Aging effects and grape variety dependence on the content of sulfur volatiles in wine

Thirteen sulfur compounds (boiling points from 35 to 231 degrees C), usually considered as possible off-flavoring volatiles, were quantified by a concurrent headspace-solid phase microextraction method coupled with gas chromatography-mass spectrometry (HS-SPME/GC-MS) on 80 not off-flavoring wines of four varieties (Merlot, Marzemino, and Teroldego as red wines and Chardonnay as a white one) and of five vintages produced in the North Italian Trentino region. The results of the research, the first Italian data-bank per variety on such volatiles, allow us to make a comparison with the data of other winegrowing areas, to investigate the aging effect on the considered volatiles, and, finally, to try a variety discrimination using statistical procedures. Dimethyl sulfide, 3-(methylthio)-1-propanol, diethyl sulfide, and diethyl disulfide were found to increase with time whereas 2-mercaptoethanol and ethylmercaptan showed a decreasing trend. Furthermore, the concentration of several compounds was found to be dependent on the variety. For instance, sulfide, disulfides, benzothiazole, and thioalcohols are at higher levels in Merlot wines, whereas thiols and thioacetates are more abundant in Marzemino and Teroldego wines. Chardonnay products, well apart from the other wines, are the poorest in 3-(methylthio)-1-propanol and rather rich in dimethyl disulfide and in diethyl disulfide, mostly in the aged wines. Applying the principal component analysis to the data, it was possible to demonstrate that Chardonnay and Merlot wines are well-discriminated from the Italian native varietal wines, which on their turn are only partially distinguishable among them. A contribution of these compounds to the variety characteristics of wine is reasonable.     

Oxygen Consumption and Development of Volatile Sulfur Compounds during Bottle Aging of Two Shiraz Wines. Influence of Pre- and Postbottling Controlled Oxygen Exposure

The evolution of different volatile sulfur compounds (VSCs) during bottle maturation of two Shiraz wines submitted to controlled oxygen exposure prior to bottling (through micro-oxygenation, MOX) and postbottling (through the closure) was investigated. H(2)S, methyl mercaptan (MeSH), and dimethyl sulfide (DMS) were found to increase during aging. Lower postbottling oxygen exposure, as obtained by different degrees of oxygen ingress through the closure, resulted in increased H(2)S and methyl mercaptan. In one wine MOX increased the concentration of H(2)S and methyl mercaptan during maturation. Dimethyl disulfide and DMS were not affected by any form of oxygen exposure. Overall, postbottling oxygen had a stronger influence than MOX on the evolution of VSCs. Data suggest that dimethyl disulfide was not a precursor to methyl mercaptan during bottle maturation. For the two wines studied, a consumption of oxygen of 5 mg/L over 12 months was the most effective oxygen exposure regimen to decrease accumulation of MeSH and H(2)S during bottle aging.     

Volatile compounds from potato-like model systems

The volatile reaction products of aqueous mixtures comprising combinations of methionine, glucose, linoleic acid, and starch heated in a modified Likens-Nickerson apparatus were extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The majority of volatile compounds were formed from linoleic acid degradation, hexanal, 2,4-decadienal, and 2-pentylfuran being identified in the greatest amounts. Dimethyl disulfide and dimethyl trisulfide were detected in every system containing methionine. 3-(Methylthio)propanal (methional) and other sulfur compounds were detected when methionine was heated with another precursor. No binding of volatile compounds to starch was observed; rather, starch appeared to act as an additional source of reactive carbohydrate. Almost all the components identified have been identified among the aroma components of cooked potato. No pyrazines, pyridines, or thiazoles were identified, probably due to the relatively low temperature/high moisture conditions.     

