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An increase in bushfires and wildfires globally and consequent smoke exposure of grapevines has seen an elevated need for remediation options to manage the impact of smoke taint in the wine industry. Two commercially available activated carbons (PS1300 and CASPF) were evaluated at 1, 2, and 4 g/L with juice from smoke-affected Pinot Noir and Chardonnay grapes. PS1300 and CASPF treatments removed up to 75 and 92% of the phenolic glycosides in the smoke-affected Pinot Noir rose juice, respectively, and both carbons removed virtually all (i.e., 98-99%) of the phenolic glycosides in the smoke-affected Chardonnay juice at the highest dose rate (4 g/L). The free volatile phenols in the wines were similarly lower in concentration following treatment. Sensory analysis confirmed that the wines made from carbon fined juice had reduced smoke aroma and flavor compared to those from the nontreated controls. However, desirable sensory properties such as color and fruity attributes were also negatively affected by the treatment. The dose rate should be optimized in industry practice to find a balance between reducing the intensity of smoke-related sensory attributes while maintaining or enhancing positive attributes.

Refereed/Peer-reviewed The occurrence in Riesling wine of the potent odorant 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) is dependent upon vineyard and winemaking conditions, and TDN can have a prominent impact on the attributes of a wine after years in a bottle. As such, immediately assessing the impact of vineyard or winery treatments on future TDN formation requires forced creation of the aroma compound under non-wine-like conditions from other precursors. Here, we use a Box–Behnken approach and known TDN end points in commercial wines to optimize the conditions (pH, temperature, and time) of a “total TDN” hydrolytic assay for Riesling wine, which was intended to not interfere with yeast-derived formation pathways. The new assay (75 °C, pH 1.7, and 60 min) was used to determine the role of industry-relevant commercial yeasts as well as novel hybrid yeast strains on total TDN concentrations in young Riesling wines. While significant differences were observed between some yeasts, the impact of defoliation as a viticultural intervention outweighed yeast effects, suggesting that elevated TDN concentrations in wine are likely due to grape growing conditions and cannot be readily reduced or compensated for in the winery.

Wine fermentations typically involve the yeast Saccharomyces cerevisiae. However, many other yeast species participate to the fermentation process, some with interesting oenological traits. In this study the species Torulaspora delbrueckii, used occasionally in mixed or sequential fermentation with S. cerevisiae to improve wine sensory profile, was investigated to understand the physiological differences between the two. Next generation sequencing was used to characterize the transcriptome of T. delbrueckii and highlight the different genomic response of these yeasts during growth under wine-like conditions. Of particular interest were the basic differences in the glucose fermentation pathway and the formation of aromatic and flavour compounds such as glycerol, esters and acetic acid. Paralog genes were missing in glycolysis and glycerol biosynthesis in T. delbrueckii. Results indicate the tendency of T. delbrueckii to produce less acetic acid relied on a higher expression of alcoholic fermentation related genes, whereas acetate esters were influenced by the absence of esterases, ATF1-2. Additionally, in the Δbap2 S. cerevisiae strain, the final concentration of short branched chain ethyl esters (SBCEEs) was related to branched chain amino acid (BCAA) uptake. In conclusion, different adaption strategies are apparent for T. delbrueckii and S. cerevisiae yeasts, an understanding of which will allow winemakers to make better use of such microbial tools to achieve a desired wine sensory outcome.

The negative effects of smoke exposure of grapes in vineyards that are close to harvest are well documented. Volatile phenols in smoke from forest and grass fires can contaminate berries and, upon uptake, are readily converted into a range of glycosylated grape metabolites. These phenolic glycosides and corresponding volatile phenols are extracted into the must and carried through the winemaking process, leading to wines with overtly smoky aromas and flavours. As a result, smoke exposure of grapes can cause significant quality defects in wine, and may render grapes and wine unfit for sale, with substantial negative economic impacts. Until now, however, very little has been known about the impact on grape composition of smoke exposure very early in the season, when grapes are small, hard and green, as occurred with many fires in the 2019–20 Australian grapegrowing season. This research summarises the compositional consequences of cumulative bushfire smoke exposure of grapes and leaves, it establishes detailed profiles of volatile phenols and phenolic glycosides in samples from six commercial Chardonnay and Shiraz blocks throughout berry ripening and examines the observed effects in the context of vineyard location and timing of smoke exposure. In addition, we demonstrate the potential of some phenolic glycosides in leaves to serve as additional biomarkers for smoke exposure of vineyards.

Wine made from grapes exposed to bushfire smoke can exhibit unpleasant smoky, ashy characters, which have been attributed to the presence of smoke-derived volatile phenols, in free or glycosylated forms. Here we report the uptake and glycosylation of volatile phenols by grapes following exposure of Cabernet Sauvignon vines to smoke, and their fate during winemaking. A significant delay was observed in the conversion of volatile phenols to their corresponding glycoconjugates, which suggests sequestration, the presence of intermediates within the glycosylation pathway and/or other volatile phenol storage forms. This finding has implications for industry in terms of detecting smoke-affected grapes following vineyard smoke exposure. The potential for an in-canopy sprinkler system to mitigate the uptake of smoke-derived volatile phenols by grapes, by spraying grapevines with water during smoke exposure, was also evaluated. While &ldquo, misting&rdquo, appeared to partially mitigate the uptake of volatile phenols by grapes during grapevine exposure to smoke, it did not readily influence the concentration of volatile phenols or the sensory perception of smoke taint in wine. Commercial sensors were used to monitor the concentration of smoke particulate matter (PM) during grapevine exposure to low and high density smoke. Similar PM profiles were observed, irrespective of smoke density, such that PM concentrations did not reflect the extent of smoke exposure by grapes or risk of taint in wine. The sensors could nevertheless be used to monitor the presence of smoke in vineyards during bushfires, and hence, the need for compositional analysis of grapes to quantify smoke taint marker compounds.

