Nitrogen isotopes in a global ocean biogeochemical model : constraints on the coupling between denitrification and nitrogen fixation

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 stable nitrogen isotopes, ¹⁴N and ¹⁵N, in the nitrate (NO₃ˉ), phytoplankton, zooplankton, and detritus variables of the marine ecosystem model. The isotope effects of algal NO₃ˉ assimilation, water column denitrification, and zooplankton excretion are considered as well as the input of newly fixed nitrogen by diazotrophs. A global database of δ¹⁵NO₃ˉ 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 the observed patterns such as high subsurface values in denitrification zones, the meridional and vertical gradients in the Southern Ocean, and the meridional gradient in the Central Equatorial Pacific. The observed subsurface minimum in the Atlantic is underestimated presumably owing to too little nitrogen fixation there. Sensitivity experiments show that algal NO₃ˉ assimilation, nitrogen fixation and water column denitrification have strong 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 isotopes distribution by reducing the fixed nitrogen inventory, which creates an ecological niche for diazotrophs and stimulates additional nitrogen fixation. Water column denitrification has a strong but rather localized effect on the nitrogen isotope distribution in model versions without iron limitation of diazotrophy, in which a tight coupling of nitrogen fixation exists. However, including iron limitation of diazotrophy inhibits a tight coupling between water column denitrification and nitrogen fixation in the Eastern Pacific and shifts the main location of nitrogen fixation from the Eastern Tropical Pacific to the Western Tropical Pacific, which results in a better agreement with N' = NO₃ˉ−16PO₄³ˉ and δ¹⁵NO₃ˉ observations. Thus, our model results suggest that iron limitation of diazotrophy can modulate the feedback between denitrification and nitrogen fixation in the ocean. We speculate that a feedback response time on the centennial to millennial time scale may exist between denitrification and nitrogen fixation, producing imbalances in the global oceanic fixed nitrogen cycle, which may well have contributed to past changes of atmospheric CO₂ via the biological pump

Nitrogen Isotopes in the Global Ocean

Nitrogen is an essential nutrient for life. Its low abundance throughout much of the sunlit surface ocean limits the growth of primary producers that form the base of ocean ecosystems. Phytoplankton also consume surface ocean CO2 during growth, preventing this greenhouse gas from outgassing to the atmosphere where it will influence climate. Since the source and sink processes that control the balance of the bio-available nitrogen inventory, N2 fixation and denitrification/anammox (N-loss), respectively, are sensitive to climate, they may have an important feedback on atmospheric CO2 during climate change. N2 fixation and N-loss processes leave a distinguishable imprint on the ratio of stable nitrogen isotopes, δ15N, making it a useful tracer to constrain their patterns and rates. This dissertation incorporates δ15N into an Earth System Climate Model to better understand and quantify important N-cycling processes in the ocean. The two stable nitrogen isotopes, 14N and 15N, are included as prognostic tracers into the ocean biogeochemistry component of an Earth System Climate Model. A global database of δ15NO3− observations is compiled from previous studies and compared to the model results. The model is able to qualitatively and quantitatively reproduce many of the observed patterns such as high subsurface values in water column denitrification zones, low values in the North Atlantic attributed to N2 fixation, and the meridional and vertical gradients in the Southern Ocean caused by phytoplankton NO3− assimilation. Experiments show the most important isotope effects that drive the global distribution of δ15N are phytoplankton NO3− assimilation, N2 fixation, and denitrification/anammox. Nitrogen isotopes trends across the Pacific Ocean support that aeolian iron deposition is an important factor regulating the distribution of N2 fixation. N2-fixers have high structural iron requirements in their N2-fixing enzyme, which could restrict their growth since iron is a limiting micronutrient. Model experiments with and without Fe limitation of N2 fixation are compared to meridional δ15NO3− observations in the central and western Pacific Ocean. Only the model with Fe limitation of N2 fixation could reproduce the observed trends. This suggests that atmospheric iron deposition is important for relieving iron limitation of N2-fixers. Water column δ15NO3− and seafloor δ15N observations are used to constrain the rates of N2 fixation, water column N-loss, and benthic N-loss in the ocean. Experiments investigating uncertainties associated with the isotope effects of N-loss in the water column and sediments led to estimates for N-loss that varied by a factor of 3. Two sensitive processes affecting the large range of these estimates in the model are NO3− utilization in suboxic zones and the net fractionation factor associated with benthic N-loss. Sensitivity experiments that best reproduce observations in the suboxic zone and seafloor sediments estimate rates of N2 fixation, water column N-loss, and benthic N-loss are in the range 220–370, 70–90, and 150–280 Tg N yr-1, respectively, assuming a balanced bio-available nitrogen budget in the pre-industrial ocean. This model result suggests rates of N2 fixation have been previously underestimated and the residence time of bio-available nitrogen in the ocean is between 1,500 and 3,000 years

