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.