Multielement analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics

Trace element fingerprints were deciphered for wines from Canada's two major wine-producing regions, the Okanagan Valley and the Niagara Peninsula, for the purpose of examining differences in wine element composition with region of origin and identifying elements important to determining provenance. Analysis by ICP-MS allowed simultaneous determination of 34 trace elements in wine (Li, Be, Mg, Al, P, Cl, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Mo, Ag, Cd, Sb, I, Cs, Ba, La, Ce, Tl, Pb, Bi, Th, and U) at low levels of detection, and patterns in trace element concentrations were deciphered by multivariate statistical analysis. The two regions were discriminated with 100% accuracy using 10 of these elements. Differences in soil chemistry between the Niagara and Okanagan vineyards were evident, without a good correlation between soil and wine composition. The element Sr was found to be a good indicator of provenance and has been reported in fingerprinting studies of other regions.     

Effects of fertilization, crop year, variety, and provenance factors on mineral concentrations in onions

Mineral concentrations of onions (Allium cepa L.) grown under various conditions, including factors (fertilization, crop year, variety, and provenance), were investigated to clarify how much each factor contributes to the variation of their concentrations. This was because the mineral concentrations might be affected by various factors. The ultimate goal of this study was to develop a technique to determine the geographic origins of onions by mineral composition. Samples were onions grown under various conditions at 52 fields in 18 farms in Hokkaido, Japan. Twenty-six elements (Li, Na, Mg, Al, P, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Mo, Cd, Cs, Ba, La, Ce, Nd, Gd, W, and Tl) in these samples were determined by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. Fertilization conditions and crop years of onions caused variations of P, Ni, Cu, Rb, Sr, Mo, Cs, and Tl concentrations in onions; different onion varieties also showed variations in numerous element concentrations. However, the variations of mineral compositions of onions by these factors were smaller than the differences between production places with a few exceptions. Furthermore, Na, Rb, and Cs in group IA of the periodic table, Ca, Sr, and Ba in group IIA, and Zn and Cd in group IIB showed similar concentration patterns by group; this result demonstrated that elements in the same periodic groups behaved similarly in terms of their absorption in onions.     

Effect of bentonite characteristics on the elemental composition of wine

Physical, chemical, and mineralogical characteristics of six bentonites were assessed and related to their elemental release to wine. Extraction essays of bentonites in wine at three pH levels were carried out. The multielemental analysis of bentonites and wines was performed by atomic absorption spectrometry (AAS) and inductively coupled plasma mass spectrometry (ICP-MS). Bentonite addition resulted in significantly higher concentrations of Li, Be, Na, Mg, Al, Ca, Sc, V, Mn, Fe, Co, Ni, Ga, Ge, As, Sr, Y, Zr, Nb, Mo, Cd, Sn, Sb, Ba, W, Tl, Bi, and W. In contrast, the concentrations of B, K, Cu, Zn, and Rb significantly decreased. A strong correlation between Na concentrations of treated wines and its content in bentonite exchange complex was observed. Al and Fe contents reflected bentonite extractable aluminous and ferruginous constituents, while Be, Mg, Ca, V, Mn, Ni, Ge, Zr, Nb, Mo, Sn, Sb, Tl, Pb, and U concentrations reflected the elemental composition of bentonites. Several nonconformances with OIV specifications demonstrated the need for an effective control.     

Accumulation and distribution pattern of macro- and microelements and trace elements in Vitis vinifera L. cv. Chardonnay berries

This paper describes the accumulation pattern of 42 mineral elements in Vitis vinifera L. berries during development and ripening and their distribution in berry skin, seeds, and flesh around harvest time. Grape berries were sampled in two different vineyards with alkaline soil and analyzed using a ICP-MS. Although elemental amounts were significantly different in the grapes from the two vineyards, the accumulation pattern and percentage distribution in different parts of the berries were generally quite similar. Ba, Eu, Sr, Ca, Mg, Mn, and Zn accumulate prior to veraison. Al, Ce, Dy, Er, Ga, Gd, Ho, La, Nd, Pr, Sm, Sn, Zr, Th, Tm, U, Y, and Yb accumulate mainly prior to veraison but also during ripening. Ag, As, B, Cd, Cs, Cu, Fe, Ge, Hg, K, Li, Na, P, Rb, Sb, Se, and Tl accumulate progressively during growth and ripening. With regard to distribution, Ba, Ca, Eu, Fe, Mn, P, Sr, and Zn accumulate mainly in the seeds, Al, B, Ga, Sn, and the rare earths analyzed, except for Eu, accumulate mainly in the skin, and Ag, As, Cd, Cs, Cu, Ge, Hg, K, Li, Mg, Na, Rb, Sb, Se, Th, Tl, U, and Zr accumulate mainly in the flesh. A joint representation of the accumulation and distribution patterns for the elements in the berry is also given.     