Influence of temperature, modified atmosphere packaging, and heat treatment on aroma compounds in broccoli

The aroma compounds in broccoli stored in different modified atmospheres were studied. The packaging materials used were oriented polypropylene (OPP), poly(vinyl chloride) (PVC), and low-density polyethylene (LDPE) containing an ethylene-absorbing sachet. All samples were stored for either 1 week at a constant temperature of 10 degrees C or for 3 days at 4 degrees C, followed by 4 days at 10 degrees C. The atmospheres that developed inside the packaging materials differed significantly. The broccoli samples were analyzed raw and after cooking, with regard to volatile compounds, using gas-phase (headspace) extraction followed by gas chromatography-mass spectrometry (GC-MS) and GC-olfactometry. Dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), hexanal, 3-cis-hexen-1-ol, nonanal, ethanol, and a group of thiocyanates were selected for a detailed study because these compounds cause off-odor and can be used as indicators of stress. Significant differences were found in the aroma profiles of the broccoli samples relative to the packaging materials used for storage. Storage in OPP (14% O(2), 10.5% CO(2)) resulted in most of the off-odors, while storage in LDPE (6% O(2), 7% CO(2)) and PVC (17.9% O(2), 4% CO(2)) was found to maintain the concentration of DMS, DMDS, and DMTS during storage. Heat treatment of the broccoli increased the content of aroma compounds as well as the number of compounds containing sulfur.     

Quality and aromatic sensory descriptors (mainly fresh and dry fruit character) of Spanish red wines can be predicted from their aroma-active chemical composition

A satisfactory model explaining quality could be built in a set of 25 high quality Spanish red wines, by aroma-active chemical composition. The quality of the wines was positively correlated with the wine content in fruity esters, acids, enolones, and wood derived compounds, and negatively with phenylacetaldehyde, acetic acid, methional, and 4-ethylphenol. Wine fruitiness was demonstrated to be positively related not only to the wine content on fruity esters and enolones, but to wine volatile fatty acids. Fruitiness is strongly suppressed by 4-ethylphenol, acetic acid, phenylacetaldehyde, and methional, this involved in the perception of dry-fruit notes. Sensory effects were more intense in the presence of β-damascenone and β-ionone. A satisfactory model explaining animal notes could be built. Finally, the vegetal character of this set of wines could be related to the combined effect of dimethylsulfide (DMS), 1-hexanol, and methanethiol.     

Model aging and oxidation effects on varietal, fermentative, and sulfur compounds in a dry botrytized red wine

From harvest until wine arrives to the consumer, oxygen plays a crucial role in the definition of the final aroma. In the present research, the effect of the model oxidative aging on a dry red Botrytis wine, such as Italian Amarone, was considered. Amarone wine was submitted to model oxidative aging and then analyzed with two different approaches (SPE-GC-MS and HS-SPME/GC-MS). The same sampling plan was adopted to study the model aging of the same Amarone wine in anaerobic conditions. The HS-SPME/GC-MS method was applied to investigate for the first time the effect of the oxidative aging on a vast number of fermentative sulfur compounds. This research highlighted peculiar evolutions for several volatile compounds. In particular, benzaldehyde showed a sensitive increment during the oxidative aging, with a rate much higher than that reported for non-Botrytis red wines. On the other hand, several sulfides (dimethyl sulfide, 3-(methylthio)-1-propanol, etc.) disappeared after just 15 days of oxidative aging. A wine oxidation marker such as 3-(methylthio)-propanal was not found in any of the oxidized wines; conversely methionol-S-oxide was tentatively identified. This evidence has not been mentioned in the literature. A possible involvement of grape withering process and Botrytis in these mechanisms was supposed: a dry red wine, produced from the same but without any grape withering process and Botrytis infection (e.g., Bardolino wine), was submitted to oxidative aging and analysis. This red wine showed an evolution similar to those reported in the literature for dry red wines but significantly different from the Amarone wine.     

