Formation and potential mechanisms of polychlorinated dibenzo-p-dioxins and dibenzofurans on fly ash from a secondary copper smelting process.

Secondary copper smelting (SeCu) is widely considered to be an important source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs and PCDFs; PCDD/Fs). Laboratory experiments were performed using SeCu fly ash as a matrix for thermochemical reactions to investigate the effects of fly ash on the formation of PCDD/Fs and the potential mechanisms. Thermochemical reactions on SeCu fly ash over a temperature range of 250-450 °C and reaction times of 10-120 min caused the PCDD/F concentrations in the fly ash to increase significantly. The PCDD/F concentrations formed in the thermal reactions were about 99-139 times higher than the PCDD/F concentrations in the original fly ash, clearly indicating that fly ash promoted the formation of PCDD/Fs. The PCDFs dominated the PCDDs, and the PCDF/PCDD concentration ratio was about 30-40. Octachlorodibenzofuran (OCDF), octachlorodibenzo-p-dioxin, and the heptachlorodibenzofurans were the most dominant homologs that were formed. A comparison of the PCDD/F patterns produced in the thermochemical reactions and the patterns in the original fly ash suggested that the chlorination of less chlorinated PCDFs might be an important pathway in the formation of higher chlorinated furans. The results of this study indicated that SeCu fly ash has a high PCDD/F formation potential. It is crucial to have the fly ash filter at low temperature and that fly ash in the cooling system should be minimized.