Elemental Fingerprints Research Articles

Nutrients and seabird biogeography: Feather elements differ among oceanic basins in the Southern Hemisphere, reflecting bird size, foraging range and nutrient availability in seawater

AbstractAimBiodiversity hotspots in wide‐ranging marine species typically overlap with regions of high productivity, which are often associated with nutrient‐rich waters. Here we investigate how element concentrations in feathers vary among highly mobile seabirds in global seabird biodiversity hotspots.LocationSouthern Hemisphere.Time periodContemporary.Major taxa studiedFifteen species in the order Procellariiformes.MethodsWe collected data on the concentration of 15 elements in feathers for 253 seabirds sampled across Australia and New Zealand and compared the “fingerprint” of micronutrient element profiles to feathers of related seabirds from global hotspots using principal component analysis (PCA), cluster analysis and permutational analysis of variance (PERMANOVA).ResultsBreast feather concentrations of some elements, including aluminium, iron, cobalt, chromium, manganese, nickel, arsenic and cadmium, were tens‐to‐hundred‐fold higher in smaller (<400 g) than larger species (≥400 g). We suggest these results reflect the dominance of pelagic crustaceans in the diet of smaller seabirds, blooms of which are influenced by input of limiting ocean nutrients. Cluster analysis revealed three broad groups of feather elements: large seabirds, and small seabirds in each of the South Pacific and South Atlantic Ocean basins. High concentrations of some elements in feathers match seawater availability and are detectable in lower‐trophic feeding seabirds with local movements. Conversely, the element fingerprints of longer‐distance, higher‐trophic foragers, including albatrosses, do not match availability in seawater at the collection site.Main conclusionsThe feather element concentrations of shorter‐range foraging, lower‐trophic feeding seabirds vary significantly among ocean basins, reflecting availability in seawater, while longer‐range, higher‐trophic species do not. We propose that geographically diverse availability of micronutrients, in addition to primary productivity, may play an underrecognized role in seabird biogeography and intra‐hemispheric migration, though more research is needed. This study has important implications, considering the role of element availability in supporting biodiversity hotspots for dispersive marine predators and for the designation of protected areas.

Discrimination of cultivation modes of Dendrobium nobile based on content of mineral elements and ratios of nitrogen stable isotopes

This study explored the feasibility of mineral element content and ratios of nitrogen isotopes to discriminate the cultivation mode of Dendrobium nobile in order to provide theoretical support for the discrimination of the cultivation mode of D. nobile. The content of 11 mineral elements(N, K, Ca, P, Mg, Na, Fe, Cu, Zn, Mn, and B) and nitrogen isotope ratios in D. nobile and its substrate samples in three cultivation methods(greenhouse cultivation, tree-attached cultivation, and stone-attached cultivation) were determined. According to the analysis of variance, principal component analysis, and stepwise discriminant analysis, the samples of different cultivation types were classified. The results showed that the nitrogen isotope ratios and the content of elements except for Zn were significantly different among different cultivation types of D. nobile(P<0.05). The results of correlation analysis showed that the nitrogen isotope ratios, mineral element content, and effective component content in D. nobile were correlated with the nitrogen isotope ratio and mineral element content in the corresponding substrate samples to varying degrees. Principal component analysis can preliminarily classify the samples of D. nobile, but some samples overlapped. Through stepwise discriminant analysis, six indicators, including δ~(15)N, K, Cu, P, Na, and Ca, were screened out, which could be used to establish the discriminant model of D. nobile cultivation methods, and the overall correct discrimination rates after back-substitution test, cross-check, and external validation were all 100%. Therefore, nitrogen isotope ratios and mineral element fingerprints combined with multivariate statistical analysis could effectively discriminate the cultivation types of D. nobile. The results of this study provide a new method for the identification of the cultivation type and production area of D. nobile and an experimental basis for the quality evaluation and quality control of D. nobile.

