Investigation of the potential utility of single-bounce attenuated total reflectance Fourier transform infrared spectroscopy in the analysis of distilled liquors and wines

A new Fourier transform infrared (FTIR) spectroscopic method based on single-bounce attenuated total reflectance (SB-ATR) spectroscopy was developed for the analysis of distilled liquors and wines. For distilled liquors, a partial least-squares (PLS) calibration was developed for alcohol determination based on the SB-ATR/FTIR spectra of mixtures of ethanol and distilled water. An independent set of 12 different distilled liquor samples was predicted from the PLS calibration, and a standard deviation of the differences for accuracy (SDD(a)) between actual and predicted values of 0.142% (v/v) was obtained. The potential utility of SB-ATR/FTIR spectroscopy for the analysis of wines was initially evaluated based on a comparison with Fourier transform near-infrared (FT-NIR) spectroscopy and FTIR spectroscopy using a flow-through transmission cell. PLS calibrations for alcohol, total reducing sugars, total acidity and pH were developed using pre-analyzed wine samples (n = 28), and for SB-ATR/FTIR spectroscopy, the SDD(a) for the leave-one-out cross-validation statistics were of the order of 0.100% (v/v), 0.707 g L(-1), 0.189 g L(-1) (H2SO4), and 0.230, respectively. Overall, the SB-ATR/FTIR results were better than those obtained using FT-NIR spectroscopy and comparable to those obtained with transmission FTIR spectroscopy. A PLS calibration based on preanalyzed wine samples (n = 72) for the prediction of 11 different components and parameters in wines by SB-ATR/FTIR spectroscopy was subsequently developed and validated using an independent sample set (n = 77). Good coefficients of correlation between the reference and predicted values for the validation set were obtained for most of the components and parameters except citric acid, volatile acids, and total SO2. The results of this study demonstrate the suitability of SB-ATR/FTIR spectroscopy for the routine analysis of distilled liquors and wines.     

Determination of 24 pesticide residues in fortified wines by solid-phase microextraction and gas chromatography-tandem mass spectrometry

The present work describes a solid-phase microextraction (SPME) gas chromatography-tandem mass spectrometry (MS/MS) method to quantify 24 pesticides in fortified white wine and fortified red wine. In this study "fortified wine" refers to a wine in which fermentation is arrested before completion by alcohol distillate addition, allowing sugar and alcoholic contents to be higher (around 80-100 g/L total sugars and 19-22% alcohol strength (v/v)). The analytical method showed good linearity, presenting correlation coefficients (R(2)) ≥ 0.989 for all compounds. Limits of detection (LOD) and quantitation (LOQ) in the ranges of 0.05-72.35 and 0.16-219.23 μg/L, respectively, were obtained. LOQs are below the maximum residue levels (MRL) set by European Regulation for grapes. The proposed method was applied to 17 commercial fortified wines. The analyzed pesticides were not detected in the wines tested.     

Discrimination between Shiraz wines from different Australian regions: the role of spectroscopy and chemometrics

This study reports the use of UV-visible (UV-vis), near-infrared (NIR), and midinfrared (MIR) spectroscopy combined with chemometrics to discriminate among Shiraz wines produced in five Australian regions. In total, 98 commercial Shiraz samples (vintage 2006) were analyzed using UV-vis, NIR, and MIR wavelength regions. Spectral data were interpreted using principal component analysis (PCA), linear discriminant analysis (LDA), and soft independent model of class analogy (SIMCA) to classify the wine samples according to region. The results indicated that wine samples from Western Australia and Coonawarra can be separated from the other wines based on their MIR spectra. Classification results based on MIR spectra also indicated that LDA achieved 73% overall correct classification, while SIMCA 95.3%. This study demonstrated that IR spectroscopy combined with chemometric methods can be a useful tool for wine region discrimination.     

Biological aging of sherry wines using pure cultures of two flor yeast strains under controlled microaeration

Sherry wines obtained after biological aging for an average of 0, 2, and 4 years were inoculated separately with the flor yeast strains Saccharomyces cerevisiae var. capensis and Saccharomyces bayanus and subjected to short, periodic microaeration to a dissolved oxygen concentration of 4 mg L(-1) after formation of the yeast film. A principal component analysis with the acetaldehyde, ethanol, volatile acidity, and glycerol concentrations obtained was performed. The first principal component was found to account for 49.5% of the overall variance and to be defined mainly by glycerol and ethanol. The second component accounted for 38.8% of the variance and was defined by volatile acidity and acetaldehyde. The conditions used in the tests allowed the biological aging of the wines to be substantially shortened. Thus, 42 days after flor-film formation by S. cerevisiae var. capensis, 0- and 2-year-old wines exhibited parameter values similar to those obtained for the wine aged for 4 years. The wines inoculated with S. bayanus exhibited high acetaldehyde concentrations and ethanol levels above 15% (v/v)-sherry wines with alcohol concentrations below 14.5% are undesirable-, so one need not exclude the sequential or simultaneous inoculation of S. bayanus together with S. cerevisiae var. capensis in order to improve the biological aging process.     