Despite numerous studies, the identity of the compounds that are responsible for 'stone fruit’ aroma in wine has not been conclusively established. This study focussed on wine varieties that often display peach and apricot characters, such as Chardonnay, Viognier and botrytis-affected sweet Semillon wines. Wines with high and low 'stone fruit’ aroma were evaluated by gas chromatography-olfactometry-mass spectrometry (GC-O-MS) using extracts representative of the aroma of the wine in a glass. No aroma-active zone was described as 'stone fruit’ aroma across all three wine varietals. However, for the individual varieties, terpenes, such as linalool and geraniol, in the Viognier wines, several esters in the Chardonnay wines, and γ-nonalactone in the botrytis Semillon were associated with 'stone fruit’ aroma. Notably, this is the first study assessing the aroma profile of Viognier wine by GC-O. In addition, an extension study of Viognier grape monoterpene profiles clarified its classification as an aromatic variety. Refereed/Peer-reviewed

Due to the increasing frequency of wildfires in recent years, there is a strong need for developing mitigation strategies to manage the impact of smoke exposure of vines and occurrence of ‘smoke taint’ in wine. One plausible approach would be to prevent or inhibit the uptake of volatile phenols from smoke into grape berries in the vineyard. In this study we describe a model system we developed for evaluating under controlled conditions the effectiveness of a range of surface coatings (including existing horticultural sprays) for reducing/preventing the uptake of volatile phenols and their subsequent conversion to phenolic glycosides. Grapes were coated with the materials to be tested and then exposed to gaseous phenols, via evaporation from an aqueous solution, in a semi-closed glass container. Analysis of volatile phenols and their glycosidic grape metabolites demonstrated that the treatments typically did not provide any significant protection, in fact, some resulted in higher concentrations of these compounds in the grapes. The highest concentrations of volatile phenols and their glycosides were observed after application of oily, hydrophobic materials, suggesting that these materials may enhance the adsorption or transfer of volatile phenols into grape berries. Therefore, it is important to consider the types of sprays that are being applied in the vineyard before and during smoke events to prevent the potential of exacerbating the uptake of smoke compounds by grape berries.

Pioneering investigations into precursors of fruity and floral flavors established the importance of terpenoid and C 13 -norisoprenoid glycosides to the flavor of aromatic wines. Nowadays flavor precursors in grapes and wine are known to be structurally diverse, encompassing glycosides, amino acid conjugates, odorless volatiles, hydroxycinnamic acids, and many others. Flavor precursors mainly originate in the grape berry but also from oak or other materials involved in winemaking. Flavors are released from precursors during crushing and subsequent production steps by enzymatic and nonenzymatic transformations, via microbial glycosidases, esterases, C-S lyases, and decarboxylases, and through acid-catalyzed hydrolysis and chemical rearrangements. Flavors can also be liberated from glycosides and amino acid conjugates by oral microbiota. Hence, it is increasingly likely that flavor precursors contribute to retronasal aroma formation through in-mouth release during consumption, prompting a shift in focus from identifying aroma precursors in grapes to understanding aroma precursors present in bottled wine. Refereed/Peer-reviewed

The impact of fermentation variables (time and temperature of maceration, yeast species, addition of pectolytic enzymes) and winemaking techniques (cold soak, thermovinification, carbonic maceration, and rose vinification) on rotundone and classical enological parameters was investigated in triplicate in red wine made from Duras at the laboratory scale. Rotundone was poorly correlated to anthocyanins and to total phenolic index, some variables reflecting the extraction of skin compounds, which suggests that the solubility of rotundone or its ability to bind to other materials may differ from anthocyanins and most of the grape proanthocyanidins. Compared with control wine, wines made from a rose and a thermovinification treatment differed largely in their enological parameters. These two treatments involving a preferment removal of skins resulted in the lowest wine rotundone concentrations of ~20% and 13%, respectively. The other treatments had a weak impact on the studied parameters, and none of them, including the use of macerating enzymes and the increase in temperature or time of maceration, resulted in enhanced rotundone concentrations. Semicarbonic maceration, fermentation with Saccharomyces uvarum, or longer skin contact during postfermentation maceration resulted in wine with a significant decrease of ~20% in rotundone concentration, indicating practical opportunities for reducing pepper aroma in wine.

Rotundone, the compound responsible for peppery aroma in red wines is positively correlated with the absence of water deficit during ripening which can make it problematic to produce red wines combining both superior concentrations in rotundone and phenolic compounds. To reach this double objective, on-vine drying with cutting of the fruit bearing cane or “Passerillage Eclaircissage sur Souche” (PES), a technique that consists in cutting the cane 2–3 weeks prior to harvest on a Guyot-trained vineyard was investigated combined or not with irrigation. We showed that PES had a limited impact on rotundone in wine. As the PES technique leads to an interruption of the sap flow, our results suggest that rotundone is synthesized in the berries and not translocated. A viticultural system combining irrigation and then PES induced significant gains in rotundone, in sugar concentration, in anthocyanins and in Total Phenolic Index in wine, and in skin to juice ratio. Measurements of bunch surface temperature indicate that the enhancement of rotundone production induced by irrigation is likely to be due to a direct rather than to an indirect effect through an increase in leaf area leading to a cooler bunch microclimate.

(Z)-6-Dodeceno-γ-lactone is a potent aroma compound that has been little studied and its prevalence in wines is unknown. An efficient stable isotope dilution assay was developed using a simple, direct immersion solid-phase microextraction and gas chromatography-tandem mass spectrometry method suitable for routine use with a low ng/L limit of quantitation. Using this method, 99 out of 104 young white wines analysed were found to contain detectable (Z)-6-dodeceno-γ-lactone. The highest concentrations were found in Riesling and Viognier wines. (Z)-6-Dodeceno-γ-lactone was found to have an aroma detection threshold of 700 ng/L in a neutral white wine. This study established that (Z)-6-dodeceno-γ-lactone is widely present in Australia's most popular white wine varieties, but generally at concentrations below its aroma detection threshold. Refereed/Peer-reviewed

International audience; A 'stone fruit' aroma is important in many white wine varieties and styles, but little is known about the chemical basis of this wine aroma attribute. A set of Viognier and Chardonnay wines that featured 'stone fruit' aroma attributes were selected by a panel of wine experts. The selected wines were characterized by sensory descriptive analysis and detailed volatile chemical composition analyses. This comprehensive data also allowed Viognier wine to be profiled for the first time. By partial least-squares regression, several esters and fatty acids and benzaldehyde were indicated as contributing to the 'peach' attribute; however, a reconstitution sensory study was unsuccessful in mimicking this attribute. A mixture of γ-lactones, monoterpenes, and aldehydes were positively correlated to the 'apricot' aroma, which were generally higher in the Viognier wines. Reconstitution studies confirmed that the monoterpenes linalool, geraniol, and nerol were the most important compounds for the mixture being perceived as having an 'apricot' aroma.

