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The levels of important oxidation-related aldehydes, such as methional, phenylacetaldehyde, (E)-2-hexenal, (E)-2-heptenal, (E)-2-octenal, (E)-2-nonenal, methylpropanal, 2-methylbutanal, and 3-methylbutanal, were determined in 41 different wines belonging to different types (young whites and reds, natural sparkling wines, oxidized young whites and reds, Sherry, aged red wines, Port wines). Except (E)-2-hexenal and (E)-2-heptenal, all of them could be found at levels above threshold. Different compositional patterns were identified: Sherry wines have large amounts of branched aldehydes but not of (E)-2-alkenals, wines exposed to oxygen can have large amounts of (E)-2-alkenals but not of branched aldehydes, while aged wine and Port have relatively large amounts of both classes of compounds. Different sensory tests confirmed the active sensory role of these compounds and revealed the existence of interactions (additive or synergic) between them and with other wine volatiles. (E)-2-Alkenals are related to flavor deterioration, while branched aldehydes enhance dried fruit notes and mask the negative role of (E)-2-alkenals.

This work presents a thorough study of some aspects critical to the quantitative performance of methods for the determination of volatile aldehydes previously derivatized to pentafluorobenzyl hydroxylamine oximes. The conclusions of the study are further applied to the validation of an optimized procedure for the determination of oxidation-related aldehydes from wine. Aspects studied include the chromatographic injection, the analytical performance of electron-capture detection (ECD) or MS detection, and the way in which the derivatization is carried out. Different injection techniques have been optimized and compared (classical splitless-hot injection; cold splitless; and large volume solvent split injection). All of them were carried out in a programmed temperature vaporization (PTV) injector, with a 350 microL internal volume liner (3.4 mm internal diameter). Classical splitless injection of hexane extracts is troublesome and requires large carrier gas flows (>10 mL min(-1)). Cold splitless injection was clearly superior. Large volume solvent split injection has been also optimized. ECD has been found to lack the necessary selectivity for the determination of unsaturated aldehydes in wine, although the quantitation of several minor aldehydes is possible. MS detection has proven to be superior for the determination of these compounds in wine. The way in which the reagent is applied is also critical and for the case of wine is important to ensure that the reagent is applied after some of the major wine aldehydes have been eliminated. The finally proposed method is extremely sensitive. Method detection limits ranged from 0.002 microg L(-1) (for unsaturated aldehydes) to 0.73 microg L(-1) (for phenylacetaldehyde) and precision (measured as relative standard deviation) is < or =6% in all cases. The method makes it possible to determine quantitatively in a single run the wine aldehydes with sensory significance (isobutyraldehyde, 2-methylbutanal, isovaleraldehyde, (E)-2-hexenal, (E)-2-heptenal, (E)-2-octenal, (E)-2-nonenal, methional and phenylacetaldehyde).

A method for the quantitative determination of octanal, nonanal, decanal, (E)-2-nonenal and (E, Z)-2,6-nonadienal in wine has been developed. In the proposed method, 200 ml of wine percolate through a solid phase extraction (SPE) cartridge packed with 200 mg of LiChrolut EN resins. The interferences are eluted with 60 ml of an aqueous solution containing 40% of methanol and 1% of NaHCO3. In the same SPE cartridge, the corresponding O-(2,3,4,5,6-pentafluorobenzyl)oximes are formed by letting percolate 2 ml of the reagent solution (5 mg ml(-1)). At room temperature the derivatization goes to completion in 15 min. The derivatives are eluted with 2 ml of dichloromethane, and the extract is concentrated and then analyzed by gas chromatography-mass spectrometry (GC-MS). The percentage of recovery in the isolation process is better than 90% in all cases with the exception of octanal, and is independent of the wine studied. In the cases of octanal, nonanal and decanal, the detection limits of the method are determined by the contamination levels of the reagent itself, and vary between 160 and 380 ng l(-1). For (E)-2-nonenal and (E, Z)-2,6-nonadienal, the detection limits were 12 and 20 and ng l(-1), respectively. The linearity of the method upheld until 10 microg l(-1) and was satisfactory in all cases. The reproducibility of the method is independent of the concentration and ranges from 30 to 190 ng (l(-1). The method has been applied to the analysis of these components in several wine samples. With the exception of (E, Z)-2,6-nonadienal, all the components can reach concentrations above their corresponding odor threshold values.

