Geographical origin assessment of extra virgin olive oil (EVOO) is recognised worldwide as raising consumers’ awareness of product authenticity and the need to protect top-quality products. The need for geographical origin assessment is also related to mandatory legislation and/or the obligations of true labelling in some countries. Nevertheless, official methods for such specific authentication of EVOOs are still missing. Among the analytical techniques useful for certification of geographical origin, nuclear magnetic resonance (NMR) and mass spectroscopy (MS), combined with chemometrics, have been widely used. This review considers published works describing the use of these analytical methods, supported by statistical protocols such as multivariate analysis (MVA), for EVOO origin assessment. The research has shown that some specific countries, generally corresponding to the main worldwide producers, are more interested than others in origin assessment and certification. Some specific producers such as Italian EVOO producers may have been focused on this area because of consumers’ interest and/or intrinsic economical value, as testified also by the national concern on the topic. Both NMR- and MS-based approaches represent a mature field where a general validation method for EVOOs geographic origin assessment could be established as a reference recognised procedure.

During the last few years, the global demand for extra virgin olive oil (EVOO) is increased. Olive oil represents a significant percentage of world fat consumption determining an important development of its market. In this context, the problems related to counterfeiting and product fraud is becoming extremely relevant. Thus, the quality and authenticity control of EVOOs is nowadays mandatory. In this study we focused on the use of ¹H NMR technique associated with multivariate statistical analysis to characterize Italian EVOOs commercial blends. In particular, a specific database including 126 monocultivar EVOOs reference samples, was used to characterize a total of 241 Italian EVOOs blends over four consecutive harvesting years. Moreover, the effect of the minor components (phenolic compounds) on the qualitative characterization of blended EVOOs was also evaluated. The correlation analysis of classification scores obtained using two pairwise orthogonal partial least square-discriminant analysis models (built with major and combined major–minor components NMR data) revealed that both could be profitably used to generally classify the studied Coratina containing blends.

In this work we have compared two different sensing platforms for the detection of morphine as an example of a low molecular weight target analyte. For this, molecularly imprinted polymer nanoparticles (NanoMIP), synthesized with an affinity towards morphine, were attached to an electrochemical impedance spectroscopy (EIS) and a quartz crystal microbalance (QCM) sensor. Assay design, sensors fabrication, analyte sensitivity and specificity were performed using similar methods. The results showed that the EIS sensor achieved a limit of detection (LOD) of 0.11 ng·mL⁻¹, which is three orders of magnitude lower than the 0.19 µg·mL⁻¹ achieved using the QCM sensor. Both the EIS and the QCM sensors were found to be able to specifically detect morphine in a direct assay format. However, the QCM method required conjugation of gold nanoparticles (AuNPs) to the small analyte (morphine) to amplify the signal and achieve a LOD in the µg·mL⁻¹ range. Conversely, the EIS sensor method was labor-intensive and required extensive data handling and processing, resulting in longer analysis times (~30–40 min). In addition, whereas the QCM enables visualization of the binding events between the target molecule and the sensor in real-time, the EIS method does not allow such a feature and measurements are taken post-binding. The work also highlighted the advantages of using QCM as an automated, rapid and multiplex sensor compared to the much simpler EIS platform used in this work, though, the QCM method will require sample preparation, especially when a sensitive (ng·mL⁻¹) detection of a small analyte is needed.

Considering the growing number of extra virgin olive oil (EVOO) producers in the world, knowing the influence of olive oils with different geographical origins on the characteristics of the final blend becomes an interesting goal. The present work is focused on commercial organic EVOO blends obtained by mixing multiple oils from different geographical origins. These blends have been studied by 1H-NMR spectroscopy supported by multivariate statistical analysis. Specific characteristics of commercial organic EVOO blends originated by mixing oils from Italy, Tunisia, Portugal, Spain, and Greece were found to be associated with the increasing content of the Italian component. A linear progression of the metabolic profile defined characteristics for the analysed samples—up to a plateau level—was found in relation to the content of the main constituent of the Italian oil, the monocultivar Coratina. The Italian constituent percentage appears to be correlated with the fatty acids (oleic) and the polyphenols (tyrosol, hydroxytyrosol, and derivatives) content as major and minor components respectively. These results, which highlight important economic aspects, also show the utility of 1H-NMR associated with chemometric analysis as a powerful tool in this field. Mixing oils of different national origins, to obtain blends with specific characteristics, could be profitably controlled by this methodology.

This study aims to evaluate the Proton Nuclear Magnetic Resonance (¹H-NMR)-based metabolomic profiles of monovarietal olive oils obtained from Arbequina and Koroneiki, which are typically present in the Mediterranean basin and grown in Spain and Greece, respectively. Micro-milled oils were obtained from olives harvested both in their cultivar home countries (Spain and Greece) and in Italy. Investigations by ¹H NMR metabolic profiling were carried out to develop a strategy for the correct interpretation of differences based on geographical origins. The NMR Spectroscopy and multivariate statistical analysis (MVA) revealed significant differences in fatty acids profile as well as the unsaponifiable fraction, not only according to the cultivars but also to the specific geographical origin of the olives used. In particular, the oils from Spain were higher in polyunsaturated fatty acids (PUFAs) content than those from Italy. Conversely, the Italian oils of Koroneiki showed higher content of monounsaturated fatty acids (MUFAs) than Greek oils. Regarding the Extra Virgin Olive Oils (EVOOs) minor fraction, for both cultivars, the olive oils obtained using olives harvested in Italy were characterized by higher relative content of phenolic compounds. It was found that each of the investigated cultivars (Arbequina and Koroneiki), very popular in super high density (SHD) planting systems, assumed a specific well-characterized metabolic EVOO profile when the olives are harvested in Italy. These results may contribute to extending and enforcing available literature data on ¹H NMR-based chemometric models as powerful tools for EVOOs geographical origin discrimination.