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The Upper Mississippi River Basin is the largest source of reactive nitrogen (N) to the Gulf of Mexico. Concentration‐discharge (C‐Q) relationships offer a means to understand both the terrestrial sources that generate this reactive N and the in‐stream processes that transform it. Progress has been made on identifying land use controls on C‐Q dynamics. However, the impact of basin size and river network structure on C‐Q relationships is not well characterized. Here, we show, using high‐resolution nitrate concentration data, that tile drainage is a dominant control on C‐Q dynamics, with increasing drainage density contributing to more chemostatic C‐Q behavior. We further find that concentration variability increases, relative to discharge variability, with increasing basin size across six orders of magnitude, and this pattern is attributed to different spatial correlation structures for C and Q. Our results show how land use and river network structure jointly control riverine N export. Plain Language Summary: Nitrate is a major agricultural pollutant that can harm freshwater and marine ecosystems. Understanding the relationships between the concentration of nitrate in a river and the river's flow rate (discharge) can allow us to infer drivers of nitrate release from land into waterways and to better manage nutrient pollution. Here, we found that artificial (i.e. tile) drainage increases the stability of nitrate concentrations in the rivers of the Upper Mississippi basin across a wide range of flow rates. We also found that the variability of nitrate concentrations, relative to discharge, increased as rivers grew larger and had more tributaries contributing to flow. This shows that both on‐land and in‐river processes control the concentration‐discharge relationships of nitrate. Key Points: Nitrate concentrations in UMRB show a threshold response, chemodynamic at low flows but chemostatic at high flowsTile drainage increases the degree of nitrate chemostasis in the UMRBNitrate concentrations for rivers within Upper Mississippi River Basin (UMRB) are more chemodynamic with increasing basin size [ABSTRACT FROM AUTHOR]