Ultra-trace-level determination of polar pesticides and their transformation products in surface and estuarine water samples using column liquid chromatography–electrospray tandem mass spectrometry

Abstract

A method is developed for the determination of polar pesticides and their transformation products [atrazine, deethylatrazine, deisopropylatrazine, hydroxyatrazine, diuron, 3,4-dichlorophenylmethylurea, 3,4-dichlorophenylurea (DPU), monuron, bentazone, anthranil-isopropylamide, chloridazon, metolachlor] in surface, estuarine and sea water samples at the low ng/l level. Solid-phase extraction is combined off-line with column liquid chromatography–electrospray ionization tandem mass spectrometric detection (LC–ESI-MS–MS). The applicability of two solid-phase materials, i.e., LiChrolut EN cartridges and graphitized carbon black extraction disks, is evaluated. The influence of the organic solvent used in gradient LC, as well as the amount of co-extracted humic material on the ESI process is studied. The eluotropic strength of the organic solvent was found to have a distinct effect on the sensitivity of ESI-MS if coupled with LC gradient separations. Methanol gave much better results than acetonitrile and phenylurea compounds are more susceptible to solvent changes than triazines. Co-extracted humic material causes signal suppression in ESI-MS–MS detection. The degree of suppression depends upon the sample pH and the nature of the samples, i.e., surface or estuarine water. Detection limits in LC–ESI-MS–MS ranged from 0.2 to 2 ng/l, with the exception of DPU (8 ng/l). The applicability of the procedure was demonstrated by analyzing surface and estuarine water.