Predicting Bordeaux red wine origins and vintages from raw gas chromatograms.

Connecting chemical properties to various wine characteristics is of great interest to the science of olfaction as well as the wine industry. We explored whether Bordeaux wine chemical identities and vintages (harvest year) can be inferred from a common and affordable chemical analysis, namely, a combination of gas chromatography (GC) and electron ionization mass spectrometry. Using 12 vintages (within the 1990-2007 range) from 7 estates of the Bordeaux region, we report that, remarkably, nonlinear dimensionality reduction techniques applied to raw gas chromatograms recover the geography of the Bordeaux region. Using machine learning, we found that we can not only recover the estate perfectly from gas chromatograms, but also the vintage with up to 50% accuracy. Interestingly, we observed that the entire chromatogram is informative with respect to geographic location and age, thus suggesting that the chemical identity of a wine is not defined by just a few molecules but is distributed over a large chemical spectrum. This study demonstrates the remarkable potential of GC analysis to explore fundamental questions about the origin and age of wine.

Highlighting the varietal origin of eugenol in Armagnac wine spirits from Baco blanc, a hybrid grape variety.

We report on the first evidence of a varietal origin of eugenol as a molecular marker in Baco blanc, one of the grape varieties used to produce Armagnac. Eugenol was identified and quantified by HS-SPME-GC-MS. For two separate vintages, the concentrations found in monovarietal wine spirits made from Baco blanc, were, on average, 10 times higher than those in other Vitis varieties, ranging from 31.0 to 174.7 µg/L. Investigations were carried out to quantify eugenol in the wines used for distillation, in the musts and finally in several parts of the plant. For all matrices over both vintages, it was confirmed that eugenol is much more abundant in Baco blanc than in Ugni blanc and Folle blanche. Moreover, enzymatic hydrolysis made it possible to release a significant quantity of eugenol from precursors, demonstrating that more than 90% of eugenol is bound in the must and in the grape berry pulp.

Investigation into mousy off-flavor in wine using gas chromatography-mass spectrometry with stir bar sorptive extraction.

Three major compounds, 2-acetyl-1-pyrroline (APY), 2-acetyltetrahydropyridine (ATHP) and 2-ethyltetrahydropyridine (ETHP), have been identified as responsible for the mousy off-flavor in wines, although to date quantification data reported in the literature are limited. A simple method for simultaneous quantitation, by SBSE-GC-MS, of these N-heterocyclic compounds was developed. Both previously reported tautomers of ATHP, 2-acetyl-1,4,5,6-tetrahydropyridine and 2-acetyl-3,4,5,6-tetrahydropyridine were identified. The limits of detection and quantification of the method were determined in white, rosé and red wines and are lower than previously published concentrations in spoiled wine. ETHP was detected in almost all wines produced with limited use of SO2. ATHP was detected in almost all wines suspected of mousiness whereas APY was only detected in few cases. This method will provide a support for further studies aimed at understanding the phenomena that influence the occurrence of mousy off-flavor and the oenological parameters that modulate its expression.

Dietary Management of Food Allergy.

Worldwide food allergy prevalence is increasing, especially in children. Food allergy management strategies include appropriate avoidance measures and identifying suitable alternatives for a nutritionally sound diet. Individualized dietary intervention begins teaching label reading, which differs among countries or regions. Dietary intervention must result in a nutritionally sound plan including alternatives to support optimal growth and development. Inappropriate or incomplete dietary advice may increase the risk of adverse reactions, growth faltering, and nutrient deficiencies. Evidence indicates input from a registered dietitian improves nutritional outcomes. Nutritional input plays a critical role managing nutritional disorders related to food allergy.

Effect of Vine Water and Nitrogen Status, as Well as Temperature, on Some Aroma Compounds of Aged Red Bordeaux Wines.