Genesis and Geodynamic Significance of Chromitites from the Fuchuan Ophiolite, Southern China, as Evidenced by Trace Element Fingerprints of Chromite, Olivine and Pyroxene

AbstractThe Fuchuan ophiolite is located in the northeasternmost segment of the Neoproterozoic Jiangnan orogen and consists mainly of harzburgites, with minor dunites, pyroxenite and gabbro veins and dykes. In order to investigate the genesis and tectonic setting of the Fuchuan ophiolite and chromitites, in situ analyses of unaltered chromites and silicates were carried out. Trace element analyses of unaltered chromites from the Fuchuan chromitites indicate the parental magma is of mid‐ocean ridge basalt (MORB)‐like origin, with the Ti/Fe3+#–Ga/Fe3+# diagram of chromites showing that the chromitites are a result of melt/rock interaction of MORB melts with mantle peridotites, and that the Fuchuan harzburgites present the dual features of MORB and supra‐subduction zone peridotites (SSZP). Trace and rare earth element (REE) analyses of olivines and orthopyroxenes from the Fuchuan harzburgites hint at the possibility of mantle metasomatism influenced by SSZ‐subducted fluids. Finally, integrating with previous study, the Fuchuan ophiolite and chromitites might have been formed in a back‐arc spreading ridge between the Yangtze and Cathaysia blocks during the Neoproterozoic.

Isotopic (Cu, Zn, and Pb) and elemental fingerprints of antifouling paints and their potential use for environmental forensic investigations

Antifouling paints (APs) are one of the important sources of Cu and Zn contamination in coastal environments. This study applied for the first-time a multi-isotope (Cu, Zn, and Pb) and multi-elemental characterization of different AP brands to improve their tracking in marine environments. The Cu and Zn contents of APs were shown to be remarkably high ∼35% and ∼8%, respectively. The δ65CuAE647, δ66ZnIRMM3702, and 206Pb/207Pb of the APs differed depending on the manufacturers and color (−0.16 to +0.36‰, −0.34 to +0.03‰, and 1.1158 to 1.2140, respectively). A PCA analysis indicates that APs, tires, and brake pads have also distinct elemental fingerprints. Combining isotopic and elemental ratios (e.g., Zn/Cu) allows to distinguish the environmental samples. Nevertheless, a first attempt to apply this approach in highly urbanized harbor areas demonstrates difficulties in source apportionments, because the sediment was chemically and isotopically homogeneous. The similarity of isotope ranges between the harbor and non-exhaust traffic emission sources suggests that most metals are highly affected by urban runoff, and that APs are not the main contributors of these metals. It is suspected that AP-borne contamination should be punctual rather than dispersed, because of APs low solubility properties. Nevertheless, this study shows that the common coastal anthropogenic sources display different elemental and isotopic fingerprints, hence the potential for isotope source tracking applications in marine environments. Further study cases, combined with laboratory experiments to investigate isotope fractionation during releasing the metal sources are necessary to improve non-traditional isotope applications in environmental forensics.

Isotopic and Elemental Fingerprint of Edible Egg Parts-The Health Risk Assessment Based on Potentially Toxic Elements Content.

The present study investigated the isotopic and elemental profile (by IRMS and ICP-MS) of edible egg parts (29 egg whites and 29 yolks) mainly collected from Romania. In order to differentiate the egg white and yolk coming from different hen rearing systems (backyard and barn), Partial Least Square-Discriminant Analysis (PLS-DA) models were developed. The models' accuracies for the discrimination according to the hen growing system were 96% for egg white and 100% for egg yolk samples, respectively. Elements that proved to have the highest discrimination power for both egg white and yolk were the following: δ13C, Li, B, Mg, K, Ca, Mn, Fe, Co, Zn, Rb, Sr, Mo, Ba, La, Ce, and Pb. Nevertheless, the important compositional differentiation, in terms of essential mineral content, between the edible egg parts (egg white and egg yolk) were also pointed out. The estimated daily intake (EDI), the target hazard quotient (THQ) for Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Cd, Pb, and As, as well as the hazard index (HI) were used to assess non-carcinogenic human health risks from egg consumption. The obtained results showed no noticeable health risks related to egg consumption for humans from the point of view of the potentially toxic metals.

