Statistical study of the influence of fungicide treatments (mancozeb,zoxamide and copper oxychloride) on heavy metal concentrations in Sicilian red wine

The aim was to assess the influence of mancozeb, zoxamide and copper oxychloride fungicide treatments on Mn, Zn, Cu, Cd and Pb concentrations in Sicilian red wines, grapes, marcs and grape stalks. The experimentation was carried out over two crop years: 2003 and 2004. Trace metals analysis was performed by derivative stripping chronopotentiometry, which allowed detection of concentrations lower than 1 ng g^?1. The data obtained gave evidence that the levels of Mn and Zn in wines from plots treated with zoxamide–mancozeb were about threefold higher than those observed in the control. Wines treated with Cu oxychloride had a significant increase in Cu(II) concentrations with respect to the control; in particular, samples from 2004 showed a 50% increase in Cu levels. Furthermore, as shown in a previous paper, the fungicides treatments studied led to a moderate increase in Pb(II) and Cd(II) levels in treated samples with respect to the control. Wines from 2004 had higher Cu and Pb amounts than wines from 2003; but the concentrations of all the other metals were similar. Statistical analysis of the data by linear discriminant analysis (LDA) and the Kruskal–Wallis test confirmed that both zoxamide–mancozeb treatments and copper oxychloride treatments exerted a significant influence on Mn(II), Zn(II) Cu(II), Pb(II) and Cd(II) concentrations in wines, grapes, marcs and grape stalks samples from both the studied vintages.     

Arsenic and other trace elements in wines of eastern Croatia

Levels of arsenic and other trace elements (Al, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, U, V and Zn) in nine brands of wine from Slavonia (eastern Croatia) were investigated. Wines from two other viticulture areas, Istria (western Croatia) and Vojvodina (northern Serbia), were used for comparison. Elemental concentrations were determined by high resolution ICP-MS. Statistical methods were applied for the interpretation of obtained data. Regional differences were identified based on a set of geogenic elements (Al, Li, Be, Ti). Elements As and Pb were found to be of predominantly natural origin. Significant differences between the obtained values for As in wines from Slavonia and Vojvodina, compared to wines from Istria indicate that the geochemical arsenic anomalies present in these regions contribute to some extent to higher As content in analysed wines. The Cd, Ni, Zn, Fe and Cr in wine were found to be primarily of anthropogenic origin.     

Varietal and geographic classification of French red wines in terms of pigments and flavonoid compounds

Thirty-four French red wines originating from six different grape varieties and three different production areas were analysed in duplicate for 15 anthocyanins, ten flavonoids and three colour parameters, F-statistics, principal component analysis and stepwise discriminant analysis were used to identify and to explain differences among samples. Clear difference between wines made from different varieties were mainly related to anthocyanin 3-acylglucosides. Malvidin and peonidin 3-acetylglucosides were found in increasing concentrations in wines made respectively from Grenache, Carignan, Cinsault, Merlot, Carbernet Sauvignon and Cabernet Franc grapes; the concentrations of peonidin and malvidin 3-p-coumarylglucosides were higher in the Cinsault wines studied. Cabernet Sauvignon and Merlot wines made near Bordeaux had a less intense colour and a higher malvidin 3-glucoside content than wines from the same varieties produced near Narbonne. Wines made from Merlot, Cabernet Sauvignon and Cabernet Franc grapes contained more catechin, epicatechin and myricetin when produced in the south than in the north (Narbonne, Bordeaux, Angers). Of the samples analysed, 96%, and all of the nine extra wines, were correctly classified according to the variety of the grapes using four anthocyanins and catechin selected by step wise discriminant analyses.     

