Azide in human blood and plasma samples was derivatized with propionic anhydride in a headspace vial without prior sample preparation. The reaction proceeds quickly at room temperature to form propionyl azide. A portion of the headspace was assayed by gas chromatography with a nitrogen-phosphorus detector. In the heated injector of the gas chromatograph, the propionyl azide undergoes thermal rearrangement, forming ethyl isocyanate, which is subsequently chromatographed and detected. Propionitrile was used as the internal standard. The method is linear to at least 20 microg/mL. Limit of quantitation was 0.04 microg/mL, and the within-run coefficient of variation was 5.6% at 1 microg/mL. There was no interference from cyanide. A fatality report in which blood and plasma azide concentrations from a 59-year-old man were monitored for 24 h following the ingestion of an unknown amount of sodium azide is presented. The patient became critically ill after his self-inflicted sodium azide ingestion. He was intubated and treated with vasopressors and aggressive supportive care, including extracorporeal membrane oxygenation therapy, in the intensive care facility but died from neurological brain damage secondary to anoxia. On admission, 1.4 h after ingestion, his azide level was 5.6 microg/mL (blood); shortly thereafter, it had risen to 13.7 microg/mL (plasma) and, subsequently, was projected to have been eliminated by 16.7 h. No azide was detected in the postmortem blood and vitreous humor.

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