Abstract
Pyrrolizidine alkaloids (PA) and PA N-oxides (PANO) are secondary plant metabolites exhibiting genotoxic and carcinogenic properties. Apart from the roots and leaves, PA/PANO are particularly present in pollen and nectar. Therefore, the spread of Jacobaea vulgaris in certain regions of northern Germany has an impact on the safety of honey produced in that region. In this study, raw honey samples (n = 437) were collected from usually three individual beehives per site (n = 73) in the district of Ostholstein and analyzed for 25 PA/PANO. The results reveal mean levels of 8.4, 1.5, and 72.6 µg/kg and maximum levels of 111, 59.4, and 3313 µg/kg, depending on the season (summer 2015 and spring/summer 2016, respectively). As far as individual data are concerned, sites near areas with J. vulgaris growth did not necessarily result in high PA/PANO values. Furthermore, intra-site investigations revealed remarkable differences in PA/PANO levels of raw honey collected by different bee colonies at the same site. Consumption of these regionally produced honeys entails an increased exposure to PA/PANO, especially in children and high consumers. Margin of exposure values of <10,000 and an exceedance of the health-based guidance value highlight that regionally produced and marketed honey must be considered with care for a proper risk assessment and risk management.
Highlights
Pyrrolizidine alkaloids (PA) and their N-oxides (PANO) are secondary plant metabolites that are primarily synthesized to protect the plants from herbivorous insects
A sensitive LC–MS/MS method based on a previously published procedure [24] was established and in-house validated for 25 pyrrolizidine alkaloids (PA)/PA N-oxides (PANO) in honey
Samples of raw, unblended honey were directly taken from individual beehives and examined for their PA/PANO content
Summary
Pyrrolizidine alkaloids (PA) and their N-oxides (PANO) are secondary plant metabolites that are primarily synthesized to protect the plants from herbivorous insects. Toxins 2020, 12, 441 are regularly found in the seeds and flowering tops of the plants [1,2,3]. 1,2-unsatured PA/PANO with a common core structure (1-hydroxymethyl-1,2-didehydropyrrolizidine, necine base), mostly of the retronecine-, heliotridine- and otonecine-type, possess genotoxic and carcinogenic properties in humans and animals [4,5]. C7-positions of the pyrrolizidine core structure with mono- or dicarboxylic acids (necic acids), forming monoesters, diesters or cyclic diesters. Their toxicity is regarded to depend on the type of esterification with cyclic diesters possessing the highest potency [2,6]. Human and animal exposure to PA/PANO should generally be kept as low as possible [10,11]
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