Combining stable isotopes and spatial stream network modelling to disentangle the roles of hydrological and biogeochemical processes on riverine nitrogen dynamics

Intensive agricultural activities have significantly altered watershed hydrological and biogeochemical processes, resulting in water quality issues and loss of ecosystem functions and biodiversity. A major challenge in effectively mitigating nitrogen (N) loss from agricultural watersheds stems from the heterogeneity of N transformation and transport processes that complicates accurate quantification and modeling of N sources and sinks at the watershed scale. This study utilized stable isotopes of water and nitrate (NO₃⁻) in conjunction with spatial stream network modeling (SSNMs) to explore watershed hydrology, N transformation, and sources within a mesoscale river network in the U.S. Corn Belt (Cannon River Watershed, Minnesota) under contrasting hydrological conditions. The results show that the wet season had elevated riverine NO₃⁻ concentration (medium: 8.4 mg N L⁻¹), driven by high watershed wetness conditions that mobilizes NO₃⁻ from the near-surface source zone. Furthermore, the strong hydrologic connectivity also reduced the denitrification potential by shortening water travel times. In comparison, the dry season showed lower NO₃⁻ concentrations (0.9 mg N L⁻¹) and stronger denitrification NO₃⁻ isotope signals. During this period, the decrease in hydrologic connectivity shifted the predominant water source to deep groundwater, with longer water travel time promoting denitrification. After accounting for isotopic fractionations during nitrification and denitrification, we identified fertilizer N as the main NO₃⁻ source during the wet season (98.2±1.3%), whereas the dry season showed contributions from diverse sources (64.4±11.9% fertilizer, 26.0±15.8% soil N, and 9.5±6.0% manure and sewage). During the dry season, karst regions with high hydrologic connectivity display increased shallow groundwater inputs, carrying elevated NO₃⁻ levels from leaching of applied chemical fertilizers. These findings highlight the importance of integrating drainage water management and N accumulation in groundwater into nutrient management strategies to develop adaptive measures for controlling N pollution in agricultural watersheds.