For areas with the diverse contamination sources, the change of 4-nitrophenol contamination and impact of potential contamination sources have been evaluated using monitoring data and a numerical model (HydroGeoSphere). The model considered several parameters including land cover, precipitation, and flow rate. And, the model has been performed to investigate the effect of decay rate of 4-nitrophenol. The results of the simulations showed that the influence on 4-nitrophenol in downstream was mainly greater than that in upstream, and the tributaries did not significantly affect the mainstream because of their low flow rates. In addition, the effect of contamination sources was simulated for each section, then the measured data were higher than the corresponding simulated data in most sections of the Geumho river. In particular, the impact of the potential contamination sources in the upstream area was much higher than that in the other area, thus more monitoring data for the upstream area is required.