Determination of Chloroethers in Aqueous Samples Using Solid‐phase Microextraction

AbstractA method for the determination of di‐ and tetrachlorinated ethers (haloethers) in aqueous samples using solid‐phase microextraction (SPME) combined with capillary GC has been developed. Using 100‐μm polydimethylsiloxane fibers, the influence of several parameters on the SPME procedure like the exposure time of the fiber in the aqueous sample, the desorption temperature, and the salt content of the sample have been studied.Salt addition has a strong effect on the extraction efficiency of the haloethers investigated. Working with saturated salt solutions, the factor increase of the peak areas was in the range from 5 to 12. These improvements are accompanied by decreased precision and increased equilibration times.The SPME method combined with several detectors (FID, ECD, MS in SIM mode) was evaluated with respect to detection limits, linearities, and precisions. Working with salt addition and FID, detection limits of all compounds investigated were in the range of 0.3 to 1.2 μg/L. Using ECD, the LOD values (limits of detection) were only improved for the tetrachlorinated bis(propyl) ethers (<10 ng/L). Employing mass‐spectrometric detection in SIM mode for all chlorinated ethers, detection limits lower than 100 ng/L could be reached. Working with saturated salt solutions, the coefficients of variation were <9% RSD. However, without salt addition, the precision is better than 2.5% RSD for all analytes.Investigations showed that the analysis of the haloethers with SPME is not influenced significantly by the matrix Elbe water. The results of two series of samples demonstrate that SPME‐GC‐MS allows the sensitive determination of the di‐ and tetrahalogenated ethers in Elbe river water.