Food Chemistry 126 (2011) 673678

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

Can spectroscopy geographically classify Sauvignon Blanc wines from Australia and New Zealand?
D. Cozzolino , W.U. Cynkar, N. Shah, P.A. Smith
The Australian Wine Research Institute, Waite Road, Urrbrae, P.O. Box 197, Adelaide, SA 5064, Australia

a r t i c l e

i n f o

a b s t r a c t
The combination of UV, visible (Vis), near-infrared (NIR) and mid-infrared (MIR) spectroscopy with multivariate data analysis was explored as a tool to classify commercial Sauvignon Blanc (Vitis vinifera L., var. Sauvignon Blanc) wines from Australia and New Zealand. Wines (n = 64) were analysed in transmission using UV, Vis, NIR and MIR regions of the electromagnetic spectrum. Principal component analysis (PCA), soft independent modelling of class analogy (SIMCA) and partial least squares discriminant analysis (PLSDA) were used to classify Sauvignon Blanc wines according to their geographical origin using full cross validation (leave-one-out) as a validation method. Overall PLS-DA models correctly classied 86% of the wines from New Zealand and 73%, 86% and 93% of the Australian wines using NIR, MIR and the concatenation of NIR and MIR, respectively. Misclassied Australian wines were those sourced from the Adelaide Hills of South Australia. These results demonstrate the potential of combining spectroscopy with chemometrics data analysis techniques as a rapid method to classify Sauvignon Blanc wines according to their geographical origin. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 16 November 2009 Received in revised form 17 June 2010 Accepted 2 November 2010

Keywords: Classication Geographical origin Sauvignon Blanc Wine Near-infrared Mid-infrared Visible UV

1. Introduction By nature, food products have a land-based and therefore geographical origin. Historically, food consumption habits were shaped by socio-cultural factors and available local natural resources (Kelly, Heaton, & Hoogerwerff, 2005; Roberts, 1994; Skaggs, Falk, Almonte, & Crdenas, 1996; Thienes, 1994; Tregear, Kuznesof, & Moxey, 1998; van der Lans, vam Ittersum, & De Ciccio, 2001). Such links between food and territory have disappeared over time by various means. These include changes in food production and transportation technologies, urbanisation, and consumer exposure to non-local experiences through travel and the media (Kelly et al., 2005; Roberts, 1994; Skaggs et al., 1996; Thienes, 1994; Tregear et al., 1998; van der Lans et al., 2001). Origin indication is a well-established means of differentiation in the agri-food sector, and is likely to become even more popular in light of market growth trends (van der Lans et al., 2001). However, agri-food producers face additional problems compared to other sectors when using origin due to the particular characteristics of agri-food products and systems (Reid, ODonnell, & Downey, 2006). The use of geographical indications allows producers to obtain market recognition and often a premium price (Tregear et al., 1998; van der Lans et al., 2001). False use of geographical
Corresponding author. Fax: +61 8 8303 6601.
E-mail address: Daniel.cozzolino@awri.com.au (D. Cozzolino). 0308-8146/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodchem.2010.11.005

indications by unauthorised parties is detrimental to consumers and legitimate producers. From this point of view, the development of new and increasingly sophisticated techniques for determining the geographical origin of agricultural products is highly desirable for consumers, agricultural farmers, retailers and administrative authorities (Arhurst & Dennis, 1996; Berrueta, AlonsoSalces, & Herberger, 2007; Tregear et al., 1998; van der Lans et al., 2001). There is growing enthusiasm among consumers for high quality food with a clear regional identity. The reasons for this vary from patriotism, specic culinary, organoleptic qualities, or purported health benets associated with regional products, a decreased condence in the quality and safety of foods produced outside their local region or country. Additionally, as well as heightened consumer awareness, there are a number of important legislative driving forces for reliable analytical techniques to verify food provenance (Arhurst & Dennis, 1996; Berrueta et al., 2007; Tregear et al., 1998; van der Lans et al., 2001). In recent years, there has been increasing interest in food production to assure to the consumers the provenance of the products. Many food properties are related to individual compounds, and their active chemical ingredients such as essential oils, terpenoids, avonoids usually are found in low concentrations (e.g. ppm or ppb) (Cordella, Moussa, Martel, Sbirrazzuoli, & Lizzani-Cuvelier, 2002; Kelly et al., 2005; Luykx & van Ruth, 2008). For many years, the use of standard separation, chromatographic and spectrometric

