Determination of dichloromethane, trichloroethylene and perchloroethylene in urine samples by headspace solid phase microextraction gas chromatography–mass spectrometry

A method for the determination of volatile chlorinated hydrocarbons, namely dichloromethane (DCM), trichloroethylene (TCE), and perchloroethylene (PCE), in urine samples was developed using headspace solid phase microextraction (HS-SPME) gas chromatography–mass spectrometry (GC–MS). HS-SPME was performed using a 75 μm Carboxen-polydimethylsiloxane fiber. Factors, which affect the HS-SPME process, such as adsorption and desorption times, stirring, salting-out effect, and temperature of sampling have been evaluated and optimized. The highest extraction efficiency was obtained when sampling was performed at room temperature (22 °C), from samples saturated with salt and under agitation. Linearity of the HS-SPME-GC–MS method was established over four orders of magnitude and the limit of detection was 0.005 μg/l for all the compounds. Precision, calculated as %R.S.D. at three different concentration levels, was within 1–8% for all intra- and inter-day determinations. The method was applied to the quantitative determination of TCE and PCE in human urine samples from exposed (TCE, n = 5; median, 9.32 μg/l and PCE, n = 39; median, 0.58 μg/l) and non-exposed individuals (n = 120; median concentrations, 0.64, 0.22 and 0.11 μg/l for DCM, TCE and PCE, respectively. In addition, two cases of acute accidental exposure to DCM are reported, and the elimination kinetics in blood and urine was followed up. The calculated half-lives of urinary and blood DCM were, respectively, 7.5 and 8.1 h for one subject and 3.8 and 4.3 h for the other.