Quantification of pyrrolizidine alkaloids in Senecio brasiliensis, beehive pollen, and honey by LC-MS/MS

This article presents the determination of eight pyrrolizidine Alkaloids (PAs) by LC-MS/MS in honeys, pollen, and Senecio brasiliensis (Asteraceae) samples, all from Santa Catarina state, Brazil. In addition, the Box-Behnken design was used to perform an optimized sample preparation on pollens and S. brasiliensis parts. Senecionine and its N-oxide, besides retrorsine N-oxide, were determined in six of the seven honeys samples. Pollen from species of the Asteraceae, Fabaceae, and Boraginaceae families were found with greater predominance in three of the seven honeys samples. In these three honeys samples were also found the highest PAs levels. In beehive pollen, flower, and leaf of S. brasiliensis, the total levels of PAs and their N-oxides reached 221, 14.1 × 10⁴, and 14.8 × 10⁴ mg kg^-1, respectively. In honeys, these compounds are chemical contaminants and therefore undesirable when the sum exceeds 71 µg kg^-1, according to EFSA. On the other hand, although PAs are naturally present in plant and pollen of some species (Senecio, Crotalaria, Bacharis, Ecchium, Mimosa scabrella, Vernonia), it is important to monitor their levels in Plants but also in honeys, and other beehive products since these compounds are transferred to the final product.