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methods such as high performance liquid chromatography (HPLC), gas chromatography (GC), liquid chromatography (LC) and mass spectrometry (MS), elemental analysis and isotopic analysis was investigated to classify wines according to their denomination or geographical origin (Arvantoyannis, Katsota, Psarra, Soueros, & Kallinthraka, 1999; Cordella et al., 2002; Kelly et al., 2005; Luykx & van Ruth, 2008). The infrared region (IR) measures the vibrations of molecules, where each functional group, or structural characteristic, of a molecule has a unique vibrational frequency that can be used to determine which functional groups are present in a sample. When the effects of all the different functional groups are taken together, the result is a unique molecular ngerprint that can be used to conrm the identity of a sample. The IR portion of the electromagnetic spectrum is divided into three regions; the near-, mid- and far-infrared, named for their relation to the visible spectrum. The mid-infrared (MIR) (approx. 4000400 cm1) is traditionally used to study the fundamental vibrations and associated rotational vibrational structure, while the higher energy near-infrared (NIR) (14,0004000 cm1) can excite overtone or harmonic vibrations. This means that NIR can provide more complex structural information than MIR (Downey, 1998). Multivariate data analysis (MDA) of the data provided by analytical instruments which have the ability to determine more than one component at a time in a sample can be a support to establish links to the food origin. If the components have sufcient discriminatory power, the set of their concentrations will form a characteristic pattern or ngerprint relating to the geographical origin of the sample. Therefore the use of MDA provides the ability to detect these patterns, and is essentially helpful when the number of components necessary to differentiate samples from different geographical origins increases (Alvarez, Aleixandre, Garcia, Casp, & Zenica, 2003; Castieira, Feldmann, Jakubowski, & Andersson, 2004; Reid, ODonnell, & Downey, 2006). Sauvignon Blanc (Vitis vinifera L., var. Sauvignon Blanc) is considered a simple and non oral white grape variety, none the less is often described as producing highly distinct and characteristic wine in terms of varietal aroma (Berna, Trowell, Clifford, Cynkar, & Cozzolino, 2009; Parr, Green, & White, 2006; Parr, Green, White, & Sherlock, 2007; Swiegers et al., 2009). This grape variety is reported as originating in the south west of France during the seventeenth century where it was known under several names. In newer grape growing regions such as South Africa, Australia and New Zealand, has become an important white cultivar (Berna et al., 2009; Parr, Green, & White, 2006; Parr et al., 2007; Swiegers

et al., 2009). Sauvignon Blanc is currently the most planted white grape variety in New Zealand and comprised 75% of all the wine exports from New Zealand in the 20062007 vintage (Parr et al., 2006, 2007). The variety was introduced in New Zealand in the 70s and subsequent plantings in the region known as Marlborough made it one of the most worldwide renown New Zealand regions for this variety (Parr et al., 2006, 2007). In Australia, Sauvignon Blanc represents 4% (approx 6000 ha) of the total grape vines planted (Iland & Gago, 2002). It is a variety which shows its best when grown in cooler wine regions such as Yarra Valley, Adelaide Hills, Margaret River, Orange in New South Wales and Tasmania, producing wines with grassy, gooseberry characters, whereas, in slightly warmer vintages the more passion fruit avour with a zing of acidity, is more typical (Iland & Gago, 2002; Swiegers et al., 2009). The objective of this study was to investigate the potential use of spectroscopy methods combined with multivariate data analysis to differentiate between the geographical origin of Sauvignon Blanc wines produced in Australia and New Zealand geographical regions. 2. Materials and methods 2.1. Wine samples A total of 34 (17 labels 2 bottles) commercially available Australian and 30 (15 labels 2 bottles) New Zealand Sauvignon Blanc wine samples (V. vinifera L., var. Sauvignon Blanc) from geographically different wine regions were used (see Table 1). All samples were from 2006 vintage, bottled under screw cap and ranging in prices between $16 and $45 Australian dollars per bottle. 2.2. Spectroscopic analysis Wine samples taken from freshly opened bottles were scanned in transmission mode in the visible (Vis) and near-infrared (NIR) regions (4002500 nm) using a scanning monochromator FOSS NIRSystems 6500 (FOSS NIRSystems, Silver Spring, MD, USA). Spectral data were collected using Vision software (version 1.0, FOSS NIRSystems, Silver Spring, USA). Samples were scanned in a rectangular cuvette in a 1 mm path length and equilibrated at 33 C for 3 min before scanning. Spectral data were stored as logarithm of the reciprocal of transmittance [log (1/T)] at two nm intervals (Cozzolino, Smyth, & Gishen, 2003). Samples were also scanned in transmission using a UVVis ow cell (1 and 0.2 mm path length) and in the mid-infrared (MIR) region (4004000 cm1) (25 lm path length) in a Multispec system Bacchus/Multispec System equipped with a Thermo Nicolet, Avatar 380 FT-MIR spectrometer (Microdom, Taverny, France). Replicate bottles from an individual commercial label were used for scanning. Bacchus acquisition software was used for spectra collection and instrument diagnostics (Quant, version 4, 2001) (Cozzolino, Holdstock, Cynkar, Dambergs, & Smith, 2009). 2.3. Multivariate data analysis and classication