Geographic classification of spanish and Australian tempranillo red wines by visible and near-infrared spectroscopy combined with multivariate analysis

Visible (vis) and near-infrared (NIR) spectroscopy combined with multivariate analysis was used to classify the geographical origin of commercial Tempranillo wines from Australia and Spain. Wines (n = 63) were scanned in the vis and NIR regions (400-2500 nm) in a monochromator instrument in transmission. Principal component analysis (PCA), discriminant partial least-squares discriminant analysis (PLS-DA) and linear discriminant analysis (LDA) based on PCA scores were used to classify Tempranillo wines according to their geographical origin. Full cross-validation (leave-one-out) was used as validation method when PCA and LDA classification models were developed. PLS-DA models correctly classified 100% and 84.7% of the Australian and Spanish Tempranillo wine samples, respectively. LDA calibration models correctly classified 72% of the Australian wines and 85% of the Spanish wines. These results demonstrate the potential use of vis and NIR spectroscopy, combined with chemometrics as a rapid method to classify Tempranillo wines accordingly to their geographical origin.     

White wine with red wine-like properties: increased extraction of grape skin polyphenols improves the antioxidant capacity of the derived white wine.

Lower antioxidant activity in white wines in comparison to red wines lies in the low grape-skin-derived polyphenol content. This paper reports the analysis of the antioxidant capacities of white wine samples obtained along two different processing procedures directed to enrich the wine with polyphenols. White wine samples derived from whole squeezed grapes stored for increasing periods of time (up to 18 h) contained increasing concentrations of polyphenols (from 0.35 to 0.55 mmol/L) and, in parallel, exhibited increased capacity to scavenge free radicals and to inhibit copper ion-induced low-density lipoprotein (LDL) oxidation. However, addition of increasing concentrations of alcohol (up to 18%) to the whole squeezed grapes remarkably augmented the extraction of grape skin polyphenols into the wine up to 1.25 mmol/L, resulting in an increased capacity of the wine to scavenge free radicals and to inhibit LDL oxidation, to an extent similar to that of red wine. The extent of LDL oxidation inhibition was directly related to the wine polyphenolic content (r = 0.986). It is concluded that processing white wine by imposing a short period of grape skin contact in the presence of alcohol leads to extraction of grape skin polyphenols and produces polyphenol-rich white wine with antioxidant characteristics similar to those of red wine.     

Feasibility study on the use of visible and near-infrared spectroscopy together with chemometrics to discriminate between commercial white wines of different varietal origins

The use of visible (vis) and near-infrared spectroscopy (NIR) was explored as a tool to discriminate between samples of Australian commercial white wines of different varietal origins (Chardonnay and Riesling). Discriminant models were developed using principal component analysis (PCA), principal component regression (PCR), and discriminant partial least-squares (DPLS) regression. The samples were randomly split into two sets, one used as a calibration set (n = 136) and the remaining samples as a validation set (n = 133). When used to predict the variety of the validation set samples, the DPLS models correctly classified 100% of Riesling and up to 96% of Chardonnay wines. These results showed that vis-NIR might be a suitable and alternative technology that can be easily implemented by the wine industry to discriminate Riesling and Chardonnay commercial wine varieties. However, the relatively limited number of samples and varieties involved in the present work suggests caution in extending the potential of such a technique to other wine varieties.     

Oenological influences on the D/H ratios of wine ethanol

Within the European Union the determination of chaptalization of wine involves the comparison of the D/H ratios of ethanol with the ratios of authentic wine samples that are similar to the suspect wine in terms of geographical origin, grape variety, and vintage. In the frame of a databank project comparison, wines are produced under official control on a small scale. To clarify the influence of the different production conditions between commercial wines and these databank wines, wines that were produced under varying conditions were investigated by the (2)H NMR method. None of the parameters under investigation, such as yeast strain, fermentation temperature, or wine fining, showed a significant influence on the (D/H)(I) ratio of wine ethanol, which is the most indicative parameter for the determination of the addition of extraneous sugar to wine. For the (D/H)(II) ratio, different values were found for different yeast strains used for fermentation and a slight decrease was observed with increasing fermentation temperature. At increasing points of fermentation yield an increase of the D/H ratios was found in the present alcohol. The total increase of the (D/H)(I) ratio throughout the fermentation was approximately 1 ppm, so that with a fermentation yield of more than 50% no statistical difference could be observed.     

