Validation and use of a QuEChERS-based gas chromatographic–tandem mass spectrometric method for multiresidue pesticide analysis in blackcurrants including studies of matrix effects and estimation of measurement uncertainty

Abstract

A triple quadrupole GC-QqQ-MS/MS method was optimized for multiresidue analysis of over 180 pesticides in blackcurrants. The samples were prepared by using a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) analytical protocol. To reduce matrix co-extractives in the final extract, the supernatant was cleaned up by dispersive-solid phase extraction (dispersive-SPE) with a mixture of sorbents: primary secondary amine (PSA), octadecyl (C18) and graphitized carbon black (GCB). The validation results demonstrated fitness for purpose of the streamlined method. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.2 mg kg(-1) spanned between 70% and 116% (102% on average) with relative standard deviation (RSD) values between 3% and 19% except for chlorothalonil (23%). Response linearity was studied in the range between 0.005 and 0.5 mg kg(-1). The matrix effect for each individual compound was evaluated through the study of ratios of the slopes obtained in solvent and blackcurrant matrix. The optimized method provided small matrix effect (<10%) for 77% of the compounds, whereas only for 14%, 5% and 4% compounds, the matrix effect was 10-20%, 20-30% and >30%, respectively. Following the application of "top-down" approach, the expanded measurement uncertainty was estimated as being 21% on average (coverage factor k=2, confidence level 95%). If compared with samples of other crops, the analyses of blackcurrants revealed a high percentage of exceedance of the legislative maximum residue levels (MRLs), as well as some instances of the detection of pesticides unapproved on this crop.