Sources and transformations of riverine nitrogen across a coastal-plain river network of eastern China: New insights from multiple stable isotopes

Riverine nitrogen pollution is ubiquitous and attracts considerable global attention. Nitrate is commonly the dominant total nitrogen (TN) constituent in surface and ground waters; thus, stable isotopes of nitrate (delta N-15/delta O-18-NO3-) are widely used to differentiate nitrate sources. However, delta N-15/delta O-18-NO3- approach fails to present a holistic perspective of nitrogen pollution for many coastal-plain river networks because diverse nitrogen species contribute to high TN loads. In this study, multiple isotopes, namely, delta N-15/delta O-18-NO3-, delta O-18-H2O, delta N-15-NH4+, delta N-15-PN, and delta N-15(bulk)/delta O-18/SP-N2O in the Wen-Rui Tang River, a typical coastal-plain river network of Eastern China, were investigated to identify transformation processes and sources of nitrogen. Then, a stable isotope analysis in R (SIAR) model-TN source apportionment method was developed to quantify the contributions of different nitrogen sources to riverine TN loads. Results showed that nitrogen pollution in the river network was serious with TN concentrations ranging from 1.71 to 8.09 mg/L (mean +/- SD: 3.77 +/- 1.39 mg/L). Ammonium, nitrate, and suspended particulate nitrogen were the most prominent nitrogen components during the study period, constituting 45.4 %, 28.9 %, and 19.9 % of TN, respectively. Multiple hydrochemical and isotopic analysis identified nitrification as the dominant N cycling process. Biological assimilation and denitrification were minor N cycling processes, whereas ammonia volatilization was deemed negligible. Isotopic evidence and SIAR modeling revealed municipal sewage was the dominant contributor to nitrogen pollution. Based on quantitative estimates from the SIAR model, nitrogen source contributions to the Wen-Rui Tang River watershed followed: municipal sewage (40.6 %) approximate to soil nitrogen (39.5 %) > nitrogen fertilizer (9.7 %) > atmospheric deposition (2.8 %) during wet season; and municipal sewage (59.1 %) > soil nitrogen (30.4 %) > nitrogen fertilizer (4.1 %) > atmospheric deposition (1.0 %) during dry season. This study provides a deeper understanding of nitrogen dynamics in eutrophic coastal-plain river networks, which informs strategies for efficient control and remediation of riverine nitrogen pollution.