On the influence of “non-Redfield” dissolved organic nutrient dynamics on the spatial distribution of N2fixation and the size of the marine fixed nitrogen inventory

Dissolved organic nitrogen (DON) and phosphorus (DOP) represent the most abundant form of their respective nutrient pool in the surface layer of the oligotrophic oceans and play an important role in nutrient cycling and productivity. Since DOP is generally more labile than DON, it provides additional P that may stimulate growth of nitrogen-fixing diazotrophs that supply fixed nitrogen to balance denitrification in the ocean. In this study, we introduce semirecalcitrant components of DON and DOP as state variables in an existing global ocean-atmosphere-sea ice-biogeochemistry model of intermediate complexity to assess their impact on the spatial distribution of nitrogen fixation and the size of the marine fixed nitrogen inventory. Large-scale surface data sets of global DON and Atlantic Ocean DOP are used to constrain the model. Our simulations suggest that both preferential DOP remineralization and phytoplankton DOP uptake are important "non-Redfield" processes (i.e., deviate from molar N:P=16) that need to be accounted for to explain the observed patterns of DOP. Additional non-Redfield DOP sensitivity experiments testing dissolved organic matter (DOM) production rate uncertainties that best reproduce the observed spatial patterns of DON and DOP stimulate additional nitrogen fixation that increases the size of the global marine fixed nitrogen inventory by 4.7±1.7% compared to the simulation assuming Redfield DOM stoichiometry that underestimates the observed nitrogen inventory. The extra 8Tgyr-1 of nitrogen fixation stimulated in the Atlantic Ocean is mainly responsible for this increase due to its large spatial separation from water column denitrification, which buffers any potential nitrogen surplus in the Pacific Ocean. Our study suggests that the marine fixed nitrogen budget is sensitive to non-Redfield DOP dynamics because access to the relatively labile DOP pool expands the ecological niche for nitrogen-fixing diazotrophs

Isotopic constraints on the pre-industrial oceanic nitrogen budget

The size of the bio-available (i.e. "fixed") nitrogen inventory in the ocean influences global marine productivity and the biological carbon pump. Despite its importance, the pre-industrial rates for the major source and sink terms of the oceanic fixed nitrogen budget, N2 fixation and denitrification, respectively, are not well known. However, these processes leave distinguishable imprints on the ratio of stable nitrogen isotopes, δ15N, which can therefore help to infer their patterns and rates. Here we use δ15N observations from the water column and a new database of seafloor measurements to constrain rates of N2 fixation and denitrification predicted by a global three-dimensional Model of Ocean Biogeochemistry and Isotopes (MOBI). Sensitivity experiments were performed to quantify uncertainties associated with the isotope effect of denitrification in the water column and sediments. They show that the level of nitrate utilization in suboxic zones, that is the balance between nitrate consumption by denitrification and nitrate replenishment by mixing (dilution effect), significantly affects the isotope effect of water column denitrification and thus global mean δ15NO3−. Experiments with lower levels of nitrate utilization within the suboxic zone (i.e. higher residual water column nitrate concentrations, ranging from 20–32 μM) require higher ratios of benthic to water column denitrification (BD:WCD = 0.75–1.4, respectively), to satisfy the global mean NO3− and δ15NO3− constraints in the modern ocean. This suggests that nitrate utilization in suboxic zones play an important role in global nitrogen isotope cycling. Increasing the net fractionation factor for benthic denitrification (ϵBD = 0–4‰) requires even higher ratios of benthic to water column denitrification (BD:WCD = 1.4–3.5, respectively). The model experiments that best reproduce observed seafloor δ15N support the middle to high-end estimates for the net fractionation factor of benthic denitrification (ϵBD = 2–4‰). Assuming a balanced fixed nitrogen budget, we estimate that pre-industrial rates of N2 fixation, water column denitrification, and benthic denitrification were approximately 195–345, 65–75, and 130–270 Tg N yr−1, respectively. Although uncertainties still exist, these results suggest that previous estimates of N2 fixation have been significantly underestimated and the residence time for oceanic fixed nitrogen is between ~ 1500–3000 yr

A Three-Dimensional Model of the Marine Nitrogen Cycle during the Last Glacial Maximum Constrained by Sedimentary Isotopes