Elemental Composition of Various Sour Cherry and Table Grape Cultivars Using Inductively Coupled Plasma Atomic Emission Spectrometry Method (ICP-OES)

Three sour cherry and three table grape cultivars were analyzed using inductively coupled plasma optical emission spectrometry. The elements: Na, K, Ca, Mg, Fe, Cu, Zn, Mn, Cr, Cd, Co, Pb, and Ni were detected in all samples; four elements are very abundant (K, Na, Ca, and Mg), and four are not abundant (Cu, Fe, Mn, and Zn). Five of them are trace elements (Cr, Cd, Co, Pb, and Ni) at <0.1 mg/kg. Among the 13 elements analyzed, potassium was the most abundant element distributed throughout all categories of fruits. Iron was the predominant minor element constituents. Manganese concentration was the highest in table grape cultivars. The accuracy of the results was evaluated by spike recovery tests. Analysis of variance was used to establish the metals with significant difference in mean content between the cultivars from sour cherries and between table grapes. Principal component analysis was used to evaluate the distribution of metals.     

Measurement and analysis of mineral and heavy metal components in grape cultivars by inductively coupled plasma-optical emission spectrometer (ICP-OES)

Mineral and heavy metal in grape flesh of different cultivars were measured by inductively coupled plasma-optical emission spectrometer. Eight grape varieties including four wine grapes (Cabernet Sauvignon, Cabernet Franc, Merlot, Cabernet Gernischt) and four table grapes (Muscat, Red Globe, Vitis labruscana Kyoho, Milk grape) from China??s main grape planting region, Changli, Hebei province were investigated. Concentrations of calcium (Ca), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), lead (Pb) and zinc (Zn) were measured. All the parameters investigated in this study significantly changed depending on the cultivar. The minor and heavy metal levels for grape were determined between 5.68 and 15.11?mg/kg Cr, 6.56 and 19.85?mg/kg Cu, 96.79 and 172.15?mg/kg Fe, 6.54 and 25.23?mg/kg Mn, 3.70 and 5.89?mg/kg Ni, 0 and 1.64?mg/kg Pb and 4.29 and 13.44?mg/kg Zn. K ranged from 7,622.87 to 15,276.51?mg/kg and Na concentration ranged from 8,932.82 to 54,343.4?mg/kg. Cadmium was not detected at all.     

Rapid Determination of Trace Elements in Macedonian Grape Brandies for Their Characterization and Safety Evaluation

A graphite furnace atomic absorption spectrometry (GFAAS) was used for determination of trace elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in “rakija” samples, a grape brandy traditionally produced in Republic of Macedonia by distillation of grape pomace or wine, for characterization and safety evaluation. Cd, Pb, Cr, and Ni were determined directly, while Cu, Fe, Mn, and Zn were quantified after appropriate dilution. The calibration curves of all elements were linear with correlation coefficients (R ²) ranging from 0.9995 to 0.9998. The accuracy of the method was checked with a standard addition method showing good repeatability and reproducibility (relative standard deviation (RSD) <10 %). Relationship between several metal concentrations (Cu, Fe, Mn, Zn) in brandies and distillation system (homemade/industrial) on one side and aging mode (oak barrels/oak chips) on the other side were demonstrated. Two homemade brandies showed Cu, Fe, and Zn concentrations higher than industrial distillates and thus were found to be not safe for consumption because of Cu and Zn over the maximum allowed values. For the industrially produced brandies, Mn was identified to be a suitable marker related to aging with oak chips regardless variety, while Cu a marker for the influence of oak chip type. Principal component analysis applied on the content of elements clearly showed a good separation in terms of distillation and aging method.     

Element fingerprinting of Okanagan Valley wines using ICP-MS: Relationships between wine composition, vineyard and wine colour

