Co-variation of nitrogen isotopes and redox states through glacial–interglacial cycles in the Black Sea

In all aquatic environments, nitrogen cycling within the water column is strongly influenced by oxygen. We hypothesize that the nitrogen isotopic composition (δ15N) of organic matter deposited in the sediments is a proxy for the redox state of the water column at the time of deposition. We tested the hypothesis by measuring the bulk sedimentary δ15N values in a drill core from the Black Sea, a basin that alternates between oxic, less saline conditions and anoxic, marine conditions on glacial–interglacial time scales. We reconstructed these changes in Black Sea redox conditions using sedimentary δ15N, total organic carbon (TOC), total nitrogen (TN), redox-sensitive metals, and micropaleontological data from a deep-sea core (DSDP Site 380). The sedimentary data reveal that during the transitions between oxic and anoxic conditions, δ15N values increased relative to the preceding and succeeding quasi-steady-state oxic and anoxic periods. The results indicate that the reciprocal transitional states from anoxic to oxic conditions were accompanied by intense denitrification; during the quasi-stable oxic and anoxic states (characterized by glacial fresh water and interglacial marine conditions) nitrification and complete nitrate utilization, respectively, dominate the nitrogen cycle. While other factors may influence the δ15N record, our results support the hypothesis that the variations in nitrogen isotopic composition of organic matter are strongly influenced by changes in redox state in the Black Sea subphotic zone on glacial–interglacial time scales, and can be explained by a relatively simple model describing the effects of oxygen on the microbial processes that drive the nitrogen cycle in marine ecosystems. Our model suggests that the nitrogen isotopic composition of marine sediments, on geological time scales, can be used to reconstruct the redox state of the overlying water column.