Assessment of the Authenticity of Whisky Samples Based on the Multi-Elemental and Multivariate Analysis.

Two hundred and five samples of whisky, including 170 authentic and 35 fake products, were analyzed in terms of their elemental profiles in order to distinguish them according to the parameter of their authenticity. The study of 31 elements (Ag, Al, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Te, Tl, U, V, Ca, Fe, K, Mg, P, S, Ti and Zn) was performed using the Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and Cold Vapor-Atomic Absorption (CVAAS) techniques. Additionally, the pH values of all samples were determined by pH-meter, and their isotopic ratios of 88Sr/86Sr, 84Sr/86Sr, 87Sr/86Sr and 63Cu/65Cu were assessed, based on the number of counts by ICP-MS. As a result of conducted research, elements, such as Mn, K, P and S, were identified as markers of whisky adulteration related to the age of alcohol. The concentrations of manganese, potassium and phosphorus were significantly lower in the fake samples (which were not aged, or the aging period was much shorter than legally required), compared to the original samples (in all cases subjected to the aging process). The observed differences were related to the migration of these elements from wooden barrels to the alcohol contained in them. On the other hand, the sulfur concentration in the processed samples was much higher in the counterfeit samples than in the authentic ones. The total sulfur content, such as that of alkyl sulfides, decreases in alcohol with aging in the barrels. Furthermore, counterfeit samples can be of variable origin and composition, so they cannot be characterized as one group with identical or comparable features. Repeatedly, the element of randomness dominates in the production of these kinds of alcohols. However, as indicated in this work, the extensive elemental analysis supported by statistical tools can be helpful, especially in the context of detecting age-related adulteration of whisky. The results presented in this paper are the final part of a comprehensive study on the influence of selected factors on the elemental composition of whisky.

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.

The Elemental Profile of Beer Available on Polish Market: Analysis of the Potential Impact of Type of Packaging Material and Risk Assessment of Consumption.

Twenty-five elements, including the most essential and toxic metals, were determined in fifty beer samples stored in cans and bottles by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Cold Vapor Atomic Absorption Spectroscopy (CVAAS) techniques. The packaging material was analyzed using the Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) technique. The control of the level of individual metals is necessary, not only to maintain the organoleptic properties of the product, but also to fulfill the standards regarding the permissible maximum concentrations. Metals can originate from different sources, including the brewing water, malt grains, hops, adjuncts, fruits, and spices. They may also come from contamination from the brewery equipment, i.e., vessels and tanks, including beer packing, storing and transporting (kegs, casks, cans). Discriminant analysis revealed that the differentiation of three types of beer (Lager, Ale, Craft) was possible, based on elemental concentrations, for the reduced data set after their selection using the Kruskal-Wallis test. The analysis of the impact of the packaging material (can or bottle) proved that when this parameter was used as a differentiating criterion, the difference in the content of Na, Al, Cu and Mn can be indicated. The risk assessment analysis showed that the consumption of beer in a moderate quantity did not have any adverse effect in terms of the selected element concentrations, besides Al. However, in the case of Al, the risk related to consumption can be considered, but only for the beer stored in cans produced from aluminum.

Determination of Metallic Impurities by ICP-MS Technique in Eyeshadows Purchased in Poland. Part I.

Eye shadows, which are products willingly and frequently used by women and even children, have been reported in literature to contain toxic metals. In this work, a total of 94 eye shadows samples available on the Polish market were collected. Eye shadow products have been selected in order to include several parameters important from the point of view of the typical consumer such as: product type (mat/pearl), consumer group (for adults and children), price range (very cheap, medium price, expensive and very expensive), color (twelve different colors were tested), manufacturer (eight brands were investigated) or country of production (four countries were included). The concentration of selected metals (Ag, Ba, Bi, Cd, Pb, Sr, Tl) was determined by ICP-MS technique after the sample extraction with a mixture of nitric acid and hydrogen peroxide in a microwave closed system. For Ag, Cd and Tl, some results were below the established limit of quantification for the employed technique. The presence of strontium, barium, lead and bismuth was confirmed in all studied samples. The obtained results for analyzed elements were, in general, quite comparable with the data reported by other authors. A small number of samples exceeding the permissible values (two samples were beyond the limit value for Cd of 0.5 mg/kg and one exceed the acceptable concentration for Pb of 10 mg/kg) also proves a relatively good condition of the Polish cosmetics market and suggests insubstantial risk for the potential consumers. The results gathered for some of the eye shadows intended for children turned out to be alarmingly high, in particular for elements such as Cd. The highest concentration of Cd reached almost 4 mg/kg, while of Pb amounted to 16 mg/kg. The presence of the statistically significant differences was confirmed for all included parameters with an exception of the color of the eye shadow. Considering the results acquired only for Cd and Pb with respect to the country of origin, the least contaminated cosmetics by metallic impurities seem to be the one produced in Canada, while the ones presenting the highest health risk among all studied eye shadows are make-up cosmetics originating from Poland and Italy. Multivariate analysis of a large data set using CA methods and PCA provided valuable information on dependencies between variables and objects.