Table 1 Geographical distribution, bottle closure and ethanol content of Sauvignon Blanc wines analysed. N Australia Adelaide Hills Victoria McLaren Valley Tasmania Yarra Valley Mornington Peninsula Western Australia Total New Zealand Otago Marlborough Martinborough Wood Thorpe Total N: number of single labels. 10 1 1 1 2 1 1 17 1 11 2 1 15 Ethanol content (v/v) 12.9 13.5 12.5 13.0 13.5 13.5 12.0 Range ethanol (v/v) 12.013.5

13.514.0

12.513.5 14.0 13.1 13.5 12.5

12.514.0 13.514.0 12.514.0

Spectra were exported from both Bacchus acquisition software and Vision in ASCII format and imported into The Unscrambler software (version 9.5, Camo ASA, Oslo, Norway) for principal component analysis (PCA), soft independent modelling of class analogy (SIMCA) and partial least squares discriminant analysis (PLS-DA). PCA was used to reduce the dimensionality of the data to a small number of components, to examine the possible grouping of samples according to their geographical origin (e.g. Australia and New Zealand) and to visualise the presence of outliers (Naes, Isaksson, Fearn, & Davies, 2002; Otto, 1999). Discriminant models were

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developed using PLS-DA regression as described elsewhere (Naes et al., 2002; Otto, 1999). In this technique, each sample in the calibration set is assigned a dummy variable as a reference value, which is an arbitrary number designating whether the sample belongs to a particular group or not; in this case wines produced or sourced from Australia were assigned a numeric value 2 and wines sourced from New Zealand as 1 and the cut-off was set to be 0.5. SIMCA is a supervised pattern recognition technique and enables to classify the samples into an already existing group, assigning new objects to the class to which they show the largest similarity (Esbensen, 2002; Urbano, Luque de Castro, Perez, Garcia-Olmo, & Gomez-Nieto, 2006). This technique is based on PCA, where each class is dened by an independent PCA, taking into account the optimal number of principal components (PC) for each class, which is endowed with a specic data structure (Esbensen, 2002; Urbano et al., 2006). The choice of the SIMCA technique in contrast to other supervised pattern recognition techniques is based on the modelling properties of SIMCA, which provides approaches more versatile than those obtained using discriminant techniques (Esbensen, 2002; Urbano et al., 2006). Both PCA and PLS-DA calibration models were developed using full cross validation. The number of latent variables used was automatically selected by the software using the PRESS function (predicted residual error sum-of-squares) (Naes et al., 2002; Otto, 1999). Additionally, the sample set was divided at random into two sets, namely calibration and validation sets, with each comprising 17 Australian and 15 New Zealand wine samples. 3. Results and discussion Figs. 1 and 2 showed the score plot of the second and third PC using MIR and the rst two PCs using NIR spectra of Sauvignon

Blanc samples analysed, respectively. The rst three PC explained more than 90% of the total variance of the spectra in the set of wines analysed. In Fig. 1, a separation was observed between Australian and New Zealand wines. However, some samples from four labels of Australian wines overlapped with the New Zealand wine samples. These Australian wines were sourced from the Adelaide Hills wine region of South Australia and matched spectrally New Zealand wines, in particular from Marlborough wine region. It has been indicated that the vines grown in Adelaide Hills produce wines in similar climate and soil conditions, to those present in New Zealand (Berna et al., 2009; Iland & Gago, 2002; Parr et al., 2006, 2007; Swiegers et al., 2009). It was also observed that replicate samples of the same label were grouped in the same cluster, but they were not overlapped, which points out bottle to bottle variation. Similar results were reported by other authors (Bevin, Fergusson, Perry, Janik, & Cozzolino, 2006; Cozzolino et al., 2003; Liu et al., 2008). The highest eigenvectors in PC1 were observed in the NIR region around 2180 to 2300 nm wavelengths (data not shown). Absorbances in this wavelength region are related to CH combination and OH stretch overtones (Bevin et al., 2006; Cozzolino et al., 2003; Liu et al., 2008). This indicated that the spectral differences observed might be caused by differences in organic components such as alcohol content, sugars as well as in compounds containing aromatic rings and organic acids (Bevin et al., 2006; Cozzolino et al., 2003; Liu et al., 2008). The highest eigenvectors in PC2 were observed around 1700 nm and 2200 to 2300 nm, related to ethanol and aromatic groups, respectively (Bevin et al., 2006; Cozzolino et al., 2003; Liu et al., 2008). The highest eigenvectors in PC1 were observed in the MIR around 10451080 cm1 related to the C-OH of ethanol, glycerol

