De novo formation of dioxins from milled model fly ash.

Municipal solid waste incineration (MSWI) fly ash has been classified as hazardous waste and needs treatment in an environmentally safe manner. Mechanochemical (MC) treatment is such a detoxification method, since it destroys dioxins and solidifies heavy metals. Milling, however, also introduces supplemental metals (Fe, Ni, Cr, Mn…), following wear of both steel balls and housing. Milling moreover reduces the particle size of fly ash and disperses catalytic metal, potentially rising the reactivity of fly ash to form and destroy 'dioxins', i.e. polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD + PCDF or PCDD/F). To test this issue, model fly ash (MFA) samples were composed by mixing of silica, sodium chloride, and activated carbon, and doped with CuCl2. Then, these samples were first finely milled without any additives for 0 h (original sample), 1 h and 8 h, and the effect of milling time (and hence particle size) was investigated on the formation of polycyclic aromatic hydrocarbons (PAHs), and of polychlorinated phenols (CP), benzenes (CBz), biphenyls (PCB) and dioxins (PCDD + PCDF) during de novo tests at 300 °C for 1 h, thus simulating the conditions prevailing in the post-combustion zone of an incinerator, where dioxins are formed and destroyed. These compounds are all characterized by their rate of generation (ng/g MFA) and their signature, i.e. internal distribution over congeners as a means of gathering mechanistic indications. PAH and CBz total yield did not decrease in MC treated MFA with milling time, while total pentachlorophenol (PeCP), PCB and PCDD/F yield decreased up to 86, 94 and 97%, respectively. International Toxic Equivalents (I-TEQ) concentration decreased more than 90%, while degree of chlorination varied inconsistently for PCB and PCDD/F, and average congener patterns of PCDD/F do not vary considerably with milling time for both gas and solid phase.