Multi-element analysis of South African wines by ICP-MS and their classification according to geographical origin

Wines from three important wine-producing regions, Stellenbosch, Robertson, and Swartland, in the Western Cape Province of South Africa, were analyzed by ICP-MS and the elemental composition used in multivariate statistical analysis to classify the wines according to geographical origin. The method is based on the assumption that the provenance soil is an important contributor to the trace element composition of a wine. A total of 40 elements were determined in 40 wines. Of these, 20 elements: Li, B, Mg, Al, Si, Cl, Sc, Mn, Ni, Ga, Se, Rb, Sr, Nb, Cs, Ba, La, W, Tl, and U showed differences in their means across the three areas. In a stepwise discriminant analysis procedure, functions based on linear combinations of the log-transformed element concentrations of Al, Mn, Rb, Ba, W, and Tl were generated to correctly classify wines from each region. In an alternative approach, a pairwise discriminant analysis procedure, not previously used in wine provenance studies, was tested. In this procedure, the classification was done in three steps, with each step classifying a wine as coming from a certain region or not. The combination of elements characterizing wines from a particular region was different in each region. The discriminant functions were based on the following elements: Al, Mn, Rb, Ba, and W for Stellenbosch; Se, Rb, Cs, and Tl for Robertson; and Al, Mn, Rb, Sr, Ba, and Tl for Swartland. After this procedure, the classification of the wines into one of the groups was 100% successful.     

Fingerprints for main varieties of argentinean wines: terroir differentiation by inorganic, organic, and stable isotopic analyses coupled to chemometrics

Our main goal was to investigate if robust chemical fingerprints could be developed for three Argentinean red wines based on organic, inorganic, and isotopic patterns, in relation to the regional soil composition. Soils and wines from three regions (Mendoza, San Juan, and Co?rdoba) and three varieties (Cabernet Sauvignon, Malbec, and Syrah) were collected. The phenolic profile was determined by HPLC-MS/MS and multielemental composition by ICP-MS; (87)Sr/(86)Sr and δ(13)C were determined by TIMS and IRMS, respectively. Chemometrics allowed robust differentiation between regions, wine varieties, and the same variety from different regions. Among phenolic compounds, resveratrol concentration was the most useful marker for wine differentiation, whereas Mg, K/Rb, Ca/Sr, and (87)Sr/(86)Sr were the main inorganic and isotopic parameters selected. Generalized Procrustes analysis (GPA) using two studied matrices (wine and soil) shows consensus between them and clear differences between studied areas. Finally, we applied a canonical correlation analysis, demonstrating significant correlation (r = 0.99; p < 0.001) between soil and wine composition. To our knowledge this is the first report combining independent variables, constructing a fingerprint including elemental composition, isotopic, and polyphenol patterns to differentiate wines, matching part of this fingerprint with the soil provenance.     

Multielement composition of wines and their precursors including provenance soil and their potentialities as fingerprints of wine origin

The influence of the provenance soil and vinification process on the wine multielemental composition was investigated. For this purpose, two different vineyards from the Douro wine district, Portugal, were selected. Monovarietal grapes from a 10 year old vineyard were used to produce a red table wine, in a very modern winery. Polyvarietal grapes from a 60-70 year old vineyard were used to produce a red fortified wine, similar to Port, through a traditional vinification process. The multielement compositions (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, Hf, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sr, Ti, Th, Tl, U, V, W, Y, Zn, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) of soil, grape juices (prepared in the laboratory), and samples collected in the different steps of each winemaking process were measured. Inductively coupled plasma mass spectrometry was used, after suitable pretreatment of the samples (by UV irradiation for liquid samples and high-pressure microwave digestion for soil). Both vinification processes influenced the multielement composition of the wines. Most of the elements presented similar or even lower concentrations in the wine as compared to that observed in the respective grape juice, probably as a result of precipitation or coprecipitation with suspended particles during fermentation and/or wine aging. Evidence of effective contamination during grape pressing, fermentation, and/or fining of wines (depending on the element) was observed for Cd, Cr, Cu, Fe, Ni, Pb, V, and Zn in the fortified wine and Al, Cr, Fe, Ni, Pb, and V in the table wine. Nevertheless, significant correlations were obtained between the multielement composition of the wine and the respective grape juice (R = 0.997 and 0.979 for the fortified and table wines, respectively, n = 31, P < 0.01), as well as between that in the wine (median of the two studied wines) and the provenance soil (R = 0.994, n = 19, P < 0.01), for the set of elements determined in common in the different types of samples. These results are promising concerning the usefulness of the elemental patterns of both soil and wine as fingerprints of the origin of the studied wines. Nevertheless, more wines from the same and other wine districts must be studied in order to consolidate this conclusion. The multielement compositions of the studied wines were compared with those of wines of different characteristics and origins, as well as with the respective legal threshold limit values, when available. Relatively low metal levels, below their threshold limit values, were found in all cases.     

