Pyrrolizidine alkaloid concentrations in local Italian and retail honeys of different origin: A scenario of human exposure

Abstract

A validated method in liquid chromatography tandem mass spectrometry was applied to assess the contamination profile of 17 pyrrolizidine alkaloids and their N-oxide metabolites (PAs/PANOs) in 775 honey samples of different origins, including from local beekeepers (579, LB), large retail and online stores (Italian (LRI) and foreign (LRF) products). Fifty-five percent of the honey samples contained the 17 monitored compounds at below the limit of quantification. The LB samples were characterised by a total mean concentration of PAs/PANOs at 6.7 and 3.3 times lower than those of the LRF and LRI samples, respectively. The PA echimidine characterised mainly honey samples from the large retail stores (75.8 % and 72.5 % of LRI- and LRF-contaminated samples, respectively). The LB samples showed a senecionine-type contamination profile, providing beekeepers clues to the plants responsible for contamination. The results highlighted that the consumption of the local honey samples analysed does not represent a double risk for human health compared to the consumption of products from large retail stores. Careful attention must be paid to honey imported from areas where lycopsamine-type and senecionine-type PAs/PANOs-producing plants are invasive. A machine learning approach could predict the origin of the sample given its contaminant profile at an accuracy of 0.74, which is useful for detecting fraud in the declared honey origin.