Wine aging bouquet is defined as a positive, complex evolution of aromas during bottle aging. The aim of this study was to look for the link between some of the vine status parameters and the development, during wine aging, of volatile compounds such as DMS, tabanones, and some wine aromatic heterocycles. The potential influence of air temperature was investigated as well as vine nitrogen and water status. Wines were obtained by microvinification from plots of Vitis vinifera L. cv. Merlot, Cabernet-Sauvignon, and Cabernet franc, over vintages from 1996 to 2007, and cellar-aged until 2014. Wine aging aromas were quantified using gas chromotography-mass spectrometry. The effects of the vintage and vine water and nitrogen status were greater than the varietal effects. The nine aroma compounds measured showed very high levels in the 2003 vintage. The results revealed a positive link between vine nitrogen status and dimethyl-sulfide and N, S, O-heterocycle levels measured in the aged wines. Levels of 4-[2-butylidene]-3,5,5-trimethyl-2-cyclohexen-1-one and 4-[( 3E)-1-butylidene]-3,5,5-trimethyl-2-cyclohexen-1-one (megastigmatrienones; tabanone) isomers increased when the vines were affected by a water deficit.

Dual solid-phase and stir bar sorptive extraction combined with gas chromatography-mass spectrometry analysis provides a suitable tool for assaying limonene-derived mint aroma compounds in red wine.

A novel analytical method was developed for quantitative determination of eight limonene-derived monoterpenes responsible for the mint aroma in red wine. As these aromatic compounds are present at trace levels, a new dual extraction approach was proposed, combining solid-phase extraction (SPE) and stir bar sorptive extraction (SBSE), followed by gas chromatography-mass spectrometry analysis. The various parameters affecting the efficiency of extracting the analytes from wine samples in both the SPE and SBSE steps were first investigated, to determine the best compromise for the simultaneous analysis of the compounds studied. Following preliminary optimization of the dilution factor, phase ratio, and methanol content in the SBSE sample, cartridge sorbent mass, type of solvent, elution volume, and wine sample volume in the pre-concentration SPE step were studied. Highest response values were obtained when a 90 mL wine sample was extracted on a 500 mg SPE C18 cartridge and eluted with 1.5 mL methanol. The wine extract was then diluted in 10 mL water to obtain a final methanol content of 15% before the SBSE step. Good linearity, repeatability, reproducibility, accuracy and the required low detection and quantification limits were obtained under the conditions described, making this SPE-SBSE combination a suitable, powerful tool for routine analysis of the selected limonene-derived mint aroma compounds in large series of wine samples. Finally, the validated method was applied to 15 commercial red Bordeaux wines, aged from 3 to 23 years. Most of the compounds studied, present within the ng.L-1 range, were easily quantified for the first time in wine.

Influence of lactic acid bacteria strains on ester concentrations in red wines: Specific impact on branched hydroxylated compounds.

This research investigated the influence of lactic acid bacteria (LAB) strains on ester levels in Bordeaux red wines. These wines were made in five Bordeaux areas in two vintages, using three yeast strains. Malolactic fermentation (MLF) was carried out using industrial starters or indigenous strains, each in triplicate. Ester concentrations were determined by liquid-liquid-extraction- or HS-SPME-GC/MS at various stages in the winemaking process. The levels of most compounds were slightly impacted by LAB, depending on grape variety. Nevertheless, branched hydroxylated esters, such as ethyl 2-hydroxy-3-methylbutanoate and ethyl 2-hydroxy-4-methylpentanoate were the only compounds to be strongly influenced by the bacteria strain, regardless of matrix composition or the yeasts used for alcoholic fermentation. Moreover, the effect observed after MLF persisted over time, for at least 12months. These esters are apparently important markers of LAB esterase activity. To our knowledge, this was the first time they had been identified in this role.

Vine Water Deficit Impacts Aging Bouquet in Fine Red Bordeaux Wine.

