Development and Validation of a Gas Chromatography-Mass Spectrometry Method for Determining Acaricides in Bee Pollen

Abstract

Pesticides can be found in beehives for several reasons, including contamination from surrounding crops or for their use by beekeepers, which poses a risk to bee ecosystems and consumers. Therefore, efficient and sensitive methods are needed for determining pesticide residues in bee products. In this study, a new analytical method has been developed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in bee pollen using gas chromatography coupled to mass spectrometry. After an optimization study, the best sample treatment was obtained when using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method employing an ethyl acetate and cyclohexane as the extractant mixture, and a mixture of salts for the clean-up step. A chromatographic analysis (<21 min) was performed in an Agilent DB-5MS column, and it was operated under programmed temperature conditions. The method was fully validated in terms of selectivity, limits of detection (0.2–3.1 µg kg−1) and quantification (0.6–9.7 µg kg−1), linearity, matrix effect (<20% in all cases), trueness (recoveries between 80% and 108%), and precision. Finally, the proposed method was applied to analyze commercial bee pollen samples, and some of the target pesticides (chlorfenvinphos, α-endosulfan, coumaphos, and τ-fluvalinate) were detected.

Contamination of Honeybee (Apis mellifera L.) Royal Jelly by Pesticides and Sample Preparation Methods for Its Determination: A Critical Appraisal

“…QuEChERS, a novel technique for determining pesticide residues in food analysis, was developed and validated by Anastassiades et al (2003) [85] and quickly adopted by numerous laboratories to study pesticides in bee products [86,87]. The QuEChERS method uses a combination of liquid-liquid extraction, mainly acidified acetonitrile [9], and solid-phase dispersion sorbents (see Table 4) and salts (e.g., magnesium sulphate or sodium acetate) to extract and then clean the extract.…”

“…Over the years, the QuEChERS procedure has been modified and used for the determination of pesticide residues in honey [88], wax [89], pollen [86], bumblebees [90] and royal jelly [9,41,44,91,92]. The insecticide pyriproxyfen and its four metabolites were extracted from royal jelly using the QuEChERS method [70].…”

Simultaneous analysis of pesticides and mycotoxins in primary processed foods: The case of bee pollen

“…However, several studies have shown the presence of contaminants of known toxicity in bee pollen, sometimes reaching potentially dangerous concentrations [ 7 ]. Particularly alarming contaminants found in bee pollen are mycotoxins, toxic metabolites produced by fungi in favorable environmental conditions [ 8 ], and pesticides, commonly employed for pest control, which pose a potential health hazard for consumers [ [9] , [10] , [11] ]. The contamination of bee pollen with such contaminants can have several sources.…”