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Both instrumental methods used shows very similar results for Cd concentration and only in some cases the results obtained by FTSCP method were slightly higher in comparison to ZGFAAS method. Also, the accuracy and limit of detection were similar (0.03 μg Cd/l). Comparison of our results for Cd content determined in Croatian wines with the previously published results shows the following. Our value of mean Cd content in Croatian wines of 0.02 to 0.25 μg Cd/l, are generally in agreement with results reported by: Freschi et al. 16) (average Cd concentration of 0.03 to 0.20 μg Cd/l in Brazilian red and white wines), Kim 20) (mean Cd concentration of 0.41 μg Cd/l for white and 0.48 μg Cd/l in red wines on the Korean market), Coetzee et al. 23) (the average concentration of 0.03 to 0.78 μg Cd/l in South African red and white wines), and Cvetković et al. 18) (cadmium content from 0.21 to 0.97 μg Cd/l in red and from 0.12 to 0.79 μg Cd/l in white Macedonian wines). Some authors reported a slightly higher concentration of Cd, like e.g. Brainina et al. 26) (mean Cd content between 0.11 and 1.41 μg Cd/l in wines on Russian market), and Lara et al. 17) (mean Cd content of 1.2–3.6 μg Cd/l in Argentine wines). However, some authors reported significantly higher Cd content (then above cited authors), like e.g. Dugo et al. 27) (they reported the mean Cd concentration in some Italian wines from 2.0 to 12.4 μg Cd/l. Such differences of Cd content in wines, reported in papers of different authors, are normal due to different brands of grape and wines, different conditions of grape and wine production, different type of soil, etc. The content of Cd in wine can be attributed (like also for Pb) to two mainly sources: “natural” Cd content (which come through transfer of cadmium from the soil via the roots to the grapes and finally to wine) and secondary contamination during the grape and winemaking process (like e.g. the use of insecticides and fungicides which contained cadmium salts, due to the contact of must or wine with the apparatus used in wine production and packaging process, etc.). Generally, the cadmium content in wines has been found to be very low. However, cadmium is highly toxic element that accumulates in the human body and has a long halflife (about 30 years). Its toxicity is manifested by a variety of syndromes and diseases which include kidney dysfunction and damage, hypertension, hepatic injury, reproductive toxicity, lung damage, bone effects, etc. 1,2) . Because of its high toxicity and the concern from a health safety point of view, many countries have set limits of the content of Cd in foods. Thus, European Commission (EC) settings the maximum level for cadmium in certain foodstuffs, but not in wines 5) . The Ministry of Health of Republic of Croatia has established a tolerable Cd concentration in wines of 10 μg Cd/l 11) . This value is the same as the maximum acceptable level of Cd in wine established by the Office International de la Vigne et du Vin (OIV) 10) . Due to the toxicity of cadmium and the potential health risks of dietary exposure of humans to cadmium, the JECFA established PTWI value of 7 μg Cd/kg of body weight at the thirty-third Meeting (1988), and this value DLR | November/Dezember 2008 « » Originalarbeiten 51 was maintained at the sixty-fourth Meeting of JECFA in 2005 8) . To evaluate the possible daily intake of Cd through the drinking the examined wines, we used the mean Cd concentration value (0.13 μg Cd/l) of all investigated wine samples. Supposing that an adult person consumes one glass of wine (0.2 l) per day, on average, then average evaluated average daily Cd intake through wine consumption would be around 0.03 μg Cd/d. The total diet studies (TDS) cited in the literature reported different total daily dietary intake (TDDI) of Cd. So, e.g. TDDI value reported for TDS in UK was 14 μg Cd/d 29) , the average daily intake of Cd in USA TDS was 13 μg Cd/d 30) , daily dietary Cd intake by adults in Belgium is 23.1 μg Cd/ d 34) , dietary intake of Cd in Germany for adults is up to 27.6 μg Cd/d 35) , Cd dietary intake in TDS in Spain population was 11.17 μg Cd/d 36) , and the average intake of Cd in adults diet investigated in 13 European countries, according recently information 1,2) is 14.4 μg Cd/d. Our evaluated value of 0.03 μg Cd/d from drinking wines is only 0.1–0.3 % of TDDI values for Cd reported in above TDS. In accordance with PTWI value for Cd established by JECFA 11) an adult person of 60 kg could consume daily up to 60 μg Cd/d (tolerable daily intake, TDI). Our estimated Cd intake (0.03 μg Cd/d) from drinking wines is only 0.05 % of this calculated TDI. Therefore, it can be concluded that the possible daily dietary Cd intake through consumption of wines is negligible in relation to the total dietary daily intake (TDDI) and tolerable daily intake (TDI) of Cd. Thus, Cd from wines is negligible source of dietary Cd intake into the human body. Copper (Cu) The results in Table 1 show that Cu content varies significantly with the brand of wines. The mean Cu concentration of investigated wines ranged from 10 μg Cu/l in white wine Graševina-Kutjevo to 413 μg Cu/l determined in white wine Traminac. The mean concentration of all wine samples investigated (78 samples) was 156 μg Cu/l. The analysis of these results shows that half of all investigated samples (54 %) contained between 100–200 μg Cu/l. Less then 100 μg Cu/l contained 23 % of investigated samples, 15 % of samples have between 200–300 μg Cu/l, and only 8 % of wines contained more then 300 μg Cu/l (up to maximum concentration determined of 413 μg Cu/l). These results show that the concentration of Cu in investigated Croatian wines is significantly below the tolerable limit of Cu content in wines established by Ministry of Health of Republic of Croatia (1000 μg Cu/l) 11) . The same maximum acceptable limit of 1000 μg Cu/l of wine was established by OIV 10) . If we compare the results obtained by FTSCP electrochemical method and spectrometry FAAS method it could be seen from Table 1 that here is no significant difference in the results obtained by these methods. Only, the limit of detection (LOD) of FTSCP method (0.3 μg Cu/l) is lower then that of FAAS (1 μg Cu/l).