The aim of this study was to investigate the influence of vine water status on bouquet typicality, revealed after aging, and the perception of three aromatic notes (mint, truffle, and undergrowth) in bottled fine red Bordeaux wines. To address the issue of the role of vine water deficit in the overall quality of fine aged wines, a large set of wines from four Bordeaux appellations were subjected to sensory analysis. As vine water status can be characterized by carbon isotope discrimination (δ13C), this ratio was quantified for each wine studied. Statistical analyses combining δ13C and sensory data highlighted that δ13C-values discriminated effectively between the most- and least-typical wines. In addition, Principal Component Analysis (PCA) revealed correlations between δ13C-values and truffle, undergrowth, and mint aromatic notes, three characteristics of the red Bordeaux wine aging bouquet. These correlations were confirmed to be significant using a Spearman statistical test. This study highlighted for the first time that vine water deficit positively relates to the perception of aging bouquet typicality, as well as the expression of its key aromatic nuances.

Influence of different yeast/lactic acid bacteria combinations on the aromatic profile of red Bordeaux wine.

BACKGROUND: The typical fruity aroma of red Bordeaux wines depends on the grape variety but also on microbiological processes, such as alcoholic and malolactic fermentations. These transformations involve respectively the yeast Saccharomyces cerevisiae and the lactic acid bacterium Oenococcus oeni. Both species play a central role in red winemaking but their quantitative and qualitative contribution to the revelation of the organoleptic qualities of wine has not yet been fully described. The aim of this study was to elucidate the influence of sequential inoculation of different yeast and bacteria strains on the aromatic profile of red Bordeaux wine. RESULTS: All microorganisms completed fermentations and no significant difference was observed between tanks regarding the main oenological parameters until 3 months' aging. Regardless of the yeast strain, B28 bacteria required the shortest period to completely degrade the malic acid, compared to the other strain. Quantification of 73 major components highlighted a specific volatile profile corresponding to each microorganism combination. However, the yeast strain appeared to have a predominant effect on aromatic compound levels, as well as on fruity aroma perception. CONCLUSION: Yeasts had a greater impact on wine quality and have more influence on the aromatic style of red wine than bacteria. © 2017 Society of Chemical Industry.

N,S,O-Heterocycles in Aged Champagne Reserve Wines and Correlation with Free Amino Acid Concentrations.

Champagne regulations allow winegrowers to stock still wines to compensate for quality shifts in vintages, mainly due to climate variations. According to their technical requirements and house style, Champagne producers use these stored wines in their blends to enhance complexity. The presence of lees and aging at low pH (2.95-3.15), as in Champagne wines, lead to several modifications in wine composition. These conditions, combined with extended aging, result in the required environment for the Maillard chemical reaction, involving aromatic molecules, including sulfur, oxygen, and nitrogen heterocycles (such as thiazole, furan, and pyrazine derivatives), which may have a sensory impact on wine. Some aromatic heterocycles in 50 monovarietal wines aged from 1 to 27 years provided by Veuve Clicquot Ponsardin Champagne house were determined by the SPME-GC-MS method. The most interesting result highlighted a strong correlation between certain heterocycle concentrations and wine age. The second revealed a correlation between heterocyclic compound and free amino acid concentrations measured in the wines, suggesting that these compounds are potential aromatic precursors when wine is aged on lees and, thus, potential key compounds in the bouquet of aged Champagnes. The principal outcome of these assays was to reveal, for the first time, that aromatic heterocycle concentrations in Champagne base wines are correlated with wine age.

A Community-Based Nutrition and Physical Activity Intervention for Children Who Are Overweight or Obese and Their Caregivers.

