Optimization of headspace solid-phase microextraction conditions for the determination of organophosphorus insecticides in natural waters

Abstract

Headspace solid-phase microextraction (HS-SPME) has been developed for the analysis of seven organophosphorus insecticides, i.e. diazinon, fenitrothion, fenthion, ethyl parathion, methyl bromophos, ethyl bromophos and ethion in natural waters. Their determination was carried out using gas chromatography with flame thermionic and mass spectrometric detection. To perform the HS-SPME, two types of fibre have been assayed and compared: polyacrylate (PA 85 μm), and polydimethylsiloxane (PDMS 100 μm). The main parameters affecting the HS-SPME process such as temperature, salt additives, memory effect, stirring rate and adsorption–time profile were studied. The method was developed using spiked natural waters such as ground, sea, river and lake water in a concentration range of 0.05–1 μg/l. The HS-SPME conditions were optimized in order to obtain the maximum sensitivity. Detection limits varied from 0.01 to 0.04 μg/l and relative standard deviations (RSD <17%) were obtained showing that the precision of the method is reliable. The method showed also good linearity for the tested concentration range with regression coefficients ranging between 0.985 and 0.999. Recoveries were in relatively high levels for all the analytes and ranged from 80 to 120%. Water samples collected from different stations along the flow of Kalamas river (NW Greece) were analyzed using the optimized conditions in order to evaluate the potential of the proposed method to the trace-level screening determination of organophosphorus insecticides. The analysis with HS-SPME has less background interference and the advantage of its non-destructive nature reveal the possibility of the repetitive use of the SPME fibre.