U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speciating halogen (X[sub2]) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl[sub2] at high levels (>20 ppm [µg/m³]) and NH[sub4]Cl in the flue gas stream have been investigated. It has been suggested that precise Cl[sub2] measurement and accuracy in quantifying HX or X[sub2] using Method 26A are difficult to achieve at Cl[sub2] concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl[sub2] in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl[sub2] in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speciate low levels of Cl[sub2] accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO[sub2] is the only component in coal combustion flue gas that has an appreciable effect on Cl[sub2] distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl[sub2] in coal combustion flue gas without modification. [ABSTRACT FROM AUTHOR]