Chromatographic Fingerprinting Enables Effective Discrimination and Identitation of High-Quality Italian Extra-Virgin Olive Oils Stilo, Federico Jiménez Carvelo, Ana María Cuadros Rodríguez, Luis Comprehensive two-dimensional gas chromatography Extra-virgin olive oil Combined untargeted and targeted (UT) fingerprinting Identitation and authentication Geographical origin The research was supported by Progetto Ager.Fondazioni in rete per la ricerca agroalimentare. Project acronym Violin. Valorization of Italian olive products through innovative analytical tools; years 2016-2021. The challenging process of high-quality food authentication takes advantage of highly informative chromatographic fingerprinting and its identitation potential. In this study, the unique chemical traits of the complex volatile fraction of extra-virgin olive oils from Italian production are captured by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry and explored by pattern recognition algorithms. The consistent realignment of untargeted and targeted features of over 73 samples, including oils obtained by different olive cultivars (n = 24), harvest years (n = 3), and processing technologies, provides a solid foundation for sample identification and discrimination based on production region (n = 6). Through a dedicated multivariate statistics workflow, identitation is achieved by two-level partial least-square (PLS) regression, which highlights region diagnostic patterns accounting between 58 and 82 of untargeted and targeted compounds, while sample classification is performed by sequential application of soft independent modeling for class analogy (SIMCA) models, one for each production region. Samples are correctly classified in five of the six single-class models, and quality parameters [i.e., sensitivity, specificity, precision, efficiency, and area under the receiver operating characteristic curve (AUC)] are equal to 1.00. 2021-10-01T10:08:04Z 2021-10-01T10:08:04Z 2021-07-28 journal article J. Agric. Food Chem. 2021, 69, 8874−8889. [https://doi.org/10.1021/acs.jafc.1c02981] http://hdl.handle.net/10481/70571 10.1021/acs.jafc.1c02981 eng http://creativecommons.org/licenses/by/3.0/es/ open access Atribución 3.0 España American Chemical Society