The
contamination of honey with hepatotoxic pyrrolizidine alkaloids
(PAs) is an actual concern for food safety. This study reports the
first application of dispersive liquid–liquid microextraction
(DLLME) in the determination of five relevant PAs, and the relative N-oxide derivatives (PANOs), in honey. The effects of different
experimental parameters (pH, ionic strength, type and volume of DLLME
solvents) affecting the extraction efficiency were carefully investigated
and optimized. PAs were extracted from honey (diluted solution 10%
w/v at pH 9.5) by injecting a mixture of chloroform and isopropyl
alcohol. A reduction step (zinc powder in acidic aqueous solution)
before DLLME was performed to convert PANOs in PAs and to obtain the
total PA levels. Both sample preparation protocols (DLLME and Zn-DLLME)
showed negligible matrix effects on PA signal intensity in honeys
of different botanical origins. The overall recoveries of DLLME and
Zn-DLLME ranged from 71 to 102% and from 63 to 103%, respectively,
with a good precision (standard deviations in the range from 1 to
12%). The attained method quantification limits stayed between 0.03
and 0.06 μg kg–1, and the linear response
range extended to 25 μg kg–1. Additionally,
the proposed method provides results comparable to those of the SPE
protocol in the analysis of real samples. An analysis of retail honeys
revealed PA residues in all analyzed samples, with a maximum level
of 17.5 μg kg–1 (total PAs). Globally, the
proposed method provides a sensitive and accurate determination of
analytes and offers numerous advantages, such as simplicity, low cost,
and a high sample throughput, which make it suitable for screening
and quality control programs in food chain and occurrence studies.