Glass authentication: Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) for origin discrimination of glass bottles.

Counterfeiting is an omnipresent issue, among others in the cosmetics industry or on the art market. Particularly in the case of very expensive perfumes or very valuable art objects, counterfeits are strongly represented and are steadily increasing. Typically, the content of perfumes is analyzed, but the bottle offers another level of authentication, as it is an essential part of the product. For art objects made of glass, glass is an essential part of the artwork and thus provides an important contribution to the authenticity of the object. In the present pilot study, we developed a laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) method to classify glass using perfume bottles manufactured at different production facilities, Germany, India, Peru and Poland as an example. Using minimally invasive laser ablation invisible to the eye, we were able to detect counterfeit flacons without having to open the vials. A total of 63 elements could be recorded during method development. After statistical evaluation (t-test, ANOVA, principal component analysis (PCA)), 15 (Li, Na, Al, Ti, V, Co, Rb, Sr, Mo, Ba, La, Ce, Pr, Er and Pb) significant marker elements were extracted from the data sets to differentiate the different glass origins. By using LDA, six different production sites from four different countries could be differentiated over a sample period of six months with a prediction accuracy of 100%.

Origin Determination of Walnuts (Juglans regia L.) on a Worldwide and Regional Level by Inductively Coupled Plasma Mass Spectrometry and Chemometrics.

To counteract food fraud, this study aimed at the differentiation of walnuts on a global and regional level using an isotopolomics approach. Thus, the multi-elemental profiles of 237 walnut samples from ten countries and three years of harvest were analyzed with inductively coupled plasma mass spectrometry (ICP-MS), and the resulting element profiles were evaluated with chemometrics. Using support vector machine (SVM) for classification, validated by stratified nested cross validation, a prediction accuracy of 73% could be achieved. Leave-one-out cross validation was also applied for comparison and led to less satisfactory results because of the higher variations in sensitivity for distinct classes. Prediction was still possible using only elemental ratios instead of the absolute element concentrations; consequently, a drying step is not mandatory. In addition, the isotopolomics approach provided the classification of walnut samples on a regional level in France, Germany, and Italy, with accuracies of 91%, 77%, and 94%, respectively. The ratio of the model's accuracy to a random sample distribution was calculated, providing a new parameter with which to evaluate and compare the performance of classification models. The walnut cultivar and harvest year had no observable influence on the origin differentiation. Our results show the high potential of element profiling for the origin authentication of walnuts.