Paper spray mass spectrometry and chemometric tools for a fast and reliable identification of counterfeit blended Scottish whiskies

•Authentic and counterfeit Scotch whiskies were discriminated by PS(-)-MS.•Mass spectra were obtained rapidly with insignificant sample consumption.•Models were built with fake samples representative of Brazilian police seizures.•PLS-DA model discriminated among samples with almost 100% of success rate.•Diagnostic ions for authentic whiskies were identified using PLS-DA. A direct method based on the application of paper spray mass spectrometry (PS-MS) combined with a chemometric supervised method (partial least square discriminant analysis, PLS-DA) was developed and applied to the discrimination of authentic and counterfeit samples of blended Scottish whiskies. The developed methodology employed the negative ion mode MS, included 44 authentic whiskies from diverse brands and batches and 44 counterfeit samples of the same brands seized during operations of the Brazilian Federal Police, totalizing 88 samples. An exploratory principal component analysis (PCA) model showed a reasonable discrimination of the counterfeit whiskies in PC2. In spite of the samples heterogeneity, a robust, reliable and accurate PLS-DA model was generated and validated, which was able to correctly classify the samples with nearly 100% success rate. The use of PS-MS also allowed the identification of the main marker compounds associated with each type of sample analyzed: authentic or counterfeit.