Comparison of three lychee cultivar odor profiles using gas chromatography-olfactometry and gas chromatography-sulfur detection

Odor volatiles in three major lychee cultivars (Mauritius, Brewster, and Hak Ip) were examined using gas chromatography-olfactometry, gas chromatography-mass spectrometry, and gas chromatography-pulsed flame photometric detection. Fifty-nine odor-active compounds were observed including 11 peaks, which were associated with sulfur detector responses. Eight sulfur volatiles were identified as follows: hydrogen sulfide, dimethyl sulfide, diethyl disulfide, 2-acetyl-2-thiazoline, 2-methyl thiazole, 2,4-dithiopentane, dimethyl trisulfide, and methional. Mauritius contained 25% and Brewster contained 81% as much total sulfur volatiles as Hak Ip. Cultivars were evaluated using eight odor attributes: floral, honey, green/woody, tropical fruit, peach/apricot, citrus, cabbage, and garlic. Major odor differences in cabbage and garlic attributes correlated with cultivar sulfur volatile composition. The 24 odor volatiles common to all three cultivars were acetaldehyde, ethanol, ethyl-3-methylbutanoate, diethyl disulfide, 2-methyl thiazole, 1-octen-3-one, cis-rose oxide, hexanol, dimethyl trisulfide, alpha-thujone, methional, 2-ethyl hexanol, citronellal, (E)-2-nonenal, linalool, octanol, (E,Z)-2,6-nonadienal, menthol, 2-acetyl-2-thiazoline, (E,E)-2,4-nonadienal, beta-damascenone, 2-phenylethanol, beta-ionone, and 4-vinyl-guaiacol.     

Kinetics of oxidative degradation of white wines and how they are affected by selected technological parameters

The negative effects of oxygen on white wine quality and the various factors which influence it (including temperature, dissolved oxygen, pH, and free SO(2)) are well documented both at the sensory and compositional levels. What is less defined is the quantitative relationship between these parameters and the kinetics of the development of the negative effects of oxidation. The experiment presented here attempts to generate data which can be used to predictively model the oxidative degradation of white wines. Bottled wines were submitted to extreme conditions (45 degrees C temperature, O(2) saturation) during 3 months witth samples taken every 15 days for both sensorial and chemical analysis (GC-O/FPD/MS, 420 nm). The synergistic effects of increasing temperature and O(2) at lower pH are evident, both on the decrease in levels of terpene alcohols and norisoprenoids (which impart floral aromas), and on the development of off-flavors such as "honey-like", "boiled-potato", and "farm-feed" associated with the presence of phenylacetaldehyde, methional, and 1,1,6-trimethyl-1,2-dihydronaphthalene.     

Clues about the role of methional as character impact odorant of some oxidized wines

A young white wine that had undergone spontaneous oxidation and showed a strong off-flavor reminiscent of cooked vegetables was demixed by salting out to obtain an ethanolic extract that retained the off-flavor of the wine, as was demonstrated by sensory analysis. This extract, together with a second one obtained from a non-oxidized wine sample, were chromatographed into a reversed-phase HPLC column using a water/ethanol gradient. The column effluents were collected in 14 different fractions that were evaluated for smell. Four fractions were found to differ between oxidized and non-oxidized wine, but only one showed a clear cooked vegetables off-flavor and, when added to a non-oxidized wine, made it significantly more similar to the oxidized wine. The fraction was analyzed by GC-MS-olfactometry, which made it possible to identify methional as the single important odorant of the fraction. The odor threshold of methional in a synthetic wine was found to be 0.5 microg L(-)(1). The analytical determination of methional through GC-FPD in several oxidized and non-oxidized wines showed that, in the former, methional can reach more than 200 Odor Units, whereas in the non-oxidized samples, it was not possible to detect methional. The methional concentration was found to increase in wines spiked with both methionol or methionine, which suggests that it can be formed from direct peroxidation of methionol or via Strecker degradation of methionine mediated, probably, by o-quinones formed during wine oxidation.     

Contribution of dimethyl sulfide to the aroma of Syrah and Grenache Noir wines and estimation of its potential in grapes of these varieties

The contribution of dimethyl sulfide (DMS) to the aroma of Syrah and Grenache Noir wines from the Rhone Valley of France was investigated by sensory analysis, and its levels in these wines were measured. The potential DMS in the corresponding grapes and wines, susceptible to release during wine aging, was evaluated. Free DMS and potential DMS assessed by a heat-alkaline treatment were measured in grape juices and wines by SPME-GC-MS using methods previously reported and slightly modified. A relationship between potential DMS from grapes and the total DMS levels in wine was demonstrated. Furthermore, a linear regression between the ratio of free DMS levels to these total DMS levels in wine and time of storage was found. Free and potential DMS levels in grapes and wines depended on grape variety, vintage, and vine location. DMS imparted a noticeable and complex contribution to the aroma of the wines investigated, depending on the mode of sensory perception used, either before or after glass swirling. It significantly enhanced the fruity notes of the wines, and additional truffle and black olive notes.     