Fig. 1. Score plot of the rst two principal components of Sauvignon Blanc wines analysed using mid-infrared spectroscopy. The 95% condence ellipse based on the Hotelling T2 statistics is included in the score plot.

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Fig. 2. Score plot of the rst two principal components of Sauvignon Blanc wines analysed using near-infrared spectroscopy. The 95% condence ellipse based on the Hotelling T2 statistics is included in the score plot.

and sugars (glucose and fructose), at 1268 cm1 related with aromatic groups and between 1419 to 1454 cm1 related with CO@O and C@C, CH2, CH3 associated with organic acids and aldehydes (Boulet, Williams, & Doco, 2007; Edelmann, Diewok, Schuster, & Lendl, 2001; Giangiacomo & Dull, 1986) (data not shown). From the interpretation of the eigenvectors, it was concluded that differences between the spectra of wines sourced from Australia and New Zealand might be related to aromatic groups. Coomans plots were used for evaluating the results from the classication of wine samples according to their geographical origin. These plots provide the orthogonal distance from all new objects to two selected classes at the same time (Esbensen, 2002). The critical cut-off class membership limits are also obtained from these plots. If an object belongs to a model (class) it should fall within the membership limit, which is on the left of the vertical line or below the horizontal line (Esbensen, 2002). The distance versus leverage plot (Si vs Hi) was used to evaluate the SIMCA models developed. Figs. 3 and 4 show the sample to model distance (Si) and sample leverage (H), showing the limits used in the classication, both the distance to the model and the leverage. The wine samples within these limits have a high probability to belong to the class at the chosen level, indicating a separation between the Australian and New Zealand wines using MIR spectra. However, no classication was achieved using NIR. These classication results conrm that either differences or similarities between Australian and New Zealand wines were detected by spectroscopic methods. The PLS-DA models were developed using the UVVis, NIR, MIR and the concatenation of NIR-MIR. Table 2 shows the PLS-DA classication rates (percent of classication) for the validation set according to geographical origin. The PLS-DA models produced an overall rate of correct classication of 86%. Wine samples belonging to New Zealand were 93% correctly predicted using

MIR and the concatenation of NIR and MIR, while and 73%, 86% and 93% of the Australian wines were correctly predicted using NIR, MIR and the concatenation of NIR and MIR, respectively. The results from this study veried that differences exist between the wines from different geographical origins (Australian and New Zealand wines) and conrmed that the spectra contain information important for discriminating among samples. Furthermore analysis of the eigenvectors from the PCA veried that the spectrum of the wine (ngerprint) contains information for prediction of the origin of wine samples. These results also suggested that spectroscopy coupled with multivariate data analysis methods hold the necessary information for a successful classication of wine samples of different geographical origins. When using PLSDA calibration models to predict wine samples, high classication rates were achieved. It was observed that some of the wines analysed in this study were produced from Australian vineyards located in similar environmental conditions (e.g. soil, climate) as those found in the Marlborough region of New Zealand (Parr et al., 2006, 2007). Spectroscopic techniques could provide a similar degree of reliability for wine classication to methods using traditional chemical composition or sensory analyses but without the traditional high-cost and time-consuming analysis. Although, the combination of multivariate data analysis and spectroscopy is qualitative in nature, it avoids the need for expensive and time consuming quantitative methods that require the use of standards and calibration. However, some factors such as the number of samples used to build the calibration models and the similarities between some wines due to environmental conditions, vineyard management or winemaking practices (e.g. type of yeast used during fermentation) limit the precision of the classication models. Therefore, before these methods can be used broadly and with condence by the Australian wine industry, robust models

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Fig. 3. Sample to model distance (Si) and sample leverage (H) for Sauvignon Blanc wine samples analysed using mid-infrared spectroscopy.

Fig. 4. Sample to model distance (Si) and sample leverage (H) for Sauvignon Blanc wine samples analysed using near-infrared spectroscopy.

