Copper smelting is an important source of unintentional persistent organic pollutants (POPs). Yet emission assessment and inventories remain limited by two key field-evidence gaps: (i) scarce measurement-based emission factors (EFs) for primary copper smelting and (ii) a lack of quantitative constraints on fugitive-derived POP releases. In this study, we conduct field measurements at three primary copper smelting plants and compare POP burdens across end-of-pipe stack gas and a secondary-capture stream capturing fugitive-derived gas. For primary copper smelting using an Ausmelt furnace with electrostatic precipitation as the end-of-pipe control, EFs of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls, and polybrominated dibenzo-p-dioxins and dibenzofurans were estimated at 0.03-0.14, 0.004-0.023, and 0.055-0.062 μg TEQ t⁻1, respectively. In contrast, reported PCDD/F EFs could be as high as 0.65 μg TEQ t⁻1 for oxygen-enriched side-blown furnace smelting equipped with baghouse filtration. These results indicate that emissions from primary copper smelting warrant attention in regions with concentrated production activity. The secondary-capture stream exhibited comparable POP concentrations to those in end-of-pipe emissions. Fugitive-related pathways could contribute emissions on the same order as end-of-pipe releases. Fugitive releases should be explicitly considered to reduce systematic underestimation in inventories and associated risk assessments.
Keywords: Copper smelting; Dioxins; Fugitive emissions; Persistentorganic pollutants; Polychlorinated biphenyls.
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