Gas chromatography-olfactometry and chemical quantitative study of the aroma of six premium quality spanish aged red wines

The aroma of six premium quality Spanish red wines has been studied by quantitative gas chromatography-olfactometry (GC-O) and techniques of quantitative chemical analysis. The GC-O study revealed the presence of 85 aromatic notes in which 78 odorants were identified, two of which-1-nonen-3-one (temptatively) and 2-acetylpyrazine-are reported in wine for the first time. Forty out of the 82 quantified odorants may be present at concentrations above their odor threshold. The components with the greatest capacity to introduce differences between these wines are ethyl phenols produced by Brettanomyces yeasts (4-ethylphenol, 4-ethyl-2-methoxyphenol, and 4-propyl-2-methoxyphenol), 2,5-dimethyl-4-hydroxy-3(2H)-furanone (furaneol), (Z)-3-hexenol, thiols derived from cysteinic precursors (4-methyl-4-mercaptopentan-2-one, 3-mercaptohexyl acetate, and 3-mercaptohexanol), some components yielded by the wood [(E)-isoeugenol, 4-allyl-2-methoxyphenol, vanillin, 2-methoxyphenol (guaiacol), and (Z)-whiskylactone], and compounds related to the metabolism (2-phenylethanol, ethyl esters of isoacids, 3-methylbutyl acetate) or oxidative degradation of amino acids [phenylacetaldehyde and 4,5-dimethyl-3-hydroxy-2(5H)-furanone (sotolon)]. The correlation between the olfactometric intensities and the quantitative data is, in general, satisfactory if olfactometric differences between the samples are high. However, GC-O fails in detecting quantitative differences in those cases in which the olfactive intensity is very high or if odors elute in areas in which the odor chromatogram is too complex.     

Similarities in the aroma chemistry of Gewürztraminer variety wines and lychee (Litchi chinesis sonn.) fruit

GC/O analysis of canned lychees indicated that cis-rose oxide, linalool, ethyl isohexanoate, geraniol, furaneol, vanillin, (E)-2-nonenal, beta-damascenone, isovaleric acid, and (E)-furan linalool oxide were the most odor potent compounds detected in the fruit extracts. However, on the basis of calculated odor activity values (OAVs), cis-rose oxide, beta-damascenone, linalool, furaneol, ethyl isobutyrate, (E)-2-nonenal, ethyl isohexanoate, geraniol, and delta-decalactone were determined to be the main contributors of canned lychee aroma. When these results were compared with GC/O results of fresh lychees and Gewürztraminer wine, 12 common odor-active volatile compounds were found in all three products. These included cis-rose oxide, ethyl hexanoate/ethyl isohexanoate, beta-damascenone, linalool, ethyl isobutyrate, geraniol, ethyl 2-methylbutyrate, 2-phenylethanol, furaneol, vanillin, citronellol, and phenethyl acetate. On the basis of OAVs, cis-rose oxide had the highest values among the common odorants in the three products, indicating its importance to the aroma of both lychee fruit and Gewürztraminer wines. Other compounds that had significant OAVs included beta-damascenone, linalool, furaneol, ethyl hexanoate, and geraniol. This indicated that while differences exist in the aroma profile of lychee and Gewürztraminer, the common odorants detected in both fruit and wine, particularly cis-rose oxide, were responsible for the lychee aroma in Gewürztraminer wine. When headspace SPME was used as a rapid analytical tool to detect the levels of selected aroma compounds deemed important to lychee aroma in Gewürztraminer-type wines, cis-rose oxide, linalool, and geraniol were found to be at relatively higher levels in Gewürztraminers. No cis-rose oxide was detected in the control wines (Chardonnay and Riesling), while lower levels were detected in the Gewürztraminer-hybrid wine Traminette. Gewürztraminers produced in the Alsace region showed differences in the levels of the 3 monoterpenes when compared to those from New York State, which could be attributed to differences in viticultural and enological practices between regions.     

Evaluation of key odorants in sauvignon blanc wines using three different methodologies

In this study three different approaches were employed to identify key odorants in Sauvignon blanc wines. First, the concentrations of the odorants were compared to their respective aroma detection thresholds. The resulting odor activity values (OAV) were transformed into a normalized and weighted measure that allows the aroma profiles of different wines to be compared and the contribution of a single aroma in a complex mixture to be evaluated. Based on their OAV, 3-mercaptohexanol and 3-mercaptohexyl acetate were the two most important aroma compounds in many Marlborough Sauvignon blanc wines. Due to limitations with the OAV approach, the study was extended to include aroma extract dilution analysis (AEDA), which revealed that β-damascenone, together with the varietal thiols, esters, and higher alcohols, are key odorants in Sauvignon blanc wines. The final approach undertaken was aroma reconstitution and omission tests using a deodorized wine base and the creation of a model Marlborough Sauvignon blanc. Single compounds and groups of compounds were omitted from the model to study their impact on the sensory properties of the model wine. Reconstitution and omission confirmed that varietal thiols, esters, terpenes, and β-damascenone are all important contributors to Sauvignon blanc aroma. The methoxypyrazines showed an important but relatively low impact in all three of the approaches undertaken in this study.     

