Artifactual formation of N-nitrosodimethylamine during the extraction procedure from aminopyrine and nitrite was examined. The use of the basic pH condition was the most effective in preventing artifactual formation. Sulfamic acid or ascorbic acid was partially effective in preventing artifactual formation. Since significant losses of volatile N-nitrosodimethylamine occur during the extraction and concentration steps, we analyzed N-nitrosodimethylamine by combined gas chromatography mass spectrometry with 15N-nitrosodimethylamine as an internal standard. The use of a fused silica capillary column enabled us to obtain a fine separation of the chromatogram. This methodology was applied to our model experiment, which was performed to locate the formation of N-nitrosodimethylamine when a rabbit was exposed to NO2 after the administration of aminopyrine. SO3 inhaled together with NO2 was found to increase the nitrosation.