AbstractThe possibility of simultaneous application of an electron capture (ECD) and a flame ionization detector (FID) connected to a glass capillary column for analyzing polynuclear aromatic hydrocarbons (PNA) has been investigated. The ECD/FID ratio is determined for 46 PNA compounds. The ratios vary from 0.02 to 117 with relative standard deviations better than 20 percent determined from 10 replicate analyses. The results suggest that the method may be used for obtaining additional evidence in identifying PNA in environmental samples.Impurities and transformation products in the standard were identified by computerized glass capillary gas chromatography/mass spectrometry. Quinones and diones are responsible for the high EC‐response determined in some trace components in the standard.An application of the method is shown for PNA from particulates in urban atmosphere