Degradation of polychlorinated dibenzo- p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash is beneficial to its risk control. Fly ash was treated in a full-scale thermal degradation system (capacity 1 t d) to remove polychlorinated dibenzo- p-dioxins and dibenzofurans. Apart from the confirmation of the polychlorinated dibenzo- p-dioxin and dibenzofuran decomposition efficiency, we focused on two major issues that are the major obstacles for commercialising this decomposition technology in China, desorption and regeneration of dioxins and control of secondary air pollution. The toxic equivalent quantity values of polychlorinated dibenzo- p-dioxins and dibenzofurans decreased to <6 ng kg and the detoxification rate was ⩾97% after treatment for 1 h at 400 °C under oxygen-deficient conditions. About 8.49% of the polychlorinated dibenzo- p-dioxins and dibenzofurans in toxic equivalent quantity (TEQ) of the original fly ash were desorbed or regenerated. The extreme high polychlorinated dibenzo- p-dioxin and dibenzofuran levels and dibenzo- p-dioxin and dibenzofuran congener profiles in the dust of the flue gas showed that desorption was the main reason, rather than de novo synthesis of polychlorinated dibenzo- p-dioxins and dibenzofurans in the exhaust pipe. Degradation furnace flue gas was introduced to the municipal solid waste incinerator economiser, and then co-processed in the air pollution control system. The degradation furnace released relatively large amounts of cadmium, lead and polychlorinated dibenzo- p-dioxins and dibenzofurans compared with the municipal solid waste incinerator, but the amounts emitted to the atmosphere did not exceed the Chinese national emission limits. Thermal degradation can therefore be used as a polychlorinated dibenzo- p-dioxin and dibenzofuran abatement method for municipal solid waste incinerator source in China.

A large amount of soils are contaminated by leakage of polychlorinated biphenyls (PCBs) from sealed-up PCB-containing electrical equipment in China. Thermal dechlorination of soils contaminated with PCBs at a level of 108 mg g(-1) and PCB77 (3,3',4,4'-tetrachlorobiphenyl) as a model isomer in conjunction with calcium oxide was investigated in this study. The PCB dechlorination rate improved with increased temperature and time. The highest dechlorination rate was 85.3 %, and temperature was the main influencing factor. Pentachlorobiphenyl and tetrachlorobiphenyl in soils decreased or disappeared in response to treatment at 350 and 400 °C for 4 h, while monochlorinated biphenyl and biphenyl were detected after the reaction, indicating the presence of a dechlorination/hydrogenation pathway. Discrepancy in chlorine balance was observed after low-temperature thermal dechlorination. The species of dechlorination products were identified as amorphous carbon containing a crystalline graphite plane structure and a carbonyl group-containing polymerized product, demonstrating the existence of a dechlorination/polymerization pathway. The yield of amorphous carbon and high-molecular-weight intermediates increased with heating time. The results showed that the discrepancy in chlorine balance was because of the generation of polymerized products and undetected intermediates.