THE VARIATION OF MINERAL PROFILES FROM GRAPE JUICE TO MONOVARIETAL CABERNET SAUVIGNON WINE IN THE VINIFICATION PROCESS
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Corresponding author. TEL: +86-532-84022879; FAX: +86-532-84863434; EMAIL: liangchw117@126.com The project was supported by National Natural Science Foundation of China (31000135) and Qingdao Municipal Apply and Basic Research Project (11-2-4-3-(5)-jch) Accepted for Publication July 18, 2011 doi:10.1111/j.1745-4549.2011.00586.x
ABSTRACT
The variation of mineral proles in the vinication process was investigated in this paper. The concentrations of 10 mineral elements (Al, Cu, Fe, Zn, Mn, Ca, K, Mg, Na and Sr) in grape juice, must and wine were analyzed by inductively coupled plasma optical emission spectrometry. Cabernet Sauvignon grapes from two districts, Yinchuan and Changli, were used in two vinication batches, respectively. The results indicated that there were signicant differences (P < 0.01) of the contents of each element among individual vinication steps for two batches. The content of Fe in the batch used grapes from Yinchuan was 6.66 mg/L, which was close to the maximum level of 8 mg/L in Chinese GB 15037-2006. Some measures should be taken in practice to control contamination. In addition, strong correlations (P < 0.01) of the mineral proles between the wines and origin grapes were observed in both batches. The prole of the 10 mineral elements in a wine can be tentatively used as a ngerprint to distinguish one wine origin from another.
PRACTICAL APPLICATIONS
This study will lay the foundations for hazard analysis and critical control point (HACCP). The results will guide the winery to control and enhance the quality of the wine. In addition, a mineral prole of a wine was potentially taken as the ngerprint of the wine origin.
INTRODUCTION
Mineral elements are important nutritional ingredients in wine, but trace metal elements are either toxic or unfavorable for wine stability when in excess (Nikolakaki et al. 2002; Lara et al. 2005). These elements are generally within the limit in grapes. For wine, concentrations of these elements may increase due to the contamination in the winemaking process. It has been conrmed in literature. Kristl et al. (2002) concluded that during the maturation of the wine, there was a slight contamination of Cd, Cr and Pb, released from wine cellar equipment (brass and stainless steel). The previous studies have reported that the concentrations of rare earth elements increased from young to nished wines, due to the use of bentonites (Jakubowski et al. 1999; Rossano et al. 2007). Catarino et al. (2008) also proved that bentonite affected the mineral composition of wines and resulted in signicantly higher concentrations of a large group of elements. In addition, Almeida and Vasconcelos (2003) found effective
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contamination during the vinication for a few elements: Cd, Cr, Cu, Fe, Ni, Pb, V and Zn in the fortied wine (traditional process) and Al, Cr, Fe, Ni, Pb and V in the table wine (modern process). Cabernet Sauvignon was the most common variety grapes in China. The grapes collected from two districts (Yinchuan City and Changli City) were used to brew monovarietial wine by a typical vinication process in modern Chinese winery. However, there are few investigations relative to the inuence of vinication process on the multielemental composition of wine. In this study, each step of the winemaking process (from grape to wine) was tracked to investigate the variation of the mineral proles. The concentrations of heavy mineral elements were analyzed. The aim was to nd in which step the contaminations of the heavy mineral elements were introduced into the wine. The possible reasons were deduced, which would lay the foundations for hazard analysis and critical control point (HACCP). The results will guide the winery to control and enhance the quality of the wine. In addition, a
Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.
mineral prole of a wine was potentially taken as the ngerprint of the wine origin (Brescia et al. 2003; Taylor et al. 2003; Castieira et al. 2004; Thiel et al. 2004; Coetzee et al. 2005; Iglesias et al. 2007). So far, there are no correlative investigations in China.
thalate (PET) bottle through a PVC hopper after their skins and seeds were removed; (3) the bottle were instantly sealed with PET cap when aliquots of grape juice were enough in triplicate for assay. From sample J1 to J7, the intermediaries were collected in triplicate in PET bottles throughout the vinication process. We sampled when the mineral prole might changed due to contamination, precipitation, coprecipitation or other unknown factors. Sample J3 was collected after 3 days of alcoholic fermentation, and sample J4 was taken when the fermentation was nished after about 7 days. In this study, the nal wine was stored in glass bottles after aging in oak barrels for about 6 months. After bottling, the wines were placed for two weeks, and then three bottles of wine were randomly selected as sample WP, which was used for later analysis.
Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.
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nents in the samples. Five milliliters of the sample obtained in sampling section was transferred into a uorocarbon microwave vessel. Six milliliters of concentrated HNO3 and 2 mL H2O2 were added to the vessel. Microwave digestion program was given below; 1,200 W power and 840 kPa pressure was employed for the digested of samples at 200C. Ramp time was 10 min, and hold time was 10 min. The total digestion time was 20 min. After cooling, the mixture was quantitatively transferred to a 50-mL volumetric ask and made up to the mark with deionized water. The ICP-OES semiquantitative mode of analysis was used in the determination of all the 10 elements in 54 samples (nine samples in triplicate for each grape region, two regions involved). To control the analysis accuracy, calibration reagent blank and instrument check were carried out together with the sample determination according to the procedures described by Jos et al. (2004).
Data Processing
To compare means and calculate correlation coefcients of different mineral proles in the vinication process, the statistical calculations, including one-way analysis of variance, Student NewmanKeuls multiple comparison, Pearson correlation and partial correlation,were carried out by the software of SPSS 10.0 (SPSS Inc., Chicago, IL) on Windows operation system
precipitated or coprecipitated with organic polymers in the must, such as polyphenols (Thiel et al. 2004). In addition, the addition of pectinase as a kind of protein possibly promoted sedimentation. From samples J2 to WP, Al maintains a neatly constant concentration in both batches. So does Fe. It seems there is no secondary contamination for these two elements. Interestingly, obvious increases of Mn and Sr concentrations were found from samples J2 to J5 (P < 0.01). However, in both batches, the concentrations of Mn and Sr were kept constant (P > 0.05) in samples J5, J6, J7 and WP. The result showed that there is no contamination in the last three steps. It is possible that these two elements come from the grape seeds and skins. So the concentrations of Mn and Sr were at a higher level in the must before the pressing stage. Almeida and Vasconcelos (2003) have described the release of the Sr element in the steps. For Cu (in the second batch) and Zn (in both batches), very obvious increases of their concentrations were observed from samples J5 to J6. That was mostly attributed to secondary contamination from the presser, pump and transfer tube. Although contamination occurs in the vinication process, the concentrations of metals in sample WP were lower than the maximum limit regulated in Chinese GB 15037-2006 (for wine) and/or presented by the International Organization of Vine and Wine (OIV). For example, the threshold limit of Cu content in both Chinese GB 15037-2006 and the OIV is 1 mg/L, and the concentrations in our experiments were 0.23 and 0.38 mg/L, respectively, in two batches. For Zn, the concentrations were 2.01 and 1.31 mg/L, respectively, in two batches, which were lower than the upper limit of 5 mg/L allowed in OIV. For Fe, the contents in two batches were 6.66 and 3.51 mg/L, respectively. The numerical value in the second batch was lower than the maximum level of 8 mg/L in Chinese GB 15037-2006. To minimize the contamination and improve the quality of wines, it is suggested that the steps of destemming and pressing should be as critical control points in the vinication process. The possible contaminating sources should be found out. And some measures should be taken to control the contamination as small as we like.
Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.
FIG. 2. CONTENTS (MEAN AND STANDARD DEVIATION, N = 3) OF 10 ELEMENTS (AL, CU, FE, ZN, MN, CA, K, MG, NA AND SR) DETERMINED IN THE SAMPLES OF GRAPE JUICES (JG), INTERMEDIATE JUICES COLLECTED IN THE STEPS OF THE VINIFICATION PROCESS (J1J7) AND THE FINAL WINE PRODUCTS (WP). grapes from the Yinchuan region (Ningxia Province). grapes from the Changli region (Hebei Province).
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CONCLUSION
In conclusion, it is found that the contents of all elements varied in the vinication process. In the steps of destemming, obvious contamination was observed for all of the trace elements, Al, Cu, Fe, Zn, Mn and Sr. In the pressing of the vinication process, contamination was mostly occurred for Cu and Zn. Although contamination occurred, the concentrations of Cu and Zn in the nal wine product were lower than the maximum limit regulated in Chinese GB 15037-2006 and/or presented by the OIV. The content of Fe in the rst batch was 6.66 mg/L, which was close to the maximum level of 8 mg/L in Chinese GB 15037-2006. In this study, a signicant correlation (P < 0.01) between the mineral prole of wines and the grape origins was observed in each batch. The mineral proles between the wines brewed in two batches were compared. No signicant correlation (P > 0.01) was obtained. Similar result (P > 0.05) was found on the correlation between the grapes. Therefore, the mineral prole of only 10 elements could be used as a ngerprint to discriminate wines originated from Yinchuan or Changli region. Nevertheless, more wines made from other grape origins must be investigated to validate this conclusion.
