Headspace–programmed temperature vaporizer–fast gas chromatography–mass spectrometry coupling for the determination of trihalomethanes in water

A new method based on the use of a headspace autosampler in combination with a GC equipped with a programmable temperature vaporizer (PTV) and an MS detector has been developed for the screening and quantitative determination of trihalomethanes (THMs) in different aqueous matrices. The use of headspace generation to introduce the sample has the advantage that no prior sample treatment is required, thus minimizing the creation of analytical artifacts and the errors associated with this step of the analytical process. The PTV inlet used was packed with Tenax-TA. The injection mode was solvent vent, in which the analytes are retained in the hydrophobic insert packing by cold trapping, while the water vapour is eliminated through the split line. This allows rapid injection of the sample in splitless mode, very low detection limits being achieved without the critical problem of initial sample bandwidth. The capillary column used allowed rapid separations with half-height widths ranging from 1.68 s (chloroform) to 0.66 s (bromoform). The GC run time was 7.3 min. The use of mass spectrometry allows the identification and quantification of the analytes at the low ppt level. The S/N ratio was at least 10-fold higher when the SIM mode was used in data acquisition as compared to the scan mode. The proposed method is extremely sensitive, with detection limits ranging from 0.4 to 2.6 ppt.