Secondary Copper Smelters as Sources of Chlorinated and Brominated Polycyclic Aromatic Hydrocarbons

The generation of and extent to which chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are formed and released from secondary copper smelters remain unknown. This field study, to our knowledge, is the first to identify secondary copper smelters as new sources of Cl/Br-PAHs. Mass concentrations of ∑ 19 Cl-PAHs and ∑ 19 Br-PAHs ranged from 5.8 to 271 ng Nm -3 and 0.59 to 52.4 ng Nm -3 , respectively. A comparison of Cl/Br-PAH concentrations in stack gas and fly ash from secondary copper smelters indicated that the use of scrap copper as raw material or the addition of coal or heavy oil as reductant may contribute to the elevated formation and emission of Cl/Br-PAHs. Congener profiles of Cl/Br-PAHs in stack gas and fly ash from secondary copper smelters were different with those of Cl/Br-PAHs from waste incinerations and other previously reported sources, thus could be used as possible fingerprints and source apportionments of environmental Cl/Br-PAHs. Atmospheric levels of Cl/Br-PAHs in the workplace or smelter surroundings were determined and potential exposures were assessed. Although chlorination of PAHs was previously recognized as an important formation pathway of Cl/Br-PAHs, it was not verified to be the major formation pathway for Cl/Br-PAHs from secondary copper smelters in this study.