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Main article: Polychlorinated dibenzodioxins
PVC produces HCl upon combustion almost quantitatively related to its chlorine content. Extensive studies in Europe indicate that the chlorine found in emitted dioxins is not derived from HCl in the flue gases. Instead, most dioxins arise in the condensed solid phase by the reaction of inorganic chlorides with graphitic structures in char-containing ash particles. Copper acts as a catalyst for these reactions.
Studies of household waste burning indicate consistent increases in dioxin generation with increasing PVC concentrations. According to the EPA dioxin inventory, landfill fires are likely to represent an even larger source of dioxin to the environment. A survey of international studies consistently identifies high dioxin concentrations in areas affected by open waste burning and a study that looked at the homologue pattern found the sample with the highest dioxin concentration was "typical for the pyrolysis of PVC". Other EU studies indicate that PVC likely "accounts for the overwhelming majority of chlorine that is available for dioxin formation during landfill fires."
The next largest sources of dioxin in the EPA inventory are medical and municipal waste incinerators. Various studies have been conducted that reach contradictory results. For instance a study of commercial-scale incinerators showed no relationship between the PVC content of the waste and dioxin emissions.Other studies have shown a clear correlation between dioxin formation and chloride content and indicate that PVC is a significant contributor to the formation of both dioxin and PCB in incinerators.