In this work, a one-dimensional (1D) finite volume numerical model for the unsteady simulation of the flow hydrodynamics and water quality is developed. The water dynamics is formulated with the 1D shallow water equations, and the water quality evolution is described by the Water Quality Analysis Simulation Program (WASP) model, allowing us to interpret and predict the transport and fate of various biochemical substances along any river reach. This combined system is solved with an explicit finite volume scheme based on Roe's linearization for the advection component of both the flow and the solute transport equations. The proposed model is able to consider temporal variations in tributaries and abstractions occurring in the river basin. This feature is transcendent in order to predict the chemical composition of natural water bodies during winter and summer periods, leading to an improvement in the agreement between computed and observed water quality evolutions. The combined model has been evaluated using literature tests in a steady state and a real-field case of the Ebro river (Spain), characterized by a marked unsteady regime. In the real case, we found that the water temperature was very sensitive to both the solar radiation and the average air temperature, requiring a careful calibration of these parameters. The numerical results are also demonstrated to be reasonably accurate, conservative and robust in real-scale field cases, showing that the model is able to predict the evolution of quality parameters as well as hydrodynamic variables in complex scenarios.