Determination of multi-class pesticide residue in dietary supplements from grape seed extracts by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry

Abstract

A new method was developed and validated for the determination of multi-class pesticide residues in nutraceutical products obtained from grape seed extracts. The extraction procedure was based on QuEChERS methodology using ethyl acetate as solvent and a dispersive solid-phase extraction (dSPE) clean-up stage with C₁₈ was included to minimise matrix effects. Pesticides determination was achieved using ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS); total running time was 11 min. Pesticides were quantified using matrix-matched calibration. The developed method was validated in terms of matrix effect, linearity, selectivity, limits of detection and quantification, trueness, repeatability and inter-day precision at three concentration levels (10, 50, 100 µg kg⁻¹). Suitable recovery values were obtained for 76% of analysed pesticides at the lowest concentration (10 µg kg⁻¹). For most of the compounds, relative standard deviation values were lower than 20% and 25% for intra- and inter-day precision, respectively. Finally, 106 pesticides were determined, and the method was applied to seven dietary supplements from grape seed extract, obtaining various positive results for piperonyl butoxide, cyromazine and diniconazole at concentrations ranging from 2.0 to 13.4 µg kg⁻¹.

Keywords:

• dietary supplements
• grape seed extract
• pesticides
• liquid chromatography
• mass spectrometry

Acknowledgements

This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) and FEDER [grant number CTQ2012-34304]. RRG is also grateful for personal funding through the ‘University Research Plan’ (Almeria University) and Cajamar. The authors declare that they have no conflict of interest.