Systematic tracing of nitrate sources in a complex river catchment: An integrated approach using stable isotopes and hydrological models

Quantitative estimation for tracking the transport of various nitrate sources is required to effectively manage nitrate loading in complex river systems. In this study, we validated an integrated framework using field isotopic data (δ15NNO3 and δ18ONO3) of nitrates and hydrological modeling (hydrological simulation program FORTRAN; HSPF) to determine anthropogenic nitrate flux among different land-use types within a watershed. Nitrate isotopic compositions showed different ranges among four land-use types (4.9 to 15.5‰ for δ15NNO3, -4.9 to 12.1‰ for δ18ONO3), reflecting the different nitrate sources (sewage, synthetic fertilizer, effluent and soil) within watersheds. Based on the integration of HSPF modeling, we also found that total nitrate loads might be partially controlled by hydrological conditions such as water discharge (12,040.3-22,793.2 L/s) from upstream to downstream. Among the nitrate sources, the sewage transport showed unique enhancement near urban boundaries, along with an increase in total nitrate load (>193.5 NO3-N g/s km2) in downstream areas. In addition, the isotopic- and model-based nitrate fluxes showed good correlation for urban sources (R2=0.73, p < 0.05) but poor correlations for agriculture-dominated land use (R2=0.13, p > 0.05), reflecting the potential influence of surface runoff and ground infiltration into the watershed. Consequently, this research provided useful information to establish nitrogen management policy controlling point and non-point nitrate source loads in various land-use types for the restoration of water quality and aquatic ecosystem in the complex river system. Considering the recent increase in human activities near aquatic environments, this framework would be effective for individually estimating the quantitative contributions of anthropogenic nitrate sources transported along river-coastal systems.