Identification of spectral regions for the quantification of red wine tannins with fourier transform mid-infrared spectroscopy

Accomplishment of fast tannin measurements is receiving increased interest as tannins are important for the mouthfeel and color properties of red wines. Fourier transform mid-infrared spectroscopy allows fast measurement of different wine components, but quantification of tannins is difficult due to interferences from spectral responses of other wine components. Four different variable selection tools were investigated for the identification of the most important spectral regions which would allow quantification of tannins from the spectra using partial least-squares regression. The study included the development of a new variable selection tool, iterative backward elimination of changeable size intervals PLS. The spectral regions identified by the different variable selection methods were not identical, but all included two regions (1485-1425 and 1060-995 cm(-1)), which therefore were concluded to be particularly important for tannin quantification. The spectral regions identified from the variable selection methods were used to develop calibration models. All four variable selection methods identified regions that allowed an improved quantitative prediction of tannins (RMSEP = 69-79 mg of CE/L; r = 0.93-0.94) as compared to a calibration model developed using all variables (RMSEP = 115 mg of CE/L; r = 0.87). Only minor differences in the performance of the variable selection methods were observed.     

3-Hydroxy-4,5-dimethyl-2(5H)-furanone levels in fortified Madeira wines: relationship to sugar content

The maturation of Madeira wines usually involves exposure to relatively high temperatures and humidity levels >70%, which affect the aroma and flavor composition and lead to the formation of the typical and characteristic bouquet of these wines. To estimate the levels of sotolon [3-hydroxy-4,5-dimethyl-2(5H)-furanone] and their behavior over time, 86 aged Madeira wines samples (1-25 years old), with different sugar concentrations, respectively, 90 g L(-)(1) for Boal, 110 g L(-)(1) for Malvazia, 25 g L(-)(1) for Sercial, and 65 g L(-)(1) for Verdelho varieties, were analyzed. Isolation was performed by liquid-liquid extraction with dichloromethane followed by chromatographic analysis by GC-MS. The reproducibility of the method was found to be 4.9%. The detection and quantification limits were 1.2 and 2.0 microg L(-)(1), respectively. The levels of sotolon found ranged from not detected to 2000 microg L(-)(1) for wines between 1 and 25 years old. It was observed that during aging, the concentration of sotolon increased with time in a linear fashion (r = 0.917). The highest concentration of sotolon was found in wines with the highest residual sugar contents, considering the same time of storage. The results show that there is a strong correlation between sotolon and sugar derivatives: furfural, 5-methylfurfural, 5-hydroxymethylfurfural, and 5-ethoxymethylfurfural. These compounds are also well correlated with wine aging. These findings indicate that the kinetics of sotolon formation is closely related with residual sugar contents, suggesting that this molecule may come from a component like sugar.     

Fourier transform infrared spectroscopy and chemometric analysis of white wine polysaccharide extracts

Monovarietal white wines from Maria Gomes and Bical Portuguese Bairrada varieties were prepared according to different maceration and pectic enzyme clarification procedures. The polysaccharide-rich extracts, obtained by wine concentration, dialysis, and lyophilization, were fractionated by graded ethanol precipitation. A wide range of fractions rich in polysaccharides were obtained. Using the spectral region between 1200 and 800 cm(-)(1) of the FTIR spectra of the wine polysaccharide dry extracts, using PCA and CCA chemometric methods, it was possible to discriminate the extracts on the basis of their polysaccharide composition. Moreover, it was possible to identify the wine-making processes involved and their influence on the wine polysaccharides. Furthermore, a calibration model using a PLS1 was proposed for the quantification of mannose in the samples obtained by precipitation with 60% ethanol aqueous solutions. This information will allow an expeditious assessment and monitoring of the polysaccharide composition and modifications that occur during the wine-making processing and evolution.     