ACKNOWLEDGMENTS
The authors gratefully thank Mr. Liu Chunsheng and Ms. Xia Guangli for help in the sampling, Ms. Zhang Huizhen and Mr. Li Zhaoyong for the measurements by the ICP spectrometer and Dr. Xu lei for valuable discussions on data treatment. REFERENCES
ALMEIDA, C.M. and VASCONCELOS, M.T. 2003. Multielement composition of wines and their precursors including provenance soil and their potentialities as ngerprints of wine origin. J. Agric. Food Chem. 51, 47884798.
BRESCIA, M.A., KOSIR, I.J., CALDAROLA, V., KIDRIC, J. and SACCO, A. 2003. Chemometric classication of Apulian and Slovenian wines using 1H NMR and ICP-OES together with HPICE data. J. Agric. Food Chem. 51, 2126. CASTIEIRA, M.M., FELDMANN, I., JAKUBOWSKI, N. and ANDERSSON, J.T. 2004. Classication of German white wines with certied brand of origin by multielement quantitation and pattern recognition techniques. J. Agric. Food Chem. 52, 29622974. CATARINO, S., MADEIRA, M., MONTEIRO, F., ROCHA, F., CURVELO-GARCIA, A.S. and DE SOUSA, R.B. 2008. Effect of bentonite characteristics on the elemental composition of wine. J. Agric. Food Chem. 56, 158165. COETZEE, P.P., STEFFENS, F.E., EISELEN, R.J., AUGUSTYN, O.P., BALCAEN, L. and VANHAECKE, F. 2005. Multi-element analysis of South African wines by ICP-MS and their classication according to geographical origin. J. Agric. Food Chem. 53, 50605066. IGLESIAS, M., BESAL, E. and ANTIC, E. 2007. Internal standardization atomic spectrometry and geographical pattern recognition techniques for the multielement analysis and classication of Catalonian red wines. J. Agric. Food Chem. 55, 219225. JAKUBOWSKI, N., BRANDT, R., STUEWER, D., ESCHNAUER, H. and GORTGES, S. 1999. Analysis of wines by ICP-MS: is the pattern of the rare earth elements a reliable ngerprint for the provenance. Fresenius J. Anal. Chem. 364, 424428. JOS, A., MORENO, I., GONZLEZ, A.G., LPEZ-ARTGUEZ, M. and CAMEN, A.M. 2004. Study of the mineral prole of Catalonian brut cava using atomic spectrometric methods. Eur. Food Res. Technol. 218, 448451. KRISTL, J., VEBER, M. and SLEKOVEC, M. 2002. The application of ETAAS to the determination of Cr, Pb and Cd in samples taken during different stages of the winemaking process. Anal. Bioanal. Chem. 373, 200204. LARA, R., CERUTTI, S., SALONIA, J.A., OLSINA, R.A. and MARTINEZ, L.D. 2005. Trace element determination of Argentine wines using ETAAS and USN-ICP-OES. Food Chem. Toxicol. 43, 293297. NIKOLAKAKI, S.G., KONTOS, N.K. and KATSANOS, A.A. 2002. Trace elements analysis of Cretan wines and wine products. Sci. Total Environ. 285, 155163. ROSSANO, E.C., SZILGYI, Z., MALORNI, A. and POCSFALVI, G. 2007. Inuence of winemaking ractices on the concentration of rare earth elements in white wines studied by inductively coupled plasma mass spectrometry. J. Agric. Food Chem. 55, 311317. TAYLOR, V.F., LONGERICH, H.P. and GREENOUGH, J.D. 2003. Multielement analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics. J. Agric. Food Chem. 51, 856860. THIEL, G., GEISLER, G., BLECHSCHMIDT, I. and DANZER, K. 2004. Determination of trace elements in wines and classication according to their provenance. Anal. Bioanal. Chem. 378, 16301636.
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Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.