Chloroform and methylene chloride were extracted from human whole blood and urine by headspace solid phase microextraction (SPME) using a Carboxen/polydimethylsiloxane (Carboxen/PDMS) fibre before capillary gas chromatography (GC)/flame ionization detection (FID). Whole blood or urine was placed in a vial and mixed with distilled water. The vial was heated at 30 degrees C, and the solvents were extracted from the headspace by SPME. The extraction efficiencies of chloroform and methylene chloride from whole blood were 40.3% and 35.8%, respectively; those for urine were 57.0% and 43.6%, respectively. The calibration curves for chloroform were linear in the range of 1-8 micrograms/ml for blood and urine samples, and those for methylene chloride in the range of 0.5-8 micrograms/ml. The detection limits for both compounds were 0.3 microgram/ml for whole blood and 0.2 microgram/ml for urine. The headspace SPME with Carboxen/PDMS fibre coupled with GC/FID seems useful for analyses of chloroform and methylene chloride in forensic toxicology and environmental chemistry.
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