How much do soil and water contribute to the composition of meat? A case study: meat from three areas of Argentina

The main goal of this study was to propose a reliable method to verify the geographical origin of meat, establishing the influence of soil and water on its isotopic and elemental composition. Thus, beef meat, soil, and water samples were collected from three major cattle-producing regions of Argentina (Buenos Aires, Córdoba, and Entre Ríos). Multielemental composition was determined on these three matrices by inductively coupled plasma mass spectrometry (ICP-MS), δ(13)C and δ(15)N by isotope-ratio mass spectrometry (IRMS), and the (87)Sr/(86)Sr ratio by thermal ionization mass spectrometry (TIMS). Soil and drinking water samples could be characterized and clearly differentiated by combining the isotopic ratios and elements, demonstrating differences in geology and climatic conditions of three regions. Similarly, meat originating at each sampling area was characterized and differentiated using only five key variables (Rb, Ca/Sr, δ(13)C, δ(15)N, and (87)Sr/(86)Sr). Generalized procrustes analysis (GPA), using the three studied matrices (soil, water, and meat) shows consensus between them and clear differences between studied areas. Furthermore, canonical correlation analysis (CCA) demonstrates significant correlation between the chemical-isotopic profile of meat with those corresponding to both soil and water (r(2) = 0.93, p < 0.001; and r(2) = 0.83, p < 0.001, respectively). So far, there are clear coincidences between the meat fingerprint and those from soil/water where cattle grew, presenting a good method to establish beef provenance. To the authors' knowledge this is the first report linking the influence of soil and water all together on the composition of beef, presenting the basis for the authentication of Argentinean beef, which could be extended to meat from different provenances.     

Relationship between soil geochemistry and grape composition in Tuscany (Italy)

The concentrations of 13 trace elements were determined in soils and Sangiovese grapes collected in vineyard zones of Tuscany (Italy). The purpose was to establish a correspondence among the chemical composition of grape, the geochemistry of vineyard soil and the geolithological features of cultivation zone, and determine the provenance of the grapes by means of their chemical fingerprints. Statistical analysis of Ba, Rb and Sr concentrations distinguished three classes of grapes according to the geochemical and geopedological characteristics of the soils. Grapes with the highest Sr levels grew on high‐Sr soils derived from calcareous, calcareous‐marly and marly‐clayey rocks, whereas the most elevated Rb concentrations characterized the berries cultivated on soils formed from clayey‐marly and sandy‐marly lithologies. Grapes with the highest Ba concentrations grew on soil derived from arenaceous rocks and carbonate lithologies of evaporitic origin. These findings suggested that Ba, Rb and Sr could be used as fingerprints for the chemical traceability of Sangiovese grapes.     

