p-Phenylenediamines (PPDs) and their derived quinones (PPD-Qs) are emerging pollutants. Information on their occurrence, fate and chiral signatures in the wastewater treatment plant (WWTP) and its receiving waters is scarce. This study explored the distribution, removal efficiency, mass balance, environmental emission and enantiomeric fractions of these pollutants in two WWTPs in Guangzhou, China. It also examined the impacts of WWTP effluents on the distribution of these contaminants in the receiving rivers. The concentrations of Σ(PPDs+PPD-Qs) ranged from 3.95 to 20.4 ng/L in influent, 0.69-3.94 ng/L in effluent, and 2.14-19.8 ng/g dry weight in sludge, respectively. PPDs (81.6 %) and PPD-Qs (78.6 %) were effectively removed in the WWTPs primarily through biotransformation, but sludge adsorption and separation also contributed to the removal. One of the WWTPs could increase the levels of these pollutants in the downstream of receiving river, suggesting that WWTP effluents are significant vectors of PPDs and PPD-Qs to the aquatic environment. The results also highlight different nonracemic chiral signatures of 6PPD and 6PPD-Q between the two WWTPs and the receiving waters, which merit further investigation for mechanism. Future studies should elucidate the environmental risks that PPDs and PPD-Qs may pose to receiving rivers and accurately assess such effects at the enantiomeric level.