Development and validation of a new analytical method for the determination of plasticizers in bee pollen

Abstract

The determination of plasticizers in bee pollen may be important not only to evaluate the contamination of the hive environment, but also to verify the safety for consumers of this food supplement, since to date it has not been studied. Therefore, a new analytical methodology for the determination of nine plasticizers (phthalate esters: di-(2-ethylhexyl) phthalate, dibutyl phthalate, dimethyl phthalate, diethyl phthalate, benzyl butyl phthalate, and di-n-octyl phthalate; diphenyl ethers: 4-bromodiphenyl ether and 4-chlorodiphenyl ether; adipate: bis(2-ethylhexyl) adipate) in bee pollen using gas chromatography-mass spectrometry was developed. An efficient sample treatment (modified QuEChERS, quick, easy, cheap, effective, rugged & safe) is proposed (with average analyte recoveries between 77 % and 104 %) involving extraction with acetonitrile followed by a dispersive solid phase extraction (enhanced matrix removal lipid sorbent). Chromatographic analysis (<21 min) was performed in an Agilent HP-5MS column under programmed temperature conditions, and analyses were performed in selected ion monitoring mode. The method was validated in terms of selectivity, limits of detection (0.2–17.2 μg kg−1) and quantification (0.5–57.5 μg kg−1), linearity, matrix effect, trueness, and precision (relative standard deviation < 15 %). Finally, an analysis of thirty samples from different sources (commercial or experimental apiaries) revealed the presence of residues of five plasticizers in all samples. Quantification was possible in several cases, with overall concentrations ranging from 0.056 to 3.152 mg kg−1. This study not only reports for the first time the presence of some plasticizers in bee pollen, but also corroborates the usefulness of bee pollen as bioindicator of environmental contamination.