Compensation of Matrix Effects by Postcolumn Infusion of a Monitor Substance in Multiresidue Analysis with LC-MS/MS

This study systematically compares matrix effects in liquid chromatography (LC) coupled by electrospray ionization (ESI) in the positive mode with tandem mass spectrometry (MS/MS) for 129 pesticides in 20 plant matrixes. In total, 2388 analyte/matrix combinations were evaluated. Permanent postcolumn infusion (PCI) of analyte standards was used to quantify matrix effects over the whole chromatographic run time. This allowed the analyte signal suppression or enhancement, by different coeluting matrix components, to be assessed throughout the duration of an entire chromatographic run, i.e., independent of a specific retention time. Matrix effects occurring at a certain retention time in one matrix were surprisingly similar for different analytes with diverse physicochemical properties. On the basis of this finding, a new approach for matrix effect compensation in multiresidue analysis was developed in which one single monitor substance is permanently added postcolumn. Signal intensities of all analytes obtained by LC-MS/MS analysis of sample extracts are then corrected for the matrix effect recorded by the monitor substance. With the use of this approach, strong matrix effects could be reduced and apparent recoveries increased from 45% to 85% on average. With dependence on the particular sample matrix, between 69% and 100% of the analytes showed recoveries between 60% and 140% after correction. Thus this approach may significantly reduce the number of cases in which standard addition is required to confirm violations of maximum residue levels