Visualisation of Amphetamine Contamination in Fingerprints Using TOF-SIMS Technique.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was applied to detect traces of amphetamine on fingerprints. In the present study, three different lift tapes and latent powder fingerprints were tested. The obtained results show that it is possible to identify traces of a drug as well as its distribution over the tested fingerprint after its transfer from the primary base onto an adhesive lifter (secondary base). Moreover, images obtained by the TOF-SIMS technique enable the observation of very small areas of the analysed fingerprint as well as the identification of micro-objects (residues of a contaminant) that were left on the fingerprint. The use of the black latent fingerprint powder did not interfere with the TOF-SIMS analysis, which makes it possible to effectively use this technique to study the traces of substances on the revealed fingerprints.

Elemental Characterization of Ciders and Other Low-Percentage Alcoholic Beverages Available on the Polish Market.

Seventy-three samples of alcoholic beverages and juices that were purchased on the Polish market and home-made were analyzed for their elemental profiles. The levels of 23 metals were determined by ICP-MS (Ag, Ba, Bi, Cd, Co, Cr, Li, Mn, Ni, Pb, Sr and Tl), ICP-OES (Al, B, Ca, Cu, Fe, K, Mg, Na, Ti and Zn) and CVAAS (Hg) techniques in twenty-five samples of ciders widely available on the Polish market; six samples of home-made ciders; two samples of juices used in the production of these ciders; and forty samples of low-percentage, flavored alcoholic beverages based on beer. The gathered analytical data confirmed that the final elemental fingerprint of a product is affected by the elemental fingerprint of the ingredients used (apple variety) as well as the technology and equipment used by the producer, and in the case of commercial ciders, also the impact of type of the packaging used was proven. These factors are specific to each producer and the influence of the mentioned above parameters was revealed as a result of the performed analysis. Additionally, the inclusion of the home-made ciders in the data set helped us to understand the potential origin of some elements, from the raw materials to the final products. The applied statistical tests revealed (Kruskal-Wallis and ANOVA) the existence of statistically significant differences in the concentration of the following metals: Ag, Al, B, Bi, Co, Cr, Cu, Fe, K, Li, Mg, Na, Ni, Ti and Zn in terms of the type of cider origin (commercial and home-made). In turn, for different packaging (can or bottle) within one brand of commercial cider, the existence of statistically significant differences for Cu, Mn and Na was proved. The concentrations of all determined elements in the commercial cider from the Polish market and home-made cider samples can be considered as nontoxic, because the measured levels of elements indicated in the regulations were lower than the allowable limits. Moreover, the obtained results can be treated as preliminary for the potential authentication of products in order to distinguish the home-made (fake) from the authentic products, especially for premium-class alcoholic beverages.

Multi-Elemental Analysis of Wine Samples in Relation to Their Type, Origin, and Grape Variety.

