Climatic and anthropogenic driving forces of the nitrogen cycling in a subtropical river basin.

To date, basin-scale understanding of nitrogen (N) cycling is lacking, which undermines riverine N pollution control efforts. Applying a multiple-isotopic approach, this study provided insights into the impacts of climate and anthropogenic activities on the N cycling at a basin scale. The isotopic compositions of the river water were regulated by a simple mixing process in winter, while unconservative processes (nitrification and denitrification) occurred in warm seasons. Denitrification dominated the N transformations in summer, while coupled nitrification-denitrification in soils after fertilization was responsible for the isotopic fractionations in spring and autumn. While at least 58.7% of the nitrate (NO) was removed from the basin, the NO loadings in the river remained high, suggesting that the ecosystem services could not balance the anthropogenic pollution. After correcting the isotopic fractionations, the sources of the riverine NO were quantified by a Markov chain Monte Carlo isotope mixing model. The contributions of point sources versus non-point sources changed dynamically with the precipitation and fertilization patterns. In summer and autumn, the soil organic N and chemical fertilizer dominated the riverine NO, with total contributions of 75.9% and 74.6%, respectively. The contributions from sewage and manure significantly increased during spring (47.9%) and winter (50.2%). Overall, the annual NO fluxes were from SON (28.7%), CF (28.1%), DS (18.2%), MA (23.9%), and AP (1.1%). In addition, we presented the large uncertainties in source apportionment that arose from the ignorance of isotope fractionations, highlighting the importance of considering the effect of isotopic fractionations in N source apportionment studies.