On-Column Trace Enrichment by Sequential Frontal and Elution Electrochromatography. 1. Application to Carbamate Insecticides

An on-column trace enrichment method for CEC of dilute samples is presented. The method involves on-line preconcentration by frontal electrochromatography under conditions of strong solute binding to the stationary phase followed by a step-gradient elution electrochromatography with a mobile phase of high eluting strength. This method is tested with dilute samples of carbamate insecticides using capillary columns of 100-m i.d. packed with a 5-m octadecyl silica (ODS) stationary phase. The effectiveness of on-line preconcentration (i.e., zone narrowing) depends on the retention factor, kʹ, of the analyte in the injection solvent as well as in the eluting mobile phase (i.e., the organic solvent content), the applied voltage during sample introduction, and elution and length of the introduced sample plug. Under optimal frontal and elution electrochromatography conditions, a 500-fold sensitivity increase is achieved for carbofuran (a carbamate insecticide) with a UV detector. The method is demonstrated with deionized and tap water samples spiked with carbamate insecticides.