Dispersive liquid–liquid microextraction coupled with programmed temperature vaporization-large volume injection-gas chromatography–tandem mass spectrometry for multiclass pesticides in water

A simple solvent-less procedure for the determination of seventeen pesticides and related compounds in environmental water and wastewater using dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–mass spectrometry in tandem (GC–MS/MS) with large-volume injection, having a programmed temperature vaporizer (PTV-LVI), is described. The parameters affecting the extraction efficiency of the target analytes from water samples were systematically investigated. A response surface Doehlert design was used. The best extraction conditions involved a rapid injection of a mixture of 1.9 mL of acetonitrile (as a dispersant) and 178 μL of trichloroethane (as an extractant) into 10 mL of water placed in a conical bottom glass tube. After manually shaken for 3.0 min and centrifugation at 3600 rpm (5 min), 50 μL of the sedimented phase was directly injected into the PTV-LVI-GC–MS/MS system. The limits of quantitation (LOQs) ranged from 0.5 to 18 ng L−1 for all pesticides, except empentrin (132 ng L−1). The relative standard deviations (RSDs) for the analytes ranged between 0.8 and 14.6% for both intraday and interday precision. Accuracy, expressed as the mean extraction recovery, was between 70 and 130%. Using the internal standard method and surrogate deuterated standards, the total concentration of pesticides was in the range from 2.7 to 440 ng L−1 in seawater, river water and sewage water.