Aerosol pollution is a serious environmental issue, especially in China where there has been rapid urbanization. To identify the intra-annual and regional distributions of health risks and potential sources of heavy metals in atmospheric particles with an aerodynamic diameter less than or equal to 2.5 μm (PM2.5), this work collected monthly PM2.5 samples from urban, industrial, suburban, and rural areas in Nanjing city during 2016 and analyzed the heavy metal compositions (Cu, Pb, Cd, Co, V, Sr, Mn, Ti, and Sb). Enrichment factors (EFs) and principal component analysis (PCA) were applied to investigate the sources. The atmospheric PM2.5 pollution level was highest in the industrial area, followed by the urban and suburban areas, and was the lowest in the rural area. Seasonally, the concentrations of PM2.5 and associated heavy metals in spring and winter were higher than those in summer and autumn. Besides natural sources, heavy metal pollution in PM2.5 might come from metallurgical dust in the industrial area, while it mainly comes from automobile exhaust in urban and suburban areas. Health risk assessments revealed that noncancerous hazards of heavy metals in PM2.5 were low, while the lifetime cancer risks obviously exceeded the threshold. The airborne metal pollution in various functional areas of the city impacted human health differently.