Metabolomics is the scientific study of the unique chemical fingerprints that result from specific biochemical processes. It enables the comprehensive detection and quantification of small molecules that are intermediates or end-products of metabolism in a biological sample, such as a grape or yeast. The metabolomics approach also provides for a holistic characterisation of complex chemical transformations and oxidation reactions during winemaking, ageing and transport. The development of metabolomics has made major advances in the last two decades. Improved chromatographic techniques for separation of polar metabolites and enhanced sensitivity and selectivity of nuclear mass resonance and mass spectrometric instrumentation now enable detection and quantification of hundreds of metabolites in a single analysis. New bioinformatics tools and statistics capabilities are available which are key to efficiently analysing and annotating comprehensive datasets. This review provides an overview of analytical methods for untargeted profiling, biomarker discovery and targeted analysis of non-volatile and volatile metabolites. It summarises bioinformatics tools for data processing, data mining and metabolite identification and explores metabolomics approaches which have been successfully employed to comprehensively analyse, annotate and understand the broad chemical diversity in grapes, yeast and wine. It also describes opportunities for the application of metabolomics in grape and wine science and provides an outlook about further development needs and emerging trends.

Background and Aims Rotundone, a potent aroma compound responsible for peppery aroma and flavour in Shiraz, was detected recently in Vitis vinifera L. cv. Duras wines. In 2011 and 2012, two separate experiments were carried out to determine the effect of ripeness and viticultural techniques on rotundone concentration in Duras wine. Methods and Results Rotundone was measured in wines prepared by microvinification techniques (1 L Erlenmeyer). Accumulation of this compound in wines depended on vintage conditions and the degree of ripening, such that a higher concentration of rotundone was reached 44 days after mid-veraison. Application of exogenous jasmonic acid and grape thinning did not significantly affect rotundone concentration, whereas leaf removal strongly reduced rotundone concentration. Wine from the irrigated treatment had a higher concentration of rotundone, and in most cases, vine water status over the veraison–harvest period was identified as a key variable that was well correlated with observed intraplot variability. Conclusions These findings confirm that some common viticultural practices can be used to manipulate the peppery character in red wine. Significance of the Study Our results may assist grape growers to produce Duras, Shiraz and other cultivars where rotundone makes an important contribution to wine aroma.

A series of five Vitis vinifera L. cv Cabernet Sauvignon wines were produced from sequentially-harvested grape parcels, with alcohol concentrations between 12% v/v and 15.5% v/v. A multidisciplinary approach, combining sensory analysis, consumer testing and detailed chemical analysis was used to better define the relationship between grape maturity, wine composition and sensory quality. The sensory attribute ratings for dark fruit, hotness and viscosity increased in wines produced from riper grapes, while the ratings for the attributes red fruit and fresh green decreased. Consumer testing of the wines revealed that the lowest-alcohol wines (12% v/v) were the least preferred and wines with ethanol concentration between 13% v/v and 15.5% v/v were equally liked by consumers. Partial least squares regression identified that many sensory attributes were strongly associated with the compositional data, providing evidence of wine chemical components which are important to wine sensory properties and consumer preferences, and which change as the grapes used for winemaking ripen.

International audience; Recent studies concerning the aroma of noble rot dessert wines revealed the importance of a well-known phenomenon in perfumery, the perceptual blending, to create the perception of "overripe orange" nuances. Thus, compounds associated with both oak wood aging (3-methyl-4-octanolide and eugenol) and Botiytis cinerea development under the form of noble rot (2-nonen-4-olide and gamma-nonalactone) contribute to a specific aroma of great noble rot dessert wines through perceptual interaction phenomena. This synthetic perception phenomenon was established from reconstitution, addition, and omission sensory experiments, using wine extract fractions supplemented with the volatile compounds previously mentioned. To better understand the sensory impact of these compounds, the goal of this research was to study the contributions of enantiomeric forms of 2-nonen-4-olide and gamma-nonalactone and the diastereoisomers of 3-methyl-4-octanolide. After multidimensional chiral chromatography-analysis, the relative proportions of enantiomers or diastereomeric forms were first established and then sensory experiments were carried out using the reference compounds with isolated fractions from dessert wines. A dominance of the R form was established for 2-nonen-4-olide, which was correlated with wine aging, while the S form is more dominant in young dessert wines. Furthermore, the reconstitution experiments confirmed perceptual interaction phenomena and revealed the sensory contribution of (R)-2-nonen-4-olide and cis-3-methyl-4-octanolide concerning the "overripe orange" nuances, whereas no sensory impact for the gamma-nonalactone isomers was observed.

The flavour of wine is derived, in part, from the flavour compounds present in the grape, which change as the grapes accumulate sugar and ripen. Grape berry terpene concentrations may vary at different stages of berry development. This study aimed to investigate terpene evolution in grape berries from four weeks post-flowering to maturity. Grape bunches were sampled at fortnightly intervals over two vintages (2012-13 and 2013-14). In total, five monoterpenoids, 24 sesquiterpenes, and four norisoprenoids were detected in grape samples. The highest concentrations of total monoterpenoids, total sesquiterpenes, and total norisoprenoids in grapes were all observed at pre-veraison. Terpenes derived from the same biosynthetic pathway had a similar production pattern during berry development. Terpenes in grapes at harvest might not necessarily be synthesised at post-veraison, since the compounds or their precursors may already exist in grapes at pre-veraison, with the veraison to harvest period functioning to convert these precursors into final products.

