New methodology for removing carbonyl compounds from sweet wines

Sweet white wines from botrytized grapes present high SO2 levels because of their high sulfur dioxide binding power. The objective of this work was to develop a new method for reducing this binding power by partially eliminating the carbonyl compounds naturally present in these wines that are responsible for this phenomenon. A selective liquid-solid removal technique was developed. Phenylsulfonylhydrazine was selected as the best candidate for removing carbonyl compounds. Its reactivity in the presence or absence of sulfur dioxide was verified in model media containing acetaldehyde, pyruvic acid, and 2-oxoglutaric acid, some of the main carbonyl compounds responsible for the SO2 binding power of sweet wines. The scavenging function was grafted on porous polymer supports, and its efficiency was evaluated in model wines. Dependent upon the supports used, different quantities of carbonyl compounds (over 90% in some cases) were removed in a few days. The presence of sulfur dioxide delayed removal without changing its quality. The results obtained showed that the method removed carbonyl compounds efficiently and was applicable to wines at any stage in winemaking.     

Effect of different strains of Saccharomyces cerevisiae on production of volatiles in Napa Gamay wine and Petite Sirah wine

Napa Gamay grapes were fermented with four different strains of the yeast Saccharomyces cerevisiae (VL1, MI16, Fermirouge, and RA17). Petite Sirah grapes were fermented with seven different strains of the same yeast (BM45, Fermirouge, RA17, NI, CX3079, A350, and A796). Volatile compounds formed in the wines were analyzed by gas chromatography/mass spectrometry. Volatile compounds found in both wines were alcohols, esters, and acids, as well as some miscellaneous compounds. Isoamyl alcohol was the compound found in the highest relative amount with all four yeast strains in the Napa Gamay wines, followed by 2-phenyl ethanol, monoethyl succinate, and hexanoic acid. The relative amounts of isoamyl alcohol ranged from 30.84% (VL1) to 43.28% (RA17). Major volatile compounds found in Petite Sirah wines were isoamyl alcohol, 2-phenyl ethanol, 2-hydroxy ethyl propanoate, monoethyl succinate, and octanoic acid. The several esters, including 2-hydroxyethyl propanoate, may contribute to the fruity flavor of Petite Sirah wines. Overall, the S. cerevisiae yeast strains used to ferment Napa Gamay grapes and Petite Sirah grapes produced the same major components, with certain variations in formation levels.     

Influence of prefermentative treatments to the major volatile compounds of Assyrtiko wines

A study of the volatile fraction of Assyrtiko wines, using gas chromatography coupled with olfactometry, was realized. Twenty-seven volatile compounds were identified as potent odorants, most of them originating from the fermentation process. Quantification of the major volatile compounds was realized developing a rapid analytical method based on fractionation of a 50 mL wine aliquot using C 18-reversed phase adsorbent. After elution of the volatile compounds with pentane-diethyl ether and concentration under nitrogen, the final wine extract was injected in a gas chromatography-flame ionization detection system. The method allows satisfactory determination of more than 15 volatile compounds of wine. The linearity of the method gave a typical r (2) between 0.990 and 0.999, while reproducibility ranged from 5.1 to 12.2% (as relative standard deviation) with 9.5% as the average. The method was applied to wines produced by Assyrtiko grapes (AOC Santorini), for two consecutive years, to compare the effect of skin contact prior to fermentation and the must clarification process. Direct press and skin contact wines were differentiated analytically; however, highly significant differences were not. Inversely, the differences found between direct press/clarified and nonclarified wines were significant. Wines produced by direct press and clarified must presented significantly higher levels of ethylic esters and fusel alcohol acetates but lower fusel alcohol levels, leading probably to more fruity wines. This difference, between clarified and nonclarified grape musts, was not significant in the case of the wines produced by skin contact of Assyrtiko berries. These findings were validated by preference sensory analysis tests.     

