Direct, automated and sensitive determination of glyphosate and related anionic pesticides in environmental water samples using solid-phase extraction on-line combined with liquid chromatography tandem mass spectrometry

An automated procedure for the simultaneous determination of six anionic pesticides, including glyphosate (GLY) and its transformation product aminomethylphosphonic acid (AMPA), was developed and applied to the analysis of environmental water samples. The proposed method combines on-line concentration of water samples (0.160 mL), with compounds separation in an anion-exchange liquid chromatography (LC) column, followed by their selective determination by tandem mass spectrometry (MS/MS). The global procedure was completed in 25 min, providing limits of quantification (LOQs) between 5 ng L^-1 and 20 ng L^-1, with reduced effect of the surface water matrix in the efficiency of process (SPE and ionization yields). The method was applied to the analysis of grab samples obtained from three watersheds, in two rural and one residential area, in Galicia (Northwest Spain). Out of six investigated compounds, Fosetyl, AMPA and GLY were noticed in the set of processed samples. Their detection frequencies increased from 12% (Fosetyl) to 88% (AMPA). Median concentrations followed the same trend varying from 9 ng L^-1 (Fosetyl) to 44 ng L^-1 (AMPA). The higher levels and the large seasonal variations in the residues of the latter species were noticed in small rivers affected by discharges of municipal sewage treatment plants (STPs).