Oleic Acid Is not the Only Relevant Mono-Unsaturated Fatty Ester in Olive Oil

(1) Background: Extra-virgin olive oil (EVOO) is a precious and universally studied food matrix. Recently, the quantitative chemical composition was investigated by an innovative processing method for the nuclear magnetic resonance (NMR) experiments called Multi-Assignment Recovered Analysis (MARA)-NMR. (2) Methods: Any EVOO 13-carbon NMR ((13)C-NMR) profile displayed inconsistent signals. This mismatch was resolved by comparing NMR data to the official gas-chromatographic flame ionization detection (GC-FID) experiments: the analyses concerned many EVOOs but also the “exotic” Capparis spinosa oil (CSO). (3) Results: NMR and GC-FID evidenced the overwhelming presence of cis-vaccenic esters in the CSO and, more importantly, cis-vaccenic (13)C-NMR resonances unequivocally matched the misunderstood (13)C-NMR signals of EVOOs. The updated assignment revealed the unexpected relevant presence of cis-vaccenic ester (around 3%) in EVOOs; it was neglected, so far, because routine and official GC-FID profiles did not resolve oleic and cis-vaccenic signals leading to the total quantification of both monounsaturated fatty esters. (4) Conclusions: The rebuilt MARA-NMR and GC-FID interpretations consistently show a meaningful presence of cis-vaccenic esters in EVOOs, whose content could be a discrimination factor featuring specific cultivar or geographical origin. The study paves the way toward new quantification panels and scientific research concerning vegetable oils.