Formation of volatile sulfur compounds by microbial decomposition of sulfur-containing amino acids in soils

Evolution of volatile sulfur compounds from soils treated with S-containing amino acids was studied by sensitive gas chromatographic techniques involving use of a flame photometric detector fitted with a sulfur filter. The following volatile sulfur compounds were identified as products of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions: methyl mercaptan, dimethyl sulfide and dimethyl disulfide (evolved from soils treated with methionine, methionine sulfoxide, methionine sulfone or S-methyl cysteine); ethyl mercaptan, ethyl methyl sulfide and diethyl disulfide (evolved from soils treated with ethionine or S-ethyl cysteine); and carbon disulfide (evolved from soils treated with cystine, cysteine, lanthionine or djenkolic acid). Small amounts of dimethyl sulfide and carbon disulfide were evolved from soils treated with homocystine, and trace amounts of carbonyl sulfide were evolved from soils treated with lanthionine or djenkolic acid. No volatile sulfur compounds were evolved from soils treated with cysteic acid, taurine, or S-methyl methionine. The amounts of sulfur volatilized from soils treated with the 14 S-containing amino acids studied represented from less than 0·1 per cent to more than 50 per cent of the sulfur added as amino acid. Hydrogen sulfide could not be detected as a gaseous product of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions.     

Sulfur volatiles in guava (Psidium guajava L.) leaves: possible defense mechanism

Volatiles from crushed and intact guava leaves (Psidium guajava L.) were collected using static headspace SPME and determined using GC-PFPD, pulsed flame photometric detection, and GC-MS. Leaf volatiles from four common citrus culitvars were examined similarly to determine the potential component(s) responsible for guava's protective effect against the Asian citrus psyllid (Diaphorina citri Kuwayama), which is the insect vector of Huanglongbing (HLB) or citrus greening disease. Seven sulfur volatiles were detected: hydrogen sulfide, sulfur dioxide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), methional, and dimethyl trisulfide (DMTS). Identifications were based on matching linear retention index values on ZB-5, DB-Wax, and PLOT columns and MS spectra in the case of DMDS and DMS. DMDS is an insect toxic, defensive volatile produced only by wounded guava but not citrus leaves and, thus, may be the component responsible for the protective effect of guava against the HLB vector. DMDS is formed immediately after crushing, becoming the major headspace volatile within 10 min. Forty-seven additional leaf volatiles were identified from LRI and MS data in the crushed guava leaf headspace.     

Relationship between potentiometric measurements, sensorial analysis, and some substances responsible for aroma degradation of white wines

Oxidative degradation of white wines can be described sensorially as developing from a loss at positive aroma characteristics, through the development of negative aromas to a linel stage of chromatic alterations. This work attempts to relate the oxidation "status" evaluate by potentiometric titrations, with sensorial degradation and the levels of substances responsible for "off-flavors", such as methional and phenylacetaldehyde. The potentiometric titration employed measures the most powerful antioxidants of white wines (e.g., those which more rapidly consume oxygen). Considering that aromatic precedes chromatic degradation, resistance to oxidation (ROX) constitutes a useful indicator of resistance to oxidation. Sensorial degradation (ID), potentiometric measures, and volatiles were determined both in samples submitted to a "forced aging" protocol and normal aged white wines. High correlation values were observed between ROX and the ID, in both sets (r > 0.87). ID is better explained by ROX values than by the indicated wine age or by the "degree of browning" (Abs = 420 nm). It was also observed that in samples with ROX values higher than 10, the concentration of methional and phenylacetaldehyde were above their respective odor threshold. Finally, it was observed that there is a relationship between oxygen consumption and the respective ROX. Although these results seem very promising, they needed to be further complemented in order to estimate the shelf life of a white wine using potentiometric titrations.     

