Pyrrolizidine alkaloids (PAs) and related N-oxides (PANOs) are secondary plant metabolites thought to be found in approximately 3% of the flowering plants worldwide and exhibiting hepatotoxic properties to humans. As a consequence, beehive products are prone to be contaminated with those compounds by bees foraging PA producing plants. Downstream contamination can also occur through food items containing honey. Analytical methods based on UHPLC separation and MS/MS detection were developed with a focus on very low LOQs and validated for the analysis of 16 PAs and 14 PANOs in honey, honey based candies and snacks as well as beehive products based food supplements. A maximum level of 182 ng/g of PAs was detected in a Mediterranean honey, and high levels of heliotrine-type compounds were reported for the first time. An extensive sampling of honeys harvested in Belgium was performed (N = 374), the concentration levels were more limited with a maximum of 60 ng/g and the contamination pattern was dominated by senecionine-type PAs. The PA levels in honey based candies and snacks were very low, with respective maxima of 7.61 ng/g and 0.36 ng/g. Seventy five percent among the pre-dosed food supplements based on beehive products were contaminated, with a maximum of 43 ng/g. The highest level was detected in a bee-collected pollen sample (1672 ng/g). The analytical results were consistent with the previously reported data for beehive products and confirmed that PAs/PANOs contamination in these food commodities is recurrent.
