Thermal experiments were conducted using real boiler ash and fly ash samples from three types of municipal or industrial solid waste incineration plants to understand the formation reactions of polychlorinated dibenzo-p-dioxin and furans (PCDD/Fs) and related bromine compounds that were chlorinated-brominated dibenzodioxins and furans (PXDD/Fs) and polybrominated dibenzo-p-dioxin and furans (PBDD/Fs). The results obtained were as follows: The formation of PCDD/Fs was clearly shown, and fly ash containing abundant carbon matter had a significant potential for de novo synthesis. The homologous distribution change apparently showed that the formation of PXDD/Fs occurred from the substitution of a bromine atom with a chlorine atom in the PCDD/F molecules. This suggests that PXDD/Fs are usually formed with PCDD/Fs on the ash. PBDD/Fs might be formed from any reaction mechanism different from that of PXDD/Fs. The existence of carbonaceous matters always does not mean the potential formation of PCDD/Fs. However, any addition of catalytic copper may influence the nature of ash to increase the formation potential. The findings suggest that there are many instances that result in the unintended production of trace hazardous pollutants in the incineration process and show that careful and sophisticated control is required to prevent the formation of pollutants. (c) 2009 Elsevier B.V. All rights reserved.