Nitrogen is a key limiting nutrient that influences marine productivity and carbon sequestration in the ocean via the biological pump. In this study, we present the first estimates of nitrogen cycling in a coupled 3D ocean-biogeochemistry-isotope model forced with realistic boundary conditions from the Last Glacial Maximum (LGM) ~21,000 years before present constrained by nitrogen isotopes. The model predicts a large decrease in nitrogen loss rates due to higher oxygen concentrations in the thermocline and sea level drop, and, as a response, reduced nitrogen fixation. Model experiments are performed to evaluate effects of hypothesized increases of atmospheric iron fluxes and oceanic phosphorus inventory relative to present-day conditions. Enhanced atmospheric iron deposition, which is required to reproduce observations, fuels export production in the Southern Ocean causing increased deep ocean nutrient storage. This reduces transport of preformed nutrients to the tropics via mode waters, thereby decreasing productivity, oxygen deficient zones, and water column N-loss there. A larger global phosphorus inventory up to 15% cannot be excluded from the currently available nitrogen isotope data. It stimulates additional nitrogen fixation that increases the global oceanic nitrogen inventory, productivity, and water column N-loss. Among our sensitivity simulations, the best agreements with nitrogen isotope data from LGM sediments indicate that water column and sedimentary N-loss were reduced by 17–62% and 35–69%, respectively, relative to preindustrial values. Our model demonstrates that multiple processes alter the nitrogen isotopic signal in most locations, which creates large uncertainties when quantitatively constraining individual nitrogen cycling processes. One key uncertainty is nitrogen fixation, which decreases by 25–65% in the model during the LGM mainly in response to reduced N-loss, due to the lack of observations in the open ocean most notably in the tropical and subtropical southern hemisphere. Nevertheless, the model estimated large increase to the global nitrate inventory of 6.5–22% suggests it may play an important role enhancing the biological carbon pump that contributes to lower atmospheric CO2 during the LGM

Nitrogen isotopes in a global ocean biogeochemical model : constraints on the coupling between denitrification and nitrogen fixation

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 stable nitrogen isotopes, ¹⁴N and ¹⁵N, in the nitrate (NO₃ˉ), phytoplankton, zooplankton, and detritus variables of the marine ecosystem model. The isotope effects of algal NO₃ˉ assimilation, water column denitrification, and zooplankton excretion are considered as well as the input of newly fixed nitrogen by diazotrophs. A global database of δ¹⁵NO₃ˉ 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 the observed patterns such as high subsurface values in denitrification zones, the meridional and vertical gradients in the Southern Ocean, and the meridional gradient in the Central Equatorial Pacific. The observed subsurface minimum in the Atlantic is underestimated presumably owing to too little nitrogen fixation there. Sensitivity experiments show that algal NO₃ˉ assimilation, nitrogen fixation and water column denitrification have strong 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 isotopes distribution by reducing the fixed nitrogen inventory, which creates an ecological niche for diazotrophs and stimulates additional nitrogen fixation. Water column denitrification has a strong but rather localized effect on the nitrogen isotope distribution in model versions without iron limitation of diazotrophy, in which a tight coupling of nitrogen fixation exists. However, including iron limitation of diazotrophy inhibits a tight coupling between water column denitrification and nitrogen fixation in the Eastern Pacific and shifts the main location of nitrogen fixation from the Eastern Tropical Pacific to the Western Tropical Pacific, which results in a better agreement with N' = NO₃ˉ−16PO₄³ˉ and δ¹⁵NO₃ˉ observations. Thus, our model results suggest that iron limitation of diazotrophy can modulate the feedback between denitrification and nitrogen fixation in the ocean. We speculate that a feedback response time on the centennial to millennial time scale may exist between denitrification and nitrogen fixation, producing imbalances in the global oceanic fixed nitrogen cycle, which may well have contributed to past changes of atmospheric CO₂ via the biological pump

Complementary constraints from carbon ¹³C and nitrogen ¹⁵N isotopes on the glacial ocean's soft-tissue biological pump