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D. Cozzolino et al. / Food Chemistry 126 (2011) 673678 organic and non-organic wines grown in Australia. Food Chemistry, 116, 761765. Cozzolino, D., Smyth, H. E., & Gishen, M. (2003). Feasibility study on the use of visible and near-infrared spectroscopy to discriminate between white wine of different varietal origin. Journal of Agricultural and Food Chemistry, 52, 77017711. Downey, G. (1998). Food and food ingredient authentication by mid-infrared spectroscopy and chemometrics. Trends in Analytical Chemistry, 17, 418424. Edelmann, A., Diewok, J., Schuster, K. C., & Lendl, B. (2001). Rapid method for the discrimination of red wine cultivars based on mid infrared spectroscopy of phenolic wine extracts. Journal of Agricultural and Food Chemistry, 49, 11391145. Esbensen, K. H. (2002). Multivariate data analysis in practice. Oslo: CAMO. Giangiacomo, R., & Dull, G. G. (1986). Near-infrared spectrophotometric determination of individual sugars in aqueous mixtures. Journal of Food Science, 51, 679683. Iland, P., & Gago, P. (2002). Australian wine: Styles and tastes. Adelaide: Patrik Iland Wine Promotions. Kelly, S., Heaton, K., & Hoogerwerff, J. (2005). Tracing the geographical origin of food: The application of multi element and multi-isotope analysis. Trends in Food Science and Technology, 16, 555567. Liu, L., Cozzolino, D., Cynkar, W. U., Dambergs, R. G., Janik, L., ONeill, B. K., et al. (2008). Preliminary study on the application of visible-near-infrared spectroscopy and chemometrics to classify Riesling wines from different countries. Food Chemistry, 106, 781786. Luykx, D. M. A. M., & van Ruth, S. M. (2008). An overview of analytical methods for determining the geographical origin of food products. Food Chemistry, 107, 897911. Naes, T., Isaksson, T., Fearn, T., & Davies, T. (2002). A user-friendly guide to multivariate calibration and classication. Chichester: NIR Publications. Otto, M. (1999). Chemometrics: Statistics and computer application in analytical chemistry. Chichester: Wiley-VCH. Parr, W. V., Green, J. A., & White, K. G. (2006). Wine judging, context and New Zealand Sauvignon Blanc. European Review of Applied Psychology, 56, 231238. Parr, W. V., Green, J. A., White, K. G., & Sherlock, R. R. (2007). The distinctive avour of New Zealand Sauvignon Blanc: Sensory characterisation by wine professionals. Food Quality and Preference, 18, 849861. Reid, L. M., ODonnell, C. P., & Downey, G. (2006). Recent technological advances for the determination of food authenticity. Trends in Food Science and Technology, 17, 344353. Roberts, D. C. E. (1994). Food authenticity. British Food Journal, 96, 3335. Skaggs, R., Falk, C., Almonte, J., & Crdenas, M. (1996). Product-country images and international food marketing: Relationships and research needs. Agribusiness, 12, 593600. Swiegers, J. H., Kievit, R. L., Siebert, T., Lattey, K. A., Bramley, B. R., Francis, I. L., et al. (2009). The inuence of yeast on the aroma of Sauvignon Blanc wine. Food Microbiology, 26, 204211. Thienes, M. (1994). Tradition and progress: Registration of geographic denominations of origin. British Food Journal, 96, 710. Tregear, A., Kuznesof, S., & Moxey, A. (1998). Policy initiatives for regional foods: Some insights from consumer research. Food Policy, 23, 383394. Urbano, M., Luque de Castro, M. D., Perez, P. M., Garcia-Olmo, J., & Gomez-Nieto, M. A. (2006). Ultraviolet-visible spectroscopy and pattern recognition methods for differentiation and classication of wines. Food Chemistry, 97, 166175. van der Lans, I., vam Ittersum, K., & De Ciccio, A. (2001). The role of the region of production and EU certicates of origin in consumer evaluation of food products. European Review of Agricultural Economics, 28, 451477.

Table 2 Partial least squares discriminant analysis (PLS-DA) prediction results of Australian and New Zealand Sauvignon Blanc wines using different wavelength regions. New Zealand (N = 15) % UVVIS NIR MIR NIR + MIR 80 80 93 93 (12) (12) (14) (13) Australia (N = 15) % 53 73 86 93 (8) (11) (13) (14) Overall classication % 67 76 90 93

N: number or samples, in brackets number of samples correctly classied.

incorporating more samples (e.g. more variation related to region) are needed to improve the precision of the classication. Acknowledgement This project is supported by Australias grapegrowers and winemakers through their investment body the Grape and Wine Research and Development Corporation. The work was conducted by The Australian Wine Research Institute. References
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