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.     

Searching the most appropriate sample pretreatment for the elemental analysis of wines by inductively coupled plasma-based techniques

Different sample preparation methods were evaluated for the simultaneous multielement analysis of wine samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Microwave-assisted digestion in closed vessel, thermal digestion in open reactor, and direct sample dilution were considered for the determination of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, and Bi in 12 samples of red wine from Valencia and Utiel-Requena protected designation of origin. ICP-MS allows the determination of 17 elements in most of the samples, and using ICP-OES, a maximum of 15 elements were determined. On comparing the sample pretreatment methodology, it can be concluded that the three assayed procedures provide comparable results for the concentration of Li, Na, Mg, Al, K, Ca, Mn, Fe, Zn, and Sr by ICP-OES. Furthermore, ICP-MS data found for Cu, Pb, and Ba were comparable. Digestion treatment provides comparable values using both total decomposition in open system and microwave-assisted treatment for Cu by ICP-OES and for Cr, Ni, and Zn by ICP-MS. Open vessel total digestion provides excess values for Cr, Mn, Fe, and Zn by ICP-OES and defect values for Se. However, direct measurement of diluted wine samples provided uncomparable results with the digestion treatment for Mn, Cu, Pb, Zn, Ba, and Bi by ICP-OES and for Mg, Cr, Fe, Ni, and Zn by ICP-MS. Therefore, it can be concluded that microwave-assisted digestion is the pretreatment procedure of choice for elemental analysis of wine by ICP-based techniques.     

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.     

Distribution of 32 Elements in Organic Surface Soils: Contributions from Atmospheric Transport of Pollutants and Natural Sources

Data are presented for 32 elements (Li, Be, B, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ge, As, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Hf, Tl, Pb, Bi) in organic-rich surface soils in Norway, based on samples from 464 sites. By considering geographical distributions based on isopleths, results from factor analysis, and ANOVA of median values from 12 different geographical regions, the contributions from natural and anthropogenic sources are estimated for each element. Long-range atmospheric transport of pollutants from areas out of Norway is a dominant source for Cd, Sb, Pb, and Bi and also a strongly contributing factor for Zn, As, Mo, and Tl. Also V, Ni, Cu, and Ge are somewhat affected, but other factors dominate for these elements. Local point sources of pollution provide significant contributions to soil concentrations of Ni, Cu, Zn, As, Mo, and Cd. The local bedrock is the overriding source of Li, Be, Ti, V, Cr, Mn, Rb, Zr, Cs, Ba, REE, Hf, and probably of Ge and Ag. Surface enrichment by root uptake in plants and return to the soil surface by decaying plant material is particularly evident for Mn, Zn, Rb, Cs, and Ba. These elements show no clear difference between south and north in the country, indicating that their plant uptake does not depend on latitude. In the case of B and Sr, atmospheric deposition of marine aerosols is an important source. Rb and Ag, and to a less extent Mn, Ga, and Ba, appear to be depleted in soils near the coast presumably due to cation exchange with airborne marine cations.     

Correlations between soil ph and metal contents in needles of Norway spruce

The concentrations of 21 elements were determined in 1 yr old needles of Norway spruce (Picea abies) at 39 different sites: The following soil parameters were measured at 3 different depths: pH, loss on ignition, total and EDTA-extractable concentrations of 28 elements. Needle concentrations were tested for correlations with soil parameters. The following significant correlations were found with pH: Al, Co, Cs, Mn, and Rb in needles increased with decreasing soil pH, whereas Ba and Sr decreased. Needle concentrations of As, Ca, Cu, Fe, K, La, Mg, P, Sb, Sc, V, and Zn had no significant correlations with soil pH. AI and Ba in needles correlated also with A1 and Ba extracted from the soil. Needle concentrations of the pairs Co and Mn, Cs and Rb, and Ba and Sr showed significant positive interelement correlations, whereas concentrations of P and K had negative interelement correlations with Mn.     