Analysis of elements in wines by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) may help protect prestigious wineries from counterfeit wines and permit source confirmation for government certification. Thirty-three elements were determined in 17 white and 10 red wines from 13 Okanagan Valley (B.C, Canada) wineries. Multidimensional scaling (MDS) shows that red wines are similar to red wines and white wines similar to white wines. Apparently processing (contact between must and skins during fermentation) affects Li, Zn, Mo, Mg, Ba, Ca and P. However, wines from grapes from the same vineyard tend to be most similar, regardless of the vintage, grape variety or winery that processed the grapes. This implies that wine element 'fingerprints' are relict soil signatures that survive metabolic and winery processing. Elements in wines behave according to geochemical water solubility principals indicating that soil Eh, pH and complexion agents affect element uptake. There is no clear relationship between vintage year or grape variety and wine element composition. However, discriminant analysis indicates that combinations of elements (˜6) from several geochemical groups can accurately classify the wines according to vineyard. Twenty-five elements (Cu, Ni, Ca, Fe, B, Mg, As, Sb, Mn, Sn, P, Al, Zn, U, Sr, Cr, S, Co, Ba, La, Mo, Ti, Pb, Ce and V), determined with high precision by ICP-MS, correlate strongly with vineyard of origin. The limited number of wines available for study requires that conclusions be confirmed with future testing.     

产地土壤重金属对贺兰山东麓酿酒葡萄的影响及风险评估

该实验以宁夏贺兰山东麓酿酒葡萄产区酿酒葡萄产区土壤为研究对象,探究产地土壤中重金属元素被葡萄吸收后对酿酒葡萄安全情况的影响及其相关关系。研究发现,贺兰山东麓酿酒葡萄产区土壤及酿酒葡萄中Cu、Cr、Pb、Cd、As、Hg、Fe、Mn、Zn元素平均含量分别为19.9 mg/kg、1.28 mg/kg,8.1 mg/kg、0.056 1 mg/kg,4.5 mg/kg、0.034 0 mg/kg,0.082 1 mg/kg、0.001 2 mg/kg,1.5 mg/kg、0.008 7 mg/kg,0.030 0 mg/kg、0.000 6 mg/kg,4.2 mg/kg、0.918 mg/kg,68 mg/kg、1.27 mg/kg,2.1 mg/kg、8.12 mg/kg。酿酒葡萄重金属含量与土壤中重金属含量均无显著正相关关系,土壤污染单因子指数表明酿酒葡萄产地土壤污染很低,每千克体质量每周可耐受摄入量（PTWI）和目标风险系数（THQ）表明,贺兰山东麓酿酒葡萄无重金属安全风险。     

Uptake of heavy metals by vegetable plants grown on contaminated soil and their bioavailability in the human gastrointestinal tract.

Lettuce, spinach, radish and carrot were grown on compost that had previously been contaminated at different concentrations of Cd, Cu, Mn, Pb and Zn. Control plants of each vegetable were also grown on unadulterated compost. The experiment was carried out under greenhouse conditions. Mature plants were harvested and their roots and leaves collected. Soil samples from each growing pot and plant materials were acid digested and analysed to determine total metal concentration. Flame-Atomic Absorption Spectroscopy (FAAS) was employed to determine metal concentrations in soil and plant samples (Mn and Zn), while Cd, Cu and Pb in plant materials were analysed by Differential Pulse Anodic Stripping Voltammetry (DP-ASV). Soil (BCR 146R and GBW 07310) and plant (tea leaves, INCT-TL-1) certified reference materials were used to assess accuracy and precision. The edible part of plants, i.e. the leaves of lettuce and spinach and the roots of radish and carrot, were also extracted using an in vitro gastrointestinal (GI) extraction to assess metal bioavailability. The results showed that the uptake of Cd, Cu, Mn and Zn by plants corresponded to the increasing level of soil contamination, while the uptake of Pb was low. Soil-to-plant transfer factor (TF) values decreased from Mn > Zn > Cd > Cu > Pb. Moreover, it was observed from this investigation that individual plant types greatly differ in their metal uptake, e.g. spinach accumulated a high content of Mn and Zn, while relatively lower concentrations were found for Cu and Pb in their tissues. From the in vitro gastrointestinal (GI) study, results indicate that metal bioavailability varied widely from element to element and according to different plant types. The greatest extent of metal releasing was found in lettuce (Mn, 63.7%), radish (Cu, 62.5%), radish (Cd, 54.9%), radish (Mn, 45.8%) and in lettuce (Zn, 45.2%).     

