Untargeted authentication of fruit juices based on electrochemical fingerprints combined with chemometrics. Adulteration of orange juice as case of study

This work presents a novel strategy for authentication of fruit juices. The methodology is based on an electrochemical method combined with chemometrics. In addition, the case of orange juice adulteration with grapefruit juices was studied using this methodology. The electrochemical fingerprint of different juices showed the influence from different polyphenols according to the type of fruit. First, Principal Component Analysis (PCA) was able to differentiate clusters of different juices, being the higher group distance within apple, orange, and grape juices samples. On the other hand, partial least-squares – discriminant analysis (PLS-DA) and PCA-linear discriminant analysis (LDA) were used as classification methods, obtaining better results for orange and apple models. Furthermore, good results were obtained for the authentication of orange juices, compared to other juices, with an error rate of 0.04 for cross-validation. In the case of adulteration of orange juice was detected using PLS-DA at an adulteration level as low as 1%. Regression vectors for all models highlighted identifiable potential values that could be related to the main polyphenols in each type of fruit. This electrochemical method is rapid, low-cost, and compatible with on-site analysis compared to other laborious analysis described in the literature. • Electrochemical fingerprint of fruit juices was explored. • Authentication of juices was performed combining electrochemistry and chemometrics. • The methodology was successfully applied for orange juice authentication. • A level of 1% of grapefruit juice adulteration was detected in orange juice.