Inductively coupled plasma optical emission spectrometric determination of minerals in thyme honeys and their contribution to geographical discrimination

Twenty-four Spanish thyme honey samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Twenty-four minerals were quantified for each honey. The elements Al, As, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, Pb, S, Se, Si, Sr, and Zn were detected in all samples; seven elements are very abundant (Ca, K, Mg, Na, P, S, and Si), and six are not abundant (Al, Cu, Fe, Li, Mn, and Zn). Eleven of them are trace elements (As, Ba, Cd, Co, Cr, Ni, Mo, Pb, Se, Sr, and V) at <1 mg kg(-)(1). Classification of thyme honeys according to their origin (coast, mountains) was achieved by pattern recognition techniques on the mineral data. By means of principal component analysis, a good separation by geographical origin is obtained when scores for the two first principal components are plotted. Classification functions of 11 metals (Al, As, Cr, Cu, K, Li, Mg, Na, P, S, and V) were obtained using stepwise discriminant analysis and applied to classify correctly approximately 100% of the honey samples.     

基于矿质元素指纹的粉葛产地溯源研究

为明确矿质元素指纹对粉葛产地鉴别的可行性,筛选出鉴别粉葛产地的有效指标,本研究采用电感耦合等离子体质谱仪(ICP-MS)测定陕西、湖北、广西3个地域粉葛和土壤样品中B、Na、Mg、P、K、Ca、Mrn、Co、Cu、Zn、Rb、Sr、Mo、Cd、Cs、Ba、La、Ce、Pr、Nd、Sm和Ti 22种矿质元素含量,并结合主...     

Surface Soil Geochemistry for Environmental Assessment in Kavala Area, Northern Greece

The aim of the present study was to estimate the geochemical background and anomaly threshold values of the surface soils in Kavala, northern Greece. In order to reach this goal, a simple and practical procedure was applied. This procedure included the extraction of 42 major and trace elements by analytical grade HNO₃ from 65 surface soil samples, analysis by inductively coupled plasma?Coptical emission spectrometry and inductively coupled plasma?Cmass spectrometry, the distribution of the elemental data displayed on probability graphs (Q-Q plots), and the visualization of the results spatially by GIS software. The results indicated that natural factors mostly influence the elevated concentrations of Al, Ca, Fe, K, Mg, Si, B, Ba, Ce, Ga, Ge, La, Li, Mn Rb, Sb, Se, Sn, Sr, Y, and Zr, while anthropogenic activities mostly influence the elevated concentrations of Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mo, Ni, Pb, Th, Ti, U, V, W, and Zn. Nevertheless, almost all the elements determined showed their elevated concentrations inside the industrial part of Kavala area, which implies that the anthropogenic activities taking place in the study area, influence importantly the spatial distribution of the elements. The methodology followed in this research seems to be an adequate alternative for soil environmental studies.     

Changes of the metal composition in German white wines through the winemaking process. A study of 63 elements by inductively coupled plasma-mass spectrometry

Elemental patterns are often used for the classification or identification of the origin of wines. A prerequisite is that the concentration of the elements is not strongly influenced by the addition of different substances such as yeast and fining products during the winemaking process. Inductively coupled plasma-mass spectrometry (ICP-MS) has been used in this study to determine in total 63 elements (including some nonmetals and the rare earth elements) in five German white wines from five regions of origin. The whole winemaking process was studied, from the must to the ready wine. Microwave acid digestion was used for sample preparation, and indium was added as internal standard for a semiquantitative analysis. Two winemaking processes were compared: with the addition of clarifying agents (bentonites) before and after the fermentation. The concentration of only a few elements such as Li, B, Mg, Ca, Rb, Cs, and Pb seems to be constant throughout the whole winemaking process (changes of <+/-50%) and are independent of the time of addition of the bentonites. When bentonites are added before fermentation, the concentration of other elements, such as V, Co, and Fe, remains constant. If bentonites are added after fermentation, the concentration of some other elements such as Sr, Zn, and Mn is nearly unaffected. These elements are therefore robust elements for origin studies in German white wines.     

Concentrations of 50 major and trace elements in Danish agricultural crops measured by inductively coupled plasma mass spectrometry. 3. Potato (Solanum tuberosum folva).

The multi-element (Ag, Al, Au, Ba, Bi, Ca, Cd, Co, Cr, Cs, Cu, Dy, Er, Fe, Ga, Gd, Ho, In, Ir, La, Lu, Mn, Mo, Nb, Nd, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Tb, Th, Ti, Tl, Tm, U, V, Y, Yb, and Zn) concentrations (microg/kg, fresh weight) in potatoes (Solanum tuberosum, Folva) were investigated in this study. The potatoes were grown in two fertilization practices; one with pig slurry and one with calcium ammonium nitrate at three levels of N fertilization (0, 60, and 120 kg of N/ha). The experiment field was located at the Riso National Laboratory Agronomy Farms in Roskilde, Denmark. High-resolution-inductively coupled plasma mass spectrometry (HR-ICPMS) was used for analyses of the samples. The effect of three levels of N fertilization on elemental concentrations of the crop are evaluated by use of discriminant partial least-squares regression (PLS). The results provide useful biological and nutritional information on potatoes.     

