Geographical Origin Discrimination of Monofloral Honeys by Direct Analysis in Real Time Ionization-High Resolution Mass Spectrometry (DART-HRMS)

An untargeted method using direct analysis in real time and high resolution mass spectrometry (DART-HRMS) combined to multivariate statistical analysis was developed for the discrimination of two monofloral (chestnut and acacia) honeys for their geographical origins—i.e., Italy and Portugal for chestnut honey and Italy and China for acacia honey. Principal Component Analysis, used as an unsupervised approach, showed samples of clusterization for chestnut honey samples, while overlapping regions were observed for acacia honeys. Three supervised statistical approaches, such as Principal Components—Linear Discriminant Analysis, Partial Least Squares—Discriminant Analysis and k-nearest neighbors, were tested on the dataset gathered and relevant performances were compared. All tested statistical approaches provided comparable prediction abilities in cross-validation and external validation with mean values falling between 89.2–98.4% for chestnut and between 85.8–95.0% for acacia honey. The results obtained herein indicate the feasibility of the DART-HRMS approach in combination with chemometrics for the rapid authentication of honey’s geographical origin.