Terpenoids were extracted from grape vine bunches during plant development and analysed by GC-MSD. The grapevines analysed were from a commercial harvest of Vitis vinifera cv. Shiraz. The terpenoids were analysed from 4 weeks post flowering (wpf) to harvest in one season. The data are presented with the structure of the compound and aroma profile and semi-quantified. The sub-class of sesquiterpenes was given special attention, and this data set describes the first analysis of these compounds during ripening of this important economic crop. Sesquiterpenes may have a hitherto described contribution to wine aroma. This data set may provide insight into biosynthetic pathways and aroma chemistry. Interpretation of our data and further discussion can be found in “Terpene evolution during the development of Vitis vinifera L. cv. Shiraz grapes” (Zhang et al., 2016) [1]. Keywords: Rotundone, Terpene, Sesquiterpene, Grape ripening

Bushfires occur frequently in the vicinity of grape growing regions, resulting in smoke drifting over the vineyards. Wine made from smoked grapes is often downgraded or unfit for sale due to negative sensory characters. To manage or avoid the risk of producing smoke-affected wine, a diagnostic assay was developed for assessing the extent of smoke exposure in grapes and the resulting wines. The method relies on the quantitation of the glycosidic grape metabolites that are formed from major volatile phenols present in smoke. Using HPLC-MS/MS with APCI, a quantitation method for phenolic glycosides as smoke marker compounds was developed and validated. The method was confirmed to be of sufficient sensitivity and reliability to use as a diagnostic assay. On the basis of phenolic glycoside concentrations, grapes or wine can be assessed as smoke exposed or not, and the relative intensity of smoke exposure can be determined.

Background and Aims: Australian grape growers and winemakers have typically relied on guaiacol and 4-methylguaiacol measurements to determine smoke exposure of grapes following bushfires or prescribed burns. However, the guaiacol and 4-methylguaiacol content of grapes does not always correlate with the extent of taint in resultant wines. This study compared several methods for the analysis of smoke related phenols and their conjugates in grapes and wine, to determine their capacity as diagnostic assays for smoke exposure. Methods and Results: Smoke-affected grapes were sourced from commercial vineyards exposed to bushfire smoke and from experimental field trials involving the application of smoke to grapevines, and small-scale wines were made from a number of these samples. Several analytical methods were applied to grapes and wine to determine the concentration of smoke related phenols and their conjugates. Strong correlations were observed between the glycoconjugate content of smoke-affected grapes and the concentration of guaiacol and 4-methylguaiacol released following acid hydrolysis of juice. Conclusions: Where smoke-affected grapes contain low or non-detectable levels of guaiacol and 4-methylguaiacol, analytical methods that quantify their glycoconjugate forms (either directly or indirectly) provide a better indication of the extent of smoke exposure. Significance of the Study: This is the first study to compare different methods for assessing smoke exposure in grapes and wine, through analysis of free and bound guaiacol and 4-methylguaiacol. These methods will allow grape growers and winemakers to more reliably assess smoke exposure of grapes, enabling better informed decisions to be made with regards to harvesting and processing smoke-affected grapes.

Measuring chemical composition is a common approach to support decisions about allocating foods and beverages to grades related to market value. Red wine is a particularly complex beverage, and multiple compositional attributes are needed to account for its sensory properties, including measurement of key phenolic components such as anthocyanins, total phenolics, and tannin, which are related to color and astringency. Color has been shown to relate positively to red wine grade; however, little research has been presented that explores the relationship between astringency-related components such as total phenolic or tannin concentration and wine grade. The aim of this research has been to investigate the relationship between the wine grade allocations of commercial wineries and total phenolic and tannin concentrations, respectively, in Australian Shiraz and Cabernet Sauvignon wines. Total phenolic and tannin concentrations were determined using the methyl cellulose precipitable (MCP) tannin assay and then compared to wine grade allocations made by winemaker panels during the companies' postvintage allocation process. Data were collected from wines produced by one Australian wine company over the 2005, 2006, and 2007 vintages and by a further two companies in 2007 (total wines = 1643). Statistical analysis revealed a positive trend toward higher wine grade allocation and wines that had higher concentrations of both total phenolics and tannin, respectively. This research demonstrates that for these companies, in general, Cabernet Sauvignon and Shiraz wines allocated to higher market value grades have higher total phenolics and higher tannin concentrations and suggests that these compositional parameters should be considered in the development of future multiparameter decision support systems for relevant commercial red wine grading processes. In addition, both tannin and total phenolics would ideally be included because although, in general, a positive relationship exists between the two parameters, this relationship does not hold for all wine styles.

Background and Aims: This study investigated flavonoid composition and C13-norisoprenoids (β-damascenone and β-ionone) in Shiraz grapes and wines, their relationships and links to wine sensory properties. Methods and Results: Differences in the grape berry flavonoid profile were created by exposing bunches to varying levels of sunlight intensity through canopy manipulation. Grapes were harvested at similar maturity and three replicate wines were made for each treatment in both vintages. Grapes produced under shaded canopy conditions had reduced anthocyanins and skin tannins, but little effect on seed tannins was observed. Pigmented polymers and tannins in wines were related to berry flavonoid composition (anthocyanins, skin and seed tannins, and their ratios). In grapes and wines, no significant effects were observed in response to canopy manipulation for two hydrolytically released C13-norisoprenoids, β-damascenone and β-ionone. Relationships were established for wine flavonoid composition, wine colour density, sensory perception of the astringency-related mouth-feel attributes and a quality scale. A positive relationship between wine quality score and hydrolytically released β-damascenone in both berries and wines was found, but not for free β-damascenone or any quantified forms of β-ionone. Conclusion: Higher concentrations of anthocyanins and skin tannins in berries, coupled with a lower concentration of seed tannins were associated with higher wine quality. The ratio anthocyanins*skin tannins/seed tannins is proposed as an indicator of wine flavonoid composition, wine colour and wine quality. Excessive canopy shade was detrimental to berry and wine composition and intensified sensory detection of ‘straw’ and ‘herbaceous’ characters in the wines. Significance of the Study: This study increases the understanding of the balance and composition of flavonoid compounds and C13-norisoprenoids in berries and their relationship with wine composition and wine sensory properties, but also highlights the importance of a canopy microclimate assessment.

A rapid technique for the isolation of polymeric polyphenols from red wine has been developed and validated. A copolymer reversed-phase SPE cartridge was utilized in conjunction with predominantly organic eluents to provide three phenolic fractions from red wine without the need for sample pretreatment. The first fraction contained the bulk of the monomeric and oligomeric phenolic material, while the second and third fractions contained the polymeric polyphenolic compounds, as determined by HPLC analysis. The two polymeric polyphenolic fractions differed in their solubility and extent of pigmentation, and the differences appeared to be related to wine age. This method contrasted with other available fractionation techniques because the interfering, nonpolymeric material can be removed in a single wash fraction, while the polymeric material is separated into two distinct fractions based on their diverse physicochemical properties. It is anticipated that the rapid access to discrete polymeric fractions afforded by this method will be of benefit in furthering the understanding of red wine polymeric polyphenols.