Selection of potential impact odorants and sensory validation of their importance in typical chardonnay wines

The aim of the present study was to validate the joint sensory impact of target compounds on the typicality degree of wine. Target compounds were selected from previous gas chromatography-olfactometry analysis. The preliminary experiment consisted in selecting odorants thought to have a positive effect on typical Chardonnay wines. Two sets of target compounds were chosen with regard to expected relationships between their concentrations and typicality scores. Target compounds were quantified in 20 wines. The second experiment was dedicated to the sensory evaluation of aroma models obtained by supplementation in wines. Three Chardonnay wines with intermediate typicality scores were supplemented with 6- or 10-compound combinations. The typicality degree of 24 samples was assessed by expert orthonasal perception. Wines supplemented with the 6-compound combinations were judged to be intermediate, whereas wines including the 10-compound combinations were considered to be quite representative of the Chardonnay concept. Such results confirm the active contribution of the 10 combined target compounds to typical Chardonnay wines.     

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.     

New method for reducing the binding power of sweet white wines

Sulfur dioxide is now considered to be a toxic chemical by most world health authorities. However, it remains an irreplaceable additive in enology for wine conservation, combining antioxidant and antibacterial properties. Sweet white wines from botrytized grapes retain particularly high SO 2 levels due to their high sulfur dioxide binding power. This paper presents a new method for reducing this binding power by removing some of the carbonyl compounds responsible, which are naturally present in these wines. The main carbonyl compounds responsible for the SO 2 binding power of sweet wines were removed, that is, acetaldehyde, pyruvic acid, 2-oxoglutaric acid, and 5-oxofructose. The method retained was selective liquid-solid removal, using phenylsulfonylhydrazine as a scavenging agent. The scavenging function was grafted on different classes of porous polymer supports, and its efficiency was evaluated on sweet white wines under conditions intended to conserve their organoleptic qualities. The results obtained showed that the method was efficient for removing carbonyl compounds and significantly reduced the binding power of the wines. Sensory analysis revealed that this process did not deteriorate their organoleptic qualities.     

Optimization of making barrel-fermented dry muscatel wines

The optimization of making barrel-fermented muscatel wines requires determining what type of must clarification is most suitable for the quality of the wine, as well as what type of barrel will yield the most acceptable wines. This is achieved by adding pectolytic enzymes to clarify part of the muscatel must statically; the rest is clarified by vacuum filtration. The musts obtained are fermented in French and American oak barrels and, once fermentation has ceased, they are kept with their lees for 2 months, with periodic stirring. Eleven conventional parameters and 31 volatile compounds were quantified, and a sensory analysis of the wines was produced, which led us to conclude that static clarification with pectolytic enzymes from the muscatel musts produces the best-structured wines and the larger content of higher alcohols, esters, and terpenic compounds. The wines fermented in American oak barrels received the highest overall marks, which may be due to the greater aromatic complexity given off by the compounds in the wood.     

Carotenoid, chlorophyll, and chlorophyll-derived compounds in grapes and port wines

Carotenoids and chlorophyll-derived compounds in grapes and Port wines were investigated by HPLC-DAD and HPLC-DAD-MS (ESP+) analysis. A total of 13 carotenoid and chlorophyll-derived compounds are formally reported in grapes, 3 are identified for the first time, pheophytins a and b and (13Z)-beta-carotene, and 3 others remain unknown. In Port wines 19 compounds with carotenoid or chlorophyll-like structures are present, 8 still unidentified. The young wines showed higher total carotenoid content and chlorophyll-like compounds compared to aged Ports, with lutein and beta-carotene as major carotenoids. Among samples analyzed of monovarietal Vitis vinifera L. cultivar wines produced with the five most important Douro varieties, Tinta Roriz contained the highest levels of carotenoids and Touriga Franca the lowest. The forced-aging study indicated that lutein was more sensitive to temperature than beta-carotene. Additionally, aged wines showed higher ratios of beta-carotene/lutein concentrations compared to new Ports. Rates of degradation of chlorophyll derivative compounds were higher than those for carotene and lutein.     

Comparative study of polyphenol scavenging activities assessed by different methods

The effect of procyanidin solutions on superoxide anion radicals was studied with an enzymatic method and their EC(50) values were determined. A comparative study of the results suggested that the free radical scavenger potential of these phenolic compounds closely depends on their chemical and stereochemical structures. Oligomeric procyanidins were isolated in different fractions from grapes and wines by low- and high-pressure liquid chromatography. These compounds were found to be efficient free radical scavengers even for the weak concentrations in wines. Their activity in grapes or wines was much stronger than that of other commercially available natural antioxidants (such as ascorbic acid and gallic acid). The effect of tannins isolated from grapes on different radicals was analyzed according to three distinct methods: an enzymatic method for superoxide anion radicals (O(2)(*)(-)), a chemical method for the stable 1,1-diphenyl-2-picrylhydrazyl radical (DPPH(*)), and an immunochemical method to study the scavenging activity of seed procyanidins on DNA lesions induced by the radical HO(*).     

