Extensive electronic waste (e-waste) recycling might be an important emission source of polycyclic aromatic hydrocarbons (PAHs) mixture, which might induce negative effects on the employees. In the present work, atmospheric pollution patterns of PAHs and their derivatives were determined in five different workshops to dismantle waste printed circuit boards (WPCBs) via thermal treatment. The results showed that mass concentrations of PAHs, chlorinated PAHs (ClPAHs), brominated PAHs (BrPAHs), oxy-PAHs (OPAHs) as well as carbazole (CBZ) were ranged from 1.53 × 104–2.02 × 105, 32.3–364, 8.29–1.13 × 103, 923–1.39 × 104 and 225–1.95 × 103 pg·m−3, respectively. Electric heating furnaces (EHF) workshops emitted relatively higher contaminants than other disposal sectors. OPAHs was found to be the most predominant derivatives of PAHs with 9,10-anthraquinone (83.0%) has the absolute superior in EHFTV, while benzo(a)anthracene-7,12-dione (>45.0%) was found to be the highest congener in other workshops, respectively. 9,10-Cl2Phe exhibited the largest contributions to the ΣClPAHs whereas the composition profiles of BrPAHs varied among five workshops. In addition to direct chlorination of parent PAHs, thermal degradation of halogenated flame retardants incorporated into plastic materials might dominate the generation of Cl/BrPAHs from e-waste dismantling activities. The specific isomeric ratios of BrPAHs (3-BrFlu/1-BrPyr and 1-BrPyr/3-BrFlu) might be used to discriminate other emission sources from pyrolysis of WPCBs. However, their specific application as novel tracers for source identification should be further verified with more studies. The emitted PAHs mixture with their derivatives in all dismantling workshops posed carcinogenic risks to these dismantling workers via inhalation, particularly the workshop using electric heating furnaces to treat router. Nevertheless, new loadings of PAHs derivatives observed from e-waste dismantling activities, as well as their comprehensive health risk assessment provides us with a fresh perspective on the source appointment and potential adverse consequences of PAHs. More attention needs to be paid to the potential carcinogenic risks of exposure to PAHs and their derivatives from e-waste dismantling processes.
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