Multiclass pesticide residue analysis in fish muscle and liver on one-step extraction-cleanup strategy coupled with liquid chromatography tandem mass spectrometry

Abstract

The analysis of pesticide residues in fish samples is challenging due to the low concentrations and large number of analytes that need to be monitored and quantified in a complex matrix. This is the first report providing a novel one-step extraction-cleanup strategy for simultaneous analysis of over 340 pesticides in a fatty fish and liver matrix, coupled with liquid-chromatography tandem mass spectrometry. The samples of fish muscle and liver were prepared according to the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure, wherein the extraction and cleanup protocol were integrated into one step. Among the tested cleanup dispersive solid phase extraction sorbents (C18, primary-secondary amine, Z-Sep), chitin yielded the best results. Spike-in experiments were carried out at three different spiking levels in fish and liver to determine the recovery, precision and limits of detection of the method as well as the matrix effect. The method's detection limits ranged from 0.05 to 1.2μgkg−1, while recoveries of most pesticides were in the range of 70–120% with associated precision - relative standard deviations below 20%. A linear relationship was observed within the range of 0.005–1mgkg−1, and the correlation coefficient was R2>0.997. Expanded measurement uncertainty was estimated to be between 7% and 52%, on average. Matrix effects were evaluated and were not significant for the vast majority of pesticides. The validated method was employed in the analysis of 54 real fish and liver samples in which 10 different pesticides with concentrations ranging from 0.005 to 0.047mgkg−1 were detected.