There are 144 EVOOs registered with protected denomination of origin (PDOs) and protected geographical indication (PGIs), which may be vulnerable to fraudulent practices because of their high economic value. This study aimed to develop an instrumental tool to assess the compliance of PDO EVOOs from Catalonia. A sample set of 350 EVOOs were collected from different regions of Catalonia (260 samples) over 3 growing seasons, and the rest of the EVOO and VOO samples (90) came from other Mediterranean producing countries (Greece, Italy, Morocco, Tunisia, and Turkey). Discriminant analysis based on the sesquiterpene hydrocarbon fingerprint determined by HS-SPME-GC-MS (headspace solid-phase microextraction coupled to gas chromatography–mass spectrometry) followed by chemometric analysis of the samples achieved a correct classification of 93.6% of samples among the four Catalan regional PDOs. However, the method achieved a discrimination between each Catalan PDO and the non-PDO samples, produced in different geographical areas with an efficiency between 95% and 99%.
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