Evolution of magnetic particulate matter during its emission process in thermal power plants

We report the evolution of the abundance, morphology, chemical species, and element fingerprints of magnetic particulate matter during its emission process in thermal power plants.

Distribution of critical metals in evolving pyrite from massive sulfide ores of the Iberian Pyrite Belt

With >90 known deposits containing original reserves of >2400 Mt of sulfide ore, the Iberian Pyrite Belt (IPB) is the largest volcanogenic massive sulfide (VMS) province on Earth. In these evolving mineral systems, texturally different pyrite exhibits characteristic mineralogy and trace element fingerprints. Pyrite (Py-1), which is well preserved in the polymetallic ores that crystallized at the earliest stage of VMS deposit formation, consists of kernels of pyrite framboids surrounded by concentric colloform bands and ended by faceted outlines. It is rich in some metals like Pb, Zn, Sb and As (mostly hosted as nano-to-micron-sized particles, including galena, tetrahedrite and arsenopyrite) but depleted in Cu, Co and Bi. In contrast, pyrite from the pyritic and Cu-rich ore overprinted by late fluids exhibits spongy-looking (Py-2) or homogenous (Py-3) cores surrounded by external facets with crystallographic continuity across the whole single grains due to re-crystallization. Py-2 is depleted in most trace elements with the exception of Au and Bi, which occur both in solid solutions and as nano-to-micron-sized inclusions. Py-3 has the highest Cu, Ag, Co and Ni (mainly associated to nano-to-micron-sized particles of tennantite, chalcopyrite and gersdorffite) and the lowest Au contents in the form of native gold. The progressive increase in metal contents from inner to outer parts of Py-1 matches with the onset of the economic metal endowment of VMS deposits in the IPB, whereas Py-2 and Py-3 are associated with metal shoot processes that led to both leached and high-grade ores, very likely when mafic rocks were emplaced into the footwall of the deposits.

Assigning the Geographical Origin of Meat and Animal Rearing System Using Isotopic and Elemental Fingerprints

In this study, the stable isotope, and elemental fingerprints of 120 meat samples were determined. The Partial Last Squares-Discriminant Analysis (PLS-DA) method was applied to build classification models for chicken and pork meat samples according to the geographical origin (different Romanian regions) and the animal growing system (animals coming from yard rearing systems versus animals coming from industrial farms). The accuracy of the geographical origin differentiation model was 93.8% for chicken and 71.8% for pork meat. The principal discrimination markers for this classification were: B, Na, K, V, As, Se, Rb, Nb, Cd, Sn, δ13C, δ2H, and δ18O (for chicken meat) and B, Na, Mg, K, Ca, V, Cr, Fe, Ni, Cu, Zn, As, Rb, Sr, Nb, Mo, Sn, Sb, Ba, Pb, δ13C, δ2H, and δ18O (for pork meat). The PLS-DA models were able to differentiate the meat samples according to the animal rearing system with 100% accuracy (for pork meat) and 98% accuracy (for chicken meat), based on the main predictors: B, K, V, Cr, Mn, Fe, Cu, Zn, Se, Rb, Nb, Sn, δ13C, and δ2H (for chicken meat) and Se, Rb, Nb, Sb, Ba, Pb, and δ13C (for pork meat).

Otoliths of marine fishes record evidence of low oxygen, temperature and pH conditions of deep Oxygen Minimum Zones