There is a need for efficacious interventions to reduce the prevalence of childhood obesity, and a limited body of research suggests that collaborative community-based programs designed for children and their caregivers may be effective in reducing obesity rates. This paper reports the results of a community-based obesity intervention, South County Food, Fitness and Fun (SCFFF), designed for preadolescent children who are overweight or obese and their caregivers. SCFFF was developed in response to community concerns. Families were referred to the program by their physician and participated in the program at no cost. The 16-week intervention includes weekly group nutrition and physical activity sessions. Analyses determined that 65 out of the 97 children who completed SCFFF provided 2-year follow-up data and had reduced BMI z-scores over 2 years following the intervention. These participants decreased their energy, fat, carbohydrate, saturated fat, and sodium intake and increased core body strength and endurance from baseline to the end of the intervention. SCFFF was effective in reducing relative weight and improving diet and core muscle strength and endurance in children who are overweight or obese.

First identification of three p-menthane lactones and their potential precursor, menthofuran, in red wines.

The p-menthane lactones constitute a family of powerful odorants, including the isomers of mintlactone and menthofurolactone that occur naturally in peppermint oil, known for their potent, mint-like olfactory properties. These lactones are closely related to the monoterpene-limonene secondary biotransformation and menthofuran has been identified as their common precursor in Mentha species. Using targeted GC-olfactometry and GC-MS analyses, together with quantification methods, we were able to demonstrate, for the first time, the presence of the diastereoisomers of these p-menthane lactones, as well as their common precursor, menthofuran, in red wines. In addition, we linked the presence of those lactones to interesting odorant zones, reminiscent of mint, detected in the studied wine. Although these p-menthane lactones may contribute individually to mint and coconut odors, sensory studies suggested for the first time that their combination at the levels found in the red wine studied resulted in a significant accentuation of freshness and mint notes.

Piperitone Profiling in Fine Red Bordeaux Wines: Geographical Influences in the Bordeaux Region and Enantiomeric Distribution.

Piperitone was recently identified in red Bordeaux wines, and this study was designed to further explore its contribution to wine aroma. Firstly, a geographical origin effect was detected within the Bordeaux region (left versus right banks of the Gironde estuary), with significantly higher mint aroma intensities and piperitone levels in wines from the left bank (Medoc appellations). Statistical analysis of chemical and sensory data highlighted a correlation with the proportion of Cabernet Sauvignon in the wine blends. Accordingly, it was suggested that these sensory and chemical differences may be of varietal origin. Secondly, the contribution of piperitone to minty aromas in the aging bouquet was confirmed by combining both sensory and chemical data from a wide range of red Bordeaux wines. Subsequent investigation of the enantiomeric distribution of piperitone found a significantly higher proportion of the (+)-(6S) enantiomeric form in wines displaying a strong aging bouquet.

Quantification of three galloylglucoside flavour precursors by liquid chromatography tandem mass spectrometry in brandies aged in oak wood barrels.

Vanillin-(6'-O-galloyl)-ß-glucopyranoside (VGG), 3,4,5-trimethoxyphenyl-(6'-O-galloyl)-ß-glucopyranoside (TMPGG), and (6R,9R)-3-oxo-α-ionol-9-O-(6'-O-galloyl)-ß-glucopyranoside (macarangioside E) were identified as aroma precursors in oak wood. An LC-MS/MS method was developed and validated to quantify these three galloylglucoside compounds in brandies aged in oak barrels. The detection system consisted of a triple quadrupole mass analyser operating in multiple reaction monitoring (MRM) mode. For the first time, vanillin-ß-d-xylopyranoside (VX) was synthesised for use as an internal standard. The detection limits (48 µg L(-1) for VGG, 52 µg L(-1) for TMPGG, and 19 µg L(-1) for macarangioside E) were low enough to quantify these aroma precursors in spirits without any sample preparation.

Quantification of megastigmatrienone, a potential contributor to tobacco aroma in spirits.

A SPME-GC-MS method was adapted and validated in order to quantify 5 megastigmatrienones and related odorous compounds from oak wood: guaiacol, cis-whisky lactone, trans-whisky lactone, γ-nonalactone, eugenol, vanillin, and acetovanillone in a single run. The five megastigmatrienone isomers (tabanones) were quantified, for the first time, in Cognac, Armagnac and rum, as contributors to tobacco-like aromas. Spirits aged in oak barrels contain higher amounts, but megastigmatrienones are also present in freshly-distilled spirits. Statistical analysis revealed that freshly-distilled and barrel-aged spirits were differentiated by their megastigma-4,7E,9-trien-3-one levels. The Armagnac and Cognac samples were distinguished by their concentrations of the megastigma-4,6Z,8E-trien-3-one isomer.

