounds, and this increase is especially important in acacia, chestnut and ash woods. The cis and trans isomers of beta-methyl-gamma-octalactone and isobutyrovanillone were only detected in oak wood, 3,4-dimethoxyphenol and 2,4-dihydroxybenzaldehyde only in acacia wood, and p-anisaldehyde and benzylsalicylate only in cherry wood, before and after toasting, and these compounds could be considered chemical markers for each one of these woods. Moreover, each wood has a characteristic volatile composition, from a quantitative point of view, and therefore we can expect a characteristic sensorial profile. The oak wood turned out to be the most balanced, since although it provides a lot of volatile compounds to the aroma and flavor of aged wine, it can do so without masking their primary and secondary aroma. On the whole, toasted acacia and chestnut woods showed a very high richness of studied compounds, as lignin as lipid and carbohydrate derivatives, while cherry and ash were much richer than toasted oak wood in lignin derivatives, but much poorer in lipid and carbohydrate derivatives.

Phenolic compounds in chestnut (Castanea sativa Mill.) heartwood. Effect of toasting at cooperage.

The phenolic and tannic composition of heartwood extracts from Castanea sativa Mill., before and after toasting in cooperage, were studied using HPLC-DAD and HPLC-DAD/ESI-MS, and some low molecular weight phenolic compounds and hydrolyzable tannins were found. The low molecular weight phenolic compounds were lignin constituents as the acids gallic, protocatechuic, vanillic, syringic, ferulic, and ellagic, the aldehydes protocatechuic, vanillic, syringic, coniferylic, and sinapic, and the coumarin scopoletin. Their patterns were somewhat different those of oak because oak does not contain compounds such protocatechuic acid and aldehyde and is composed of much lower amounts of gallic acid than chestnut. Vescalagin and castalagin were the main ellagitannins, and acutissimin was tentatively identified for the first time in this wood. Moreover, some gallotannins were tentatively identified, including different isomers of di, tri, tetra, and pentagalloyl glucopyranose, and di and trigalloyl-hexahydroxydiphenoyl glucopyranose, comprising 20 different compounds, as well as some ellagic derivatives such as ellagic acid deoxyhexose, ellagic acid dimer dehydrated, and valoneic acid dilactone. These ellagic derivatives as well as some galloyl and hexahydroxydiphenoyl derivatives were tentatively identified for the first time in this wood. The profile of tannins was therefore different from that of oak wood because oak only contains tannins of the ellagitannins type. Seasoned and toasted chestnut wood showed a very different balance between lignin derivatives and tannins because toasting resulted in the degradation of tannins and the formation of low molecular weight phenolic compounds from lignin degradation. Moreover, the different toasting levels provoked different balances between tannins and lignin constituents because the intensity of lignin and tannin degradation was in relation to the intensity of toasting.

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

Abstract. A red Rioja wine was aged in barrels made of Spanish oak wood for 21 months. The evolutions of colour percentage intensity, families of phenolic compounds and low molecular weight phenolic compounds were studied in these wines and compared with those of the same wine aged in barrels made of French and American oak. The analysis of chromatic parameters and total anthocyanins indicates that the wines aged in Spanish and French oak wood barrels have similar chromatic characteristics, but are significantly different to those of wines aged in barrels made of American oak wood, indicating a different degree of modification of the colour. The ageing process also had an important influence on the low molecular weight polyphenols composition of wine. The evolution of these components allowed the production of wines with different characteristics, in relation to the type of wood used in barrel making process. On the other hand, Spanish oak wood can be considered suitable for barrel production for quality wines, since a wine aged in barrels made of Spanish oak wood showed similar and intermediate characteristics to those of the same wine aged in French and American oak woods.

Phenolic Compounds in Cherry (Prunus avium) Heartwood with a View to Their Use in Cooperage

The phenolic and tannic composition of heartwood extracts from Prunus avium , commonly known as cherry tree, before and after toasting in cooperage were studied using HPLC-DAD and HPLC-DAD/ESI-MS. Nonflavonoid (16 compounds) and flavonoid (27 compounds) polyphenols were identified, 12 of them in only a tentative way. The nonflavonoids found were lignin constituents, and their pattern is different compared to oak, since they include compounds such as protocatechuic acid and aldehyde, p-coumaric acid, methyl vanillate, methyl syringate, and benzoic acid, but not ellagic acid, and only a small quantity of gallic acid. In seasoned wood we found a great variety of flavonoid compounds which have not been found in oak wood for cooperage, mainly, in addition to the flavan-3-ols (+)-catechin, a B-type procyanidin dimer, and a B-type procyanidin trimer, the flavanones naringenin, isosakuranetin, and eriodictyol and the flavanonols aromadendrin and taxifolin. Seasoned and toasted cherry wood showed different ratios of flavonoid to nonflavonoid compounds, since toasting results in the degradation of flavonoids, and the formation of nonflavonoids from lignin degradation. On the other hand, the absence of hydrolyzable tannins in cherry wood, which are very important in oak wood, is another particular characteristic of this wood that should be taken into account when considering its use in cooperage.

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.

LC-DAD/ESI-MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage.

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC-DAD/ESI-MS/MS. Low-molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium-toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium-toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage.

