Thermochemical formation of polychlorinated dibenzo-p-dioxins and dibenzofurans on the fly ash matrix from metal smelting sources

Metal smelting processes are important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The present work aims to clarify the formation characteristics of PCDD/Fs by heterogeneous mechanisms on fly ash from typical multiple secondary aluminum (SAl), secondary lead (SPb) smelting, and iron ore sintering (SNT) sources in China. The formation characteristics of PCDD/Fs on fly ash were studied in the temperature range 250-450 °C for 10-150 min. Substantial thermochemical formation of PCDD/Fs on SAl and SNT ash was observed. The maximum increase of PCDD/F concentrations under 350 °C for 30 min was 604 times greater than the initial concentration in SAl ash. The concentration of PCDD/Fs was 77 times greater than that of SNT fly ash under 350 °C for 30 min. However, the maximum increase of PCDD/F concentrations was less than 8 times that in raw SPb ash under 350 °C. Contents of total organic carbon (TOC), Cu, Al, Zn and Cl, which are widely recognized as important elements for promoting PCDD/F formation, were obviously higher in SAl and SNT ash than in SPb ash. This may explain the greater observed formation times of PCDD/Fs on SAl and SNT ash than that on SPb ash. It was found that several congeners tended to form at higher temperatures than those for SAl ash. Activation energy calculation according to the Arrhenius equations could explain the dominant formation of those congeners at much higher temperatures on SAl ash.