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Groundwater pollution caused by agricultural and atmospheric inputs is a pressing issue in environmental management worldwide. Various researchers have studied different aspects of nitrate contamination since the substantial increase of the agriculture pollution in the second half of the 20th century. This study addresses large scale reactive solute transport in a typical Germany hilly landscapes in a transect crossing 2 valleys: River Neckar and Ammer. The numerical model was constructed compromising a 2-D cross-section accounting for typical fractured mudstones and unconsolidated sediments. Flow modelling showed that the groundwater divide significantly deviates from the surface water divide providing conditions for inter-valley flow and transport. Reactive transport modelling of redox-sensitive solutes (e.g. agriculture nitrate and natural sulfate, DOC, ammonium) with MIN3P was used to elucidate source of nitrate in aquifers and rivers. Since both floodplains, in the Ammer and Neckar valley contain Holocene sediments relatively high in organic carbon, agricultural nitrate is reduced therein and does not reach the groundwater. However, nitrate applied in the hillslopes underlain by fractured oxidized mudrock is transported to the high yield sand and gravel aquifer in the Neckar valley. Therefore, the model predicts that nitrate in the Neckar valley comes, to a large extent, from the neighboring Ammer valley. Moreover, nitrate observed in the rivers and drains in the Ammer valley is very likely geogenic since frequent peat layers there release ammonium which is oxidized as it enters the surface water. Such findings are relevant for land and water quality management.