Targeted and nontargeted wine analysis by (1)h NMR spectroscopy combined with multivariate statistical analysis. Differentiation of important parameters: grape variety, geographical origin, year of vintage.

The authenticity, the grape variety, the geographical origin, and the year of vintage of wines produced in Germany were investigated by (1)H NMR spectroscopy in combination with several steps of multivariate data analysis including principal component analysis (PCA), linear discrimination analysis (LDA), and multivariate analysis of variance (MANOVA) together with cross-validation (CV) embedded in a Monte Carlo resampling approach (MC) and others. A total of about 600 wines were selected and carefully collected from five wine-growing areas in the southern and southwestern parts of Germany. Simultaneous saturation of the resonances of water and ethanol by application of a low-power eight-frequency band irradiation using shaped pulses allowed for high receiver gain settings and hence optimized signal-to-noise ratios. Correct prediction of classification of the grape varieties of Pinot noir, Lemberger, Pinot blanc/Pinot gris, Müller-Thurgau, Riesling, and Gewürztraminer of 95% in the wine panel was achieved. The classification of the vintage of all analyzed wines resulted in correct predictions of 97 and 96%, respectively, for vintage 2008 (n = 318) and 2009 (n = 265). The geographic origin of all wines from the largest German wine-producing regions, Rheinpfalz, Rheinhessen, Mosel, Baden, and Württemberg, could be predicted 89% correctly on average. Each NMR spectrum could be regarded as the individual "fingerprint" of a wine sample, which includes information about variety, origin, vintage, physiological state, technological treatment, and others.

[1]  D. Salazar,et al.  Regional origin assignment of red wines from Valencia (Spain) by (2)H NMR and (13)C IRMS stable isotope analysis of fermentative ethanol. , 1999, Journal of agricultural and food chemistry.

[2]  F. V. D. van den Berg,et al.  1H nuclear magnetic resonance-based metabolomic characterization of wines by grape varieties and production areas. , 2008, Journal of agricultural and food chemistry.

[3]  C. Pappas,et al.  Differentiation of Greek red wines on the basis of grape variety using attenuated total reflectance Fourier transform infrared spectroscopy , 2008 .

[4]  G. Gremaud,et al.  Classification of Swiss wines on a regional scale by means of a multi-isotopic analysis combined with chemometric methods , 2002 .

[5]  G. Martin,et al.  Characterization of the Geographic Origin of Bordeaux Wines by a Combined Use of Isotopic and Trace Element Measurements , 1999, American Journal of Enology and Viticulture.

[6]  Kashif Ali,et al.  Metabolic characterization of Palatinate German white wines according to sensory attributes, varieties, and vintages using NMR spectroscopy and multivariate data analyses , 2011, Journal of biomolecular NMR.

[7]  Giulia Papotti,et al.  Application of one- and two-dimensional NMR spectroscopy for the characterization of Protected Designation of Origin Lambrusco wines of Modena. , 2013, Journal of agricultural and food chemistry.

[8]  G. Martin,et al.  Deuterium transfer in the bioconversion of glucose to ethanol studied by specific isotope labeling at the natural abundance level , 1986 .

[9]  A. Avenoza,et al.  A thorough study on the use of quantitative 1H NMR in Rioja red wine fermentation processes. , 2009, Journal of agricultural and food chemistry.

[10]  G. Hwang,et al.  Characterization of wines from grape varieties through multivariate statistical analysis of 1H NMR spectroscopic data , 2009 .

[11]  I. Košir,et al.  Use of modern nuclear magnetic resonance spectroscopy in wine analysis: determination of minor compounds , 2002 .

[12]  D. L. García-González,et al.  13C NMR as a primary method for determining saturates, cis‐ and trans‐monounsaturates and polyunsaturates in fats and oils for nutritional labeling purposes , 2009 .

[13]  Claude Guillou,et al.  Natural factors of isotope fractionation and the characterization of wines , 1988 .

[14]  G. Hwang,et al.  Metabolomics reveals alterations in both primary and secondary metabolites by wine bacteria. , 2009, Journal of agricultural and food chemistry.

[15]  I. Košir,et al.  Identification of amino acids in wines by one- and two-dimensional nuclear magnetic resonance spectroscopy. , 2001, Journal of agricultural and food chemistry.

[16]  A. Sacco,et al.  Chemometric classification of Apulian and Slovenian wines using 1H NMR and ICP-OES together with HPICE data. , 2003, Journal of agricultural and food chemistry.

[17]  Ivano Bertini,et al.  Evidence of different metabolic phenotypes in humans , 2008, Proceedings of the National Academy of Sciences.

[18]  Emmanuel Mikros,et al.  1H NMR-based metabonomics for the classification of Greek wines according to variety, region, and vintage. Comparison with HPLC data. , 2009, Journal of agricultural and food chemistry.

[19]  J. Spangenberg,et al.  The application of NMR and MS methods for detection of adulteration of wine, fruit juices, and olive oil. A review , 2003, Analytical and bioanalytical chemistry.

[20]  Won-Mok Park,et al.  Metabolomic studies on geographical grapes and their wines using 1H NMR analysis coupled with multivariate statistics. , 2009, Journal of agricultural and food chemistry.

