Multiresidue determination of 160 pesticides in wines employing mixed-mode dispersive-solid phase extraction and gas chromatography–tandem mass spectrometry

Abstract

A new multiresidue method for the efficient screening, identification and quantification of over 160 pesticides belonging to different chemical classes in red, rose and white wines have been developed. The analysis was based on gas chromatographic-tandem quadrupole mass spectrometric determination (GC-QqQ–MS/MS). An optimization strategy involved the selection of buffering conditions and sorbents for dispersive-solid phase extraction (dispersive-SPE) in order to achieve acceptably high recoveries and reduce co-extractives in the final extracts. As a result, the optimized procedure allowed us to obtain consistent recoveries of the target pesticides including problematic ones such as captan, chlorothalonil, dichlofluanid, folpet and tolylfluanid. The attained recoveries were typically between 80 and 110% (89% on average) with RSD values typically lower than 10% (8% on average) at three spiking levels of 0.01, 0.05 and 0.2mgkg−1. Linearity was studied in the range between 0.005 and 0.2mgkg−1 using pesticide standards prepared both in pure solvent and in the presence of matrix, showing coefficients of determination (R2) higher than 0.99 for all the pesticides except for desmedipham, thiabendazole and thiamethoxam in pure solvent. The study of the ratio of the slopes obtained in solvent and in matrix provided information about the matrix effects, which was <10%, 10–20% and >20% for 33, 36 and 31% of the studied pesticides, respectively. To improve accuracy, matrix matched standards were always used for calculation of the quantification results. The expanded uncertainties were estimated by using a “top-down” approach as being 17% on average (coverage factor k=2, confidence level 95%). Finally, the method was used with success to detect and quantify pesticide residues in commercial wines.