High accuracy air pollution monitoring in a smart city requires the deployment of a huge number of sensors in this city. One of the most appropriate wireless technologies expected to support high density deployment is LoRaWAN which belongs to the Low Power Wide Area Network (LPWAN) family and offers long communication range, multi-year battery lifetime and low cost end devices. It has been designed for End Devices (EDs) and applications that need to send small amounts of data a few times per hour. However, a high number of end devices breaks the orthogonality of LoRaWAN transmissions, which was one of the main advantages of LoRaWAN. Hence, network performances are strongly impacted. To solve this problem, we propose a solution called OAPM (Orthogonal Air Pollution Monitoring) which ensures the orthogonality of LoRaWAN transmissions and provides accurate air pollution monitoring. In this paper, we show how to organize EDs into clusters and sub-clusters, assign transmission times to EDs, configurate and synchronize them, taking into account the specificities of LoRaWAN and the features of the air pollution monitoring application. Simulation results corroborate the very good behavior of OAPM.