ALBERT

Description: The ocean is an important source of nitrous oxide (N2O) to the atmosphere, yet the factors controlling N2O production and consumption in oceanic environments are still not understood nor constrained. We measured N2O concentrations and isotopomer ratios, as well as O2, nutrient and biogenic N2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast (~5–16°S, 75–81°W) in December 2012 and January 2013. N2O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L−1 in surface waters. We used a 3-D-reaction-advection-diffusion model to evaluate the rates and modes of N2O production in oxic waters and rates of N2O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N2O isotopomer was relatively low in surface waters (generally −3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier-denitrification or incomplete denitrifier-denitrification, corresponding to an efflux of up to 0.6 Tg N yr−1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN2O and apparent O2 utilization and significant relationships between nitrate, a substrate during denitrification, and N2O isotopes, suggest that N2O production by incomplete denitrification or nitrifier-denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N2O accumulation in newly upwelled surface waters. We observed imbalances between N2O production and consumption in the ODZ, with the modeled proportion of N2O consumption relative to production generally increasing with biogenic N2. However, N2O production appeared to occur even where there was high N loss at the shallowest stations.

Description: Nitrogen (N) fixation by specialized microorganisms (diazotrophs) influences global plankton productivity because it provides the ocean with most of its bio-available N. However, its global rate and large-scale spatial distribution is still regarded with considerable uncertainty. Here we use a global ocean nitrogen isotope model, in comparison with δ15NO3− observations, to constrain the pattern of N2 fixation across the Pacific Ocean. N2 fixation introduces isotopically light atmospheric N2 from to the ocean (δ15N = 0‰) relative to the oceanic average near 5‰, which makes nitrogen isotopes suitable to infer patterns of N2 fixation. Including atmospheric iron limitation of diazotrophy in the model shifts the pattern of simulated N2 fixation from the South Pacific to the North Pacific and from the East Pacific westward. These changes considerably improve the agreement with meridional transects of available δ15NO3− observations, as well as excess P (PO43− − NO3−/16), suggesting that atmospheric iron deposition is indeed important for N fixation in the Pacific Ocean. This study highlights the potential for using δ15N observations and model simulations to constrain patterns and rates of N fixation in the ocean.

Description: Mesoscale eddies in Oxygen Minimum Zones (OMZ's) have been identified as important fixed nitrogen (N) loss hotspots that may significantly impact both the global rate of N-loss as well as the ocean's N isotope budget. They also represent ‘natural tracer experiments’ with intensified biogeochemical signals that can be exploited to understand the large-scale processes that control N-loss and associated isotope effects (ε; the ‰ deviation from 1 in the ratio of reaction rate constants for the light versus the heavy isotopologues). We observed large ranges in the concentrations and N and O isotopic compositions of nitrate (NO3−), nitrite (NO2−) and biogenic N2 associated with an anticyclonic eddy in the Peru OMZ during two cruises in November and December 2012. In the eddy's center where NO3− was nearly exhausted, we measured the highest δ15N values for both NO3− and NO2− (up to ~70‰ and 50‰) ever reported for an OMZ. Correspondingly, N deficit and biogenic N2-N concentrations were also the highest near the eddy's center (up to ~40 µmol L−1). δ15N-N2 also varied with biogenic N2 production, following kinetic isotopic fractionation during NO2− reduction to N2 and, for the first time, provided an independent assessment of N isotope fractionation during OMZ N-loss. We found apparent variable ε for NO3− reduction (up to ~30‰ in the presence of NO2−). However, the overall ε for N-loss was calculated to be only ~13-14‰ (as compared to canonical values of ~20-30‰) assuming a closed system and only slightly higher assuming an open system (16-19‰). Our results were similar whether calculated from the disappearance of DIN (NO3− + NO2−) or from the appearance of N2 and changes in isotopic composition. Further, we calculated the separate ε for NO3− reduction to NO2− and NO2− reduction to N2 of ~16-21‰ and ~12‰, respectively, when the effect of NO2− oxidation could be removed. These results, together with the relationship between N and O of NO3− isotopes and the difference in δ15N between NO3− and NO2-, confirm a role for NO2− oxidation in increasing the apparent ε associated with NO3− reduction. The lower ε for NO3− and NO2− reduction as well as N-loss calculated in this study could help reconcile the current imbalance in the global N budget if they are representative of OMZ N-loss.

Description: We present a new nitrogen isotope model incorporated into the three-dimensional ocean component of a global Earth system climate model designed for millennial timescale simulations. The model includes prognostic tracers for the two stable nitrogen isotopes, 14N and 15N, in the nitrate (NO3−), phytoplankton, zooplankton, and detritus variables of the marine ecosystem model. The isotope effects of algal NO3− uptake, nitrogen fixation, water column denitrification, and zooplankton excretion are considered as well as the removal of NO3− by sedimentary denitrification. A global database of δ15NO3− observations is compiled from previous studies and compared to the model results on a regional basis where sufficient observations exist. The model is able to qualitatively and quantitatively reproduce many of the observed patterns such as high subsurface values in water column denitrification zones and the meridional and vertical gradients in the Southern Ocean. The observed pronounced subsurface minimum in the Atlantic is underestimated by the model presumably owing to too little simulated nitrogen fixation there. Sensitivity experiments reveal that algal NO3− uptake, nitrogen fixation, and water column denitrification have the strongest effects on the simulated distribution of nitrogen isotopes, whereas the effect from zooplankton excretion is weaker. Both water column and sedimentary denitrification also have important indirect effects on the nitrogen isotope distribution by reducing the fixed nitrogen inventory, which creates an ecological niche for nitrogen fixers and, thus, stimulates additional N2 fixation in the model. Important model deficiencies are identified, and strategies for future improvement and possibilities for model application are outlined.

Description: High‐resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high‐sedimentation rate core (MD84‐527: 43°50′S; 51°19;′E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point‐by‐point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment δ15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate‐induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa‐231/Th‐230 ratios, suggesting increased scavenging from the water column. Sediment δ15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.