Development of a New Method for the Quantitative Analysis of Aroma Compounds Potentially Related to the Fruity Aroma of Red Wines.

To determine the concentrations of aroma compounds involved in the fruity aroma of red wines, an analytical method was developed and optimized using liquid-liquid extraction and gas chromatography coupled to mass spectrometry (GC/MS). The aim was to reduce sample preparation and analysis time, with a single sample preparation and a single injection being needed to quantify 43 compounds. 19 esters, 13 monoterpenes, 5 C13-norisoprenoids, and 6 C6-aldehyde and alcohol compounds were quantified in 14 red wines made from different grape varieties grown in the Mediterranean basin. Samples were selected based on typical varietal aroma by a panel of experts, who produced 7 olfactory descriptors linked to desirable or non-desirable wine aromas. The instrumental analysis showed variations in concentrations of the quantified compounds among the wines. The wines described using positive fruity descriptors had higher mean total concentrations of esters, C6-alcohols, monoterpenes, and C13-norisoprenoids. Some non-ester compounds were positively correlated with the fruity descriptors. Sensory profile results obtained by a panel of 16 trained judges revealed that the addition of non-ester compounds (including 2 cyclic esters) to a red wine initially described as having cooked fruit aromas had a positive contribution to some fresh fruity notes. This study opens up new avenues for research on the potential involvement of non-ester compounds in the fruity expression of red wines.

Sensory Specificities Involving Acetaldehyde and Diacetyl in Wines Produced without Added Sulfur Dioxide.

Nowadays, the development of naturality concept is illustrated in the oenological field by the development of wine produced without the addition of SO2. Among its chemical properties, SO2 is able to react with carbonyl compounds to form carbonyl bisulfites. Acetaldehyde and diacetyl are the main carbonyl compounds of red wines, which could influence product perception. The goal of this paper was to evaluate their chemical and sensory impact in red wines produced without any addition of SO2. A first quantification approach revealed a lower concentration of these compounds in wines without added SO2 than in those produced with SO2. A sensory approach involving aromatic reconstitutions in wines in the presence or absence of SO2 revealed that analytical differences observed for acetaldehyde and diacetyl were able to impact wine freshness, with diacetyl being, moreover, involved in wine fruity aroma changes.

Toward a Better Understanding of Perceptive Interactions between Volatile and Nonvolatile Compounds: The Case of Proanthocyanidic Tannins and Red Wine Fruity Esters-Methodological, Sensory, and Physicochemical Approaches.

The impact of commercial proanthocyanidic tannins on fruity pool of esters, representing the fruitiness of Bordeaux red wines, was assessed in model solutions. It was shown that the presence of tannins in the matrix significantly attenuated perception of fruity notes (p = 0.013). Physicochemical analysis demonstrated that the presence of proanthocyanidic tannins in dilute alcohol solution resulted in a decrease in ester partition coefficients and thus in a decrease in ester contents in the headspace (p < 0.05). This fact highlighted the changes that may occur in wines at a pre-sensory level, prior to sensory evaluation. Finally, a new sensory tool was developed, consisting in an ISO glass containing two compartments separated by a glass wall, providing a way to compare perceived odors according to whether or not the components of the odor mixtures were actually mixed in solution (p < 0.001). This new tool was used to demonstrate the impact and the only implication of pre-sensory level in the consequences of physical mixture between proanthocyanidic tannins and esters on their odor perception.

Impact of Whisky Lactone Diastereoisomers on Red Wine Fruity Aromatic Expression in Model Solution.

The impact of whisky lactone diastereoisomers on the typical fruity expression of red Bordeaux wines was evaluated by sensory analysis. The detection thresholds of cis- and trans-whisky lactone in a dilute alcohol solution (12% v/v) were 20 and 130 µg/L, respectively. Consequently, considering their average concentrations found in oak-aged red wines, cis-whisky lactone was present at supra threshold levels, whereas trans-whisky lactone was below its detection threshold. Adding these diastereoisomers to a red wine fruity aromatic reconstitution at these average concentrations led to a decrease in the perception of this last one, highlighting a masking effect. Sensory profiles of cis- and trans-whisky lactone confirmed that these compounds modified the perception of fruity aromas, decreasing the intensity of red berry fruit notes and increasing that of blackberry fruit and spicy descriptors.