Classification of German white wines with certified brand of origin by multielement quantitation and pattern recognition techniques

A procedure is proposed for the determination of the authenticity of white wines from four German wine-growing regions (Baden, Rheingau, Rheinhessen, and Pfalz) based on their content of some major, trace, and ultratrace elements. One hundred and twenty-seven white wine samples possessing a certificate of origin, all of the 2000 vintage, were analyzed. The concentrations of 13 elements (Li, B, Mg, Ca, V, Mn, Co, Fe, Zn, Rb, Sr, Cs, and Pb) were determined in wine diluted 1:20 by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Indium was routinely used as internal standard. Supervised pattern recognition techniques such as discriminant analysis and classification trees were applied for the interpretation of the data. A quadratic discriminant analysis (QDA) allowed the four regions to be discriminated with 83% accuracy when using only eight variables (Li, B, Mg, Fe, Zn, Sr, Cs, and Pb), and the prediction ability for classifying new samples was 76%. By use of a second method, a decision tree, the classification of samples coming from the four regions could be performed with an accuracy of 84% when only four elements were used: Li (very low in samples from Baden), Zn (abnormally low in the samples from the Rheingau), and Mg and Sr (both important for the differentiation between Pfalz and Rheinhessen samples). For this method, the prediction ability was only 74% in the identification of unknown samples. The robustness of the QDA model was not good enough, and therefore the tree is better recommended for the classification of new wine samples from these areas of German wine production.     

洞庭湖地区红土微量与稀土元素地球化学特征及其环境意义

Trace element (TE) and rare earth element (REE) contents in red soils from the Dongting Lake area of China were determined to understanding the provenance and weathering characteristics of the red soils. The results showed similar REE distribution patterns among red soils from the Dongting Lake area, Xiashu loess from Zhenjiang, loess and the Pliocene red soil from the Loess Plateau. These patterns implied a similar provenance from dust-storms, except for red soil R5 which formed by bedrock weathering and had significant light REE (LREE) enrichment and heavy REE (HREE) depletion due to longer weathering periods and higher intensity of weathering. Trace element, especially the Rb/Sr and Li/Ba ratios, and REE, especially the LREE/HREE ratio and δEu could trace weathering intensity. Higher Rb/Sr, Li/Ba, and LREE/ HREE ratios and negative Eu anomalies were present in the red soil from the Dongting Lake area. The weathering intensity was in the decreasing order of R5 in the Dongting Lake area > red soil from the Dongting Lake area (including reticulate red soil, weak reticulate red soil, and homogeneous red soil formed by dust storms) > Xiashu loess from Zhenjiang > Loess-paleosol and Pliocene red soil from the Loess Plateau. Variations in the TE and REE contents of soil could be effectively used to study the provenance and the weathering intensity.     

Trace elements in Bangladesh paddy soils

Abstract

A study was carried out to investigate the status of four micronutrients, iron (Fe), copper (Cu), manganese (Mn), and zinc (Zn), and five other trace elements, cobalt (Co), chromium (Cr), nickel (Ni), lead (Pb), and strontium (Sr), in paddy soils of Bangladesh. Soil samples were digested by hydrofluoric acid (HF)‐nitric acid (HNO₃)‐perchloric acid (HClO₄) for determination of total contents of the nine elements, while DTPA, ASI and 0.1 Mhydrochloric acid (HC1) methods were used for determination of available Fe, Cu, Mn, and Zn. Total trace element contents were found to vary with physiography on which soils are distributed. In general, Ganges Tidal Floodplain soils had the highest content, whereas terrace soils had the lower content. Among the soil properties examined, clay content had a good relation with total trace element contents in the topsoil, except for Sr. Based on the variation with physiography or clay content, the nine trace elements could be grouped into six groups: Cu, Fe and Zn, Pb, Co and Cr and Ni, Mn, Sr. According to the extractable levels of four micronutrients, Bangladesh paddy soils had the medium to optimum amounts of Fe and Cu, but were deficient sporadically in Mn and extensively in Zn. It was indicated that paddy soils of Bangladesh are yet to be polluted with heavy metals.     