Identification of Piperitone as an Aroma Compound Contributing to the Positive Mint Nuances Perceived in Aged Red Bordeaux Wines.

Although a sensory definition of the aging bouquet of red Bordeaux wines was recently established, its chemical transcription has only partially been elucidated. A multiple-step approach, combining sensory evaluations of red Bordeaux wines and aromatic reconstitutions of wine extract fractions, was used to identify the molecular markers involved. One wine with a high aging-bouquet score and a mint nuance has received particular attention. Various reconstitution and omission tests highlighted the contribution of two specific fractions to the intensity of the perception of mint aroma. Gas chromatography coupled to olfactometry and mass spectrometry was applied to the targeted fractions to identify molecular marker(s) responsible for the mint nuance in fine red Bordeaux wines. A similar analytical process was applied to selected fractions of essential oils presenting mint odors to characterize them and interpret the mass spectrometry data. This approach resulted in the detection of piperitone, a monoterpene ketone that, to the best of our knowledge, was reported for the first time as a contributor to the positive mint aroma of aged red Bordeaux wines.

How do esters and dimethyl sulphide concentrations affect fruity aroma perception of red wine? Demonstration by dynamic sensory profile evaluation.

Our study focused on variations in wine aroma perception and molecular composition during tasting over a period of 30min. In parallel, dynamic analytical and sensory methods were applied to study changes in the wines' molecular and aromatic evolution. Dynamic sensory profile evaluations clearly confirmed the evolution of the wine's fruity notes during sensory analysis, highlighting significant differences for red-berry and fresh fruit as well as black berry and jammy fruit, after 5 and 15min, respectively. Dynamic analytical methods revealed a decrease in ester and dimethyl sulphide (DMS) concentrations in the first few minutes. Sensory profiles of aromatic reconstitutions demonstrated that the aromatic modulation of fruity notes observed during wine tasting was explained by changes in ester and DMS concentrations. These results revealed that variations in concentrations of DMS and esters during wine tasting had a qualitative impact, by modulating fruity aromas in red wine.

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.

2-bromo-4-methylphenol, a compound responsible for iodine off-flavor in wines.

This study focuses on an off-flavor in wines treated by an acidification technique involving ion-exchange resins. Applying reversed-phase HPLC on a C18 column to a contaminated wine extract resulted in 25 fractions in dilute alcohol medium, and only one, fraction 19, presented this off-flavor. Its composition was analyzed using gas chromatography coupled to olfactometry (GC-O) and mass spectrometry (GC-MS), leading to the identification of 2-bromo-4-methylphenol for the first time as a compound associated with an "iodine" aroma in white, rosé, and red table wines. Contaminated wines presented a wide range of levels, with maximum concentrations of 28900, 7556, and 48000 ng/L and minimum values of 260, 35, and 63 ng/L in white, rosé, and red wines, respectively. Sensory studies investigating 2-bromo-4-methylphenol gave very interesting results. Individual thresholds ranged from 0.15 to >77.4 ng/L in reverse osmosis water, from 0.4 to >193.5 ng/L in white wine, from 0.5 to >774 ng/L in rosé wine, and from 0.5 to >774 ng/L in red wine. The very wide distribution of individual thresholds suggested the presence of two populations, sensitive and nonsensitive, with a bimodal frequency distribution. The odor descriptions quoted by the more sensitive group characterized 2-bromo-4-methylphenol using terms with "iodine" connotations in both the reverse osmosis water and red wine matrices. The descriptors for commercial wines naturally affected by this defect were seafood, iodine, mud, and fish.