The performance of gas chromatography coupled with tandem mass spectrometry (GC/MS/MS) was tested for the simultaneous determination of twelve pyrethroid insecticides. First, a comparison of two different ionization modes, electron ionization (EI) and negative chemical ionization (NCI), was carried out using MS and MS/MS. NCI-MS/MS provided the best results in terms of selectivity and sensitivity giving very low detection limits of 0.11 to 450 fg injected. The reliability of the method was confirmed through the evaluation of quality parameters such as accuracy (70–100%), and repeatability and reproducibility, with coefficients of variation below 15% and 10%, respectively.
The applicability of the GC/MS/MS method to real samples and influence of matrix effects were evaluated through the analysis of spiked water, sediment and milk at 0.25 ng L−1, 5 ng g−1 dry weight (dw) and 25 ng g−1 (dw), respectively, of each pyrethroid insecticide considered. Using GC/NCI-MS/MS, matrix spectral interferences were minimized providing method limits of detection (MLODs) of 0.05–2.59 ng L−1, 0.10–87.7 pg g−1 dw, 2.29–1071 pg g−1 lipid weight (lw) for water, sediment and milk, respectively. To the best of our knowledge, the MLOD values found in our study were better than those reported in previous studies; in particular for sediment and food samples, they were one order of magnitude lower. Copyright © 2011 John Wiley & Sons, Ltd.