Volatile compounds are chemical species responsible for the distinctive aroma of virgin olive oil. Monovarietal olive oils have a peculiar composition of volatiles, some of which are varietal descriptors. In this paper, the total phenolic content (TPC), fatty acid composition, volatile compounds, and sensory profile of monovarietal olive oils from four Dalmatian most common olive cultivars—Oblica, Lastovka, Levantinka, and Krvavica—were studied. The volatile composition of olive oils was analyzed using headspace solid-phase microextraction with gas chromatography/mass spectrometry. The highest mean TPC value was measured in Oblica and Krvavica oils (around 438 mg/kg). The difference among cultivars for fatty acids composition was detected for C16:1, C17:0, C18:1, C18:2, and the ratio C18:1/C18:2. Krvavica oils showed clear differences in fatty acid composition compared to oils from other cultivars. The most prevalent volatile compound in all oils was C6 aldehyde E-2-hexenal, with the highest value detected in Levantinka oils (75.89%), followed by Lastovka (55.27%) and Oblica (54.86%). Oblica oils had the highest value of Z-3-hexen-1-ol, which influenced its characteristic banana fruitiness, detected only in this oil. Lastovka oils had the highest amount of several volatiles (heptanal, Z-2-heptenal, hexanal, hexyl acetate), with a unique woody sensation and the highest astringency among all studied cultivars. Levantinka oils had the highest level of almond fruitiness, while Krvavica oils had the highest level of grass fruitiness.

In order to differentiate the extra virgin olive oils (EVOO) of different origin of purchase, such as monovarietal Italian EVOO with protected denomination of origin (PDO) and commercial-blended EVOO purchased in supermarkets, a number of samples was subjected to the analysis of volatile aroma compounds by both targeted gas chromatography/mass spectrometry (GC-MS) and untargeted profiling by comprehensive two-dimensional gas chromatography/mass spectrometry (GC×GC-TOF-MS), analysis of phenols by targeted high-performance liquid chromatography/mass spectrometry (HPLC-DAD-ESI/MS), and quantitative descriptive sensory analysis. Monovarietal PDO EVOOs were characterized by notably higher amounts of positive LOX-derived C6 and C5 volatile compounds, which corresponded to the higher intensities of all the assessed positive fruity and green odor sensory attributes. Commercial-blended EVOOs had larger quantities of generally undesirable esters, alcohols, acids, and aldehydes, which coincided with the occurrence of sensory defects in many samples. Many minor volatile compounds that were identified by GC×GC-TOF-MS were found to differentiate each of the two investigated groups. The differences between the groups with respect to phenols and taste characteristics were evident, but less pronounced. The results that were obtained in this study have undoubtedly confirmed the existence of the large heterogeneity of oils that are sold declared as EVOO. It was shown that GC-MS, GC×GC-TOF-MS, and HPLC-DAD-ESI/MS analyses have complementary outputs, and that their use in combination has advantages in supporting the results of sensory analysis and objectively differentiating these groups of EVOO.

A set of 334 commercial virgin olive oil (VOO) samples were evaluated by six sensory panels during the H2020 OLEUM project. Sensory data were elaborated with two main objectives: (i) to classify and characterize samples in order to use them for possible correlations with physical–chemical data and (ii) to monitor and improve the performance of panels. After revision of the IOC guidelines in 2018, this work represents the first published attempt to verify some of the recommended quality control tools to increase harmonization among panels. Specifically, a new “decision tree” scheme was developed, and some IOC quality control procedures were applied. The adoption of these tools allowed for reliable classification of 289 of 334 VOOs; for the remaining 45, misalignments between panels of first (on the category, 21 cases) or second type (on the main perceived defect, 24 cases) occurred. In these cases, a “formative reassessment” was necessary. At the end, 329 of 334 VOOs (98.5%) were classified, thus confirming the effectiveness of this approach to achieve a better proficiency. The panels showed good performance, but the need to adopt new reference materials that are stable and reproducible to improve the panel’s skills and agreement also emerged.