Interest in virgin olive oil (VOO) is growing among consumers and industry due to its well‐received sensorial attributes and to its higher oxidative stability, as well as to its positive health effects. Furthermore, attention is being increasingly paid to other quality attributes of VOO, such as sustainability and geographical origin. For these reasons, this oil has an important added value and is exposed to fraudulent practices. In order to guarantee its origin, the European Union (EU) has developed the Protected Designation of Origin (PDO) quality scheme that links the characteristics of a VOO to its geographical origin. In recent years attempts to develop tools that enable the authentication of PDO‐labeled VOOs are carried out. In this regard, studies using Nuclear Magnetic Resonance (NMR) to this aim are here reviewed. Practical Applications: Due to the added value of PDO VOOs, their authentication is of great importance for administration, consumers and producers. The studies in which NMR spectroscopy has been used to this aim are analyzed here. In this context, this review provides a view of the state of the art that can be of practical interest not only for the researchers of the subject but also for the aforementioned groups. Approaches based on NMR spectroscopic data combined with different statistical analysis are used to develop predictive models with the aim of discriminating PDO VOOs from non‐PDO oils, or even to discriminate a VOO from a certain PDO from other different PDO oils.

Oxidized lipids containing a wide variety of potentially toxic compounds can be ingested through diet. However, their transformations during digestion are little known, despite this knowledge being essential in understanding their impact on human health. Considering this, the in vitro digestion process of highly oxidized soybean oil, containing compounds bearing hydroperoxy, aldehyde, epoxy, keto- and hydroxy groups, among others, is studied by 1H nuclear magnetic resonance. Lipolysis extent, oxidation occurrence and the fate of oxidation products both present in the undigested oil and formed during digestion are analyzed. Furthermore, the effect during digestion of two different ovalbumin proportions on all the aforementioned issues is also addressed. It is proved that polyunsaturated group bioaccessibility is affected by both a decrease in lipolysis and oxidation occurrence during digestion. While hydroperoxide level declines throughout this process, epoxy-compounds, keto-dienes, hydroxy-compounds, furan-derivatives and n-alkanals persist to a great extent or even increase. Conversely, a,b-unsaturated aldehydes, especially the very reactive and toxic oxygenated ones, diminish, although part of them remains in the digestates. While a low ovalbumin proportion hardly affects oil evolution during digestion, at a high level it diminishes oxidation and reduces the concentration of potentially bioaccessible toxic oxidation compounds.