Wine is one of the most popular alcoholic beverages. Therefore, the control of the elemental composition is necessary throughout the entire production process from the grapes to the final product. The content of some elements in wine is very important from the organoleptic and nutritional points of view. Nowadays, wine studies have also been undertaken in order to perform wine categorization and/or to verify the authenticity of products. The main objective of this research was to evaluate the influence of the chosen factors (type of wine, producer, origin) on the levels of 28 elements in 180 wine samples. The concentration of studied elements was determined by ICP-MS (Ag, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Sn, Sr, Te, Tl, U, Zn), ICP-OES (Ca, Fe, K, Mg, Ti), and CVAAS (Hg) techniques in 79 red, 75 white, and 26 rose wine samples. In general, red wines contained higher values of mean and median of B, Ba, Cr, Cu, Mn, Sr and Zn in contrast to other wine types (white and rose). In white wines (when compared to red and rose wines) higher levels of elements such as Ag, Be, Bi, Cd, Co, Li, K and Ti were determined. In contrast, rose wines were characterized by a higher concentration of Fe and U. The study also revealed that in the case of 18 samples, the maximum levels of some metals (Cd-8 samples, Pb-9 samples, Cu-1 sample) were slightly exceeded according to the OIV standards, while for Zn and Ti in any wine sample the measured concentrations of these metals were above the permissible levels. Thus, it can be stated that the studied wines contained, in general, lower levels of heavy metals, suggesting that they should have no effect on the safety of consumption. The results also showed higher pH level for red wines as a consequence of the second fermentation process which is typically carried out for this type of wine (malolactic fermentation). The highest median value of pH was reported for Merlot-based wines, while the lowest was for Riesling. It is assumed that dry Riesling has a higher content of tartaric and malic acid than dry Chardonnay grown in the same climate. From all of the studied countries, wines from Poland seemed to present one of the most characteristic elemental fingerprints since for many elements relatively low levels were recorded. Moreover, this study revealed that also wine samples from USA and Australia can be potentially discriminated from the rest of studied wines. For USA the most characteristic metal for positive identification of the country of origin seems to be uranium, whereases for Australia - strontium and manganese. Based on the highly reduced set of samples, it was not possible to differentiate the studied wine products according to the grape variety other than Syrah, and partially Chardonnay. Since all the Syrah-based samples originated from the same country (Australia) thus, the observed grouping should be more related with the country of origin than the grape variety.

Risk of Mercury Ingestion from Canned Fish in Poland.

In this study, total mercury content was determined in 84 canned fish corresponding to commonly consumed brands (over 14 different producers), which were purchased from local markets in Poland in the years 2019-2020. For comparison purposes, samples of both the matrix in which the fish were kept along with the seafood samples were measured. The analyses were carried out using the cold vapor AAS technique. Statistical analyses were employed to identify significant differences in mercury content in relation to the selected criteria such as fish species, type of fish (predatory, non-predatory) and the producer brand. The obtained results were compared against domestic and international standards as well as with the literature data in order to evaluate the safety of the canned fish consumption. The study revealed that none of canned fish exceeded the acceptable levels set by the FAO/WHO. The highest amount of Hg was recorded for canned tuna (maximum 351.30 µg/kg, mean 74.38 µg/kg). Further, the estimated tolerable dose of weekly mercury intake suggests that the consumption of over 1.8 cans of fish with the highest mean mercury content should not pose a risk to consumers in Poland according to international standards. Among the ten highest mean results for mercury, five of them belonged to canned tuna (Bonito species) kept in different matrices. These consisted of seven domestic and three imported brands of fish products, which is a worrying message for a local community. Mercury content in predatory fish differed significantly from the results gathered for non-predatory fish and the total amount of mercury in studied canned fish corresponded to their status in the aquatic food chain. Moreover, significant differences were stated between various fish species and fishing areas. Fish caught in the Atlantic Ocean (cod and herring) presented higher mercury content than the ones from closed seas.

Multielemental Analysis of Various Kinds of Whisky.

Whisky (whiskey) consists of many trace elements coming from the raw materials used in its fermentation, distillation and maturation processes. These ingredients assure the exceptional organoleptic characteristics of the beverage. Their analysis is important to better control the stages of fermentation, distillation, taste repeatability and for product quality assurance as well as from the brand protection point of view. This article presents the usefulness of modern analytical techniques based on elemental analysis. ICP mass spectrometry and CV atomic absorption spectroscopy were applied to distinguish whisky produced in Scotland from whisky coming from Ireland and the United States. The collected semi-quantitative data were used for multivariate analysis performed using the Statistica 10.0 software. The results showed that Irish whiskey is characterized by quite a high amount of Ba and Ti compared with other samples, which made it possible to distinguish this sample from the others. No strict correlation was found between the type of whisky and the amount of trace elements, however, the projection of objects on the first two components revealed that single malt samples created one cluster.