Coupling stable isotopes and water chemistry to assess the role of hydrological and biogeochemical processes on riverine nitrogen sources.

Accurate source identification is critical for optimizing water pollution control strategies. Although the dual stable isotope (N-NO/O-NO) approach has been widely applied for differentiating riverine nitrogen (N) sources, the relatively short-term (<1 yr) N-NO/O-NO records typically used in previous studies often hinders rigorous assessment due to high temporal variability associated with watershed N dynamics. Estimated contributions of legacy N sources in soils and groundwater to riverine N export by modeling approaches in many previous studies also lack validation from complementary information, such as multiple stable isotopes. This study integrated three years of multiple stable isotope (N-NO/O-NO and H-HO/O-HO) and hydrochemistry measurements for river water, groundwater and rainfall to elucidate N dynamics and sources in the Yongan watershed (2474 km) of eastern China. Nonpoint source N pollution dominated and displayed considerable seasonal and spatial variability in N forms and concentrations. Information from δN-NO and δO-NO indicated that riverine N dynamics were regulated by contributing sources, nitrification and denitrification, as well as hydrological processes. For the three examined catchments and entire watershed, slow subsurface and groundwater flows accounted for >75% of river discharge and were likely the major hydrological pathways for N delivery to the river. Riverine NO sources varied with dominant land use (p < 0.001), with the highest contributions of groundwater (60%), wastewater (35%), and soil (50%) occurring in agricultural, residential and forest catchments, respectively. For the entire watershed, groundwater (∼50%) and soil N (>30%) were the dominant riverine NO sources, implying considerable potential for N pollution legacy effects. Results were consistent with observed nitrous oxide dynamics and N sources identified in previous modeling studies. As the first attempt to apply multiple isotope tracers for exploring and quantifying N transformation and transport pathways, this study provides an integrated approach for verifying and understanding the N pollution legacy effects observed in many watersheds worldwide. This study highlights that river N pollution control in many watersheds requires particular attention to groundwater restoration and soil N management in addition to N input control strategies.