Quick and Green Microextraction of Pyrrolizidine Alkaloids from Infusions of Mallow, Calendula, and Hibiscus Flowers Using Ultrahigh-Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry Analysis

Abstract

A sustainable microextraction of pyrrolizidine alkaloids (PAs) from edible flower infusions using the innovative μSPEed technique is proposed. Different sorbents and extraction conditions were tested, achieving the highest extraction efficiency with an octadecylsilane sorbent (4 mg). The extraction procedure just took 1 min per sample, and only 300 μL of methanol and 300 μL of the sample were used per extraction. Ultrahigh-performance liquid chromatography coupled to tandem mass spectrometry was used for analysis. The method was properly validated, providing suitable linearity, selectivity, sensitivity (quantification limits 0.3–1 μg/L), overall recoveries (79–97%), and precision (≤17% relative standard deviation). Its application to the analysis of different infusions of mallow, calendula, and hibiscus flowers revealed similar total PA values (23–41 μg/L) and contamination profile among the mallow and hibiscus samples, with predominance of senecionine-type and heliotrine-type PAs, respectively. Conversely, calendula samples showed more variations (23–113 μg/L), highlighting the occurrence of intermedine N-oxide and europine N-oxide on them.