An important tributary of the Danube River, the Olt River, was characterized in its middle and lower catchment in terms of volatile organic compounds (1,2 -dichloroethane and perchlorethylene) and volatile aromatic hydrocarbons (benzene, toluene and xylene isomers) to better assess their transfer in the environmental compartments (air, water, sediment and biota). A fugacity based calculation model was applied to establish the bio-concentration factors (BCFs) that relates the compounds concentration from sediment-, water- or air- to the biota based on experimental data. Thus, conclusive suggestions can be achieved for a rapid preliminary risk assessment as support tool for the preventive measures in the contaminated areas resulting from accidental chemical discharges or continuous pollution. For thus, water and sediment samples were collected and analyzed by gas chromatography for the selected compounds, the results being applied as input data for the model. The modeling revealed the tendency of the investigated compounds to transfer from water section to air. Simulated values obtained for section sediment as validation tool, are comparable and compatible with the values obtained by analytical measurements, and thus a rapid estimation of the pollution level in the environmental compartment of interest can be achieved based on a limited number of analytical measurements. Thus, by applying the fugacity model to estimate a pollution footprint, conclusive indications for a rapid environmental risk assessment can be achieved.