Abstract

Pyrrolizidine alkaloids (PAs) are secondary metabolites produced by plants as a chemical defense against herbivores. Plants containing PAs are widely distributed in almost all geographical regions posing a risk of honey contamination. To provide safety of honey and decrease the potential risk for the consumers, a sensitive method based on gas chromatography-mass spectrometry enabling determination of a content of 1,2-unsaturated PAs in honey was developed. Honey samples were purified on MCX cartridges, and PAs were eluted with a solvent mixture consisting of ethyl acetate, methanol, ammonia, and triethylamine. Subsequently, 1,2-unsaturated alkaloids were reduced to their common backbone structures and derivatized with heptafluorobutyric anhydride. The method was validated according to SANTE 2015. All received parameters are in consistence with the document requirements as recovery ranged from 73.1 to 93.6%. The repeatability and reproducibility were calculated as relative standard deviation and ranged from 3.9 to 8.6% and from 10.6 to 17.8%, respectively. The limit of quantification was determined as 1 μg kg−1. Good linearity of the method was obtained with the coefficient of determination R2 > 0.99. The method was applied to 40 Polish and 14 Asian honey sample analyses.

Highlights

  • Honey is used and consumed worldwide for its sweet taste, nutritive, and pro-health properties

  • Due to complexity of the matrix and low levels of PAs present, many of the procedures developed for the determination of pyrrolizidine alkaloids in honey have been based on LC-MS/MS methodology (Table 2)

  • gas chromatography-mass spectrometry (GC-MS) can be a useful technique for an analysis of honey samples for the presence of 1,2-unsaturated PAs, especially when the sum parameter approach is used (Kempf et al 2008, Cramer and Beuerle 2012)

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Summary

Introduction

Honey is used and consumed worldwide for its sweet taste, nutritive, and pro-health properties. Honey is produced in a natural environment, which is why it can be contaminated with many natural substances (Dubreil-Chéneau et al 2013). Certain types of flower nectar and pollen have been reported to result in honey that is psychoactive or that can lead to toxicity (Islam et al 2014). The natural toxic substances that can be transferred to honey are, among others, pyrrolizidine alkaloids (PAs). PAs are considered to be the most widely spread toxins of natural origin. They are produced by many plants, estimated as 3% of all flowering plants; the main sources of PAs are the families Boraginaceae, Asteraceae, Fabaceae, and Apocynaceae (Kempf et al 2008).

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