Volatile and color composition of young and model-aged Shiraz wines as affected by diammonium phosphate supplementation before alcoholic fermentation

A Shiraz must with low yeast assimilable nitrogen (YAN) was supplemented with two concentrations of diammonium phosphate (DAP) and then fermented with maceration on grape skins. The nonvolatile, volatile, and color composition of the final wines were investigated. Ethanol and residual sugars were not affected by DAP supplementation, while glycerol, SO 2, and residual YAN increased and acetic acid decreased. DAP-supplemented treatments gave rise to higher concentrations of acetates, fatty acids, and fatty acid ethyl esters but lower concentrations of branched-chain fatty acids and their ethyl esters. No major difference between treatments was observed for higher alcohols, monoterpenes, norisoprenoids, and low-molecular-weight sulfur compounds. DAP-supplemented fermentations resulted in wines with higher concentrations of malvidin-3-glucoside, higher color intensity, and altered color tonality. Model aging studies indicated that higher concentrations of esters are still present in wines from the DAP-treated fermentations after aging. DAP supplementation also resulted in increased concentrations of dimethyl sulfide after model aging. It can be concluded that DAP treatment of a low YAN must fermented by maceration on skins can significantly affect wine color, aroma, and flavor.     

Formation of furfurylthiol exhibiting a strong coffee aroma during oak barrel fermentation from furfural released by toasted staves

Furfurylthiol (FFT) is formed in white wines during alcoholic fermentation in the barrel from the furfural released by toasted staves. The quantity of furfural released into the must has a decisive effect on the quantity of FFT in the finished wine. Wines fermented in new barrels thus contain larger quantities of FFT than those fermented in used barrels. Fermentation conditions favorable to an excess production of H(2)S (hydrogen sulfide) by the yeast promote the formation of this volatile thiol. The presence of this volatile thiol in white wines is, therefore, closely related to the yeast's sulfur metabolism.     

Identification of impact odorants in Bordeaux red grape juice, in the commercial yeast used for its fermentation, and in the produced wine

The aroma extract dilution analysis method was used to detect the impact odorants of Bordeaux Cabernet Sauvignon and Merlot wines extracts, as well as those of the extracts of the corresponding Cabernet Sauvignon juice and dry yeasts used for its fermentation. The wines and the yeasts were extracted using dichloromethane, and the juice was extracted using Amberlite XAD-2. Structural identification of the impact odorants using gas chromatography-mass spectrometry and atomic emission detection (sulfur acquisition) was achieved after enrichment of these extracts by silica gel and Affi-Gel 501 chromatography. The same odorants (with the exception of dimethyl sulfide among 48) were detected in both wine extracts, with about the same flavor dilution (FD) factors. The 18 impact odorants detected in the Cabernet Sauvignon juice and dry yeast extracts were also found in the wine extracts. The odorants with the highest FD factors were 3-(methylsulfanyl)propanal, (E,Z)-nona-2, 6-dienal, and decanal in the juice extract, 2-methyl-3-sulfanylfuran, 3-(methylsulfanyl)propanal, 2-/3-methylbutanoic acids, and phenylethanal in the dry yeast extract, and 2-/3-methylbutanols, 2-phenylethanol, 2-methyl-3-sulfanylfuran, acetic acid, 3-(methylsulfanyl)propanal, 2-/3-methylbutanoic acids, beta-damascenone, 3-sulfanylhexan-1-ol, Furaneol, and homofuraneol in the wine extracts. Determination of the odor thresholds of some of these impact odorants was carried out.     

An assessment of the role played by some oxidation-related aldehydes in wine aroma

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.     

Study of the formation mechanisms of some volatile compounds during the aging of sweet fortified wines.

