Identification, Quantitation, and Sensory Evaluation of Thiols in Bordeaux Red Wine with Characteristic Aging Bouquet.

Great Bordeaux red wines are known for their distinctive aging bouquet. However, the nature of volatile chemicals underpinning this sensory expression is not fully understood. This work investigated the empyreumatic aging bouquet of a collection of premium Bordeaux red wines using silver-ion (Ag+) solid-phase extraction, cryogenic heart-cutting multidimensional gas chromatography mass spectrometry/olfactometry, and comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry. In doing so, a substantial number of "meaty" odors were revealed. Three detected "meaty" notes were tentatively or unequivocally attributed to furan thiols. Among them, 2-methyltetrahydrofuran-3-thiol (1) with a pleasant "meaty" aroma was reported in wine for the first time. Its trans isomer (trans-1a) was resolved from its racemate by chemical modification, which confirmed its presence in wine. The odor detection threshold of trans-1a in the model wine was determined at 55 ng/L. Moreover, an additive effect between 1 and literature-known 2-methyl-3-furanthiol was observed. By a new ultra high-performance liquid chromatography quadrupole Orbitrap high-resolution mass spectrometry method, the concentration of trans-1a, in addition to those of 2-methyl-3-furanthiol and 2-furfuryl thiol, was measured in the wines at ng/L levels.

Impact of the Closure Oxygen Transfer Rate on Volatile Compound Composition and Oxidation Aroma Intensity of Merlot and Cabernet Sauvignon Blend: A 10 Year Study.

This study evaluated the impact of closure type on unoaked 100 %-Merlot, oak-aged 70%-Merlot/30%-Cabernet Sauvignon, and 30%-Merlot/70%-Cabernet Sauvignon during a 10 year period. Closures were microagglomerate corks, screw caps, and synthetics with the known oxygen transfer rate (OTR), ranging from 0.1 to 4.6 mg/y, including natural corks. Oxidation intensity perception, dissolved oxygen, sulfite, and 3-methyl-2,4-nonanedione (MND) were monitored on a regular basis. After 10 years of aging, additional aroma impact markers were evaluated (3-sulfanylhexan-1-ol, H2S, DMS, methional, and phenylacetaldehyde). Low OTR levels (≤0.3 mg/y) delayed the oxidation of red wines in this long-term experiment. In addition, our results led us to hypothesize that the MND concentration in young wines might be linked with their ability to produce it during bottle aging that is with their aging potential. Finally, we found that the kinetic accumulation of MND in wines was first strongly impacted by its intrinsic composition and thereafter by the OTRT0 of the stopper.

Impact of Closure OTR on the Volatile Compound Composition and Oxidation Aroma Intensity of Sauvignon Blanc Wines during and after 10 Years of Bottle Storage.

The oxygen transfer rate (OTR) of closures is a well-known parameter impacting the quality of Sauvignon blanc wines (SBw) within the first years of storage, but little research has been published on its long-term effects. The chemical changes in oxidation odor intensity in three SBw sealed with natural cork and other closures that had different known OTRs, ranging from <0.1 to 4.6 mg/year, were monitored over a 10 year period. During aging, free SO2 and 3-sulfanylhexanol loss, concomitant with increases in dissolved O2, OD420, and sotolon, were correlated with closure OTR levels. After 10 years of aging, sensory analysis was conducted, supported by additional chemical analysis of aroma impact markers, including methional, phenylacetaldehyde, 2-furanmethanthiol, 4-methyl-4-sulfanylpentan-2-one, ethyl-2-sulfanylacetate, and hydrogen sulfide, as well as total SO2 and dissolved CO2. These analyses revealed that selected SBw were protected from oxidation over a 10 year aging period, provided that the closure OTR did not exceed 0.3 mg/year.

Methyl salicylate, a grape and wine chemical marker and sensory contributor in wines elaborated from grapes affected or not by cryptogamic diseases.

Methyl salicylate (MeSA) is a plant metabolite that induces plant defence resistance and an odorous volatile compound presenting green nuances. This volatile compound was shown to be present in wine samples, sometimes at concentrations above its olfactory detection threshold. MeSA is localized in grapes, particularly in the skins and stems, and is extracted during red wine vinification. It was detected at the highest concentrations in wines of several grape varieties, made from grapes affected by cryptogamic diseases, namely downy mildew caused by Plasmopara viticola, and black rot caused by Guignardia bidwellii. It has also been detected in wines from vines affected by Esca, a Grapevine Trunk Disease. MeSA can also be considered to be a chemical marker in grapes and wine indicative of the level of development of several vine cryptogamic diseases.

Comparison of electron and chemical ionization modes for the quantification of thiols and oxidative compounds in white wines by gas chromatography-tandem mass spectrometry.

A rapid, sensitive method for assaying volatile impact compounds in white wine was developed using gas chromatography-tandem mass spectrometry (GC-MS/MS) technology, with a triple quadrupole analyzer operating in chemical ionization and electron impact mode. This GC-MS/MS method made it possible to assay volatile thiols (3SH: 3-sulfanylhexanol, formerly 3MH; 3SHA: 3-sulfanylhexyl acetate, formerly 3MHA; 4MSP: 4-methyl-4-sulfanylpentan-2-one, formerly 4MMP; BM: benzenemethanethiol; E2SA: ethyl 2-sulfanylacetate; and 2FM: 2-furanmethanethiol) and odoriferous oxidation markers (Sotolon: 4,5-dimethyl-3-hydroxy-2(5)H-furanone, methional, and phenylacetaldehyde) simultaneously in dry white wines, comparing electron impact (EI) and chemical ionization (CI) modes. More molecular ions were produced by CI than protonated molecules, despite the greater fragmentation caused by EI. So, even using the best reactant gas giving the highest signal for thiols, EI was the best ionization mode, with the lowest detection limits. For all compounds of interest, the limits of quantification (LOQ) obtained were well below their detection thresholds (ranging from 0.5 to 8.5ng/L for volatile thiols and 65-260ng/L for oxidation markers). Recovery rates ranged from 86% to 111%, reproducibility (in terms of relative standard deviation; RSD) was below 18% in all cases, with correlation coefficients above 0.991 for all analytes. The method was successfully applied to the analysis of compounds of interest in Sauvignon Blanc wines from a single estate and ten different vintages.

Involvement of Dimethyl Sulfide and Several Polyfunctional Thiols in the Aromatic Expression of the Aging Bouquet of Red Bordeaux Wines.

The development of an aromatic bouquet during fine wine aging depends on complex transformations occurring in a reductive atmosphere, favorable to the formation and preservation of sulfur odorants, such as dimethyl sulfide (DMS) and polyfunctional thiols. The aim of this study was to address their role in the occurrence, evolution, and perceived sensory nuances of the aging bouquet of red Bordeaux wines. These compounds were quantified in 24 wines and scored by a professional wine panel for the degree to which they reflected the aging bouquet olfactory concept. Partial least square (PLS) analysis, combining sensory and quantitative chemical data, predicted that DMS, 2-furanmethanethiol, and 3-sulfanylhexanol concentrations correlated with the typicality score, discriminating highly-typical wines from less-typical ones. Several vintages from three vineyards were then subjected to sensory and chemical analysis to determine how aging bouquet typicality and the intensity of five key aromatic notes (undergrowth, truffle, fresh fruit, toasted, and empyreumatic) evolved during bottle storage in relation to these three sulfur odorants. PCA analysis emphasized their combined impact on aging bouquet typicality and their contribution to undergrowth, truffle, and empyreumatic attributes.