The interferences of cobalt chloride on the determination of bismuth by electrothermal atomic absorption spectrometry (ETAAS) were examined using a dual cavity platform (DCP), which allows the gas-phase and condensed phase interferences to be distinguished. Effects of pyrolysis temperature, pyrolysis time, atomization temperature, heating rate in the atomization step, gas-flow rate in the pyrolysis and atomization steps, interferent mass and atomization from wall on sensitivity as well as atomization signals were studied to explain the interference mechanisms. The mechanism proposed for each experiment was verified with other subsequent sets of experiments. Finally, modifiers pipetted on the thermally treated sample+interferent mixture and pyrolyzed at different temperatures provided very useful information for the existence of volatilization losses of analyte before the atomization step. All experiments confirmed that when low pyrolysis temperatures are applied, the main interference mechanisms are the gas-phase reaction between bismuth and decomposition products of cobalt chloride in the atomization step. On the other hand, at elevated temperatures, the removal of a volatile compound formed between analyte and matrix constituents is responsible for some temperature-dependent interferences, although gas-phase interferences still continue. The experiments performed with colloidal palladium and nickel nitrate showed that the modifier behaves as both a matrix modifier and analyte modifier, possibly delaying the vaporization of either analyte or modifier or both of them. (c) 2004 Elsevier B.V All rights reserved.