Exceeding the latest Canadian Ambient Air Quality Standards (CAAQS) for NO2 concentration in Canadian cities motivates discussions on new policies and directives. Advanced air quality modeling and machine learning clustering algorithms integrating the Weather Research Forecast (WRF) and Community Multiscale Air Quality (CMAQ) models were used to classify air quality monitoring (AQM) stations based on pollution concentration modeling results. The sensitivity of ambient NO2 to the primary anthropogenic emission sources was investigated in Alberta, Canada. Emissions from two main sources, upstream oil and gas (UOG) and transportation sources, have been identified as the reason Alberta fails to meet the newly adopted NO2 CAAQS objectives. The air quality model was validated with ground-level observation data and the atmospheric model accurately replicates spatiotemporal NO2 variations. Despite contributing 62% of Alberta’s total NOx emissions, UOG influences ambient NO2 concentrations modestly in urban areas (<10%) but significantly affects rural regions. In contrast, transportation emission sources, responsible for 23% of NOx emissions, dominate ambient NO2 levels (up to 63%) in large cities. The discrepancy of emission contribution and ground-level concentrations, obtained from the chemical transport model, was resolved using a k-prototypes clustering algorithm to propose a new approach for categorizing AQM stations which led to improving the conventional classifications. The new approach considered the sensitivity of NO2 to emission reduction scenarios and provided an improved classification to be used for emission reduction interventions. Based on the updated classification, one set of AQM stations clearly showed sensitivity to NO2 emission reduction in the transportation sector despite their lower contributions to overall emissions. These stations were categorized as population exposure stations in large cities.