- Acknowledgements: Projects (EQC2018-004453-P and RTI2018-097043-B-I00) financed by MCIN/AEI /10.13039/501100011033/ FEDER “Una manera de hacer Europa” and Junta de Andalucía-Programa Operativo FEDER (B-AGR-202-UGR20). Spanish Network of Excellence in Sample preparation (RED2018-102522-T) financed by MCIN/AEI /10.13039/501100011033. B.H. is thankful for the support via the project EFSA-CDN (No. CZ.02.1.01/0.0/0.0/16_019/0000841) co-funded by ERDF and an Erasmus+ scholarship. LCR gratefully acknowledges Francisco Gerardo C.M and Pasión R.S for their technical support during sampling stage. Funding for open access charge: Universidad de Granada/CBUA.
- Authors: L. Carbonell-Rozas, B. Horstkotte, A.M. García-Campaña, F.J. Lara.
- Reference: Journal of Chromatography A 1672 (2022) 463023.
In this work, it is proposed for the first time an electrophoretic approach based on micellar electrokinetic chromatography coupled with tandem mass spectrometry (MEKC-MS/MS) for the simultaneous determination of nine neonicotinoids (NNIs) together with the fungicide boscalid in pollen and honeybee samples. The separation was performed using ammonium perfluorooctanoate (50 mM, pH 9) as both volatile surfactant and electrophoretic buffer compatible with MS detection. A stacking strategy for accomplishing the on-line pre-concentration of the target compounds, known as sweeping, was carried out in order to improve separation efficiency and sensitivity. Furthermore, a scaled-down QuEChERS was developed as sample treatment, involving a lower organic solvent consumption and using Z-Sep+ as dispersive sorbent in the clean-up step. Regarding the detection mode, a triple quadrupole mass spectrometer was operating in positive ion electrospray mode (ESI+) under multiple reaction monitoring (MRM). The main parameters affecting MS/MS detection as well as the composition of the sheath-liquid (ethanol/ultrapure water/formic acid, 50:49.5:0.5 v/v/v) and other electrospray variables were optimized in order to achieve satisfactory sensitivity and repeatability. Procedural calibration curves were established in pollen and honeybee samples with LOQs below 11.6 µg kg−1 and 12.5 µg kg−1, respectively. Precision, expressed as RSD, lower than 15.2% and recoveries higher than 70% were obtained in both samples. Two positive samples of pollen were found, containing imidacloprid and thiamethoxam. Imidacloprid was also found in a sample of honeybees. The obtained results highlight the applicability of the proposed method, being an environmentally friendly, efficient, sensitive and useful alternative for the determination of NNIs and boscalid in pollen and honeybee samples.
