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The overall hypothesis of this research is that the use of passive samplers is an effective method to measure spatial and seasonal trends of atmospheric PCBs in an urban environment. In support of this, I extracted, analyzed and quantified congener specific concentrations from over 200 passive samples and over 200 active sampler, or Hi-Vols. I studied best practices for the use of methods to derive R-values and the application of R-values on mass accumulated on passive samplers for both indoor and outdoor air and found that indoor air uptake of PCBs was consistent over time and at different locations. I suggest that depuration compounds be used for outdoor sampling when using passive samplers for the most accurate measurement of effective sampling volume. I then applied these practices to passive samplers deployed in two major cities along the Great Lakes, Cleveland and Chicago. I found that these cities had different concentrations as well as different congener profiles. I compared toxicological equivalencies (TEQ) of the WHO dioxin-like PCBs between the two cities and discovered that although Cleveland had higher total PCB concentrations, it had a lower TEQ. I then compared spatial distributions and temporal trends between Hi-Vols and passive samplers and found that passive samplers were accurate at collecting spatial and seasonal trends when compared to Hi-vols, and were consistent at identifying hot-spots of atmospheric PCBs in Chicago. Finally, I developed an instrumental method to identify and quantify OH-PCBs from environmental samples to be used in future research involving the fate of atmospheric PCBs.