Red wine was made from the same batch of Cabernet Sauvignon grapes but with two different yeasts, Saccharomyces cerevisiae (SC) or Saccharomyces bayanus (SB). The colour properties and pigment profiles of SC and SB wines were compared at 8 days and 387 days after yeast inoculation. Grape anthocyanin concentration was found to be lower in SB wines than in SC wines at day 8 and 387, but SB wine exhibited greater wine colour density, a* and b*. The anthocyanin concentration did not correlate with wine colour density. The levels of pigmented polymers and SO2 non-bleachable pigments were found to be higher in SB wine at day 387, demonstrating that the formation of stable pyranoanthocyanins and pigmented polymers was enhanced by SB yeast. Electrospray mass spectrometry was used for the compositional analysis of pyranoanthocyanins, and direct and ethyl-bridged linked condensation dimers of malvidin 3-O-glucoside (MvG) with flavanols (catechin or epicatechin). The data demonstrated that the formation of acetaldehyde-mediated pigments was enhanced by the use of the SB yeast. The compositional analysis suggested that the differences in colour properties and pigment profiles of SC and SB wines were largely due to the greater production of acetaldehyde-mediated pigments by the use of SB yeast.

The aim of this study was to determine how changes in grape composition brought about by artificial shading (sunlight exclusion) influence wine properties including colour, flavonoid composition and sensory attributes. Prior to flowering, bunches of Shiraz grapes were enclosed in boxes designed to eliminate light without altering bunch temperature and humidity. This artificial bunch shading had little effect on berry ripening and accumulation of sugar but at harvest the shaded bunches had smaller berries and higher seed weight, juice pH and titratable acidity. The amount of anthocyanins in the fruit was not changed significantly but anthocyanin composition in the shaded berries was shifted towards dioxygenated anthocyanins (the glucosides of cyanidin and peonidin derivatives). Shaded fruit had increased seed tannins and decreased skin tannins but the largest relative change in flavonoids was a marked decrease in flavonols in the shaded fruit, similar to previous studies. Wines made from shaded fruit had lower wine colour density, total phenolics, anthocyanins and tannins when the wine was bottled and after ageing for up to three years. Analysis of potential flavour compounds following acid hydrolysis indicated that the wines made from shaded fruit had decreased levels of glycosides of β-damascenone and 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN). Sensory analysis of the wines indicated no significant difference in aroma attributes but the wines made from shaded fruit were rated lower for astringency, fruit flavour and flavour persistence in-mouth sensory attributes. The results indicate that extreme shading of Shiraz fruit can decrease wine colour, anthocyanins and tannins as well as altering sensory attributes.

The methyl cellulose precipitable (MCP) tannin assay and a modified version of the Somers and Evans color assay were adapted to high-throughput (HTP) analysis. To improve efficiency of the MCP tannin assay, a miniaturized 1 mL format and a HTP format using 96 well plates were developed. The Somers color assay was modified to allow the standardization of pH and ethanol concentrations of wine samples in a simple one-step dilution with a buffer solution, thus removing inconsistencies between wine matrices prior to analysis and allowing for its adaptation to a HTP format. Validation studies showed that all new formats were efficient, and results were reproducible and analogous to the original formats.

To assess the effects of exogenous tannin addition on the properties of a red wine made from Vitis vinifera cv. Shiraz, a winemaking study was performed with pre- and post-alcoholic fermentation additions of 200 mg/L of a commercial grape seed-derived oenotannin product. The influence of the added oenotannin on wine tannin concentration, pigmented polymer concentration and colour parameters was monitored throughout the winemaking process and for up to two years of post-bottling storage. Additionally, after one year of storage, the in-mouth sensory attributes of the wines were characterised using sensory descriptive analysis. No significant differences in wine colour properties and pigment profiles were found between treatments. Tannin concentration as measured by HPLC was not significantly different at the end of the experiment, but when considered over the whole time-course it was significantly higher in the post-ferment treatment. The magnitude of the effect on astringency of the oenotannin addition at 200 mg/L during winemaking was small and the sensory response was the same regardless of addition pre- or post-fermentation. The magnitude of the sensory response to the wines was not significantly different from that of the control wine assessed after (i) 200 mg/L of the oenotannin was added immediately prior to sensory evaluation, or (ii) addition of 200 mg/L of two other commercial tannin preparations. For the type of red wine and oenotannin studied, tannin addition did not affect wine colour properties and had only a minor effect on perceived astringency.

Rotundone is a sesquiterpene that gives grapes and wine a desirable 'peppery' aroma. Previous research has reported that growing grapevines in a cool climate is an important factor that drives rotundone accumulation in grape berries and wine. This study used historical data sets to investigate which weather parameters are mostly influencing rotundone concentration in grape berries and wine. For this purpose, wines produced from 15 vintages from the same Shiraz vineyard (The Old Block, Mount Langi Ghiran, Victoria, Australia) were analysed for rotundone concentration and compared to comprehensive weather data and minimal temperature information. Degree hours were obtained by interpolating available temperature information from the vineyard site using a simple piecewise cubic hermite interpolating polynomial method (PCHIP). Results showed that the highest concentrations of rotundone were consistently found in wines from cool and wet seasons. The Principal Component Analysis (PCA) showed that the concentration of rotundone in wine was negatively correlated with daily solar exposure and grape bunch zone temperature, and positively correlated with vineyard water balance. Finally, models were constructed based on the Gompertz function to describe the dynamics of rotundone concentration in berries through the ripening process according to phenological and thermal times. This characterisation is an important step forward to potentially predict the final quality of the resultant wines based on the evolution of specific compounds in berries according to critical environmental and micrometeorological variables. The modelling techniques described in this paper were able to describe the behaviour of rotundone concentration based on seasonal weather conditions and grapevine phenological stages, and could be potentially used to predict the final rotundone concentration early in future growing seasons. This could enable the adoption of precision irrigation and canopy management strategies to effectively mitigate adverse impacts related to climate change and microclimatic variability, such as heat waves, within a vineyard on wine quality.