The deep-sea is rapidly losing oxygen, with profound implications for marine organisms. Within Eastern Boundary Upwelling Systems, such as the California and the Benguela Current Ecosystems, an important question is how the ongoing expansion, intensification and shoaling of Oxygen Minimum Zones (OMZs) will affect deep-sea fishes throughout their lifetimes. One of the first steps to filling this knowledge gap is through the development of tools and techniques to track fishes’ exposure to hypoxic (<45 μmol kg-1), low-temperature (∼4–10°C) and low-pH (∼7.5) waters when inhabiting OMZs. Here, we examine if the otoliths of deep-sea fishes living in OMZs exhibit distinct patterns of elemental and isotopic composition, which could be used to monitor their exposure history to severely hypoxic and low-pH waters. We hypothesize that the unique biogeochemistry of OMZs (i.e., low-oxygen, low-pH, and the presence of dissolved elements) will impart unique elemental and isotopic signatures upon the otoliths of both long-lived and short-lived deep-sea fishes living within it. We analyzed the otoliths of six deep-sea fish species from three OMZ regions: the Southern California Bight and the Gulf of California in the Northeast Pacific Ocean, and the Namibian shelf in the Southeast Atlantic Ocean. Three complementary techniques were applied: laser ablation inductively coupled plasma mass spectrometry, secondary ion mass spectrometry and scanning X-ray fluorescence microscopy. We observed that deep-water OMZ-dwelling fishes spanning a range of life-history traits (e.g., longevity, maximum size, growth rate, parental investment and thermal history inferred by δ18O) exhibited a common elemental fingerprint (with respect to Sr:Ca, Mn:Ca, Ba:Ca, Cu:Ca and Mg:Ca) when compared to a shallow-water marine fish from better-oxygenated waters. Our findings suggest that the underlying mechanism for the common elemental fingerprinting of otoliths of OMZ-dwelling fishes is attributed to the unique biogeochemistry found on the margins of these highly productive upwelling systems as well as the physiological constraints resident organisms are perennially exposed to, including low oxygen, pH and temperature conditions.

Authenticity and Typicity of Traditional Cheeses: A Review on Geographical Origin Authentication Methods.

Food fraud, corresponding to any intentional action to deceive purchasers and gain an undue economical advantage, is estimated to result in a 10 to 65 billion US dollars/year economical cost worldwide. Dairy products, such as cheese, in particular cheeses with protected land- and tradition-related labels, have been listed as among the most impacted as consumers are ready to pay a premium price for traditional and typical products. In this context, efficient food authentication methods are needed to counteract current and emerging frauds. This review reports the available authentication methods, either chemical, physical, or DNA-based methods, currently used for origin authentication, highlighting their principle, reported application to cheese geographical origin authentication, performance, and respective advantages and limits. Isotope and elemental fingerprinting showed consistent accuracy in origin authentication. Other chemical and physical methods, such as near-infrared spectroscopy and nuclear magnetic resonance, require more studies and larger sampling to assess their discriminative power. Emerging DNA-based methods, such as metabarcoding, showed good potential for origin authentication. However, metagenomics, providing a more in-depth view of the cheese microbiota (up to the strain level), but also the combination of methods relying on different targets, can be of interest for this field.

Differentiation of Transylvanian fruit distillates using supervised statistical tools based on isotopic and elemental fingerprint.

The spirit drinks industry is one of the largest in the world. Fruit distillates require adequate analysis methods combined with statistical tools to build differentiation models, according to distinct criteria (geographical and botanical origin, producer's fingerprint, respectively). Over time a database of alcoholic beverage fingerprints can be generated, being very important for product safety and authenticity control. To control the distillates' geographical origin, linear discriminant analysis (LDA) revealed that the cross-validation classification was correct for 88.2% of samples, but partial least squares discriminant analysis (PLS-DA) was slightly better suited for this purpose, with a correct classification rate of 91.2%. LDA effectiveness was proven for the trademark fingerprint differentiation, which was achieved at 93.5%, compared to 89.1% for PLS-DA. The principal predictors obtained by LDA were the same both for geographical origin and producer differentiation: B, δ13 C, Na, Cu, Ca and Be; highlighting the fact that in the production process of distillates each producer used fruits coming from the respective specific region. Through PLS-DA, some of the discrimination markers were the same for geographical origin and producer's identification, but others were completely specific: the rare earth elements Eu and Er only for geographical origin differentiation, and Cu solely as predictor for producer's identification. Regarding distillates' fruit variety, the correct discrimination rates of plum spirits from the rest were 84.2% for PLS-DA and 63% for LDA. LDA and PLS-DA were suitable for differentiation models development of fruits spirits according to geographical region, producer and fruit variety based on isotopic and elemental fingerprint. © 2022 Society of Chemical Industry.

