Optimisation and validation of a solid-phase microextraction method for simultaneous determination of different types of pesticides in water by gas chromatography–mass spectrometry

A solid-phase microextraction (SPME) method for the simultaneous determination of a large number of pesticides (46) with a wide range of polarities and chemical structures (organochlorine, organophosphorous, triazines, pyrethroids and others) in water samples by GC–MS has been developed. Three different fibres and parameters that influence the extraction and desorption efficiency were studied. The selected conditions were: a 60 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre, 45 min of extraction time, sample agitation and temperature control at 60 °C; neither pH adjustment nor ionic strength correction were applied. Good detection limits, linearity and repeatability were obtained with this method for the 46 pesticides studied. The method was validated for 29 pesticides following the recommendations of the international norm ISO/IEC 17025 including the calculation of the uncertainties. The detection limits ranged from 4 to 17 ng l−1. Furthermore, repeatability (6.9–20.5%) and intermediate precision (4.5–19.7%) were shown to be satisfactory. To validate matrix effects for drinking and surface water analytical recoveries were calculated for these matrices. The accuracy of the method was also evaluated by participating in a proficiency inter-laboratory test.