After elevated levels of lead (Pb) were found in the blood of children living near the antimony (Sb) mine and battery smelter in Zajača, Republic Serbia, studies were carried out to determine the health risk assessment (HRA) effects of the soil. In this study, for the first time a combination of Network Analysis, CoDA (Compositional Data Analysis) and receptor modelling was used to determine the geopedological and atmospheric origin of PTEs in soil and their historical significance. It was found that arsenic (As) and Pb are the main pollutants in the area. The largest contribution to the environmental risk (Er) was made by Pb. In addition to perception methods Network Analysis (NA) was used to determine the source of pollution and, for the first time, the strength of the positive and negative connections of the network nodes of the mutual influence of PTE. Lead pollution was found to originate from two sources: historical and present, and As was found to originate from a wider area. For the child population, an unacceptable risk for the occurrence of chronic diseases with a probability of 95% was found, with As and Pb accounting for the highest percentage. Similarly, As has the greatest impact on occurrence of cancer at the unacceptable risk level, while Pb is at the notable risk level. The historical exposure to Pb is slightly lower and the difference is slightly more pronounced for total pollution for HRA.