Analysis of polar pesticides in rainwater in Denmark by liquid chromatography–tandem mass spectrometry

A new LC–MS–MS method for analysis of rainwater has been developed and validated for 53 pesticides, degradation products of pesticides and selected nitrophenols. The method was used to monitor the concentration of pesticides in rainwater at one location near Roskilde, Denmark from February 2000 to August 2000. Sampling was done in periods of up to 4 weeks using a cooled wet-only sampler. Water samples were extracted by solid-phase extraction on Oasis HLB columns. The analysis of the extracts was performed by LC–MS–MS with electrospray ionization. All samples were analysed in negative and in positive ionization mode, respectively for acidic and neutral compounds. All analyses were done in the selected reaction monitoring mode in order to obtain a better signal-to-noise ratio. The method has been validated for the following parameters: recovery, detection limit, uncertainty and linearity. Atrazine, terbuthylazine, isoproturon, mechlorprop and (2-methyl-4-chlorophenoxy)acetic acid were measured at concentrations above 0.100 μg/l, mainly during the period of agricultural use. Nitrophenols were measured at high concentrations all year with peaks in the cold season (February–March).