The gasification behavior of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in fly ash by thermal treatment has been investigated to estimate gas-particle partition in flue gas. The results obtained in thermal experiments under various conditions showed that gasification of PCDD/Fs depends on air flow rate and treatment weight of fly ash as well as treatment temperature. On the other hand, the results obtained in the thermal experiments using dioxin-free fly ash revealed that during thermal treatment, the de novo synthesis, gasification, and decomposition of PCDFs proceeded at different rates. This difference in the reaction rates indicates that thermal treatment time is also a factor in determining the gas-particle partition of PCDD/Fs in fly ash. Therefore, reasonable thermal treatment conditions were established and applied to three ash samples. For all samples, PCDD/Fs started to gasify at 350 degrees C treatment, whereas 53-98% of PCDD/F homologs gasified at 400 degrees C treatment, implying that gaseous PCDD/Fs are dominant in flue gas at temperatures in the range 350-400 degrees C regardless of particle concentration. (c) 2007 Elsevier B.V. All rights reserved.