Polyphenols and colour variability of red wines made from grapes harvested at different ripeness grade

Several red wines were elaborated in order to study the influence of the grape harvesting date (degree of maturity of the grape) on their chromatic characteristics and polyphenolic contents. Wines made from two grape varieties, at three different harvesting dates and from two consecutive vintages, were selected for this study. The results showed that the harvesting date of grapes (directly correlated with the degree of maturity of the grapes), influenced the chromatic characteristics of the wines, although their polyphenolic compositions were clearly different, especially in Cabernet Sauvignon wines. In general, higher intensities of blue or violet tones were detected in wines made from the grapes collected on the second harvesting date, in which the ratios anthocyanins/proanthocyanidins and anthocyanins/(proanthocyanidins + catechins) were the lowest. These ratios are proposed as probable indicators of the aptitude for wine ageing.     

A survey of metal contents in some popular brands of wines in the Nigerian market: estimation of dietary intake and target hazard quotients

The concentrations of metals (Cd, Pb, Ni, Cr, Cu, Co, Fe, Mn and Zn) were examined in some popular brands of wine in the Nigerian market after HNO₃/H₂O₂ digestion by atomic absorption spectrophotometry. The mean concentrations (mg/L) of metals in these categories of wines ranged from 0.01 to 0.02, 0.27 to 0.35, 0.10 to 0.12, 0.02 to 0.02, 0.15 to 0.21, 0.09 to 0.10, 3.47 to 4.55, 0.79 to 0.86 and 0.78 to 1.10 for Cd, Pb, Ni, Cr, Cu, Co, Fe, Mn and Zn, respectively. The estimated dietary intakes of metals based on the ingestion of 250?mL/day of these brands of wine were below the specified provisional tolerable daily intake (PTDI) value for each metal. However, only Pb intake from the consumption of these wines constituted 31–41% of its PTDI value as a single source. The estimated target hazard quotients (THQ) for the metals (except for Pb and Cr) are of concern in that they were above the safe level of THQ?相似文献   

Heavy metal content in different types of smoked meat in Serbia

Concentrations of Fe, Cu, Ni, Cr, Pb, Mn, Zn and Cd in pork, beef, turkey and chicken samples were determined using inductively coupled plasma-optical emission spectrometry (ICP-OES). The mean concentration ranges in milligrams per 100?g of the studied metals in all samples were 0.6924–1.2154 for Fe, 0.6492–0.9831 for Cu, 0.0012–0.0027 for Pb, 0.041–0.0510 for Ni, 0.1186–0.1481 for Mn, 0.7257–5.2726 for Zn and 0.0042–0.0050 for Cd. The levels of analysed elements were in accordance with European standards for all metals except for manganese in all samples and for nickel in a certain number of samples. Zn level in beef was significantly higher compared to other samples, and Pb and Cd were found in concentrations well below the recommended daily intake.     

Effect of refermentation conditions and micro-oxygenation on the reduction of volatile acidity by commercial S. cerevisiae strains and their impact on the aromatic profile of wines

Herein, we evaluate the applicability of previously characterized commercial and indigenous Saccharomyces cerevisiae strains and non-S. cerevisiae species for the deacidification of white and red wines at a pilot scale. The effect of the refermentation process (mixture of acidic wine with musts from freshly crushed grapes or with residual marc) as well as micro-oxygenation (MO) on acetic acid removal efficiency and wine aromatic composition was also assessed in a red wine. The commercial strains S26 and S29 efficiently reduced both acetic acid (43 and 47%, respectively) and sugar (100%) after 264 h of refermentation of an acidic white wine that was supplemented with grape must. Similar results (60-66% of acetic acid removal) were observed for red wine deacidification using grape must, independently of MO. When residual marc was used for deacidification, strain S26 removed 40% of acetic acid, whereas strain S29 did not initiate refermentation with or without MO. Wines obtained by refermentation with the must had significantly lower acetic acid and a higher total SO₂ concentration in comparison to the wines deacidified by the grape marcs. The volatile aroma compound's composition of deacidified red wines was dependent on the refermentation process used, rather than on MO. The marc-deacidified wine obtained by the use of strain S26 and without MO achieved the best sensory classification. When data from all analytical and sensory evaluation were combined, Principal Component Analysis (PCA) separated the wines into three distinct groups according to the strain and the refermentation process independently of MO. We successfully established an efficient and cheap enological solution for the rectification of volatile acidity of wines.     

