Abstract Nitrogen determination by gas chromatography with atomic emission (microwave-induced plasma) detection (GC–AED) has been accomplished using the 174 nm atomic emission line, but with very limited selectivity and sensitivity. Nitrogen can also be detected using the cyanogen (CN) molecular band at 388 nm. A commercial GC–AED system was modified to allow the use of the 388 nm line for nitrogen detection, giving an improvement of 100-fold in sensitivity and selectivity, when compared with the 174 nm mode. Limits of detection of 10 pg/s were common, representing a 10-fold improvement. Compound-independent behavior was found for the system, working with optimum operating conditions, while instrumental problems were clearly reflected by a drastic compound dependent behavior. Response factors showed an important dependency upon the concentration of the element present. This dependency affected the accuracy of the determination of empirical formulae using GC–AED.