Quantitative gas chromatography-olfactometry carried out at different dilutions of an extract. Key differences in the odor profiles of four high-quality Spanish aged red wines

Four Spanish aged red wines made in different wine-making areas have been extracted, and the extracts and their 1:5, 1:50, and 1:500 dilutions have been analyzed by a gas chromatography-olfactometry (GC-O) approach in which three judges evaluated odor intensity on a four-point scale. Sixty-nine different odor regions were detected in the GC-O profiles of wines, 63 of which could be identified. GC-O data have been processed to calculate averaged flavor dilution factors (FD). Different ANOVA strategies have been further applied on FD and on intensity data to check for significant differences among wines and to assess the effects of dilution and the judge. Data show that FD and the average intensity of the odorants are strongly correlated (r(2) = 0.892). However, the measurement of intensity represents a quantitative advantage in terms of detecting differences. For some odorants, dilution exerts a critical role in the detection of differences. Significant differences among wines have been found in 30 of the 69 odorants detected in the experiment. Most of these differences are introduced by grape compounds such as methyl benzoate and terpenols, by compounds released by the wood, such as furfural, (Z)-whiskey lactone, Furaneol, 4-propylguaiacol, eugenol, 4-ethylphenol, 2,6-dimethoxyphenol, isoeugenol, and ethyl vanillate, by compounds formed by lactic acid bacteria, such as 2,3-butanedione and acetoine, or by compounds formed during the oxidative storage of wines, such as methional, sotolon, o-aminoacetophenone, and phenylacetic acid. The most important differences from a quantitative point of view are due to 2-methyl-3-mercaptofuran, 4-propylguaiacol, 2,6-dimethoxyphenol, and isoeugenol.     

Differences in odor-active compounds of trincadeira wines obtained from five different clones

Odorant compounds of five young clonal red wines made from cv. Trincadeira, a native grape variety of Vitis vinifera L. grown in Portugal, were studied using 2001 and 2003 vintages. The study was carried out using gas chromatography-mass spectrometry (GC-MS) for compound identification and the gas chromatography-olfactometry (GC-O) posterior intensity method to detect the potentially most important aroma compounds. Forty-one odorant peaks were detected by GC-O analysis, from which 31 were identified by GC-MS. The odorant compounds with the highest odorant average intensities are 3-methylbutanoic acid, 2-phenylethanol, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, and 4-vinylguaiacol. The GC-O analysis showed odor intensity differences among compounds, which was confirmed by analysis of variance (ANOVA). Principal component analysis (PCA) and hierarchical cluster analysis (HCA) showed that the five clonal wines from the 2001 vintage were more similar than those from the 2003 vintage. Moreover, stepwise linear discriminant analysis (SLDA) demonstrated that the factor vintage has influence on the Trincadeira clonal red wine odorant profile differentiation.     

Quantitative determination of sulfur-containing wine odorants at sub parts per billion levels. 2. Development and application of a stable isotope dilution assay

[(2)H(10)]-4-Mercapto-4-methylpentan-2-one (d(10)-1), [(2)H(2)]-3-mercaptohexan-1-ol (d(2)-2), and [(2)H(5)]-3-mercaptohex-1-yl acetate (d(5)-3), deuterated analogues of impact odorants of wines, were used to determine quantitatively the natural compounds in white wines (Muscadet, Sauvignon, and Bacchus) with a stable isotope dilution assay using gas chromatography coupled either with ion trap tandem mass spectrometry (GC-ITMS-MS) or with atomic emission detection monitored on sulfur-selective acquisition (GC-AED). The thiol compounds were recovered from wines by liquid-liquid extraction, then purified from the wine extracts by covalent chromatography, and analyzed. The quantitative determination of 4-mercapto-4-methylpentan-2-one 1 in the wines that were analyzed was performed better with GC-AED than with GC-ITMS-MS under the conditions that were used. However, the detection limit of the method was higher than the odor threshold of 4-mercapto-4-methylpentan-2-one 1 in wine (5 vs 0.8 ng/L). The levels of this compound in the Sauvignon and Bacchus wines were much higher than its odor threshold, but it was not detectable in the Muscadet wines. On the contrary, GC-ITMS-MS was much more sensitive than GC-AED for detection of 3-mercaptohexan-1-ol 2 and 3-mercaptohex-1-yl acetate 3, and the detection limits were much lower than their odor thresholds in wine. The former compound was detected in all of the Muscadet wines that were analyzed at levels always higher than its odor detection threshold, while the latter occurred at levels higher than its odor threshold in only one Muscadet wine.     

