This paper reports for the first time the occurrence, fates, and carcinogenic risks of 20 substituted polycyclic aromatic hydrocarbons (SPAHs) and 16 priority PAH species in two coking wastewater treatment plants (WWTPs) (plant E and central WWTP). The measured total concentrations of PAHs and SPAHs in raw wastewater of coking plant E were 3700 and 1200 mu g.L-1, respectively, with naphthalene (1400 mu g.L-1), and fluoranthene (353 mu g.L-1) as dominant PAH species and 2-methylnaphthalene (167 mu g.L-1), anthraquinone (133 mu g.L-1), and 1-methylnaphthalene ( 132 mu g.L-1) as dominant SPAHs. For the 11 methyl-PAHs (MPAHs), 4 oxygenated PAHs (OPAHs), and 5 nitrated-PAHs (NPAHs) investigated, the biological wastewater treatment process removed 98.6% MPAHs, 83.9% OPAHs, and 89.1% NPAHs. Mass balance analysis result revealed that transformation was the major mechanism to remove low-molecular-weight (LMW) MPAHs (59.9-77.3%), a large part of OPAHs, including anthraquinone, methylanthraquinone, and 9-fluorenone (46.7-49.6%), and some NPAHs, including 2-nitrofluorene and 9-nitroanthrancene (52.9-59.1%). Adsorption by activated sludge mainly accounted for removing high-molecular-weight (HMW) SPAHs (59.6-71.01%). The relatively high concentrations of SPAHs in excess sludge (15,000 mu g.g(-1)) and treated effluent (104 mu g.L-1) are of great concern for their potential adverse ecological impacts. SPAHS exhibited similar behaviors in central WWTP, though the influent concentrations were much lower. The concentration levels of SPAHs in the ambient air of coking plant E and central WWTP may also pose potential lung cancer risks (LCR) to the workers through inhalation, where all studied SPAHs except 3-nitrofluoranthene and 7-nitrobenz[a]anthracene exceeded the acceptable cancer risk standards (>10(-6)) recommended by U.S EPA. This study could help identify the ecological and healthy risks during coking wastewater treatment and provide useful information for policy-making. (C) 2021 Elsevier B.V. All rights reserved.