Determination of phenyl-<i>N</i>-methylcarbamates and their hydrolysis products in water, using solid-phase extraction and reversed-phase liquid chromatography with UV and electrospray mass spectrometric detection

Abstract

In this study, eight phenyl-N-methylcarbamates (PNMCs) were considered. Reversed-phase LC was set up for UV and mass spectrometry (MS) detection mode. Gradient elution was used, and the mobile phase was composed of acetonitrile and water. UV–vis was performed at 220 nm. The method was tested with different reversed-phase columns. Comparison between chromatographic parameters: retention time (t R ), resolution (R S ), and selectivity (α) was established. Hydrolysis kinetics of three of the PNMCs were reported. The major hydrolysis products were determined by LC–UV, and the effect of pH on hydrolysis was also studied. Also, chromatographic separation of a mixture of PNMCs and four of their hydrolysis products was carried out. The preconcentration of 12 studied solutes was realized by solid-phase extraction. C18 extraction cartridges of 1 g were used to extract solutes from a 100 mL volume of tap and surface water spiked at 10 µg/L. The recoveries were, respectively, between 68–86% and 62–83% with relative a standard deviation of less than 11%. Limits of detection (LODs) and limits of quantitation (LOQs) ranged, respectively, from 1–4 µg/L and from 4–10 µg/L. Since standard UV detection does not provide adequate selectivity for water samples, an electrospray (ES)-MS instrument equipped with a triple quadrupole mass filter was used. MS data acquisition was performed by a time-scheduled, selected-ion monitoring (SIM) program. Limits of quantitation gave values between 0.1–0.5 µg/L.Key words: phenyl-N-methylcarbamates, water analysis, solid-phase extraction, LC–UV–vis, LC–ES-MS.