A precipitation assay is presented that enables tannin measurement in matrices of red wine, 50% ethanol grape extract and aqueous tannin solutions. By exploiting the polysaccharide polymer methyl cellulose to precipitate tannins, the absorbance of phenolics at 280 nm before and after tannin precipitation (subtractive approach) can be obtained, thus enabling selective measurement of tannin only. This methyl cellulose precipitable (MCP) tannin assay allows complete precipitation of tannin from red wine and from grape homogenate extracts. The subtractive assay is both simple and robust, selective for condensed tannins and does not suffer interference from other 280 nm-absorbing phenolics such as anthocyanins or catechins. Matrix effects have only minimal impact on the assay performance and validation parameters indicate a robust performance. There was good correlation between tannin measured by reverse-phase HPLC and the MCP tannin assay for 121 Australian red wines (r = 0.74) and also 54 grape extracts (r = 0.79). We envisage that the technical simplicity of this tannin assay will enable widespread research and field applications. In addition, an alternative format that requires re-solubilisation of the tannin-polymer pellet in acetonitrile is reported, which is particularly suitable for measurement of smaller tannin concentrations. Notwithstanding that option, technical requirements of the re-solubilisation step lead us to suggest that the subtractive format would be simple for adoption by wine industry practitioners.

Tannins are polyphenolic secondary metabolites, which can be found in many higher plants and are identified by their ability to complex with and precipitate proteins. This key property is believed to be responsible for the mouth-feel and astringency caused by wine tannins. The analysis of tannins is of interest to practitioners in a diverse range of fields, including chemistry, pharmacology, food science, animal nutrition, ecology and plant physiology. There is a desire within the Australian wine industry to exploit objective tannin measures to complement human sensory assessment for style and quality specifications. This review, therefore, concentrates on grape-derived condensed tannins, also known as proanthocyanidins, and wine tannins formed from grape tannins. We summarise recent advances with the development of analytical methods for the quantification of tannins, review techniques for the structural characterisation of tannin molecules and emphasise the need to refine these techniques.

The aim of this study was to quantify, in a single analysis, 31 volatile fermentation-derived products that contribute to the aroma of red and white wine. We developed a multi-component method based on headspace solid-phase microextraction coupled with gas chromatography mass spectrometry (HS-SPME-GC-MS). The 31 volatile compounds analysed include ethyl esters, acetates, acids and alcohols. Although these compounds have a range of functional groups, chemical properties, volatilities, affinities for the SPME fibre, and are found in wine at various concentrations, the accuracy of the analysis was achieved with the use of polydeuterated internal standards for stable isotope dilution analyses (SIDA). Nine of the labelled standards were commercially available, while 22 were synthesised. The method was validated by a series of duplicate spiked standard additions to model, white and red wine matrices over the concentration range relevant for each compound in wine. This demonstrated that the appropriate use of SIDA helped to account for matrix effects, for instance potential sources of variation such as the relative response to the MS detector, ionic strength, ethanol content and pH of different wine matrices. The resultant calibration functions had correlation coefficients (R(2)) ranging from 0.995 to 1.000. Each compound could be quantified at levels below its aroma threshold in wine. Relative standard deviations were all5%. The method was optimised for the best compromise (over the 31 compounds) of wine dilution factor, level of sodium chloride addition, SPME fibre, SPME temperature, SPME time, GC column and MS conditions. Confirmation of identity was achieved by retention time and peak shape, and measurement of at least three ions for each analyte and internal standard with the MS operating in selected ion monitoring mode to facilitate more precise quantitation with a high sampling rate. The method is a valuable research tool with many relevant applications. A novel method for the combined chiral separation and SIDA quantification of 2- and 3-methylbutanoic acid is also demonstrated.

Near infrared (NIR) spectroscopy was used to simultaneously predict the concentrations of malvidin-3-glucoside (M3G), pigmented polymers (PP) and tannins (T) in red wine. A total of 495 samples from 32 commercial scale red wine fermentations over two vintages using two grape varieties (Cabernet Sauvignon and Shiraz), and also including as additional variables two types of fermenters, two different yeasts, and three fermentation temperatures were used. Samples were scanned in transmission mode (400–2500 nm) using a monochromator instrument (NIRSystems6500). Calibration equations were developed from high performance liquid chromatography (HPLC) and NIR data using partial least squares (PLS) regression with internal cross validation. Using PLS regression, very good calibration statistics (Rcal2>0.80) were obtained for the prediction of M3G, PP and T with standard deviation (S.D.)/standard error in cross validation (SECV) ratio (residual predictive deviation, RPD)) ranging from 1.8 to 5.8. It was concluded that near infrared spectroscopy could be used as rapid alternative method for the prediction of the concentration of phenolic compounds in red wine fermentations.

Two new red pigments were synthesized by nucleophilic addition of vinylphenols to malvidin 3-glucoside. The structures of the resulting pyranoanthocyanins were confirmed by electrospray-mass spectrometry and NMR spectroscopy (gHMQC, gHMBC and CIGAR experiments). By means of UV–vis spectroscopy the colour properties of the pigments were characterized; it could be demonstrated that the pyranoanthocyanins retained their red colour at pH 3.6 in model wine and were resistant to bisulfite-mediated bleaching. Finally, HPLC–MS analysis confirmed the presence of both anthocyanin-derived pigments in red wine.

The volatile phenols guaiacol, 4-methylguaiacol, syringol, 4-methylsyringol, o-, m-, and p-cresol, as well as their glycoconjugates, have previously been shown to be present in elevated concentrations in smoke-tainted wine. Sensory descriptive analysis experiments, with addition of free volatile phenols in combination with their glycosidically bound forms, were used to mimic smoke taint in red wines. The addition of volatile phenols together with glycoconjugates gave the strongest off-flavor. The hydrolysis of glycosidically bound flavor compounds in-mouth was further investigated by in vitro and in vivo experiments. The results indicate that enzymes present in human saliva are able to release the volatile aglycones from their glycoconjugates even under low pH and elevated ethanol conditions, confirming that in-mouth breakdown of monosaccharide and disaccharide glycosides is an important mechanism for smoke flavor from smoke affected wines, and that this mechanism may play an important general role in the flavor and aftertaste of wine.

A biomimetic synthesis of solerone (5-oxo-4-hexanolide, 1) using both enzymatic and acid-catalyzed reactions was performed. Starting from l-glutamic acid 5-ethyl ester (2) enzymatic oxidative deami...