环洞庭湖区两种典型红土理化特性比较研究

通过环洞庭湖区两种典型成因红土的野外勘察与取样、室内磁化率、粒度、微量元素(Li、Rb、Sr、Ba)分析,进行两种不同成因的红土理化性质的比较。研究结果表明,风成成因的红土粒度比基岩风化成因红土明显较细,风成成因红土以粉砂为主,基岩风化型红土为砂和粉砂为主;两种成因红土受到长江中游地区高温高湿的气候条件影响,磁化率均显示为低值,明显低于黄土高原黄土和长江下游下蜀黄土;微量元素Li/Ba、Rb/Sr比值显示为高值,显著高于黄土高原黄土和长江中下游地区下蜀黄土,表明两种红土均经历了强烈的风化淋溶过程,但基岩风化型红土的风化成壤强于风成成因红土,可能基岩风化型红土经历了更长的风化成壤过程。     

天山山地土壤中微量元素的含量与分布

天山山地土壤中微量元素含量是比较丰富的。全量含量大多超过我国和世界土壤平均含量。有效态元素含量差异较大,但多数元素含量都超过已知临界值。在分布规律上全量元素垂直差异较明显,但水平上差异不明显,有效态元素的分布某些元素与有机质含量成正相关和全量元素之间无明显的相关性。锶元素在土壤的垂直分布中比较特殊。在动植物体中的生理作用尚需继续深入研究。山地土壤中除锰、锌的有效态含量在剖面中受有机质影响使上下层变化较大之外,其它元素则与母质相似,但土壤类型、质地、pH以及氧化还原电位等因素的影响也是不可忽视的。     

Trace elements in tropical Asian paddy soils

Attempts were made to evaluate correlations of total trace elements with various soil characters in the hope that such correlations would allow prediction of the trace element status of paddy soils in Tropical Asia.

Among the 11 trace elements studied, Ni and Cr showed by far the highest correlation, followed by the pairs of V and Zn, Ni and Zn, and Cr and Zn.

High positive correlations of trace elements with soil characters were found for the following pairs: total Fe₂O³, and V and Zn, total K₂0 and Rb, total CaO and Sr, total TiO₂, and V, total Al₂0³ and Zn, 10 Å clay content and Rb, clay and V, and sand and Zr. Among the negative correlations, the highest was between total SiO₂ and V, followed by those between total SiO₂ and Zn and sand and Zn.

Soil material classes and inherent potentiality ratings previously established were found to have some value for the prediction of the status of certain trace elements in soil.     

Elemental deposition downwind of a coal-fired power plant

Dry deposition of fly ash emitted by a coal-fired power plant has been calculated using a surface depletion Gaussian plume model. The subject plant is located in the southwestern United States. Soil samples collected downwind of this power plant have been chemically analyzed for selected trace elements (As, B, F, Hg, Se, Sr, U, and V) to determine concentration vs. distance trends. Gaussian plume deposition calculations predict very little increase of trace element concentrations in soils, except for those elements highly concentrated in fly ash emissions compared to soils. Trace element soil concentrations as a function of downwind distance generally confirm these predictions, with the possible exception of Se.     

Internal standardization--atomic spectrometry and geographical pattern recognition techniques for the multielement analysis and classification of Catalonian red wines

Major and minor (K, P, Ca, Mg, Na, Fe, Mn, Zn, and Sr) and trace (Ba, Ni, Pb, V, Co, Cd, and Sb) elements from wine samples from the Denomination of Origin (DO) Empordà-Costa Brava (Catalonia, Spain) were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) respectively. Previously, a comparison of different calibration methodologies and sample digestion treatments had been carried out using ANOVA statistical tool. The obtained results demonstrated that internal standardization provides reliable results with the advantage that no further manipulation of the sample is needed. A principal component analysis of the concentration data was performed to differentiate the samples of DO Empordà-Costa Brava from wine samples from other wine-producing regions in Spain (i.e., Penedès, Somontano, and Rioja). It was found that Sr and Ba contents discriminate the two DO groups. Moreover, a discriminant analysis function involving both variables distinguishes the two groups with a 100% classification rate. At the level of the leave-one-out cross-validation, all of the Empordà-Costa Brava samples were well classified, whereas the other DOs presented two borderline misclassifications.     

