In this study, we collected 308 serum samples from 17 to 20 year old first-year university students who were recruited from Lanzhou University in China a few days after their enrollment to measure the serum Pb, Cd, Hg, and As levels, and specific questionnaires for age, sex, settlement and dietary structure were designed. A 3-D atmospheric transport model was used to simulate the atmospheric concentration and dry deposition across China based on gridded Pb emission inventory to examine the association between the spatial distribution of serum concentrations and environmental fates of Pb. The mean serum Pb, Cd, Hg, and As concentrations averaged over all participating young students were 21.38, 1.46, 3.86, and 4.69 μg/L, respectively. The Pb, Cd, and Hg levels in 3%, 7%, and 20% serum samples exceeded the standards. The minimum serum As and Hg concentrations and the maximum serum Pb and Cd concentrations occurred in urban areas. Seafood diet habits (P < 0.05), sex (P < 0.05), and relocation (P < 0.01) caused significant differences in serum As, Pb, and Cd concentrations. A cluster analysis was carried out to classify the exposure pathways for target contaminants. The results indicated that 4 heavy metals in the serum of volunteers from northern China could be grouped into the same category, in which significant positive correlations were found between the serum heavy metal levels and background concentrations of surface soil. However, in other provinces and metropolises, the atmospheric pollution level played a critical role involving in the inhalation exposure pathway. We demonstrated that serum Pb levels in freshman students were related to the atmospheric transport and dry deposition of Pb.