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 fingerprinting as a tool in origin authentication of PGI food products: Tropea red onion

Tropea red onion ( Allium cepa L. var. Tropea) is among the most highly appreciated Italian products. It is cultivated in specific areas of Calabria and, due to its characteristics, was recently awarded with the protected geographical indications (PGI) certification from the European Union. A reliable classification of onion samples in groups corresponding to "Tropea" and "non-Tropea" categories is now available to the producers. This important goal has been achieved through the evaluation of three supervised chemometric approaches. Onion samples with PGI brand (120) and onion samples not cultivated following the production regulations (80) were digested by a closed-vessel microwave oven system. ICP-MS equipped with a dynamic reaction cell was used to determine the concentrations of 25 elements (Al, Ba, Ca, Cd, Ce, Cr, Dy, Eu, Fe, Ga, Gd, Ho, La, Mg, Mn, Na, Nd, Ni, Pr, Rb, Sm, Sr, Tl, Y, and Zn). The multielement fingerprint was processed using linear discriminant analysis (LDA) (standard and stepwise), soft independent modeling of class analogy (SIMCA), and back-propagation artificial neural network (BP-ANN). The cross-validation procedure has shown good results in terms of the prediction ability for all of the chemometric models: standard LDA, 94.0%; stepwise LDA, 94.5%; SIMCA, 95.5%; and BP-ANN, 91.5%.     

基于矿物元素指纹的羊肉产地溯源技术

为探讨矿物元素指纹对羊肉产地溯源的有效性,找寻表征地域特性的元素指标,利用电感耦合等离子体质谱仪分析中国内蒙古自治区阿拉善盟、锡林郭勒盟和呼伦贝尔市3个牧区,及重庆市和山东省菏泽市2个农区脱脂羊肉和土壤样品中4种常量元素(K、Ca、Na、Mg)和13种微量元素(V、Mn、Fe、Cr、Ni、Cu、As、Be、Sb、Zn、Se、Ba、Tl)的含量,对其进行方差分析、相关分析和判别分析。结果表明,羊肉中矿物元素含量组成在地域间有明显差异,农区元素含量普遍高于牧区。脱脂羊肉中Ca、Zn、Be、Ni、Fe、Ba、Sb、Mn和Se9种元素含量的地域差异与土壤相关,它们对农牧区的正确判别率达90%以上,对5个地域的正确判别率在70%～100%之间。利用羊肉中矿物元素指纹分析技术可鉴别和追溯羊肉的产地来源,为羊肉及其他食品的产地溯源研究提供方法参考。     

啤酒花中矿物元素在生长期的动态变化研究

利用电感耦合等离子体-质谱(ICP-MS)和电感耦合等离子体-发射光谱(ICP-OES)对不同种植地的青岛大花、札一和马可波罗3个新疆主产啤酒花品种中的22种矿物元素在生长期的含量进行跟踪测定。结果表明,啤酒花对矿物元素的吸收和积累存在"地域差异"和"时间差异",其中Sr、Na、Rb、Li、Ba、Ga、Co和V的含量受种植地的影响较大;但在整个生长周期内,啤酒花对重金属无明显吸收和富集作用。基于22种元素的主成分分析结果进一步证实,前3个主成分的累计贡献率达到84.36%,且由PC 1和PC 2构成的得分散点图可以很好地区分不同产地的啤酒花样本;而由PC 1和PC 3组成的得分散点图主要可以区分啤酒花的"成熟度"。其中,Mg、K、Li、Na可以用来判别啤酒花的产区;Al、Pb、V对于评价啤酒花的成熟度具有较大价值。     

Determining the geographic origin of wheat using multielement analysis and multivariate statistics

The element contents of wheat from four major wheat-producing regions of China were analyzed and used in multivariate statistical analysis to classify wheat according to geographical origin. The concentrations of 15 elements (Be, Na, Mg, Al, K, Ca, V, Mn, Fe, Cu, Zn, Mo, Cd, Ba, and Th) in 240 samples from the 2007/2008 and 2008/2009 harvests were determined by inductively coupled plasma mass spectrometry. The analysis of variance and linear discriminant analysis were applied to classify wheat origin, and the effects of region, variety, and harvest year on the element contents were analyzed in this study. It was concluded that the multielement analysis is a promising method to provide reliable origin information for wheat, although the element profiles and discriminant models were affected by wheat varieties, harvest years, and agricultural practices.     

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.