Abstract: An analytical method was developed for C8–C11 aliphatic aldehydes in wine consisting of solid phase extraction (SPE) followed by multidimensional gas chromatography/mass spectrometry (MDGC/MS). The method achieves low detection limits (<30ngL−1), minimises problems of blank contamination and shows high repeatability (RSD%<5%), but strong matrix effects were noticed during validation. These matrix effects were attributed to strong interactions between aliphatic aldehydes and other matrix elements. Three fractions were differentiated: free extractable aldehydes, aldehydes bound in hydrophilic complexes (extractable in the presence of acetaldehyde) and aldehydes bound in hydrophobic complexes (extractable in the presence of heptanal). The distribution of the three aldehyde species in wine samples was estimated using a surrogate (3,5,5-trimethylhexanal) and an internal standard (methyl phenylacetate) in double determinations (directly and after incubation with 1000mgL−1 acetaldehyde). These components had a clear additive sensory effect in mixtures and odour thresholds in wine were very low. This caused that although they were present at very low levels, in 2 out of 24 white wine samples were clearly above threshold, and in six more were at levels close to threshold. These results suggest that these components are active contributors to the citrus fruit notes of some white wines. [Copyright &y& Elsevier]

Abstract: In wine making, the redox phenomena are responsible for profound changes in the wine’s chemical composition. Twenty wines set has been selected trying to cover a wide range of behaviors against to oxidation–reduction phenomenon. Free SO2 level was adjusted to the maximum level found to avoid its influence from the wine oxidative trend. Samples of this set of wines were submitted to extreme conditions during 1month. Samples were taken in different days for sensorial and chemical analysis. It is proved that red wines oxidation velocity is much higher than white wines. Aldehydes were quantified by gas chromatography–negative ion mass spectrometry (GC–NCI–MS) using a previous derivatization procedure. In conclusion, it can be said that the speed at which the sensory characteristics of wine changes are loosely related to the production of relevant odor active aldehydes, particularly to levels of methional and phenylacetaldehyde. In general, red wines produce those aldehydes during oxidation at a much higher speed than white wines, which is in agreement with the observed changes in sensory properties. However, it was not possible to find good correlations between sensory changes and aldehyde production within the red or white subsets. [Copyright &y& Elsevier]

A method for the determination of wine carbonyl compounds with 5–8 carbon atoms including 3-methylbutanal, E-2-hexenal, E-2-heptenal, E-2-octenal and phenylacetaldehyde has been developed. Aldehydes are retained in a solid phase extraction cartridge and derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine takes place in the same cartridge at room temperature (25 °C) in 15 min. The corresponding oximes are further eluted and determined by gas chromatography–mass spectrometry. Isolation, derivatization and elution conditions were examined. Recoveries from red wines are all >94%, and are consistent from wine to wine. For white wines, recoveries for E-2-heptenal, E-2-octenal and phenylacetaldehyde are 80–85%, but are consistent from wine to wine. Precision (measured as relative standard deviation) is <7% in all cases. Method detection limits ranged from 0.12 to 0.70 μg L-1 and linearity holds at least up to 60 μg L-1 with r2 in the range 0.9957–0.9997. The method has been applied to the determination of these components in several wine samples. Results show that phenylacetaldehyde, E-2-octenal and 3-methylbutanal can be found at concentrations above their corresponding odor thresholds in normal wines. [Copyright &y& Elsevier]