Stack emissions of metals from stationary sources are of present interest to the United States Environmental Protection Agency (USEPA), to state and local governments, to industries, and to the public. When regulations require limitation of metals stack emissions, it follows logically that measurement methodology is necessary for determining compliance to the established limits. Isokinetic sampling from a grid of points produces a representative sample from which the multiple emissions of up to sixteen metals can be measured in the sample from one train. Metals in the stack particulate matter and in the gases are measured separately. The samples are prepared by digestion for subsequent instrumental analysis by inductively coupled plasma or atomic absorption spectroscopy. The sixteen metals are total Cr, Cd, As, Ni, Mn, Be, Cu, Zn, Pb, Se, P, Tl, Ag, Sb, Ba, and Hg. Emission factor development, research requiring quantification of metals emissions, and determining emission compliance are important potential applications of this methodology.