52 Originalarbeiten « Tab. 1 Heavy metals content (µg/l) of some Croatian wines Brand of Location Year FTSCP FAAS GFAAS wine (Mean ± SD) (Mean ± SD) Zn Cu Pb White Cd Zn Cu Pb Cd Hvarsko bijelo Hvar Dalmacija 2005 314.3±10.8 37.8±1.5 33.17±2.05 0.17±0.03 311±12 40±3 35.52±2.16 0.15±0.03 Rizling Mandić evac Slavonija 2006 445.4±18.9 150.3±7.1 9.43±0.82 0.25±0.07 453±23 144±9 8.95±0.70 0.22±0.06 Graševina Kutjevo Slavonija 2005 503.5±9.6 10.3±1.3 9.44±0.87 0.15±0.04 502±15 10±2 8.28±0.96 0.11±0.03 Graševina Banovo Brdo Baranja 2005 959.5±16.8 245.7±2.6 16.61±1.05 0.18±0.05 946±21 252±8 15.70±1.13 0.14±0.04 Traminac Ilok Srijem 2005 673.7±10.6 404.0±12.0 5.31±0.43 Rosé 0.12±0.03 683±14 413±16 4.39±0.57 0.10±0.03 Rose Benkovac 2006 687.0±15.5 185.5±5.2 23.69±1.27 0.10±0.03 680±18 193±6 25.47±1.35 0.09±0.03 Benkovac Dalmacija Red Zweigelt Erdut Slavonija 2006 674.6±20.1 129.8±3.3 5.41±0.72 0.05±0.03 690±23 126±4 6.51±0.61 0.05±0.03 Frankovka Orahovica Slavonija 2005 648.6±15.6 131.0±3.4 8.57±0.81 0.13±0.03 630±17 130±6 7.82±0.84 0.10±0.03 Frankovka Ferić anci Slavonija 2006 492.9±10.8 107.4±2.5 6.17±0.78 0.09±0.03 483±12 100±3 6.26±0.73 0.10±0.03 Pinot Noir Kutjevo Slavonija 2006 1176±26.6 264.6±4.0 8.50±0.95 0.06±0.03 1180±35 271±6 7.99±0.69 0.06±0.03 Klikun Noir Kutjevo Slavonija 2005 455.3±11.4 139.9±2.8 9.07±0.93 Fruit Wine 0.18±0.04 463±13 148±4 8.13±0.97 0.16±0.04 Blackberry Ðakovo 2005 574.7±12.5 47.3±2.3 9.17±0.97 0.16±0.04 563±14 44±3 8.34±0.80 0.15±0.04 wine 1 Slavonija Blackberry Požega 2005 720.3±18.3 146.5±3.5 14.44±1.58 0.13±0.03 710±21 140±8 12.87±1.30 0.10±0.03 wine 2 Slavonija Comparison of our results to those of previously reported in the literature show the following. Our results that Cu content in investigated wines ranged from 10 to 413 μg Cu/l are generally in agreement with the results of: Karadjova et al. 15) (they measured Cu content from 160–460 μg Cu/l, in some Macedonians, Bulgarians and Turkish wines, Šperkova and Suchanek 22) (reported mean content of Cu from 45–260 μg Cu/l in some wines from Czech Republic, Catarino et al. 24) (they found between 44 and 237 μg Cu/l in some Portuguese white and red wines), Brainina et al. 26) (they analysed wines on Russian market and found between 25 and 185 μg Cu/l. Some authors reported higher concentration of Cu in wines, like e.g. Coetzee et al. 23) (from 178–600 μg Cu/l in South African wines), Šebečić et al. 14) (between 90 and 930 μg Cu/l in some Croatian wines), Garcia-Esparza et al. 21) (reported that the mean Cu content found in red and white Italian wines was 710 and 1010 μg Cu/l), and Dugo et al. 27) (between 600–900 μg Cu/l in some Sicilian wines). However, in some papers significantly lower values of Cu content were reported; e.g. in paper of Lara et al. 17) , from 23–28 μg Cu/l in some Argentina wines. Such a great differences in Cu content of wines in papers of different authors were probable (mainly) due to great differences of grape, must and wine production conditions (type of soil, different pesticides, fertilizers and chemicals used during the grape production, different winemaking technology used, etc.). The content of Cu in wine may be explained by the natural sources as well as those related to the production processes. Natural Cu come from the soil via the roots to the grapes and finally to wine and the content of Cu in wine from this source significantly depend on type of soil. Second and mainly source of Cu in wine are: different agrochemical products used in grapes production as insecticides and fungicides as well as fertilizers (which contained copper), the use of CuSO 4 for the removal of hydrogen sulfide and other sulfidic off-odours during vinification procedure, the contact of grapes, must and wine with Cu-based equipment during winemaking process, etc. Copper, at low concentration, is important in the fermentative process of wine, while at higher concentration negatively influence the quality of wine, particularly on its organoleptic proper- » November/Dezember 2008 | DLR
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