U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of approximately 5 min per sample, this instrumental methodology can directly analyze total Hg--with no discrete sample preparation--in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.