Multiresidue analysis of pesticides in soil by gas chromatography with nitrogen-phosphorus detection and gas chromatography mass spectrometry

A rapid multiresidue method for the simultaneous determination of 25 fungicides and insecticides in soil was developed. Soil samples are extracted by sonication with a water-acetonitrile mixture, and the pesticides are partitioned into dichloromethane. Final determination was made by gas chromatography (GC) with nitrogen-phosphorus detection (NPD). Confirmation analysis of pesticides was carried out by GC-MS in the selected ion monitoring (SIM) mode. The identification of compounds was based on retention time and on comparison of the primary and secondary ions. The average recovery by the GC-NPD method obtained for these compounds varied from 68.5% to 112.1% with a relative standard deviation between 1.8% and 6.2%. The GC-NPD method presents good linearity over the range assayed 50-2000 microg/L, and the detection limit for the pesticides studied varied from 0.1 to 10.4 microg/kg. The proposed method was used to determine pesticide levels in soil samples from experimental greenhouse pepper cultivation.     

Aroma chemical composition of red wines from different price categories and its relationship to quality

The aroma chemical composition of three sets of Spanish red wines belonging to three different price categories was studied by using an array of gas chromatographic methods. Significant differences were found in the levels of 72 aroma compounds. Expensive wines are richest in wood-related compounds, ethyl phenols, cysteinil-derived mercaptans, volatile sulfur compounds, ethyl esters of branched acids, methional, and phenylacetaldehyde and are poorest in linear and branched fatty acids, fusel alcohols, terpenols, norisoprenoids, fusel alcohol acetates, and ethyl esters of the linear fatty acids; inexpensive wines show exactly the opposite profile, being richest in E-2-nonenal, E-2-hexenal, Z-3-hexenol, acetoin, and ethyl lactate. Satisfactory models relating quality to odorant composition could be built exclusively for expensive and medium-price wines but not for the lower-price sample set in which in-mouth attributes had to be included. The models for quality reveal a common structure, but they are characteristic of a given sample set.     

Influence of oak wood on the aromatic composition and quality of wines with different tannin contents

The aromatic compounds associated with aging in wood have been studied in Monastrell wines containing different quantities of tannin. Analyses were carried out before and after a six month period in wooden barrels (225 L) of American and French (Allier) medium-toasted oak. Three classes of wine were made: one from a free-run must; one to which enological tannin was added; and one to which was added the wine obtained by pressing the grape pomaces. The aromas were determined by GC-MS, and the quality was evaluated by a group of expert tasters. The aromatic compounds, some of which came from the wines themselves and others which came from the wood, all increased in concentration by the end of the aging process. The ratio between cis- and trans-whiskylactone contents in wines reflected the different types of oak wood used. The note "vanilla" used by the tasters is probably not totally due to the presence of vanillin. The wines of best quality were those with a natural tannin content which had been aged in American oak, whereas the wines to which enological tannin had been added but aged in the same wood were considered the worst. An equalizing effect on the sensorial wines qualities was seen to result from the use of French oak. The furfural, eugenol, and cis-, and in some cases trans-, whiskylactone contents identified the wines from the different classes of wood. The wood from which the barrels were made had a greater effect on wines differentiation than the tannin content.     

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.     

Odor potency of aroma compounds in Riesling and Vidal blanc table wines and icewines by gas chromatography-olfactometry-mass spectrometry

This study aimed to elucidate the odor potency of aroma compounds in Riesling and Vidal blanc (syn. Vidal) table wines and icewines from the Niagara Peninsula using stir bar sorptive extraction-gas chromatography-olfactometry-mass spectrometry. Dilution analysis determined the most odor-potent compounds in Vidal and Riesling icewines (n = 2) and table wines (n = 2) from a commercial producer. The top 15 odor-potent compounds in each wine were identified and quantified, resulting in 23 and 24 compounds for Riesling and Vidal, respectively. The most odor-potent compounds were β-damascenone, decanal, 1-hexanol, 1-octen-3-ol, 4-vinylguaiacol, ethyl hexanoate, and ethyl 3-methylbutyrate. In general, icewines had higher concentrations of most aroma compounds compared to table wines. Through computation of odor activity values, the compounds with the highest odor activity for the icewines were β-damascenone, 1-octen-3-ol, ethyl octanoate, cis-rose oxide, and ethyl hexanoate. In table wines the highest odor activity values were found for ethyl octanoate, β-damascenone, ethyl hexanoate, cis-rose oxide, ethyl 3-methylbutyrate, and 4-vinylguaiacol. These findings provide a foundation to determine impact odorants in icewines and the effects of viticultural and enological practices on wine aroma volatile composition.     