The phenolic composition of red wine impacts upon the color and mouthfeel and thus quality of the wine. Both of these characteristics differ depending on the age of a wine, with the purple of young wines changing to brick red and the puckering or aggressive astringency softening in older wines. This study investigated the color parameters, tannin concentrations and tannin composition of a 50 year series of Cabernet Sauvignon wines from a commercial label as well as 30 year series of Cabernet Sauvignon and Shiraz wines from a separate commercial label to assess the impact of wine age on phenolic composition and concentration. The wine color density in wines of 40 to 50 years old was around 5 AU compared with 16 AU of wine less than 12 months old, which correlated well with the concentration of non-bleachable pigments and pigmented polymers. Conversely, the anthocyanin concentrations in 10 year old wines were substantially lower than that of recently bottled wines (around 100 mg/L compared with 627 mg/L, respectively), adding further evidence that non-bleachable pigments including pigmented polymers play a much larger role in long-term wine color than anthocyanins. No age-related trend was observed for tannin concentration, indicating that the widely noted softer astringency of older red wines cannot necessarily be directly related to lower concentrations of soluble wine tannin and is potentially a consequence of changes in tannin structure. Wine tannins from older wines were generally larger than tannins from younger wines and showed structural changes consistent with oxidation.

The study aimed to quantify the effects of grape maturity on wine alcohol, phenolics, flavour compounds and polysaccharides in Vitis vinifera L. cv Cabernet Sauvignon. Grapes were harvested at juice soluble solids from 20 to 26 °Brix which corresponded to a range of wine ethanol concentrations between 12% and 15.5%. Grape anthocyanin and skin tannin concentration increased as ripening progressed, while seed tannin declined. In the corresponding wines, monomeric anthocyanin and wine tannin concentration increased with harvest date, consistent with an enhanced extraction of skin-derived phenolics. In wines, there was an observed increase in yeast-derived metabolites, including volatile esters, dimethyl sulfide, glycerol and mannoproteins with harvest date. Wine volatiles which were significantly influenced by harvest date were isobutyl methoxypyrazine, C 6 alcohols and hexyl acetate, all of which decreased as ripening progressed. The implications of harvest date for wine composition is discussed in terms of both grape composition and yeast metabolism.

Guaiacol and 4-methylguaiacol are well-known as contributors to the flavor of wines made from smoke-affected grapes, but there are other volatile phenols commonly found in smoke from forest fires that are also potentially important. The relationships between the concentration of a range of volatile phenols and their glycoconjugates with the sensory characteristics of wines and model wines were investigated. Modeling of the attribute ratings from a sensory descriptive analysis of smoke-affected wines with their chemical composition indicated the concentrations of guaiacol, o-cresol, m-cresol, and p-cresol were related to smoky attributes. The best-estimate odor thresholds of these compounds were determined in red wine, together with the flavor threshold of guaiacol. Guaiacol β-D-glucoside and m-cresol β-D-glucoside in model wine were found to give rise to a smoky/ashy flavor in-mouth, and the respective free volatiles were released. The study indicated that a combination of volatile phenols and their glycosides produces an undesirable smoke flavor in affected wines. The observation of flavor generation from nonvolatile glycoconjugates in-mouth has potentially important implications.

The presence of glycosides of smoke-derived volatile phenols in smoke-affected grapes and the resulting wines of Chardonnay and Cabernet Sauvignon was investigated with the aid of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). All volatile phenols studied (phenol, p-, m-, and o-cresols, methylguaiacol, syringol, and methylsyringol) could be detected as glycosylated metabolites in smoke-affected grapes in a similar fashion to that previously reported for guaiacol. These phenolic glycosides were found in smoke-affected grapes and wines at significantly elevated levels compared to those in non-smoked control grapes and wines. The extraction of these glycosides from grapes into wine was estimated to be 78% for Chardonnay and 67% for Cabernet Sauvignon. After acid hydrolysis, a large proportion of these phenolic glycosides in grapes (50%) and wine (92%) disappeared but the concentrations of volatile phenols determined by gas chromatography-mass spectrometry (GC-MS) were lower than expected. In the case of wine, the majority of the glycosides of phenol, cresols, guaiacol, and methylguaiacol were decomposed upon acid hydrolysis without releasing their respective aglycones, while syringol and methylsyringol were more effectively released.

Fermentation of grapes that had been exposed to bushfire smoke can potentially yield unpalatable, smoke-affected wine. Guaiacol and its glucoconjugate were previously found in smoke-affected grapes at an elevated concentration. To find and identify further guaiacol conjugates in smoke-affected grapes, a stable isotope feeding experiment combined with extensive HPLC-MS and MS/MS investigations was carried out. Leaves and berries of a potted grapevine were placed in contact with an aqueous mixture of d(0)- and d(3)-guaiacol for 1-2 days and collected 5 weeks later. Screening for potential guaiacol conjugates in the leaves and berries was facilitated by monitoring the unique mass spectrometric signature of an isotopic doublet separated by 3 Da. Seven different conjugates were detected in leaves and berries and were tentatively identified as mono- and diglycosides of guaiacol. Quantitative analysis demonstrated that the guaiacol conjugates were translocated between leaves and berries to a very limited extent and were also present as low-level natural compounds of untreated leaves and berries. The same guaiacol conjugates were also found at a considerably elevated concentration in leaves and berries obtained from grapevines exposed to bushfire smoke.

Background and Aims: Winemakers from a commercial winery observed sensory differences in Cabernet Sauvignon wines made from three pruning treatments in a single vineyard, particularly in mouthfeel characteristics. This study examined the relationships between wine composition and wine sensory characteristics, then related these to berry weight and composition and wine quality scores. Methods and Results: Cabernet Sauvignon from three pruning treatments � Machine, Cane and Spur � was harvested at commercial harvest date, and replicate wines were made from each for three vintages. The composition of the wines from all three pruning systems was generally similar. Differences in individual descriptive attributes did not separate the wines from the three treatments, or across vintages, despite differences in overall quality scores. Principal component analysis (PCA) could separate the wines by pruning and by vintage using wine composition or sensory parameters. Higher concentrations of anthocyanins, tannins and phenolics in berries did not always result in higher concentrations in wines. Conclusions: In this study, higher wine tannin or wine phenolic concentrations did not result in higher wine astringency, and wine colour measures and phenolic composition were not good indicators of individual wine sensory properties or wine quality. Wine composition was not necessarily directly influenced by berry composition. Significance of the Study: Few studies focus on the berry to wine to sensory continuum, particularly over more than one vintage or in a commercial context. This study highlighted how complex the relationships among berries, wine sensory properties and wine quality can be, particularly within a single vineyard.