Sensory threshold of 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) and concentrations in young Riesling and non-Riesling wines

1,1,6-Trimethyl-1,2-dihydronaphthalene (TDN) is well-known to contribute "petrol" aromas to aged Riesling wines, but its prevalence and contribution to young Riesling or non-Riesling wines is not well understood. TDN concentrations were measured in 1-3-year-old varietal wines produced from Cabernet franc (n = 14 wines), Chardonnay (17), Cabernet Sauvignon (4), Gewurztraminer (4), Merlot (9), Pinot gris (6), Pinot noir (9), Riesling (28), or Sauvignon blanc (6). TDN concentrations in the Riesling wines, 6.4 ± 3.8 μg/L, were significantly higher than in all other varietals, 1.3 ± 0.8 μg/L. The odor detection thresholds for TDN were then determined in both model wine and a neutral white wine. Group sensory thresholds were found to be the same in both matrices, 2 μg/L, indicating little masking of TDN due to the odorants in the neutral white. The TDN sensory threshold was a factor of 10 below the previously reported odor threshold. On the basis of this revised threshold, 27 of 28 Riesling wines had suprathreshold TDN, whereas only 7 of 69 non-Riesling wines had suprathreshold TDN. The monoterpenes linalool and geraniol were also measured in the Riesling wines, and odor activity values (OAVs) were calculated for the monoterpenes and TDN. The OAV for TDN was higher than for the monoterpenes in 25 of 28 Riesling wines.     

Coinoculated fermentations using saccharomyces yeasts affect the volatile composition and sensory properties of Vitis vinifera L. cv. sauvignon blanc wines

Alcoholic fermentation using Saccharomyces wine yeast is an effective means of modulating wine aroma. This study investigated the impact of coinoculating commercial yeast strains (Vin7, QA23, Vin13) on the volatile composition and sensory profile of Sauvignon Blanc wines. Small-scale replicated fermentations were conducted using single-strain and coinoculations of Vin7 with QA23 and with Vin13. The results showed that the chemical and sensory profiles of the coinoculated wines were different from both the single-strain wines and equal blends of the single-strain wines. Volatile thiol analysis indicated that the Vin7/QA23 coinoculated wines were highest in 3-mercaptohexan-1-ol (3MH) and 3-mercaptohexyl acetate (3MHA), although this pattern was not observed for the Vin7/Vin13 yeast combination. The negative white vinegar aroma and high volatile acidity measured in the Vin7 single-strain wines were not present in the coinoculated wines. This study demonstrates that coinoculations can modify the aroma profile of wines, when complementary yeasts are used.     

Comparison of odor-active compounds in grapes and wines from vitis vinifera and non-foxy American grape species

Native American grape (Vitis) species have many desirable properties for winegrape breeding, but hybrids of these non-vinifera wild grapes with Vitis vinifera often have undesirable aromas. Other than the foxy-smelling compounds in Vitis labrusca and Vitis rotundifolia , the aromas inherent to American Vitis species are not well characterized. In this paper, the key odorants in wine produced from the American grape species Vitis riparia and Vitis cinerea were characterized in comparison to wine produced from European winegrapes (V. vinifera). Volatile compounds were extracted by solid-phase microextraction (SPME) and identified by gas chromatography-olfactometry/mass spectrometry (GC-O/MS). On the basis of flavor dilution values, most grape-derived compounds with fruity and floral aromas were at similar potency, but non-vinifera wines had higher concentrations of odorants with vegetative and earthy aromas: eugenol, cis-3-hexenol, 1,8-cineole, 3-isobutyl-2-methoxypyrazine (IBMP), and 3-isopropyl-2-methoxypyrazine (IPMP). Elevated concentrations of these compounds in non-vinifera wines were confirmed by quantitative GC-MS. Concentrations of IBMP and IPMP were well above sensory threshold in both non-vinifera wines. In a follow-up study, IBMP and IPMP were surveyed in 31 accessions of V. riparia, V. rupestris, and V. cinerea. Some accessions had concentrations of >350 pg/g IBMP or >30 pg/g IPMP, well above concentrations reported in previous studies of harvest-ripe vinifera grapes. Methyl anthranilate and 2-aminoacetophenone, key odorants responsible for the foxiness of V. labrusca grapes, were undetectable in both the V. riparia and V. cinerea wines (<10 μg/L).     

