Marine sediments are the most important sink for nitrogen and also an important reaction interface for biogeochemical processes. The nitrogen transformation processes within the sediments and the isotope fractionation deeply control the nitrogen exchange at the sediment-water interface, and further influence the nitrogen cycling process in the marine environment. This study utilized dual isotopes of nitrogen and oxygen tracing technology to investigate the spatial and temporal changes in the nitrogen cycling process in the sediments of the Bohai Sea. Four expeditions were conducted in May, August, October, and December 2019, collecting sediment and overlying water samples from 35 stations. By measuring the concentrations of dissolved inorganic nitrogen (DIN), nitrate (NO3-), and ammonium nitrogen (NH4+), as well as the nitrogen-oxygen isotope compositions (δ15N-NH4+, δ15N-NO3-, δ18O-NO3-, and δ15N-TN), the main nitrogen transformation processes and their control mechanisms were identified.
The concentration of NH4+ in pore water shows significant seasonal variations, with the highest levels in summer. The δ15N-NH4+ indicator presents three distinct patterns: increasing with depth, decreasing with depth, and remaining relatively stable, reflecting the complex interactions among mineralization, nitrification, denitrification, and anaerobic ammonium oxidation (anammox). Stations with higher δ15N-NH4+ values are mainly concentrated in the western part of the Bohai Sea and the strait area, while the downward trend is mainly observed in winter. The concentration of NO3- is generally low in all seasons, but reaches a peak within the top 3 cm and drops sharply with depth. The ratio of δ15N-NO3- to δ18O-NO3- shows a good 1:1 relationship, indicating the role of denitrification. The total nitrogen (TN) content in sediment is significantly higher in clayey sediments and nearshore/horizonal areas. There is a strong positive correlation between TN and δ15N-TN values, and the δ15N-NH4+ value in the deep interstitial water is close to the δ15N value of marine organic matter after decomposition, indicating that TN is preferentially decomposed by heavy 15N-containing marine organic matter during the mineralization process.
Furthermore, we employed a non-steady-state diagenesis model to simulate the vertical distribution of nutrients and isotopes, taking into account molecular diffusion, sediment transport, and biogeochemical reactions. The model results indicated that the coupling process of nitrification and denitrification, as well as the mineralization and ammonia oxidation processes, are the main driving forces influencing the nitrogen isotope fractionation in the sediments of the Bohai Sea. This study provides new insights into the nitrogen transformation mechanism in shallow marginal sea sediments and emphasizes the importance of seasonal dynamics and sediment resuspension events in regulating the nitrogen cycle.
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