Sweet fortified wines, traditionally aged under strong oxidation conditions, have a characteristic aroma. An experimental laboratory study investigated the aging of red and white sweet fortified wines under various conditions. The formation of various molecules, previously identified as characteristic of the aroma of this type of wine, was monitored by analysis. The development of these compounds during accelerated aging was affected by oxidation and the color of the wine. Among the molecules studied, sotolon [3-hydroxy-4, 5-dimethyl-2(5H)-furanone] was one of the few molecules present in concentrations above the perception threshold, in both red and white wines. Buildup was strongly affected by the presence of oxygen in white wine subjected to accelerated aging. (Ethoxymethyl)furfural, formed from 5-(hydroxymethyl)furfural, and furfural, derived from sugars, are also involved in the aroma of sweet fortified white wines aged in oxygen-free conditions. The substances most characteristic of accelerated aging of sweet fortified red wines were 5-(hydroxymethyl)furfural, acetylformoin, and hydroxymaltol, the formation of which is affected by oxidation, and dihydromaltol, formed in the absence of oxidation.     

Aroma extract dilution analysis of Cv. Marion (Rubus spp. hyb) and Cv. Evergreen (R. laciniatus L.) blackberries

Cultivar Marion and Evergreen blackberry aromas were analyzed by aroma extract dilution analysis. Sixty-three aromas were identified (some tentatively) by mass spectrometry and gas chromatography-retention time; 48 were common to both cultivars, and 27 have not been previously reported in blackberry fruit. A comparison of cultivars shows that both have comparable compound types and numbers but with widely differing aroma impacts, as measured by flavor dilution (FD) factors. Ethyl 2-methylbutanoate, ethyl 2-methylpropanoate, hexanal, furanones (2,5-dimethyl-4-hydroxy-3-(2H)-furanone, 2-ethyl-4-hydroxy-5-methyl-3-(2H)-furanone, 4-hydroxy-5-methyl-3-(2H)-furanone, 4,5-dimethyl-3-hydroxy-2-(5H)-furanone, and 5-ethyl-3-hydroxy-4-methyl-2-(5H)-furanone), and sulfur compounds (thiophene, dimethyl sulfide, dimethyl disulfide, dimethyl trisulfide, 2-methylthiophene, and methional) were prominent in Evergreen (FD 512-2048). Except for ethyl 2-methylpropanoate, these same compounds were also prominent in Marion, but the FD factors varied significantly (FD 8-256) from Evergreen. The aroma profile of blackberry is complex, as no single volatile was unanimously described as characteristically blackberry.     

Identification of characteristic aroma components of Thai fried chili paste

Three forms of Thai fried chili pastes (CP) were prepared, consisting of an unheated CP (UH-CP), a CP heated at 100 degrees C for 25 min (H25-CP, typical product), and a CP excessively heated for 50 min (H50-CP). The potent odorants in the CPs were investigated by two gas chromatography-olfactometry methods: dynamic headspace dilution analysis (DHDA) and aroma extract dilution analysis (AEDA). DHDA revealed that the predominant odorants in heated CPs were mainly sulfur-containing compounds, followed by lipid-derived compounds, Strecker aldehydes, and Maillard reaction products. Dimethyl sulfide, allyl mercaptan, 2- (or 3-) methylbutanal, ally methyl sulfide, 2,3-butanedione, 3,3'-thiobis(1-propene), and methyl propyl disulfide were among the most potent headspace odorants detected by DHDA. By AEDA, 2-vinyl-4 H-1,3-dithiin and diallyl trisulfide had the highest FD factors in H25-CP. On the basis of their high FD factors by both GCO methods, the predominant odorants in H25-CP were 3-vinyl-4 H-1,2-dithiin, allyl methyl disulfide, and allyl methyl trisulfide. Furthermore, dimethyl trisulfide and diallyl disulfide had the highest odor activity values in H25-CP, suggesting that these were also potent odorants in CP. In addition, methional, 3-methylbutanoic acid, 4-hydroxy-2,5-dimethyl-3-(2 H)-furanone, and 3-hydroxy-4,5-dimethyl-2( 5H)-furanone (sotolon) were indicated as potent thermally derived odorants of H25-CP.