Trace element concentrations and background values in the arid soils of Hormozgan Province of southern Iran

Trace element concentrations in soils of arid regions of southern Iran are described to assess the concentration ranges of selected elements in a variety of soils and rocks, and to evaluate the potential bioavailability of trace elements in relation to soil properties. The study area was classified into three sub-regions consisting of (1) shale, gypsum, and limestone (western part), (2) igneous rocks and limestone (northern part), and (3) sandstone and limestone (eastern and northeastern part). The gained background values of trace elements were used for evaluating the quality and degree of contamination with native and also with anthropogenic elements of studied soils. Some soil samples indicated a significant enrichment for Pb and Ni, with an enrichment factor (EF) of around 6.0. Soils have only been cultivated for few years compared to hundreds and thousands of years for many agricultural soils; therefore, there has been less crop removal. Furthermore, soils are not highly weathered because they are in an arid climate with low precipitation, which results in a slow rate of weathering. However, slight elemental differences between soil horizons indicated that most soils are poorly developed and also represented the similarity of trace element contents between soils and parent materials.     

贵州喀斯特地区草地开垦对土壤微量元素的影响与评价

为探明生态脆弱区土地利用方式转换对土壤有效态微量元素的影响,以贵州喀斯特地区草地及其相应开垦的农田为对象,采用成对设计的方法研究了草地开垦对土壤微量元素（铜、锰、铁、钼、硼、锌）的影响,并探索基于土壤微量元素密度的区域土壤微量元素丰缺评价指标。结果表明：研究区土壤有效态微量元素在土壤剖面上呈表面富集现象,其含量随土层深度的增加而降低;草地开垦导致土壤有效态铜、铁、硼和钼的含量出现不同程度的降低,降幅为4.97%～79.17%,而土壤有效锌含量则增加,增幅为11.76%～46.06%;开垦导致土壤有效锰含量在剖面上的下降速率加快。建立了研究区6种有效微量元素的丰缺评价指标,该指标以土壤微量元素密度为参数,以参数值的不同范围界定微量元素的丰缺程度,消除了微量元素空间异质性对判定结果的影响。根据该评价指标,研究区土壤有效铁、锰处于极高水平,草地开垦导致土壤有效铜、钼、硼的丰度下降,而有效锌的丰度上升;结合微量元素有效性评价指数,整个研究区土壤有效硼处于低水平,不能够满足植物正常生长发育的需要。该研究结果可为生态脆弱区土地的科学管理和土壤微量元素科学评价体系的建立提供参考。     

神府矿区复垦土地土壤微量元素有效性影响因素研究

为了研究矿区不同复垦条件下,复垦土地土壤中有效微量元素与土壤环境的关系,采用实地试验与实验室分析相结合的方法,研究了不同复垦时间和复垦措施条件下土壤有效铜(Cu)、铁(Fe)、锰(Mn)、锌(Zn)4种微量元素有效态含量与土壤环境之间的关系。结果表明,研究区内土壤有效微量元素含量总体属于极低水平;土壤环境整体呈碱性,土壤pH值均在8.5以上,且变异系数属于小变异;土壤有机质无论是在不同恢复年限条件下,还是在不同治理措施条件下,其变异系数均属于高度变异。土壤环境与土壤有效微量元素相关关系分析结果表明,土壤pH值与土壤有效微量元素呈负相关关系,有效锰、有效铜与土壤pH值的相关性较高;土壤有机质与土壤有效微量元素呈正相关关系,其中有效锌、有效铜与土壤有机质含量的相关性较高。     