Characterisation and evolution of grape polyphenol profiles of Vitis vinifera L. cv. Tannat during ripening and vinification

Background and Aims: Changes in different polyphenol families during grape ripening and vinification were determined in Tannat grapes. This was done to establish a polyphenol profile for Tannat grapes during ripening and for young wines. Methods and Results: We demonstrated, by high‐performance liquid chromatography with diode array detection and mass spectrometry (HPLC‐DAD‐MS) analysis, that the content of flavan‐3‐ols in Tannat seeds was higher than that reported for a large number of other grape varieties analysed. Forty per cent of the total flavan‐3‐ols in seeds were galloylated compounds, whereas the flavan‐3‐ol profile in skins was characterised by the absence of galloylated forms. Prodelphinidins in skins ranged between 30 and 35% with very low values for epigallocatechin. Epicatechin gallate was not detected in Tannat wine and galloylated forms represented a low percentage of total flavan‐3‐ols. Tannat grapes had very high concentrations of anthocyanins in skins with levels increasing during ripening. Eleven phenolic acids were identified in Tannat grape skins and wines, but only gallic and protocatechuic acids were found in the seeds. Conclusions: Tannat wines were shown to have one of the highest levels of phenolic compounds reported for vinifera grape varieties. The profiles for different polyphenol families present in Tannat grapes (skins and seeds) and wines were determined. Significance of the Study: The results presented will help to better understand the phenolic winemaking potential of this variety and its functional properties within food chemistry.     

Analysis of wines for metals using atomic-absorption spectrophotometry

Summary Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb and Zn were determined using Atomic-Absorption Spectrophotometry (AAS) in 59 Finnish (n =10) and foreign (n = 49) wines sold in Finland. Cd and Pb were determined in a graphite furnace and the other metals with an air-acetylene flame. All wines contained only low levels of heavy metals; in all cases the concentration of Pb was under 0.3 mg/1, that of Cu was under 1.0 mg/1, that of Zn was under 5.0 mg/1 and that of Cd was under 0.1 mg/l, which are the maximum levels permitted in some countries. Finnish wines contained less Pb and Mg and more Cr and Na than the foreign wines analysed.

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Die Analyse von Weinen auf Metalle mittels Atomabsorptionsspektrophotometrie

Zusammenfassung Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb und Zn wurden unter Anwendung der Atomabsorptionsspektrophotometrie (AAS) in 59 finnischen (n =10) und ausländischen (n = 49) in Finnland zum Verkauf gelangenden Weinen analysiert. Die Bestimmung von Cd und Pb wurde im Graphitofen, die der übrigen in einer Luft-Acetylenflamme vorgenommen. Alle untersuchten Weine enthielten nur geringe Mengen von Schwermetallen; in allen Fällen blieb die Pb-Konzentration unter 0,3 mg/l, die Cu-Konzentrationunter 1,0 mg/1, die Zn-Konzentration unter 5,0 mg/1 und die Cd-Konzentration unter 0,1 mg/1. Die angegebenen Konzentrationen stellen die in einigen Ländern zugelassenen Höchstwerte dar. Die finnischen Weine enthielten weniger Pb und Mg, aber mehr Cr und Na als die zur Untersuchung gelangten ausländischen Weine.