Elemental Fingerprinting of Wild and Farmed Fish Muscle to Authenticate and Validate Production Method.

In the context of expanding fish production and complex distribution chains, traceability, provenance and food safety tools are becoming increasingly important. Here, we compare the elemental fingerprints of gilthead seabream (Sparus aurata) muscle from wild and different aquaculture productions (semi-intensive earth ponds and intensive sea cages from two locations) to confirm their origin and evaluate the concentrations of elements with regulatory thresholds (Cu, Hg, Pb and Zn). Using a chemometric approach based on multi-elemental signatures, the sample origin was determined with an overall accuracy of 90%. Furthermore, in a model built to replicate a real-case scenario where it would be necessary to trace the production method of S. aurata without reliable information about its harvesting location, 27 of the 30 samples were correctly allocated to their original production method (sea-cage aquaculture), despite being from another location. The concentrations of the regulated elements ranged as follows: Cu (0.140–1.139 mg/Kg), Hg (0–0.506 mg/Kg), Pb (0–2.703 mg/Kg) and Zn (6.502–18.807 mg/Kg), with only Pb presenting concentrations consistently above the recommended limit for human consumption. The present findings contribute to establishing elemental fingerprinting as a reliable tool to trace fish production methods and underpin seafood authentication.

Technology-critical elements in Rhine sediments - A case study on occurrence and spatial distribution

Despite their presence in almost every technical device, little is known about the occurrence, distribution, and fate of technology-critical elements (TCEs) within the environment. Due to high economic demands and short product lifespans as well as low recycling rates, many TCEs appear to become emerging contaminants.Within the scope of this work, 57 sediment samples from the German part of the Rhine river, as well as various tributaries, were collected to study the occurrence and distribution of TCEs. This specific catchment area has consistently been subjected to strong anthropogenic influences over the last century. Hierarchical cluster analysis, as well as principal component analysis were used to gain first insights into the spatial distribution and possible sources of TCEs along the Rhine.Obtained mass fractions in conjunction with corresponding geoaccumulation indices (Igeo) provide first indications of a possible enrichment along the Rhine for the TCEs of interest (Ga, Ge, Nb, In, Te, rare earth elements, and Ta). Especially the mass fractions of Zn, Ge, In, La, Sm, and Gd exhibit significant anthropogenic inputs. For stations characterized by high Ge and In mass fractions, element fingerprints imply possible atmospheric deposition stemming from e.g. combustion processes. Distinct anomalies of La and Sm most likely originate from discharges located at the city of Worms into the Upper Rhine. Statistical analysis of all analyzed 55 elemental mass fractions revealed similar behavior of TCEs compared to classical heavy metals. Diffuse as well as point sources of TCEs are likely. As a result, this study provides further insight into the role of TCEs as potential emerging contaminants in the environment.

Chemistry Combining Elemental Profile, Stable Isotopic Ratios, and Chemometrics for Fine Classification of a Chinese Herb Licorice (Glycyrrhiza uralensis Fisch.) from 37 Producing Area.

A method based on elemental fingerprint, stable isotopic analysis and combined with chemometrics was proposed to trace the geographical origins of Licorice (Glycyrrhiza uralensis Fisch) from 37 producing areas. For elemental fingerprint, the levels of 15 elements, including Ca, Cu, Mg, Pb, Zn, Sr, Mn, Se, Cd, Fe, Na, Al, Cr, Co, and K, were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). Three stable isotopes, including δ13C, δ15N, and δ18O, were measured using an isotope-ratio mass spectrometer (IRMS). For fine classification, three multiclass strategies, including the traditional one-versus-rest (OVR) and one-versus-one (OVO) strategies and a new ensemble strategy (ES), were combined with two binary classifiers, partial least squares discriminant analysis (PLSDA) and least squares support vector machines (LS-SVM). As a result, ES-PLSDA and ES-LS-SVM achieved 0.929 and 0.921 classification accuracy of GUF samples from the 37 origins. The results show that element fingerprint and stable isotope combined with chemometrics is an effective method for GUF traceability and provides a new idea for the geographical traceability of Chinese herbal medicine.