广东阳春双滘原产地产品沙姜的特征元素

植物特征元素及其组合能一定程度上反映特定区域对该地植被生长产生的影响。为了探讨元素及其组合能否作为原产地产品的元素指纹标记,分析了广东阳春双滘地区沙姜与土壤中十多种元素的含量、相关性及元素吸收系数。该研究中微量元素在沙姜和土壤中均具有较好的传承性;沙姜对各种元素的吸收具有差异性,沙姜与土壤中元素也具有一定的相关性;通过权重分析初步认定该区域沙姜特征元素为Mn、Zn、Mg、Sr、Cu、Ni、Fe。区域地球化学背景对原产地产品的影响值得深入探讨。     

Red soils derived from limestone contain higher amounts of trace elements than those derived from various other parent materials

The concentrations of 48 trace elements (Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, As, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, In, Cd, Sn, Sb, I, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Tl, Pb, Bi, Th and U) in 14 soils derived from limestone, sampled at three sites, are compared with the concentrations in 500 soil samples derived from a variety of other parent materials. The 500 samples were collected from 75 sites nationwide in order to include the wide range of common soil types in Japan. Most analytical results were obtained by inductively coupled plasma mass spectrometry (ICP-MS), but Cr, As, Br, Zr, Sn, and I concentrations were determined by energy dispersive X-ray fluorescence spectrometry (EDXRF), because the acid dissolution techniques employed in this study were found to be incapable of recovering these elements completely. In order to examine the reliability of analyses, the concentrations of many elements were also determined by EDXRF, inductively coupled plasma-atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). Box and whisker diagrams (Tukey plots), constructed using log-transformed values of each element, show clearly that geometric means of nearly all the trace elements in soils derived from limestone are higher than those in soils derived from other parent materials. The only exceptions are Sr, Ag and Eu, though statistical analysis (Student’s t-test) shows that the differences for these three elements were not significant at p < 0.05. Similarly, the observed differences of geometric means for Sc, Br and Ba between limestone soils and other types of soils were also not significant at p < 0.05. It can be concluded, therefore, that the concentrations of the above-mentioned 48 trace elements in soils derived from limestone are significantly higher than those in other types of soils, with the exception of Sc, Br, Sr, Ag, and Ba, though it was necessary to exclude 81 soil samples, developed on scoriaceous (basaltic) volcanic ash from Mt. Fuji, as an exceptional group for comparisons of V and Cu, as these soils contain higher levels of these two elements. The above results can be attributed to the gradual accumulation of trace elements in the limestone soils due to the intense weathering processes.     

Isotopes as tracers of the Hawaiian coffee-producing regions

Green coffee bean isotopes have been used to trace the effects of different climatic and geological characteristics associated with the Hawaii islands. Isotope ratio mass spectrometry (IRMS) and inductively coupled plasma mass spectrometry ((MC)-ICP-SFMS and ICP-QMS) were applied to determine the isotopic composition of carbon (δ13C), nitrogen (δ15N), sulfur (δ34S), and oxygen (δ18O), the isotope abundance of strontium (87Sr/86Sr), and the concentrations of 30 different elements in 47 green coffees. The coffees were produced in five Hawaii regions: Hawaii, Kauai, Maui, Molokai, and Oahu. Results indicate that coffee plant seed isotopes reflect interactions between the coffee plant and the local environment. Accordingly, the obtained analytical fingerprinting could be used to discriminate between the different Hawaii regions studied.     

我国北部草原系列土壤中成土作用对微量元素含量影响的经向分异

根据我国北部草原系列土壤中１０种微量元素的实测结果，用方差分析和多重比较方法研究了母质和土类因素对该地区土壤微量元素含量的影响。并以主成分得分的调整独立方差为依据，探讨了成土作用对土壤微量元素含量影响的方向，强度及地域分异特征。研究结果证实，不同母质和土类单元草原土壤中微量元素含量有明显差异，其中母质单元间的差别尤为显著，影响草原土壤表层微量元素含量的主要成土因素包括两种类型：导致元素含量下降的淋