Metabolomic approaches for orange origin discrimination by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry

• We performed an untargeted metabolic fingerprint for oranges origin differentiation.
• UHPLC-(Q)TOF MS data have been processed using XCMS and multivariate analysis.
• Results have been validated by increasing the sample number and additional season and origin.
• Citrusin D has been tentatively identified has an optimal marker for the geographical authentification.

In this work, hybrid quadrupole time-of-flight mass spectrometer (QTOF MS) coupled to ultra high performance liquid chromatography (UHPLC) has been used for biomarkers identification for correct authentication of Valencia (Spain) oranges. Differentiation from foreign Argentinean, Brazilian and South African oranges has been carried out using XCMS application and multivariate analysis to UHPLC-(Q)TOF MS data acquired in both, positive and negative ionisation modes. Several markers have been found and corroborated by analysing two seasons samples. A seasonal independent marker was found and its structure elucidated using accurate mass data and MSE fragmentation spectrum information. Empirical formula was searched in Reaxys database applying sub-structure filtering from the fragments obtained. Three possible structures were found and citrusin D, a compound present in sweet oranges, has been identified as the most plausible as it fits better with the product ion scan performed for this compound. As a result of data obtained in this work, citrusin D is suggested as a potential marker to distinguish the geographic origin of oranges.