Stir bar sorptive extraction combined with GC-MS analysis and chemometric methods for the classification of South African Wines according to the volatile composition

A simple method for the analysis of major wine volatiles and semivolatiles by stir bar sorptive extraction in combination with thermal desorption and gas chromatography-mass spectrometry (SBSE-TD-GC-MS) was developed. Significant experimental parameters such as extraction time, temperature, salt addition, pH, and thermal desorption parameters were optimized to provide a sensitive and robust analytical method. The method provided good repeatability (%RSD < 10%) for 38 major wine volatile compounds, including alcohols, acids, esters, phenols, aldehydes, ketones, and lactones. Quantitative data for 62 South African red and white wines were used to study the suitability of major volatile data for the differentiation of wine samples according to grape variety or cultivar. Principal component analysis (PCA) and cluster analysis (CA) showed that most of the variation in volatile composition between wine samples could be ascribed to differences in wine age, wood contact, and fermentation practices. Despite the contribution of these factors, discriminant analysis (DA) was successfully applied to the classification of red and white wine samples according to cultivar.     

Metabolic influence of Botrytis cinerea infection in champagne base wine

Botrytis cinerea infection of grape berries leads to changes in the chemical composition of grape and the corresponding wine and, thus, affects wine quality. The metabolic effect of Botrytis infection in Champagne base wine was investigated through a (1)H NMR-based metabolomic approach. Isoleucine, leucine, threonine, valine, arginine, proline, glutamine, γ-aminobutyric acid (GABA), succinate, malate, citrate, tartarate, fructose, glucose, oligosaccharides, amino acid derivatives, 2,3-butanediol, acetate, glycerol, tyrosine, 2-phenylethanol, trigonelline, and phenylpropanoids in a grape must and wine were identified by (1)H NMR spectroscopy and contributed to metabolic differentiations between healthy and botrytized wines by using multivariate statistical analysis such as principal component analysis (PCA). Lowered levels of glycerol, 2,3-butanediol, succinate, tyrosine, valine derivative, and phenylpropanoids but higher levels of oligosaccharides in the botrytized wines were main discriminant metabolites, demonstrating that Botrytis infection of grape caused the fermentative retardation during alcoholic fermentation because the main metabolites responsible for the differentiation are fermentative products. Moreover, higher levels of several oligosaccharides in the botrytized wines also indicated the less fermentative behavior of yeast in the botrytized wines. This study highlights a metabolomic approach for better understanding of the comprehensive metabolic influences of Botrytis infection of grape berries in Champagne wines.     

Rapid method for the discrimination of red wine cultivars based on mid-infrared spectroscopy of phenolic wine extracts

Mid-infrared spectroscopy and UV-vis spectroscopy combined with multivariate data analysis have been applied for the discrimination of Austrian red wines, including the cultivars Cabernet Sauvignon, Merlot, Pinot Noir, Blaufr?nkisch (Lemberger), St. Laurent, and Zweigelt. Both authentic wines and their phenolic extracts were investigated by attenuated total reflectance (ATR)-mid-infrared spectroscopy. Phenolic extracts were also investigated by UV-vis spectroscopy. The wine extracts were obtained by solid-phase extraction with C-18 columns and elution by methanol containing 0.01% hydrochloric acid. Hierarchical cluster analysis was performed with mid-infrared spectra of both wines and extracts, as well as with UV-vis spectra of the phenolic extracts. Data processing involved vector normalization and derivation of the spectra. Due to varying concentrations of main components including sugar and organic acids, satisfactory classification of untreated wines was not achieved. However, when using mid-infrared spectra of the phenolic extracts, almost complete discrimination of all cultivars investigated was achieved. The use of UV-vis spectroscopy for cultivar discrimination was found to be limited to the authentication of the Burgundy species Pinot Noir. In addition, soft independent modeling of class analogy was applied to the mid-infrared spectra of the extracts. It was possible to establish class models for five different wine cultivars and to classify test samples correctly.     

Red wine making by immobilized cells and influence on volatile composition

Red wine making using yeast cells immobilized in two types of raisin berries, at various temperatures (6-30 degrees C), was studied. A modification of the batch bioreactor was used to separate the grape skins used for color extraction from the biocatalyst and the fermenting grape must. The evaluation of the immobilized biocatalysts was made on terms of productivity and organoleptic quality, including color intensity and formation of volatiles. The immobilized cells were found capable of low-temperature wine making, producing red wines containing more than 11% v/v alcohol in 8 days at 6 degrees C. The quality of wines was examined by gas chromatography (GC) and GC-MS analysis and sensory evaluation. Higher alcohol concentrations were decreased, and ethyl acetate concentrations increased by the drop of temperature. Many esters, alcohols, carbonyls, and miscellaneous compounds were identified in wines produced by immobilized cells, revealing no significant qualitative differences as compared to wines produced by free cells. The sensory evaluation showed that the best red wine was produced at 6 degrees C.     