Characterization of Volatile Constituents in Commercial Oak Wood Chips

The volatile composition of the different oak wood pieces (chips of Quercus spp.) that can be found on the market to be used as alternatives to barrels for aging wines, as well as of chips of Quercus pyrenaica which are being introduced, was studied, evaluating the contents of volatile phenols, lactones, furanic compounds, pyranones, phenolic aldehydes, phenolic ketones, and others. In regard to the overall results, the volatile composition of these products varies widely and has not been clearly laid out according to either the oak species or the wood toasting intensity. Taking into account that the different characteristics of alternatives to barrel products are reflected in the wine treated with them and that an oenological profile based on these variables (origin and toasting level) cannot be defined, only an appropriate chemical analysis would reveal the quality of alternative-to-barrel products and allow us to attempt to foresee its effects on the chemical and organoleptic characteristics of the wines treated with them. On the other hand, the Q. pyrenaica alternative products are very similar to those of other species, with some aromatic particularities, such as their high levels of furanic compounds, eugenol, Furaneol, and cis-whiskylactone, and low levels of vanillin.

Polyphenolic profile as a useful tool to identify the wood used in wine aging

Although oak wood is the main material used in cooperage, other species are being considered as possible sources of wood for the production of wines and their derived products. In this work we have compared the phenolic composition of acacia (Robinia pseudoacacia), chestnut (Castanea sativa), cherry (Prunus avium) and ash (Fraxinus excelsior and F. americana) heartwoods, by using HPLC-DAD/ESI-MS/MS (some of these data have been showed in previous paper), as well as the changes that toasting intensity at cooperage produce in each polyphenolic profile. Before toasting, each wood shows a different and specific polyphenolic profile, with both qualitative and quantitative differences among them. Toasting notably changed these profiles, in general, proportionally to toasting intensity and led to a minor differentiation among species in toasted woods, although we also found phenolic markers in toasted woods. Thus, methyl syringate, benzoic acid, methyl vanillate, p-hydroxybenzoic acid, 3,4,5-trimethylphenol and p-coumaric acid, condensed tannins of the procyanidin type, and the flavonoids naringenin, aromadendrin, isosakuranetin and taxifolin will be a good tool to identify cherry wood. In acacia wood the chemical markers will be the aldehydes gallic and β-resorcylic and two not fully identified hydroxycinnamic compounds, condensed tannins of the prorobinetin type, and when using untoasted wood, dihydrorobinetin, and in toasted acacia wood, robinetin. In untoasted ash wood, the presence of secoiridoids, phenylethanoid glycosides, or di and oligolignols will be a good tool, especially oleuropein, ligstroside and olivil, together verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. In toasted ash wood, tyrosol, syringaresinol, cyclolovil, verbascoside and olivil, could be used to identify the botanical origin. In addition, in ash wood, seasoned and toasted, neither hydrolysable nor condensed tannins were detected. Lastly, in chestnut wood, gallic and ellagic acids and hydrolysable tannins of both the gallotannin and ellagitannin type, can be used as chemical markers.

Effect of Toasting Intensity at Cooperage on Phenolic Compounds in Acacia (Robinia pseudoacacia) Heartwood

The phenolic composition of heartwood from Robinia pseudoacacia, commonly known as false acacia, before and after toasting in cooperage was studied by HPLC-DAD and HPLC-DAD/ESI-MS/MS. A total of 41 flavonoid and nonflavonoid compounds were identified, some tentatively, and quantified. Seasoned acacia wood showed high concentrations of flavonoid and low levels of nonflavonoid compounds, the main compounds being the dihydroflavonols dihydrorobinetin, fustin, tetrahydroxy, and trihydroxymethoxy dihydroflavonol, the flavonol robinetin, the flavanones robtin and butin, and a leucorobinetinidin, none of which are found in oak wood. The low molecular weight (LMW) phenolic compounds present also differed from those found in oak, since compounds with a β-resorcylic structure, gallic related compounds, protocatechuic aldehyde, and some hydroxycinnamic compounds are included, but only a little gallic and ellagic acid. Toasting changed the chromatographic profiles of extracts spectacularly. Thus, the toasted acacia wood contributed flavonoids and condensed tannins (prorobinetin type) in inverse proportion to toasting intensity, while LMW phenolic compounds were directly proportional to toasting intensity, except for gallic and ellagic acid and related compounds. Even though toasting reduced differences between oak and acacia, particular characteristics of this wood must be taken into account when considering its use in cooperage: the presence of flavonoids and compounds with β-resorcylic structure and the absence of hydrolyzable tannins.

Micro-oxygenation strategy depends on origin and size of oak chips or staves during accelerated red wine aging

The practice of wine aging in stainless steel tank involves storing wine in contact with wood and dosing it with small oxygen quantities in order to obtain a final wine more stable in time and with the same characteristics of barrel-aged wines. Oxygen dosing is a key factor and, to achieve a correct development of wine, needs to be applied according to wine necessities and to the kind of wood chosen. This paper shows the results obtained from the study of oxygen required by a same wine aged in tanks with different alternative products (chips and staves) made of American (Q. alba), French (Q. petraea) and Spanish oak (Q. pyrenaica), with a strategy of micro-oxygenation as required. The results indicate that the size and origin of the wood used determine the oxygen management during the process. In fact, wine treated with big pieces (staves) consumes more oxygen and, with regard to wood origin, wine aged with French oak (Q. petraea) products needs of a higher oxygen dosage.