A spatially resolved, dynamic version of the Multimedia Urban Model (MUM) and the boundary layer forecast and air pollution transport model BLFMAPS were coupled to build Spatially Oriented MUM (SO-MUM), to estimate emissions and fate of POPs in an urban area on a 5 × 5 km(2) cell resolution. SO-MUM was used to back-calculate emissions from spatially resolved measured air concentrations of PCBs and PBDEs in Toronto, Canada. Estimated emissions of Σ(88)PCBs were 230 (40-480) kg y(-1), 280 (50-580) g y(-1) km(-2), or 90 (16-190) mg y(-1) capita(-1), and Σ(26)PBDEs were 28 (6-63) kg y(-1), 34 (7-77) g y(-1) km(-2), or 11 (2-25) mg y(-1) capita(-1). A mass inventory of penta- and octa-BDEs in Toronto was estimated to be 200 tonnes (90-1000 tonnes) or 80 (40-400) g capita(-1). Using this estimate and that of 440 (280-800) tonnes of PCBs, estimated emissions of Σ(88)PCBs and Σ(26)PBDEs per mass of chemical inventory in Toronto were 0.5 (0.05-1.6) and 0.1 (0.01-0.7) g y(-1) kg(-1), respectively. The results suggest annual emission rates of 0.04% and 0.01% from the mass inventories with downtown accounting for 30% and 16% of Toronto's chemical inventory and emissions of PCBs and PBDEs, respectively. Since total PBDE emissions are a function of mass inventory, which is proportional to building volume, we conclude that building volume can be used as a proxy to predict emissions. Per mass inventory emission rates were negatively related to vapor pressure within a compound class, but not consistently when considering all compound congeners.