Formation pathways of polychlorinated dibenzo-p-dioxins and dibenzofurans from burning simulated PVC-coated cable wires.

Open burning of PVC-coated cables is a major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). In the present study, the formation characteristics of PCDD/F from burning of PVC-based samples with and without metallic copper were evaluated over the dioxin formation temperature window (200-500 °C). This temperature range also inevitably occurs under open burning conditions. The PCDD/F yield from PVC added with Cu increased by factors of 1390 (300 °C), 65 (400 °C) and 17 (500 °C) compared with that from PVC alone, confirming the stimulatory effect of metallic Cu on PCDD/F production. For the first time, a relatively complete isomer-specific analysis is established for PVC acting as source of PCDD/F. Formation pathways of PCDD/F and the reaction mechanisms were investigated using a combined analysis of PCDD/F isomer signatures, thermogravimetric results and Cl K-edge X-ray absorption spectra. De novo synthesis is the major pathway leading to massive production of PCDD/F. Copper extends the temperature range for the concurrence of de(hydro)chlorination of PVC with cross-linking and aromatisation of polyenes and then stimulates cracking of the chlorine-embedded carbon network. Together, these processes contribute to the strongly enhanced formation of PCDD/F via de novo synthesis.