The article considers the task and a new approach to monitoring of soil and groundwater contamination by harmful emissions of nitrogen dioxide from motor vehicles. The approach is based on combination of measurement procedure of the harmful emissions concentrations in the surface atmospheric layer and mathematical modeling of the impact of these emissions on soil and groundwater contamination. The scheme of this harmful emission concentrations measurement using a mobile complex Sniffer4D Hyper-local Air Quality Analyzer is given. Based on these results, a mathematical model of diffusion of this harmful substance in the upper layers of soil and water resources is proposed. As a result of the computations, the distribution of concentrations of soil and water contamination in the neighborhood of separate observation points has been built. Also, the field of nitrogen dioxide concentrations at various depths for observation points has been modeled. For a waterbody, the concentration of nitric acid, which is formed due to the interaction of nitrogen dioxide with water, is higher in water than in the surface layer of the soil. This concentration can be significantly increased during prolonged downpours when acidic solutions drain from surrounding soil areas into the waterbodies. The obtained research results are fully consistent with the practical and theoretical results on the diffusion of gases into soils and water resources. It means that the proposed approach can be used instead of the existing very expensive approach to analysis of soil and groundwater contamination in the laboratory.