ALBERT

Description: According to current best estimates, the modern ocean's N cycle is in severe deficit. N isotope budgeting provides an independent geochemical constraint in this regard as well as the only means for past reconstruction. Overall, it is the relative proportion of N2 fixation consumed by water column denitrification that sets average oceanic δ15N under steady-state conditions. Several factors (conversion of organic N to N2, Rayleigh closed and open system effects) likely reduce the effective fractionation factor (ε) for water column denitrification to about half the inherent microbial value for εden. If so, the average oceanic δ15N of ~5‰ is consistent with a canonical contribution from water column denitrification of 50% of the source flux from N2 fixation. If an imbalance in oceanic N sources and sinks changes this proportion then a transient in average oceanic δ15N would occur. Using a simple model, changing water column denitrification by ±30% or N2 fixation by ±15% produces detectable (〉1‰) changes in average oceanic δ15N over one residence time period or more with corresponding changes in oceanic N inventory. Changing sedimentary denitrification produces no change in δ15N but does change N inventory. Sediment δ15N records from sites thought to be sensitive to oceanic average δ15N all show no detectible change over the last 3 kyr or so implying a balanced marine N budget over the latest Holocene. A mismatch in time scales is the most likely meaningful interpretation of the apparent conflict with modern flux estimates. Decadal to centennial scale oscillations between net N deficit and net surplus may occur but on the N residence timescale of several thousand years, net balance is achieved in sum. However, sediment δ15N records from the literature covering the period since the last glacial maximum show excursions of up to several ‰ that are consistent with sustained N deficit during the deglaciation followed by readjustment and establishment of balance in the early Holocene. Since imbalance was sustained for one N residence time period or longer, excursions in ocean N inventory of 10 to 30% likely occurred. The climatic and oceanographic changes that occurred over this period evidently overcame, for a time, the capacity of ocean biogeochemistry to maintain N balance.

Description: 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 isotope analysis to examine the time-scales 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 core-top 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 either contribution from N2-fixation or direct uptake of ammonium from deeper waters. 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, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, 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 isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

Description: We present new data for the stable isotope ratio of inorganic nitrogen species from the contrasting oxygen minimum zones (OMZs) of the Eastern Tropical North Atlantic, south of Cape Verde, and the Eastern Tropical South Pacific off Peru. Differences in minimum oxygen concentration and corresponding N-cycle processes for the two OMZs are reflected in strongly contrasting δ15N distributions. Pacific surface waters are marked by strongly positive values for δ15N-NO3–) reflecting fractionation associated with subsurface N-loss and partial NO3– utilization. This contrasts with negative values in NO3– depleted surface waters of the Atlantic which are lower than can be explained by N supply via N2 fixation. We suggest the negative values reflect inputs of nitrate, possibly transient, associated with deposition of Saharan dust. Strong signals of N-loss processes in the subsurface Pacific OMZ are evident in the isotope and N2O data, both of which are compatible with a contribution of canonical denitrification to overall N-loss. However the apparent N isotope fractionation factor observed is relatively low (ϵd=11.4 ‰) suggesting an effect of influence from denitrification in sediments. Identical positive correlation of N2O vs. AOU for waters with oxygen concentrations ([O2] 〈 5 μmol l−1) in both regions reflect a nitrification source. Sharp decrease in N2O concentrations is observed in the Pacific OMZ due to denitrification under oxygen concentrations O2 〈 5 μmol l−1.

Description: Excess nitrogen gas (N2xs) was measured in samples collected at six locations in the eastern and western sub-basins of the Cariaco Basin, Venezuela, in September 2008 (non-upwelling conditions) and March 2009 (upwelling conditions). During both sampling periods, N2xs concentrations were below detection in surface waters, increasing to ~ 22 μmol N kg−1 at the oxic–anoxic interface ([O2] 〈 ~ 4 μmol kg−1, ~ 250 m). Below the oxic–anoxic interface (300–400 m), the average concentration of N2xs was 24.7 ± 1.9 μmol N kg−1 in September 2008 and 27.5 ± 2.0 μmol N kg−1 in March 2009, i.e., N2xs concentrations within this depth interval were ~ 3 μmol N kg−1 higher (p 〈 0.001) during the upwelling season compared to the non-upwelling period. These results suggest that N-loss in the Cariaco Basin may vary seasonally in response to changes in the flux of sinking particulate organic matter. We attribute the increase in N2xs concentrations, or N-loss, observed during upwelling to: (1) higher availability of fixed nitrogen derived from suspended and sinking particles at the oxic–anoxic interface and/or (2) enhanced ventilation at the oxic–anoxic interface during upwelling.

Description: In order to determine and understand the stable isotope fractionation of 18O and 15N manifested during assimilation of NO3− in marine macro-benthic algae, two species (Ulva sp. and Agardhiella sp.) have been grown in a wide range of NO3− concentrations (2–500 μM). Two types of experiments were performed. The first was one in which the concentration of the NO3− was allowed to drift downward as it was assimilated by the algae, between 24 hour replacements of media. These experiments proceeded for periods of between 7 and 10 days. A second set of experiments maintained the NO3− concentration at a low steady-state value by means of a syringe pump. The effective fractionation during the assimilation of the NO3− was determined by measuring the δ15N of both the (i) new algal growth and (ii) residual NO3− in the free-drift experiments after 0, 12, 24 and 48 h. Modelling these data show that the fractionation during assimilation is dependent upon the concentration of NO3− and is effectively 0 at concentrations of less than ~2 μM. The change in the fractionation with respect to concentration is the greatest at lower concentrations (2–10 μM). The fractionation stablizes between 4 and 6‰ at concentrations of between 50 and 500 μM. Although the δ18O and δ15N values of NO3− in the residual solution were correlated, the slope of relationship also varied with respect to NO3− concentration, with slopes of greater than unity at low concentration. These results suggest shifts in the dominant fractionation mechanism of 15N and 18O between concentrations of 1 and 10 μM NO3−. At higher NO3− concentrations (〉10–50 μM), fractionation during assimilation will lead to δ15N values in algal biomass lower than the ambient NO3− and 15N enrichments in the residual NO3−.

Description: 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.