Oak Wood Volatiles Impact on Red Wine Fruity Aroma Perception in Various Matrices.

This research examined the impact of oak wood volatile compounds on the perception of red wine fruity aroma in several matrices. Several aromatic reconstitutions were prepared, consisting of 13 esters, representing the fruity pool of red wine, and 14 oak wood compounds at the various concentrations corresponding to the levels released by light, medium, and heavy toasting of barrels. These reconstitutions were prepared in dilute alcohol solution, dearomatized red wine, and commercial red wine. Sensory analysis revealed the impact of the addition or omission of some oak wood compounds. The "detection threshold" of the fruity pool was then evaluated. The presence of 2-furanmethanethiol individually and the oak wood compound mixture, at concentrations representing various toasting levels, had a significant masking effect on the fruity pool, whereas vanillin had a significant enhancing effect in model solution. Sensory profiles highlighted changes in the perception of fruity nuances in the presence of the oak wood compound mixture. The addition of compounds at concentrations representing different toasting levels led to a predictable increase in the perception of the oak wood descriptors (spicy, smoky, and toasty) in all of the matrices tested. The perception of fruity notes also varied depending upon the toasting level and the complexity of the matrix. In dilute alcohol solution and dearomatized red wine, light toasting preserved or intensified the fruity notes. Generally, in all matrices tested, fresh-fruit and red-berry-fruit notes decreased with the addition of wood at medium and heavy toasting levels.

Static Headspace Analysis Using Low-Pressure Gas Chromatography and Mass Spectrometry, Application to Determining Multiple Partition Coefficients: A Practical Tool for Understanding Red Wine Fruity Volatile Perception and the Sensory Impact of Higher Alcohols.

To evaluate the partition coefficients of volatiles between the liquid and gas phases, an analytical method was developed and optimized using static headspace analysis and low-pressure injection gas chromatography coupled to mass spectrometry (SHS-LP-GC/MS). Two different types of analytical columns were coupled for low-pressure chromatography injection: a narrow restriction microbore column on the inlet side and a mega-bore column on the mass spectrometer side. Coupling these two columns and static headspace analysis to gas chromatography and mass spectrometry resulted in a simple, fast, sensitive, and accurate approach. Several points have been optimized: time to reach the thermodynamic equilibrium in the gas phase, syringe filling rate, gas injection rate, and volume ratio between the gas and liquid phases. This new method was used to determine partition coefficients between the liquid and gas phases and study multicomponent mixtures for which particular perceptive interactions had previously been highlighted. The partition coefficients of 9 esters and 5 higher alcohols were determined in dilute alcohol solution (12% v/v) and dearomatized red wine. These partition coefficients revealed modifications in ester headspace release in the presence of higher alcohols for the first time in this type of matrix. The correlation of these results with sensory data highlighted the role of physicochemical, presensory effects on sensory modifications for the first time, suggesting that this type of interaction may partly modulate qualitative and quantitative fruity perception.

2-Methylbutyl acetate in wines: Enantiomeric distribution and sensory impact on red wine fruity aroma.

Enantiomers of 2-methylbutyl acetate were assayed in red and white commercial wines from various vintages and origins, using chiral gas chromatography (γ-cyclodextrin), revealing the exclusive presence of the S-enantiomeric form. Results also confirmed that (S)-2-methylbutyl acetate levels were generally higher in red than white wines of the same age, and that acetate levels increased gradually during ageing. Olfactory threshold of (S)-2-methylbutyl acetate was evaluated at 313µg/L in dilute alcohol solution (12% v/v) and 1083µg/L in a fruity aromatic reconstitution, reflecting its presence in wines at subthreshold concentrations. At concentrations considerably lower than its olfactory threshold, 2-methylbutyl acetate was associated with blackberry-fruit and banana notes. It was also revealed that, even at subthreshold concentrations, this compound had a modification on the perception of fruity aromas in the matrices studied. Sensory profiles highlighted, for the first time, its specific contribution to black-, fresh-, and jammy-fruit notes, despite its subthreshold concentrations.

Study of Substituted Ester Formation in Red Wine by the Development of a New Method for Quantitative Determination and Enantiomeric Separation of Their Corresponding Acids.

