Methods have been developed for the determination of aluminum, barium, calcium, lead, magnesium and silver in ferrous alloys and steels by flame emission and atomic absorption spectrometry. The samples are dissolved in a mixture of nitric, hydrochloric, hydrofluoric, and perchloric acids. Flame emission spectrometry with repetitive optical scanning was found to be the method of choice for the determination of aluminum, barium, and calcium at the trace or subtrace levels. Atomic absorption spectrometry was used for lead, magnesium, and silver. For subtraces of lead in ferrous alloys and steels, it was necessary to use atomic absorption spectrometry with electrothermal atomization. To overcome interferences of lead in a ferrous matrix, ammonium orthophosphate was used as matrix modifier. The precision and accuracy of electrothermal atomization was improved with the L'vov platform. The techniques developed were used to characterize trace elements in NBS Standard Reference Materials of ferrous alloys and steels.