The sensitivity and precision of headspace solid-phase micro extraction (HS-SPME) at an analyte solution temperature (T (as)) of +35 degrees C and a fiber temperature (T (fiber)) of +5 degrees C were compared with those for HS-SPME at T (as) and T (fiber) of -20 degrees C for analysis of the volatile organic compounds benzene, 1,1,1-trichloroethane, trichloroethylene, toluene, o-xylene, ethylbenzene, m/p-xylene, and tetrachloroethylene in water samples. The effect of simultaneous fiber cooling and analyte solution freezing during extraction was studied. The compounds are of different hydrophobicity, with octanol/water partition coefficients (Kow) ranging from 126 and 2511. During a first set of experiments the polydimethylsiloxane (PDMS) SPME fiber was cooled to +5 degrees C with simultaneous heating of the aqueous analyte solution to +35 degrees C. During a second set of experiments, both SPME fiber holder and samples were placed in a deep freezer maintained at -20 degrees C for a total extraction time of 30 min. After approximately 2 min the analyte solution in the vial began to freeze from the side inwards and from the bottom upwards. After approximately 30 min the solution was completely frozen. Analysis of VOC was performed by coupling HS-SPME to gas chromatography-mass spectrometry (GC-MS). In general, i.e. except for tetrachloroethylene, the sensitivity of HS-SPME increased with increasing compound hydrophobicity at both analyte solution and fiber temperatures. At T (as) of +35 degrees C and T (fiber) of +5 degrees C detection limits of HS-SPME were 0.5 microg L(-1) for benzene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene, 0.125 microg L(-1) for toluene, and 0.025 microg L(-1) for ethylbenzene, m/p-xylene, and o-xylene. In the experiments with T (as) and T (fiber) of -20 degrees C, detection limits were reduced for compounds of low hydrophobicity (Kow<501), for example benzene, toluene, 1,1,1-trichloroethane, and trichloroethylene. In the concentration range 0.5-62.5 microg L(-1), the sensitivity of HS-SPME was enhanced by a factor of approximately two for all compounds by performing the extraction at -20 degrees C. A possible explanation is that freezing of the water sample results in higher concentration of the target compounds in the residual liquid phase and gas phase (freezing-out), combined with enhanced adsorption of the compounds by the cooled fiber. The precision of HS-SPME, expressed as the relative standard deviation and the linearity of the regression lines, is increased for more hydrophobic compounds (Kow>501) by simultaneous direct fiber cooling and freezing of analyte solution. Background contamination during analysis is reduced significantly by avoiding the use of organic solvents.