h i g h l i g h t s• Variations in PCN emissions from different smelting stages were observed.• Factors influencing PCN emission levels and profiles were identified.• Addition of chloride additives possibly promote PCN formations.• Emission factors for gaseous and various solid discharges were derived.• This study is helpful for developing better control strategies for PCN reduction. Keywords: Secondary aluminum production Smelting stages Polychlorinated naphthalene Solid residues Chloride additives a b s t r a c t Secondary aluminum production has been recognized as an important source of polychlorinated naphthalenes (PCNs). Large variations in PCN emissions as the smelting process proceeds have not been determined. In this study, solid and gaseous discharges, including fly ash, slag, and stack gas samples collected from four secondary smelting plants during different smelting stages were analyzed for PCNs. The average emission factor of 1−8 PCNs to air was calculated to be 17.4 mg t −1 , with a range of 4.3-29.5 mg t −1 . The average emission factors of 1-8 PCNs from fly ash and slag were 55.5 ng t −1 and 0.13 ng t −1 , respectively. The derived emission factors may enable a more accurate estimation of annual emissions and a more comprehensive knowledge of the distribution of PCNs emitted from secondary aluminum production. The emission levels and characteristics of PCNs during different smelting stages were compared. Possible factors, including the organic impurities from aluminum scrap, fuel, and chloride additives, which could contribute to variations in PCN emissions and characteristics were discussed. These results may provide useful information for developing better control strategies for reducing PCN emissions in secondary aluminum production.