Nitrogen isotope constraint on the zonation of multiple transformations between dissolved and particulate organic nitrogen in the Changjiang plume

Information on the sources and transformations of particulate organic N (PN) and dissolved organic N (DON) at the coastal interface remains insufficient due to technological difficulties and complicated features of intensive physical mixing and rapid biological activities. Here, we investigated the spatial distribution of concentrations and isotopic compositions of PN and DON in the Changjiang plume during the summer flood period. In average, DON and PN accounted for 25.6 ± 12.1% and 8.1 ± 9.1% (n = 55), respectively, of the total N pool, with the remaining N primarily in the form of nitrate (NO3-). Mean δ15N values were the lowest for DON (-0.1 ± 2.7‰, n = 58) and slightly higher for PN (2.0 ± 1.6‰, n = 101), and the highest for NO3- (6.5 ± 2.2‰, n = 67), suggesting multiple transformations had occurred to differentiate isotopic characteristics among the three N pools. By applying a conservative mixing model, we found DON deficits (-3.5 ± 3.7 μmol L-1, n = 43) and negative shift in δ15NDON (-3.6 ± 2.2‰, n = 43) in the Changjiang plume, revealing nonconservative DON behaviors. In the offshore surface plume where Chlorophyll a was high, the most likely cause is the DON uptake by phytoplankton with a strong inverse isotope effect (around -40‰). This DON assimilation by phytoplankton contributed to ~16 ± 12% of the PN production, with the remaining supported by NO3- assimilation, producing an overall isotope effect of 4-9‰. However, in waters near the river mouth and at the bottom of the offshore plume where total suspended matter concentrations were high (>5 mg L-1), the DON deficit was most likely induced by the selective adsorption of 15N enriched moieties of DON onto particulate surfaces (with an isotope effect of -20‰ to -5‰). Unlike dissolved organic carbon to behave conservatively in most estuaries, our results show that active transformations had occurred between the DON and PN pools in the Changjiang plume.