A headspace-mass spectrometry (HS-MS) coupling designed for the sensory characterization and classification of extra virgin olive oil on the basis of its protected designation of origin, olive variety and geographical origin is reported. The procedure involves the headspace generation and the direct injection of the homogenized gaseous phase into a mass spectrometer through a transfer line. The results obtained were chemometrically treated to achieve the best model capable of discriminating between the different olive oil categories. For this purpose, several procedures for variables selection, data pretreatments and unsupervised techniques were evaluated. In addition, K-nearest neighbor and soft independent modeling of class analogy algorithms were employed to the classification models building. Taking into account the prediction results obtained (ca. 87% of samples correctly classified and a specificity of ca. 97%), it can be concluded than the HS-MS coupling is, with an adequate chemometric treatment, an appropriate technique for routine control.
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