A three-dimensional, process-based model of the ocean’s carbon and nitrogen cycles, including 13C and 15N isotopes, is used to explore effects of idealized changes in the soft-tissue biological pump. Results are presented from one preindustrial control run (piCtrl) and six simulations of the Last Glacial Maximum (LGM) with increasing values of the spatially constant maximum phytoplankton growth rate μmax, which accelerates biological nutrient utilization mimicking iron fertilization. The default LGM simulation, without increasing μmax and with a shallower and weaker Atlantic Meridional Overturning Circulation and increased sea ice cover, leads to 280 Pg more respired organic carbon (Corg) storage in the deep ocean with respect to piCtrl. Dissolved oxygen concentrations in the colder glacial thermocline increase, which reduces water column denitrification and, with delay, nitrogen fixation, thus increasing the ocean’s fixed nitrogen inventory and decreasing δ15NNO3 almost everywhere. This simulation already fits sediment reconstructions of carbon and nitrogen isotopes relatively well, but it overestimates deep ocean δ13CDIC and underestimates δ15NNO3 at high latitudes. Increasing μmax enhances Corg and lowers deep ocean δ13CDIC, improving the agreement with sediment data. In the model’s Antarctic and North Pacific Oceans modest increases in μmax result in higher δ15NNO3 due to enhanced local nutrient utilization, improving the agreement with reconstructions there. Models with moderately increased μmax fit both isotope data best, whereas large increases in nutrient utilization are inconsistent with nitrogen isotopes although they still fit the carbon isotopes reasonably well. The best fitting models reproduce major features of the glacial δ13CDIC, δ15N, and oxygen reconstructions while simulating increased Corg by 510–670 Pg compared with the preindustrial ocean. These results are consistent with the idea that the soft-tissue pump was more efficient during the LGM. Both circulation and biological nutrient utilization could contribute. However, these conclusions are preliminary given our idealized experiments, which do not consider changes in benthic denitrification and spatially inhomogenous changes in aeolian iron fluxes. The analysis illustrates interactions between the carbon and nitrogen cycles as well as the complementary constraints provided by their isotopes. Whereas carbon isotopes are sensitive to circulation changes and indicate well the three-dimensional Corg distribution, nitrogen isotopes are more sensitive to biological nutrient utilization

Global impact of benthic denitrification on marine N2 fixation and primary production simulated by a variable-stoichiometry Earth system model

Nitrogen (N) is a crucial limiting nutrient for phytoplankton growth in the ocean. The main source of bioavailable N in the ocean is delivered by N2-fixing diazotrophs in the surface layer. Since field observation of N2 fixation are spatially and temporally sparse, the fundamental processes and mechanisms controlling N2 fixation are not well understood and constrained. Here, we implement benthic denitrification in an Earth System Model of intermediate complexity (UVic-ESCM 2.9) coupled to an optimality-based plankton ecosystem model (OPEM v1.1). Benthic denitrification occurs mostly in coastal upwelling regions and on shallow continental shelves, and is the largest N-loss process in the global ocean. We calibrate our model against three different combinations of observed Chl, NO3-, PO43-, O2 and N* = NO3- −16PO43- +2.9. The inclusion of N* provides a powerful constraint on biogeochemical model behavior. Our new model version including benthic denitrification simulates higher global rates of N2 fixation with a more realistic distribution extending to higher latitudes that are supported by independent estimates based on geochemical data. Oxygen deficient zone volume and water column denitrification rates are reduced in the new version, indicating that including benthic denitrification may improve global biogeochemical models that commonly overestimate anoxic zones. With the improved representation of the ocean N cycle, our new model configuration also yields better global net primary production (NPP) when compared to the independent datasets not included in the calibration. Benthic denitrification plays an important role shaping N2 fixation and NPP throughout the global ocean in our model, and should be considered when evaluating and predicting their response to environmental change

Extensive hydrogen supersaturations in the western South Atlantic Ocean suggest substantial underestimation of nitrogen fixation

The nitrogen cycle is fundamental to Earth's biogeochemistry. Yet major uncertainties of quantification remain, particularly regarding the global oceanic nitrogen fixation rate. Hydrogen is produced during nitrogen fixation and will become supersaturated in surface waters if there is net release from diazotrophs. Ocean surveys of hydrogen supersaturation thus have the potential to illustrate the spatial and temporal distribution of nitrogen fixation, and to guide the far more onerous but quantitative methods for measuring it. Here we present the first transect of high resolution measurements of hydrogen supersaturations in surface waters along a meridional 10,000 km cruise track through the Atlantic. We compare measured saturations with published measurements of nitrogen fixation rates and also with model-derived values. If the primary source of excess hydrogen is nitrogen fixation and has a hydrogen release ratio similar to Trichodesmium, our hydrogen measurements would point to similar rates of fixation in the North and South Atlantic, roughly consistent with modelled fixation rates but not with measured rates, which are lower in the south. Possible explanations would include any substantial nitrogen fixation by newly discovered diazotrophs, particularly any having a hydrogen release ratio similar to or exceeding that of Trichodesmium; under-sampling of nitrogen fixation south of the equator related to excessive focus on Trichodesmium; and methodological shortcomings of nitrogen fixation techniques that cause a bias towards colonial diazotrophs relative to unicellular forms. Alternatively our data are affected by an unknown hydrogen source that is greater in the southern half of the cruise track than the northern