A new method was developed for quantifying substituted acids including, where applicable, their various unexplored enantiomeric forms. A new step was added to acids' usual quantification methods, consisting of extraction, derivatization to methyl esters, and gas chromatography analysis: preliminary extraction was performed at basic pH to eliminate ethyl esters, thus avoiding their transesterification during derivatization. Quantitation and enantiomeric distribution of some substituted esters and their corresponding acids were established in 31 commercial Bordeaux red wines from 0 to 20 years old. A strong positive correlation was observed between the age of wine and levels of ethyl 2-methylpropanoate, ethyl 3-methylbutanoate, ethyl 2-methylbutanoate, ethyl (3R)-3-hydroxybutanoate, both enantiomeric forms of ethyl 2-hydroxy-3-methylbutanoate, and ethyl (2S)-2-hydroxy-4-methylpentanoate, but not ethyl (3S)-3-hydroxybutanoate. However, the standard deviations of average concentrations for the corresponding substituted acids were so large that only few correlations between concentrations and age were observed. Concentrations of (2S)-2-hydroxy-3-methylbutanoic acid and (2S)-2-hydroxy-4-methylpentanoic acid increased slightly over time, while (2R)-2-hydroxy-4-methylpentanoic acid levels decreased slightly with the age. Variations in the ratio of substituted ethyl esters to their corresponding acids over time detected thanks to these analytical advances suggested that, in general, acids were continuously esterified during aging.

Distribution and Organoleptic Impact of Ethyl 3-Hydroxybutanoate Enantiomers in Wine.

Enantiomers of ethyl 3-hydroxybutanoate were assayed in 87 commercial wines from various vintages and origins, using chiral gas chromatography (ß-cyclodextrin). Generally, ethyl 3-hydroxybutanoate levels were higher in red than in white wines of the same age. The average S/R enantiomeric ratio of this compound in red wine was approximately 75:25 (± 13), with an average total concentration of ∼ 450 (± 150) µg/L. In red wines, R-form levels increased gradually during aging, but no variations were observed in S-form concentrations. To our knowledge, no previous research had determined the enantiomeric distribution of this compound in wine. The olfactory threshold of the S-form in dilute alcohol solution was 21 mg/L, one-third that of the R-form: 63 mg/L. The S- and R-forms had different aromatic nuances. The olfactory threshold of their mixture (85:15, m/m) was 14 mg/L, indicating a simple additive effect in this binary mixture. Furthermore, the concentrations found in red wines were considerably below the olfactory threshold under the same experimental conditions. Sensory analysis revealed that ethyl 3-hydroxybutanoate (S/R, 85:15, m/m) had an enhancing effect on the perception of fruity aromas in the matrices studied. Sensory profiles highlighted the contribution of ethyl 3-hydroxybutanoate to red-berry and fresh-fruit descriptors, despite its subthreshold concentrations.

Olfactory Impact of Higher Alcohols on Red Wine Fruity Ester Aroma Expression in Model Solution.

This study focused on the impact of five higher alcohols on the perception of fruity aroma in red wines. Various aromatic reconstitutions were prepared, consisting of 13 ethyl esters and acetates and 5 higher alcohols, all at the average concentrations found in red wine. These aromatic reconstitutions were prepared in several matrices. Sensory analysis revealed the interesting behavior of certain compounds among the five higher alcohols following their individual addition or omission. The "olfactory threshold" of the fruity pool was evaluated in several matrices: dilute alcohol solution, dilute alcohol solution containing 3-methylbutan-1-ol or butan-1-ol individually, and dilute alcohol solution containing the mixture of five higher alcohols, blended together at various concentrations. The presence of 3-methylbutan-1-ol or butan-1-ol alone led to a significant decrease in the "olfactory threshold" of the fruity reconstitution, whereas the mixture of alcohols raised the olfactory threshold. Sensory profiles highlighted changes in the perception of fruity nuances in the presence of the mixture of higher alcohols, with specific perceptive interactions, including a relevant masking effect on fresh- and jammy-fruit notes of the fruity mixture in both dilute alcohol solution and dearomatized red wine matrices. When either 3-methylbutan-1-ol or butan-1-ol was added to the fruity reconstitution in dilute alcohol solution, an enhancement of butyric notes was reported with 3-methylbutan-1-ol and fresh- and jammy-fruit with butan-1-ol. This study, the first to focus on the impact of higher alcohols on fruity aromatic expression, revealed that these compounds participate, both quantitatively and qualitatively, in masking fruity aroma perception in a model fruity wine mixture.