A comprehensive sampling program was conducted at four sampling sites in the vicinity area of a Waelz plant prior to and after the retrofitting of this plant for reducing PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) and polychlorinated biphenyl (PCB) emission to evaluate its effects on atmospheric PCDD/F and PCB concentrations. During the shutdown stage of the Waelz plant investigated, the atmospheric PCDD/F and PCB concentrations measured in the vicinity area (sites A, B and C) range from 24 to 170 fg-I-TEQ/m(3) and 5.0 to 8.2 fg-TEQ(WHO)/m(3), respectively. As the facility restarted to operate, the atmospheric PCDD/F and PCB concentrations measured increased to 570-1460 fg-I-TEQ/m(3) and 23-59 fg-TEQ(WHO)/m(3), respectively. When activated carbon injection (ACI) was adopted in the facility in early 2006, the PCDD/F concentrations measured in stack gas decreased dramatically from 190 to 3.4 ng-I-TEQ/Nm(3), while the PCB concentrations decreased from 4.9 to 0.08 ng-TEQ(WHO)/Nm(3). In the meantime, the atmospheric PCDD/F and PCB concentrations measured at sites A, B and C decreased to 150-340 fg-I-TEQ/m(3) and 13-19 fg-TEQ(WHO)/m(3), respectively. However, relatively high PCDD/F (180-1460 fg-I-TEQ/m(3)) and PCB (9.3-59 fg-TEQ(WHO)/m(3)) concentrations were measured at site D during all sampling stages. Overall, atmospheric sampling results indicate that over 50% of PCDD/Fs distributed in solid phase, while over 90% of PCBs distributed in vapor phase during all sampling stages.