[21]  A. M. Gil,et al.  Characterization of the aromatic composition of some liquid foods by nuclear magnetic resonance spectrometry and liquid chromatography with nuclear magnetic resonance and mass spectrometric detection , 2003 .

[22]  Manfred Spraul,et al.  NMR-Spectroscopy for Nontargeted Screening and Simultaneous Quantification of Health-Relevant Compounds in Foods: The Example of Melamine , 2009, Journal of agricultural and food chemistry.

[23]  G. Martin,et al.  A new method for the identification of the origin of ethanols in grain and fruit spirits: high-field quantitative deuterium nuclear magnetic resonance at the natural abundance level , 1983 .

[24]  Angelo Cichelli,et al.  Classification of Montepulciano d'Abruzzo Wines by Linear Discriminant Analysis and Artificial Neural Networks , 2000 .

[25]  M. Spraul,et al.  NMR and chemometric methods: a powerful combination for characterization of Balsamic and Traditional Balsamic Vinegar of Modena. , 2008, Analytica chimica acta.

[26]  M. Spraul,et al.  Application of automated eightfold suppression of water and ethanol signals in 1H NMR to provide sensitivity for analyzing alcoholic beverages , 2011, Magnetic resonance in chemistry : MRC.

[27]  Robert G. Dambergs,et al.  Combining mass spectrometry based electronic nose, visible-near infrared spectroscopy and chemometrics to assess the sensory properties of Australian Riesling wines , 2006 .

[28]  杜媛媛,et al.  Classification of Wines Based on Combination of ^1H NMR Spectroscopy and Principal Component Analysis , 2007 .

[29]  P. Mazzei,et al.  NMR spectroscopy evaluation of direct relationship between soils and molecular composition of red wines from Aglianico grapes. , 2010, Analytica chimica acta.

[30]  Hartmut Schäfer,et al.  Classification of olive oils according to geographical origin by using 1H NMR fingerprinting combined with multivariate analysis , 2012 .

[31]  F. V. D. van den Berg,et al.  Evidence of vintage effects on grape wines using 1H NMR-based metabolomic study. , 2009, Analytica chimica acta.

[32]  Philippe Jeandet,et al.  Metabolic influence of Botrytis cinerea infection in champagne base wine. , 2011, Journal of agricultural and food chemistry.

[33]  M. Spraul,et al.  Mixture analysis by NMR as applied to fruit juice quality control , 2009, Magnetic resonance in chemistry : MRC.

[34]  Daniel Cozzolino,et al.  Varietal discrimination of Australian wines by means of mid-infrared spectroscopy and multivariate analysis. , 2008, Analytica chimica acta.

[35]  Jerry Zweigenbaum,et al.  The use of high performance liquid chromatography-quadrupole time-of-flight mass spectrometry coupled to advanced data mining and chemometric tools for discrimination and classification of red wines according to their variety. , 2011, Analytica chimica acta.

[36]  Miguel Ángel Gómez-Nieto,et al.  Ultraviolet-visible spectroscopy and pattern recognition methods for differentiation and classification of wines , 2006 .

[37]  Cherl‐Ho Lee,et al.  Characterization of fermentative behaviors of lactic acid bacteria in grape wines through 1H NMR- and GC-based metabolic profiling. , 2009, Journal of agricultural and food chemistry.

[38]  A. Sacco,et al.  Characterization of the geographical origin of Italian red wines based on traditional and nuclear magnetic resonance spectrometric determinations , 2002 .

[39]  J. Kidrič.  Chapter 5 NMR Study of Beverages , 2008 .

[40]  M. Spraul,et al.  Quality control of beer using high-resolution nuclear magnetic resonance spectroscopy and multivariate analysis , 2005 .

[41]  M. Pérez-Coello,et al.  Determination of anthocyanins in red wine using a newly developed method based on Fourier transform infrared spectroscopy , 2007 .

[42]  A. Moing,et al.  1H NMR metabolite fingerprints of grape berry: Comparison of vintage and soil effects in Bordeaux grapevine growing areas , 2006 .

[43]  O. Fiehn,et al.  Comparison of gas chromatography-coupled time-of-flight mass spectrometry and 1H nuclear magnetic resonance spectroscopy metabolite identification in white wines from a sensory study investigating wine body. , 2009, Journal of agricultural and food chemistry.

[44]  Edoardo Saccenti,et al.  Individual human phenotypes in metabolic space and time. , 2009, Journal of proteome research.

[45]  N. Ogrinc,et al.  Determination of authenticity, regional origin, and vintage of Slovenian wines using a combination of IRMS and SNIF-NMR analyses. , 2001, Journal of agricultural and food chemistry.

[46]  D. Dubourdieu,et al.  Differentiation of white wines by their aromatic index. , 2001, Talanta.

[47]  M. Morelli,et al.  Characterization of wines by nuclear magnetic resonance: a work study on wines from the Basilicata region in Italy. , 2008, Journal of agricultural and food chemistry.

[48]  G. Wider,et al.  Measuring protein concentrations by NMR spectroscopy. , 2006, Journal of the American Chemical Society.

[49]  Francesco Savorani,et al.  Investigations of La Rioja terroir for wine production using 1H NMR metabolomics. , 2012, Journal of agricultural and food chemistry.