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Fixed nitrogen (N) loss to biogenic N2 in intense oceanic O2 minimum zones (OMZ) accounts for a large fraction of the global N sink and is an essential control on the ocean's N-budget. However, major uncertainties exist regarding microbial pathways as well as net impact on the magnitude of N-loss and the ocean's overall N-budget. Here we report the discovery of a N-loss hotspot in the Peru OMZ associated with a coastally trapped mesoscale eddy that is marked by an extreme N-deficit matched by biogenic N2 production, high NO2- levels, and the highest isotope enrichments observed so far in OMZ's for the residual NO3-. High sea surface chlorophyll in seaward flowing streamers provides evidence for offshore eddy transport of highly productive, inshore water. Resulting pulses in the downward flux of particles likely stimulated heterotrophic dissimilatory NO3-. reduction and subsequent production of biogenic N2 within the OMZ. A shallower biogenic N2 maximum within the oxycline is likely a feature advected by the eddy streamer from the shelf. Eddy-associated temporal-spatial heterogeneity of N-loss, mediated by a local succession of microbial processes, may explain inconsistencies observed among prior studies. Similar transient enhancements of N-loss likely occur within all other major OMZ's exerting a major influence on global ocean N and N isotope budgets. [ABSTRACT FROM AUTHOR]

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotopic analysis to examine the timescales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 13², 17³-cyclopheophorbide-a-enol until burial in Black Sea surface sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment δ15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates contribution from N2-fixation. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. However, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotopic analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and assess their precise timescales. [ABSTRACT FROM AUTHOR]