Automated determination of phenylcarbamate herbicides in environmental waters by on-line trace enrichment and...

A fully automated liquid chromatographic method using on-line trace-enrichment, gradient elution and diode array detection is described for the trace-level determination of several phenylcarbamate herbicides, such as carbetamide, propham, desmedipham, phenmedipham, chlorbufam and chlorpropham, in environmental water samples. In this work, two different enrichment pre-columns have been assayed, a 5.8 x 4.6 mm I.D., 10 microns ODS Prelute cartridge and a 10 x 2 mm I.D. cartridge filled with 10 microns PRP-1 polymer, both coupled to a 150 x 4.6 mm I.D. analytical column filled with 5 microns ODS. Using the C18 pre-column, up to 50 ml of water sample could be percolated without peak broadening of any compound. However, a lack of reproducibility was observed in the case of carbetamide, the most polar analyte, after performing recovery experiments by percolating drinking and surface water samples spiked at several levels (0.5 and 4 micrograms l-1). On the other hand, the PRP-1 pre-column allowed the enrichment up to 100 ml of water sample with satisfactory results for every compound, including carbetamide. The procedure was validated by recovery experiments in environmental water samples spiked at 0.2 and 1 microgram l-1 yielding average recoveries between 84-108% with relative standard deviations in the range 2-12%. Detection limits as low as 0.04 microgram l-1 were achieved. It was observed that desmedipham and phenmedipham degraded rapidly in the environmental water samples as showed the degradation studies performed along 24 h in drinking and surface waters spiked at 4 micrograms l-1. Although the standard mixture, prepared in HPLC water, was stable for around one week, in the environmental water matrices more than 95% of each herbicide degraded after 6 h, and new chromatographic peaks corresponding to the degradation products were detected.