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.     

Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol,methionol, and dimethyl sulfone in port wines

Volatile sulfur compounds of 15 young port wines and 12 old port wines were determined. As there is a great difference in the pool of sulfur compounds between the two groups of wines, an experimental protocol was performed to determine which technological parameter (dissolved O(2), free SO(2) levels, pH, and time/temperature) was related with the formation/consumption of these compounds. Four sulfur compounds were selected for this purpose: dimethyl sulfide, 2-mercaptoethanol, dimethyl sulfone, and methionol. The synergistic effects of increasing temperature and O(2) at lower pH had the largest impact. Dimethyl sulfide was formed during the experimental period in the presence of O(2). Dimethyl sulfone had the same behavior. Methionol decreased significantly in the presence of O(2), but no methional was formed. 2-Mercaptoethanol, considered to be an important "off-flavor" in dry wines, also decreased during the experimental period (54 days) in the presence of O(2), and the respective disulfide was formed. These results corroborate the fact that old port wine (barrel aged) never develops "off-flavors" associated with the presence of methionol (cauliflower), 2-mercaptoethanol (rubber/burnt), or methional (cooked potato). In fact, temperature and oxygen are the major factors in the consumption of these molecules. However, some notes of "quince" and "metallic" can appear during port wine aging, and these can be associated with the presence of dimethyl sulfide.     

Study of low molecular weight phenolic compounds during the aging of sparkling wines manufactured with red and white grape varieties

Thirty-two phenolic compounds of low molecular weight were identified in 36 white, blanc de noir, and rosé sparkling wines by using HPLC with photodiode array and mass spectrometry detection. Some of the identified compounds, such as cis- and trans-ethylcaftaric, cis- and trans-ethylcaffeic, and cis- or trans-ethyl-p-coumaric acids, 2R,3R-dihydroquercetin, 2R,3R-dihydrokaempferol 3-O-beta-d-glucoside, and a lignan derivative are described for the first time in sparkling wines manufactured with grapes of red varieties. This is also the first time that cis- or trans-diethylfertaric acids have been identified in wines. When cluster analysis was applied to the data of 19 of the 32 identified compounds, the greatest differences found in the low molecular weight phenolic compounds in sparkling wines were due to the grape variety from which they were manufactured, whereas aging time did not significantly influence phenolic composition. Nine phenolic compounds, that is, trans-p-coumaric and trans-caftaric acids, trans-resveratrol glucoside, cis-coutaric, trans-coutaric, cis-p-coumaric, and cis-caftaric acids, tryptophol, and syringic acid, permit the wines to be classified correctly in accordance with the grape variety from which they were manufactured.     

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.     

Butyltin compounds in Portuguese wines

Butyltin compounds are widespread contaminants that have also been found in some wines. The purpose of the present work was to make a survey of butyltin compounds in Portuguese wines. Forty-three table wines and 14 Port wines were analyzed for butyltin contents by using solid-phase microextraction gas chromatography mass spectrometry (SPME-GC-MS). In 14% of the analyzed wine samples, measurable dibutyltin (DBT) was found at concentrations ranging between 0.05 and 0.15 microg/L as Sn. Monobutyltin (MBT) was also observed (0.05 microg/L as Sn) in just a single wine. A search for the possible sources of DBT residues found in the wines was carried out. Therefore, some plastics and oak wood used in the process of wine-making, which have been directly in contact with the musts or the wines, were studied to check their possible release of butyltins. The eventual presence of DBT was also tested directly along the vinification process, from the must to the finished product. The results suggest that high-density polyethylene containers used in the transfer of wine in an early stage of the vinification process may be the main sources of these contaminants. Therefore, it is recommendable that plastic materials to be used in wineries be previously tested for the release of butyltin compounds.