The chemical characterization of the aroma of dessert and sparkling white wines (Pedro Ximénez, Fino, Sauternes, and Cava) by gas chromatography-olfactometry and chemical quantitative analysis

Wines from Pedro Ximénez (PX), Fino, botrytized Sauternes, and Cava were screened by gas chromatography-olfactometry (GC-O), and the most relevant aroma compounds were further quantified in six different wines of each group. The comparison of GC-O and quantitative data with similar data from white young wines has made it possible to identify the aroma compounds potentially responsible for the specific sensory characteristics of these wines. Results have shown that all these wines are relatively rich in 3-methylbutanal, phenylacetaldehyde, methional, sotolon, and the ethyl esters of 2-, 3-, and 4-methylpentanoic acids. While Cava has a less specific aroma profile halfway between these special wines and young white wines, PX is richest in 3-methylbutanal, furfural, beta-damascenone, ethyl cyclohexanoate, and sotolon; Fino in acetaldehyde, diacetyl, ethyl esters of branched aliphatic acids with four, five, or six carbon atoms, and 4-ethylguaiacol; and Sauternes in phenylacetaldehyde, 3-mercaptohexanol, and 4-methyl-4-mercaptopentanone.     

Investigation of potent odorants and afterodor development in two Chardonnay wines using the buccal odor screening system (BOSS)

Potent odorants of two Chardonnay wines were characterized according to their specific overall aroma profiles and their intraoral release patterns after wine consumption. Therefore, aroma compounds were isolated and analyzed by means of high resolution gas chromatography-olfactometry (HRGC/O), leading to the detection of 36 odor-active compounds in both wines. All compounds were identified. Of the most potent odorants, 25 were quantified in both wines by means of stable isotope dilution assays. For the intraoral investigation of odor compounds at defined times after Chardonnay wine consumption, the recently developed buccal odor screening system was used. Significant differences in the oral persistence of characteristic odor notes were observed for both wines with mainly the characteristic barrique-notes being highly persistent, while fruity notes quickly disappeared from the oral cavity. The obtained analytical data were related to time-resolved retronasal aroma evaluation.     

Anthocyanin transformation in Cabernet Sauvignon wine during aging

Anthocyanins in Cabernet Sauvignon grapes and wines were elucidated by HPLC-MS/MS. Major anthocyanins in Cabernet Sauvignon grape extract are malvidin 3-O-glucoside and malvidin 3-O-acetylglucoside. In matured wine, anthocyanins are transformed to anthocyanin-vinyl derivatives, ethyl bridged anthocyanin-flavanol adducts, and anthocyanin-flavanol adducts. The major anthocyanin pigments are malvidin 3-O-glucoside-pyruvate, malvidin 3-O-acetylglucoside-pyruvate, malvidin 3-O-coumaroylglucoside-pyruvate, malvidin 3-O-glucoside-4-vinylphenol, malvidin 3-O-acetylglucoside-4-vinylphenol, and malvidin 3-O-coumaroylglucoside-4-vinylphenol. The presence of syringetin 3-O-glucoside and syringetin 3-O-acetylglucoside has been established for the first time in grape and wine.     

Chemical characterization of the aroma of Grenache rosé wines: aroma extract dilution analysis,quantitative determination,and sensory reconstitution studies

The aroma of a Grenache rosé wine from Calatayud (Zaragoza, Spain) has been elucidated following a strategy consisting of an aroma extract dilution analysis (AEDA), followed by the quantitative analysis of the main odorants and the determination of odor activities values (OAVs) and, finally, by a series of reconstitution and omission tests with synthetic aroma models. Thirty-eight aroma compounds were found in the AEDA study, 35 of which were identified. Twenty-one compounds were at concentrations higher than their corresponding odor thresholds. An aroma model prepared by mixing the 24 compounds with OAV > 0.5 in a synthetic wine showed a high qualitative similarity with the aroma of the rosé wine. The addition of compounds with OAV < 0.5 did not improve the model, whereas the aroma of a model containing only odorants with OAV > 10 was very different from that of the wine. Omission tests revealed that the most important odorant of this Grenache rosé wine was 3-mercapto-1-hexanol, with a deep impact on the wine fruity and citric notes. The synergic action of Furaneol and homofuraneol also had an important impact on wine aroma, particularly in its fruity and caramel notes. The omission of beta-damascenone, which had the second highest OAV, caused only a slight decrease on the intensity of the aroma model. Still weaker was the sensory effect caused by the omission of 10 other compounds, such as fatty acids and their ethyl esters, isoamyl acetate, and higher alcohols.