A fully automated system for analysis of pesticides in water: On-line extraction followed by liquid chromatography-tandem photodiode array/postcolumn derivatization/fluorescence detection

Abstract

A fully automated system for on-line solid phase extraction (SPE) followed by high-performance liquid chromatography (HPLC) with tandem detection with a photodiode array detector and a fluorescence detector (after postcolumn derivatization) was developed for analysis of many chemical classes of pesticides and their major conversion products in aquatic systems. An automated on-line-SPE system (Prospekt) operated with reversed-phase cartridges (PRP-1) extracts analytes from 100 mL acidified (pH = 3) filtered water sample. On-line HPLC analysis is performed with a 15 cm C18 analytical column eluted with a mobile phase of phosphate (pH = 3)-acetonitrile in 25 min linear gradient mode. Solutes are detected by tandem diode array/derivatization/fluorescence detection. The system is controlled and monitored by a single computer operated with Millenium software. Recoveries of most analytes in samples fortified at 1 μg/L are >90%, with relative standard deviation values of <5%. For a few very polar analytes, mostly N-methylcarbamoyloximes (i.e., aldicarb sulfone, methomyl, and oxamyl), recoveries are <20%. However, for these compounds, as well as for the rest of the N-methylcarbamates except for aldicarb sulfoxide and butoxycarboxim, the limits of detection (LODs) are 0.005-0.05 μg/L. LODs for aldicarb sulfoxide and butoxycarboxim are 0.2 and 0.1 μg, respectively. LODs for the rest of the analytes except 4-nitrophenol, bentazone, captan, decamethrin, and MCPA are 0.05-0.1 μg/L. LODs for the latter compounds are 0.2-1.0 μg/L. The system can be operated unattended.