Determination of pyrimethanil and kresoxim-methyl in green groceries by headspace solid-phase microextraction and gas chromatography–mass spectrometry

A method for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in green groceries, previous headspace solid-phase microextraction (HSSPME), was developed using gas chromatography–mass spectrometry and selected ion monitoring (GC–MS, SIM). Both fungicides were extracted with a fused-silica fiber coated with 85 μm polyacrylate. The effects of pH, ionic strength, extraction and desorption times as well as the extraction temperature were studied. The linear concentration range of application was 12.5–250 ng g−1 for both compounds, with detection limits of 1.8–2.0 ng g−1 for pyrimethanil and 2.8–3.1 ng g−1 for kresoxim-methyl. SPME/GC–MS analysis yielded good reproducibility (RSD between 7.4 and 15.0%). It was applied to check the eventual existence of pyrimethanil and kresoxim-methyl above the detection limits on grapes, strawberries, tomatoes and ketchup samples. The method validation was completed with spiked matrix samples. It can be applied as a monitoring tool in grapes, strawberries, tomatoes and ketchup samples.