Stable isotopic and elemental characteristics with chemometrics for the geographical origin authentication of Dendrobium officinale at two spatial scales

Dendrobium officinale Kimura et Migo (D. officinale) is a healthy tea with protected designation of origin labels, which requires of authenticating its geographical origin. Stable isotope ratios of 87Sr/86Sr, δ13C, δ15N, δ2H, and δ18O and 24 element contents of D. officinale in 379 samples from 11 sites in six provinces were compared at two spatial scales: regional scale among the six provinces, and local scale among six sites within Zhejiang province. 87Sr/86Sr, δ13C, and Ca were significantly different only at regional scale, while Fe was different only at the local scale. Combined with chemometric methods such as Linear Discriminant Analysis and Random Forest high accuracies were obtained for the geographical origin authentication at both regional (100%) and local scale (98.81%). Moreover, ranks of variable importance differed between the regional and local scale discrimination. The top ten important variables at the regional scale were Zn, Sr, δ2H, Ba, Mn, δ15N, Cu, 87Sr/86Sr, Nd, Rb, while those at the local scale were Na, δ15N, Cu, δ2H, Zn, Ni, La, Rb, Nd, and Pb. This study established a stable isotope and element fingerprints dataset of D. officinale, provided potential authenticating methods, and revealed different variable importance ranks for the two scales.

Mineral element fingerprints verified the geographical origin of years and quantities of rice

Mineral element fingerprint analysis technology is one of the effective methods for grain origin identification. The accuracy of the identification model is closely related to sample geographical origin, including sample year and sample quantity. In order to study the influence of sample year and quantity on the origin identification of mineral elements. The content of mineral elements in rice was determined by inductively coupled plasma mass spectrometry (ICP-MS). Stoichiometry methods were combined to establish provenance models for different years and sample quantities. The results showed that the accuracy rate of the origin traceability model based on multi-year rice (2018–2020) was 100.0 %. It improved the accuracy of the model by 12.0 % compared with the model established in a single year (2019). The accuracy of origin tracing model for rice with 236 varieties was 98.8 %. The accuracy of rice model with smaller sample size (83 samples) increased by 3.8 %. It verifies and compares the model accuracy of origin discrimination of 15 randomly collected rice samples from three producing areas. The number of correct discriminations (15) for the model of multi-year rice was more than that of single year (13). The number of correct discriminations (15) was more than the number of small samples (12). This indicates that the year and the quantity of samples are two important factors to be considered in the establishment of discriminant model. Multiple sample years and multiple sample quantities were used to improve the accuracy of the model. It also provides a theoretical basis for the establishment and standardization of agricultural product traceability method.

Elemental fingerprinting of sea urchin (Paracentrotus lividus) gonads to assess food safety and trace its geographic origin

Sea urchin gonads are an economically valuable seafood item, considered a delicacy in many parts of the world. However, its consumption can either pose a food safety threat, as they accumulate potentially toxic elements from contaminated environments or promote the depletion of natural stocks due to the high demand. Knowing their harvesting location is therefore paramount to guarantee food safety and the conservation of natural stocks. In this study, the elemental fingerprints of sea urchin (Paracentrotus lividus) gonads collected in several locations along the Portuguese coast, in 2020 and 2021, were used to assess the levels of some potentially toxic elements (i.e., As, Cu, Pb and Zn) and to trace the harvesting location of this marine resource. P. lividus gonads presented mean levels of As, Cu, Pb and Zn above the thresholds recommended for human consumption (considering mollusks due to the absence of safety thresholds for echinoderms), in at least one of the sampling locations. The elemental fingerprints of gonads hold the potential to trace the harvesting location of P. lividus, even when it was used elemental fingerprints of different years to train and test the models.