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Paper presented at the 27th IUPAC Congress, 27–31 August, 1979, Helsinki     

Detection of ochratoxin A in tropical wine and grape juice from Brazil

BACKGROUND: Ochratoxin A (OTA) is the main mycotoxin found in grapes, wines and grape juices and is considered one of the most harmful contaminants to human health. In this study, samples of tropical wines and grape juices from different grape varieties grown in Brazil were analysed for their OTA content by high‐performance liquid chromatography. RESULTS: The detection and quantification limits for OTA were 0.01 and 0.03 µg L^?1 respectively. OTA was detected in 13 (38.24%) of the samples analysed, with concentrations ranging from < 0.03 to 0.62 µg L^?1. OTA was not detected in any of the grape juice samples. Most of the red wine samples proved to be contaminated with OTA (75%), while only one white wine sample was contaminated. However, the OTA levels detected in all samples were well below the maximum tolerable limit (2 µg L^?1) in wine and grape juice established by the European Community and Brazilian legislature. CONCLUSION: The results of this study indicate a low risk of exposure to OTA by consumption of tropical wines and grape juices from Brazil. © 2012 Society of Chemical Industry     

Regional classification of New Zealand red wines using inductively-coupled plasma-mass spectrometry (ICP-MS)

Red wines in a dataset of 120 single-region wines could be classified into seven of the major New Zealand winegrowing regions with an overall accuracy of 80.8% using leave-one-out linear discrimination with the elements Sr, Rb, Ni, Co, Pb, Mn, Cd, Ga and Cs. A higher classification accuracy of 94.4% was achieved when regions were combined into North Island, Nelson, and other South Island regions. The rare earth elements did not prove useful for regional classification, both because of their low and variable concentrations and because their concentrations can be increased upon bentonite fining. Wines originating in the Gimblett Gravels Winegrowing District could be discriminated from wines grown in the remainder of the Hawke's Bay region with a high degree of accuracy using Ba, Cs, Rb, and Pb. A small difference in elemental composition between Pinot Noir, Cabernet Sauvignon, and Merlot wines originating from the Hawke's Bay region was observed. However, despite this difference greater classification accuracy was obtained with a database containing all the red wines than a subset containing only Pinot Noir wines.     

低温处理葡萄对爱格丽干白葡萄酒香气成分的影响

目的：以不同温度处理爱格丽葡萄原料,寻找增加爱格丽干白葡萄酒香气的最适温度。方法：以白色酿酒葡萄品种爱格丽为原料,16 ℃处理为对照,分别在4、－8、－20、－32 ℃条件下进行低温处理,采用小容器酿酒规范酿制葡萄酒并测定葡萄酒的理化指标,搅拌棒吸附萃取（stir bar sorptive extraction,SBSE）提取葡萄酒中的香气成分,再通过热脱附-气相色谱-质谱联用仪来定性和定量分析葡萄酒的香气成分,用SPSS 19.0软件进行香气成分的主成分分析（principal component analysis,PCA）,8 名经过培训的感官品尝小组成员对酒样进行感官评价。结果：低温处理能促使葡萄酒中香气成分种类的增加和含量的提高。结论：－8、－20 ℃低温处理葡萄可以显著提高爱格丽干白葡萄酒的香气质量,可在一定程度上使葡萄酒的香气更加浓郁。     

Monitoring the Authenticity of Organic Grape Juice via Chemometric Analysis of Elemental Data

Elemental determination was carried out on 36 grape juice samples (19 organic and 17 ordinary), with the goal of identifying significant differences between the two types of juice for classification purposes. Inductively coupled plasma-mass spectrometry was used for the determination of 24 elements, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, La, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Se, Sn, Ti, V, and Zn. Ba, Ce, La, Mg, P, Pb, Rb, Sn, and Ti concentrations were found to be higher in organic versus ordinary samples, while Na and Va concentrations were higher in ordinary versus organic samples. The remaining investigated elements exhibited statistically equivalent concentration levels in both types of samples. Principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA) statistical techniques of the elemental fingerprints were readily able to discriminate organic from ordinary samples and can be used as alternative methods for adulteration evaluation.