Fly ash-mediated formation of polychlorinated naphthalenes during secondary copper smelting and mechanistic aspects

Thermal experiments (at 250-450 °C for 10-240 min) on fly ash from secondary copper smelting process (SeCu) were performed to study the polychlorinated naphthalene (PCN) formation in the post-zone of a secondary copper smelter. Unexpectedly high concentrations of PCNs were formed. Total PCN concentrations and toxic equivalents were 47-104 and 44-80 times higher than the initial concentration and toxic equivalent, respectively. The thermal disposal of SeCu fly ash should therefore be reconsidered. The kinetic of each homolog was determined under different thermal conditions. Less chlorinated homologs favored 350 °C and more chlorinated homologs favored higher temperature. Most of the homologs reached an equilibrium of formation and degradation within 30 min, except octachloronaphthalene which did not appear to reach such an equilibrium even after 240 min. Chlorine substitution of the formed PCNs was identified and a similar pattern was found in chlorination products starting with naphthalene and chlorine. Furthermore, inorganic chlorine and unsubstituted naphthalene were found in the reaction products, confirming that the formation of naphthalene and the chlorination of that naphthalene could occur and could be suggested to be an important PCN formation route. A detailed formation pathway from naphthalene through octachloronaphthalene is proposed.