Journal of Food Processing and Preservation ISSN 1745-4549

THE VARIATION OF MINERAL PROFILES FROM GRAPE JUICE TO MONOVARIETAL CABERNET SAUVIGNON WINE IN THE VINIFICATION PROCESS
jfpp_586 262..266

JIANGFENG CHENG and CHENGWEI LIANG1

Department of Biotechnology, Qingdao University of Science and Technology, Qingdao 266042, China

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.

J. CHENG and C. LIANG

THE VARIATION OF MINERAL PROFILES

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.

MATERIALS AND METHODS

Sampling
The vinication process is illustrated in Fig. 1. The majority of the containers and tubes used in the production are made of stainless steels, and only tiny parts of the tubes are polyvinyl chloride (PVC) plastic. The sampling strategy was also shown in Fig. 1. The Cabernet Sauvignon grapes from two regions, Yinchuan and Changli, were respectively used to produce monovarietal wine by the same vinication process. The grapes from Yinchun City were used in the rst brewing batch, and the grapes in the second brewing batch were from Changli City. All of the samples were collected from two batches. Sample JG (grape juice) was obtained by the procedure as follows: (1) before tipped into a destemmer, the grapes were randomly selected and collected into a plastic bag from baskets and sent to the laboratory; (2) nonwashed grapes were smashed with gloved hands into a polyethylene tereph-

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.

Apparatus and Reagents

A Varian 710-ES inductively coupled plasma optical emission spectrometer (ICP-OES) was used to determine all of 10 mineral elements (Al, Cu, Fe, Zn, Mn, Ca, K, Mg, Na and Sr). The operational conditions were shown in Table 1. A microwave digestion oven (CEM Corporation) was used for sample decomposition. An ICP-multielement standard stock solution, which was consisted of above elements with of 1,000 mg/L concentration of each element, was used for calibration, and working solutions of mineral elements were prepared daily by serial dilution of stock solutions with deionized water. The range of concentration was determined depending on the variety of element. H2O2 and concentrated HNO3, both from Merck (Merck KGaA, Darmstadt, Germany), pro analysis, were used for the decomposition of samples.

Sample Treatments and ICP-OES Measurements

In order to use aqueous calibration standards, the microwave digestion method was used to remove the organic compoTABLE 1. ICP-OES OPERATING CONDITIONS Parameter RF frequency (MHz) Power (kW) Plasma gas ow (L/min) Auxiliary gas ow (L/min) Nebuliser ow (L/min) Pump rate (rpm) Sample delay time (s) Rinse time (s) Replicate readings FIG. 1. THE SAMPLING POINTS IN THE VINIFICATION PROCESS Instrument operating conditions 27.12 1.0 15 1.5 0.75 15 30 10 3

ICP-OES, inductively coupled plasma optical emission spectrometer.

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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

RESULTS AND DISCUSSION

The Concentration Variation of Mineral Proles in Vinication Process
The concentrations of 10 mineral elements in the samples of grape juices, intermediates in the winemaking process and nal wine products, were indicated in Fig. 2. The samples were collected during two producing batches; the grapes from Yinchuan region were only used in the rst batch, and those from the Changli region only in the second batch. There were signicant differences (P < 0.01) of the contents of each element among different steps of the vinication process for both batches. The trace elements (Al, Cu, Fe, Zn, Mn and Sr), which have either potential toxicity or effect on the organoleptic attribute of wine in case of excess, have attracted concerns. The concentrations of almost all those elements (Al, Fe, Mn and Sr in both batches, Cu and Zn in the second batch) in sample J1 were much higher than in sample GJ (P < 0.01). When the grapes were destemmed and crushed, those elements existing in the nonwashed face of the grapes might probably contaminate the must. In addition, the destemmer and transfer tube were another possible contamination sources. From samples J1 to J2, the concentrations of almost all those elements (except Cu in the rst batch) signicantly decreased (P < 0.01). This was because these elements
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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.

Correlation of Mineral Proles between Grape Juice and Wine

Although the concentrations of mineral elements varied throughout the vinication process, a linear correlation of mineral proles between samples GJ andWP in each of the two batches was statistically detected, respectively. In the rst batch, grapes from the Yinchuan region, Pearson correlation R = 0.992 (P < 0.01,n = 10) was obtained between the mineral proles of samples JG and WP.And in the second batch, grapes from the Changli region, the coefcient of Pearson correlation (R) was 0.999 (P < 0.01, n = 10). It was clear that the mineral prole of wine was strongly dependent on the grape origin.

Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.

J. CHENG and C. LIANG

THE VARIATION OF MINERAL PROFILES

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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Difference of Mineral Proles between Wines Brewed in Two Batches

Partial correlation R = 0.836 (P > 0.01, df = 6) between the mineral proles of two sample WP collected separately in two batches was gured out, and partial correlation R = 0.642 (P > 0.05, df = 6) was also obtained between that of two sample JGs. Although only 10 mineral elements were investigated in the present study, the difference of mineral proles between wines brewed by the grapes from two districts was observed. It seemed that the mineral prole of a wine was the ngerprint of a winemaking grape origin. However, the result must be cautiously extrapolated to other wines, and more grape origins should be added in the future study.

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
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Journal of Food Processing and Preservation 36 (2012) 262266 2011 Wiley Periodicals, Inc.