Background and Aims: Commercial winemakers observed differences in wine sensory properties among wines produced from vines of three different pruning treatments in a single vineyard. To clarify the relationships between berries and wine quality, this study examined berry size and berry composition and the quality rating for wines produced from the pruning treatments. Methods and Results: The study was conducted over three seasons. Berries from Machine-, Cane- and Spur-pruned vines were sampled at commercial harvest for analysis of berry size and berry phenolic composition. Wines made from each treatment were assessed for quality by a panel of winemakers. Machine berries were lighter and had higher concentrations of anthocyanins, tannins and total phenolics than Cane or Spur. Machine wines had the lowest quality scores. Comparing vintages, berries from 2004 were lighter, but did not always differ in phenolic composition to other vintages, and wines from 2004 had lower quality scores than the other vintages. Vintage effects were generally stronger than pruning effects. Conclusions: In this study, high berry anthocyanins, total phenolics and tannin concentration measures were not good indicators of wine quality scores. Changes in vineyard treatments and, in particular, vintage influences, produce incremental, but potentially important, changes to berry size and composition and to wine quality. Significance of the Study: This study is unique in its focus on the commercial reality of producing wines to a specific style and quality, while bringing scientific rigour to investigating the relationships between berries and wine quality in this vineyard over a number of vintages.

An obscure sesquiterpene, rotundone, has been identified as a hitherto unrecognized important aroma impact compound with a strong spicy, peppercorn aroma. Excellent correlations were observed between the concentration of rotundone and the mean 'black pepper' aroma intensity rated by sensory panels for both grape and wine samples, indicating that rotundone is a major contributor to peppery characters in Shiraz grapes and wine (and to a lesser extent in wine of other varieties). Approximately 80% of a sensory panel were very sensitive to the aroma of rotundone (aroma detection threshold levels of 16 ng/L in red wine and 8 ng/L in water). Above these concentrations, these panelists described the spiked samples as more 'peppery' and 'spicy'. However, approximately 20% of panelists could not detect this compound at the highest concentration tested (4000 ng/L), even in water. Thus, the sensory experiences of two consumers enjoying the same glass of Shiraz wine might be very different. Rotundone was found in much higher amounts in other common herbs and spices, especially black and white peppercorns, where it was present at approximately 10000 times the level found in very 'peppery' wine. Rotundone is the first compound found in black or white peppercorns that has a distinctive peppery aroma. Rotundone has an odor activity value in pepper on the order of 50000-250000 and is, on this criterion, by far the most powerful aroma compound yet found in that most important spice.

Mousy off-flavor is an insidious and economically disastrous microbiologically derived spoilage characteristic of wine and other fermented beverages. Tainted wines are rendered unpalatable and there is currently no satisfactory procedure for removal of the off-flavor. Here we report the confirmation of that both d- and l-lysine can act as a precursor for the formation of mousy off-flavor N-heterocycles. Further, through the use of stable isotope feeding experiments, we could establish that a pentylamine group from lysine is incorporated into the piperideine moiety of two off-flavor N-heterocycles. A biochemical pathway for the formation of mousy off-flavor compounds is proposed.

'Black pepper' aroma and flavor is important to some Australian Shiraz red wine styles but the aroma compounds involved have yet to be identified, and no objective analytical method to assess 'pepper' grape aromas is available to date. Samples of potentially 'spicy'/'peppery' grapes were obtained from vineyards in South Australia and Victoria over two vintages. The important sensory attributes of the grapes, including the aroma descriptor 'pepper', were rated by a sensory panel. The sensory study revealed a strong correlation between the intensity of 'pepper' aroma and the intensity of 'pepper' flavor perceived on the palate. The grape homogenates were analyzed by static headspace GC-MS using a cool inlet system. Vectors obtained by analysis of over 13 000 individual mass spectra per grape sample were then subjected to multivariate analyses. Both principal component analysis and partial least-squares regression were used to develop multivariate models based on mass spectra and aroma descriptors to explain the intensity of the rating of the 'pepper' character. Corresponding differences in mass spectra and aroma were observed among vineyards and from the same vineyards in different years. Additional optimization of the methodology enabled selection of a single region of the GC-MS chromatogram that allowed prediction of 'pepper' aroma intensity with a correlation coefficient0.98 and led to the identification of alpha-ylangene, a tricyclic sesquiterpene. To assess the potential of alpha-ylangene as a marker for this sensory characteristic, a method for alpha-ylangene analysis of grapes and wine using HS-SPME-GC-MS was developed. Although not a significant aroma compound by itself, alpha-ylangene was a satisfactory marker for the 'pepper' aroma in grapes and wine, and its concentration showed similar discrimination between 'peppery' vineyards and vintages as that obtained using the multivariate models. Despite its presence in grapes, we could not detect alpha-ylangene in wine.

The modern wine industry needs tools for process control and quality assessment in order to better manage fermentation or bottling processes. During wine fermentation it is important to measure both substrate and product concentrations (e.g. sugars, phenolic compounds), however, the analysis of these compounds by traditional means requires sample preparation and in some cases several steps of purification are needed. The combination of visible/near-infrared (Vis/NIR) spectroscopy and chemometrics potentially provides an ideal solution to accurately and rapidly monitor physical or chemical changes in wine during processing without the need for chemical analysis. The aim of this study was to assess the possibility of combining spectral and multivariate techniques, such as principal component analysis (PCA), discriminant partial least squares (DPLS), or linear discriminant analysis (LDA), to monitor time-related changes that occur during red wine fermentation. Samples (n = 652) were collected at various times from several pilot scale fermentations with grapes from either Cabernet Sauvignon or Shiraz varieties, over three vintages (2001-2003) and scanned using a monochromator instrument (Foss-NIRSystems 6500, Silver Spring, MD) in transmission mode (400-2,500 nm). PCA was used to demonstrate consistent progressive spectral changes that occur through the time course of the fermentation. LDA using PCA scores showed that regardless of variety or vintage, samples belonging to a particular time point in fermentation could be correctly classified. This study demonstrates the potential of Vis/NIR spectroscopy combined with chemometrics, as a tool for the rapid monitoring of red wine fermentation.