Effect of oxygen on volatile and sensory characteristics of Cabernet Sauvignon during secondary shelf life

The oxidation of Cabernet Sauvignon wines during secondary shelf life was studied by headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-quadrupole mass spectrometry (GC-qMS) and sensory tests, with the support of multivariate statistical analyses such as OPLS-DA loading plot and PCA score plot. Four different oxidation conditions were established during a 1-week secondary shelf life. Samples collected on a regular basis were analyzed to determine the changes of volatile chemicals, with sensory characteristics evaluated through pattern recognition models. During secondary shelf life the separation among collected samples depended on the degree of oxidation in wine. Isoamyl acetate, ethyl decanoate, nonanoic acid, n-decanoic acid, undecanoic acid, 2-furancarboxylic acid, dodecanoic acid, and phenylacetaldehyde were determined to be associated with the oxidation of the wine. PCA sensory evaluation revealed that least oxidized wine and fresh wine was well-separated from more oxidized wines, demonstrating that sensory characteristics of less oxidized wines tend toward "fruity", "citrous", and "sweetness", while those of more oxidized wines are positively correlated with "animal", "bitterness", and "dairy". The study also demonstrates that OPLS-DA and PCA are very useful statistical tools for the understanding of wine oxidation.     

Rapid method for proline determination in grape juice and wine

Proline is typically the most abundant amino acid present in grape juice and wine. The amount present is influenced by viticultural and winemaking factors and can be of diagnostic importance. A method for rapid routine quantitation of proline would therefore be of benefit for wine researchers and the industry in general. Colorimetric determination utilizing isatin as a derivatizing agent has previously been applied to plant extracts, biological fluids, and protein hydrolysates. In the current study, this method has been successfully adapted to grape juice and wine and proved to be sensitive to milligram per liter amounts of proline. At sugar concentrations above 60 g/L, interference from the isatin-proline reaction was observed, such that proline concentrations were considerably underestimated in grape juice and dessert wine. However, the method was robust for the analysis of fermentation samples and table wines. Results were within ±10% agreement with data generated from typical HPLC-based analyses. The isatin method is therefore considered suitable for the routine analysis required to support research into the utilization or release of proline by yeast during fermentation.     

Analysis of wine components in Cynthiana and Syrah wines

Red wine is composed of a complex matrix of compounds that can interfere with analysis. A high-performance liquid chromatography (HPLC) procedure was developed to efficiently analyze organic acids, sugars, glycerol, and ethanol in Cynthiana (Vitis aestivalis) wine. Standard laboratory procedures (pH, titratable acidity, and color attributes) and HPLC were found reproducible for Cynthiana wine. HPLC recovery efficiency was determined by analysis of spiked and unspiked samples (model, Cynthiana, and Syrah (Vitis vinifera) wines). Although recovery of components was greater in the model wine, recovery in Cynthiana and Syrah wine was comparable. The HPLC procedure was further compared to commercial rapid enzyme analysis tests using model, Cynthiana, and Syrah wines. HPLC analyses were more accurate than enzymatic tests for determining components in the model, Cynthiana, and Syrah wines. Considering the complexity of the wines analyzed, reproducibility and recovery of the HPLC procedure was demonstrated and showed improvement and precision when compared to existing methods.     

Changes in the sotolon content of dry white wines during barrel and bottle aging

GC-MS in electron ionization mode (EI) was used as a simple, sensitive method for assaying sotolon [4,5-dimethyl-3-hydroxy-2(5) H-furanone] in various dry white wines. The impact of barrel-aging conditions, that is, whether yeast lees were present or not, on the formation of sotolon in dry white wines was then studied. The sotolon content was highest in dry white wines aged in new barrels without lees, often exceeding the perception threshold (8 microg/L). These results demonstrated that yeast lees were capable of minimizing the formation of sotolon in dry white wines during aging. The sotolon and oxygen contents of several bottle of the same white wine were also compared 7 years after bottling. At the range of dissolved oxygen concentrations generally measured, between 5 and 100 microg/L, the sotolon content remained below its perception threshold in wine. The perception threshold was exceeded only in wines with oxygen concentrations above 500 microg/L. The presence of dissolved oxygen in the wine samples analyzed also resulted in a decrease in their free sulfur dioxide content.