A method to propagate the uncertainty of measurements in principal component analysis applied to the elemental composition of cooking salts measured by instrumental neutron activation analysis

Cooking salt is one of the most diffused food commodities, with high relevance both for flavour exaltation and food preservation. In commerce are present peculiar cooking salts with a high commercial value due to their colour and organoleptic characteristics, which are subjected to fraud and adulteration. The elemental composition of different cooking salts from different geographical origins was investigated with instrumental neutron activation analysis (INAA), as a calibrated and validated multi-element technique, suitable for the accurate determination of trace concentration of most natural elements. The elemental fingerprint differences between samples were explored by principal component analysis (PCA), which was expanded with a simple data augmentation method called “Data explosion” with the scope of propagating the uncertainty budget associated with the raw data in the PCA model, using a Monte Carlo simulation. The PCA models with and without considering the uncertainty of measurement were compared using common figures of merit, attesting that, in the absence of the uncertainty regions associated with the scores, erroneous conclusion about sample similarities and differences could be drawn.

Identifying the Geographical Origin of Tobacco Leaf by Strontium and Lead Isotopic with Mineral Elemental Fingerprint

The primary aim of this paper was to identifying the geographical origin of tobacco leaves based on stable isotopic and mineral elemental fingerprint. We collected eighty-one tobacco leaf samples from Argentina, Brazil, Zimbabwe, the U.S., Zambia, and China. And nine mineral element contents and four strontium and lead isotope ratios of the tobacco leaves were determined by thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS). After variance and stepwise discriminant analysis, the discriminant functions of the tobacco leaf’s geographical origin were established. The results indicate that: (1) the contents of six mineral elements including Cu, Zn, Cr, Ni, Cd, and Pb, together with four strontium and lead isotope ratios containing 87Sr/86Sr, 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb, were significantly different among six countries. (2) Different countries presented some characteristic mineral elemental and isotopic fingerprint. The even contents of mineral elements from Zambian tobacco leaf were much lower than the other countries, among which four elements consisting of Zn, Cr, As, and Cd were not detected. The three average lead isotope ratios including 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb from Zimbabwe tobacco leaves were far higher than the other countries, and the range of which was unoverlapped. (3) The effective identification of the geographical origin of tobacco leaf was accomplished by Fisher stepwise discriminant analysis and the characteristic tracing elements consisted of Cu, Zn, Cr, Ni, Cd, Pb, 87Sr/86Sr, 207Pb/204Pb, and 206Pb/204Pb. Based on the established discriminant functions, the original and cross-validation accuracy towards different geographical origins of tobacco leaves were 98.8% and 95.1%, respectively. The study shows that the strontium and lead isotopic with mineral elemental fingerprints is a potential effective method to identify the geographical origin of tobacco leaves from different countries.

The Elemental Fingerprints of Different Types of Whisky as Determined by ICP-OES and ICP-MS Techniques in Relation to Their Type, Age, and Origin.

A total of 170 samples of whisky from 11 countries were analysed in terms of their elemental profiles. The levels of 31 elements were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS): Ag, Al, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Te, Tl, U, and V, Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) Ca, Fe, K, Mg, P, S, Ti, and Zn and Cold Vapor-Atomic Absorption (CV-AAS): Hg techniques in those alcoholic samples. A comparative analysis of elemental profiles was made on the basis of the content of chosen elements with regard to selected parameters: country of origin, type of whisky (single malt and blended) and age of products. One of the elements which clearly distinguishes single malt and blended types of whisky is copper. Single malt Scotch whisky had a uniform concentration of copper, which is significantly higher for all malt whisky samples when compared with the blended type. Analysis of samples from the USA (n = 26) and Ireland (n = 15) clearly revealed that the objects represented by the same product but originating from independent bottles (e.g., JB, JDG, BUS brands) show common elemental profiles. On the other hand, comparative analysis of Scotch whisky with respect to aging time revealed that the longer the alcohol was aged, (i.e., the longer it stayed in the barrel), the higher the content of Cu and Mn that was recorded.