Description: A significant decrease of dissolved iron (DFe) concentration has been observed after dust addition into mesocosms during the DUst experiment in a low Nutrient low chlorophyll Ecosystem (DUNE), carried out in the summer of 2008. Due to low biological productivity at the experiment site, biological consumption of iron can not explain the magnitude of DFe decrease. To understand processes regulating the observed DFe variation, we simulated the experiment using a one-dimensional model of the Fe biogeochemical cycle, coupled with a simple ecosystem model. Different size classes of particles and particle aggregation are taken into account to describe the particle dynamics. DFe concentration is regulated in the model by dissolution from dust particles and adsorption onto particle surfaces, biological uptake, and photochemical mobilisation of particulate iron. The model reproduces the observed DFe decrease after dust addition well. This is essentially explained by particle adsorption and particle aggregation that produces a high export within the first 24 h. The estimated particle adsorption rates range between the measured adsorption rates of soluble iron and those of colloidal iron, indicating both processes controlling the DFe removal during the experiment. A dissolution timescale of 3 days is used in the model, instead of an instantaneous dissolution, underlining the importance of dissolution kinetics on the short-term impact of dust deposition on seawater DFe. Sensitivity studies reveal that initial DFe concentration before dust addition was crucial for the net impact of dust addition on DFe during the DUNE experiment. Based on the balance between abiotic sinks and sources of DFe, a critical DFe concentration has been defined, above which dust deposition acts as a net sink of DFe, rather than a source. Taking into account the role of excess iron binding ligands and biotic processes, the critical DFe concentration might be applied to explain the short-term variability of DFe after natural dust deposition in various different ocean regions.

Description: During phytoplankton growth a fraction of dissolved inorganic carbon (DIC) assimilated by phytoplankton is exuded in the form of dissolved organic carbon (DOC), which can be transformed into extracellular particulate organic carbon (POC). A major fraction of extracellular POC is associated with carbon of transparent exopolymer particles (TEP; carbon content = TEPC) that form from dissolved polysaccharides (PCHO). The exudation of PCHO is linked to an excessive uptake of DIC that is not directly quantifiable from utilisation of dissolved inorganic nitrogen (DIN), called carbon overconsumption. Given these conditions, the concept of assuming a constant stoichiometric carbon-to-nitrogen (C:N) ratio for estimating new production of POC from DIN uptake becomes inappropriate. Here, a model of carbon overconsumption is analysed, combining phytoplankton growth with TEPC formation. The model describes two modes of carbon overconsumption. The first mode is associated with DOC exudation during phytoplankton biomass accumulation. The second mode is decoupled from algal growth, but leads to a continuous rise in POC while particulate organic nitrogen (PON) remains constant. While including PCHO coagulation, the model goes beyond a purely physiological explanation of building up carbon rich particulate organic matter (POM). The model is validated against observations from a mesocosm study. Maximum likelihood estimates of model parameters, such as nitrogen- and carbon loss rates of phytoplankton, are determined. The optimisation yields results with higher rates for carbon exudation than for the loss of organic nitrogen. It also suggests that the PCHO fraction of exuded DOC was 63±20% during the mesocosm experiment. Optimal estimates are obtained for coagulation kernels for PCHO transformation into TEPC. Model state estimates are consistent with observations, where 30% of the POC increase was attributed to TEPC formation. The proposed model is of low complexity and is applicable for large-scale biogeochemical simulations.

Description: A one-dimensional model of Fe speciation and biogeochemistry, coupled with the General Ocean Turbulence Model (GOTM) and a NPZD-type ecosystem model, is applied for the Tropical Eastern North Atlantic Time-Series Observatory (TENATSO) site. Among diverse processes affecting Fe speciation, this study is focusing on investigating the role of dust particles in removing dissolved iron (DFe) by a more complex description of particle aggregation and sinking, and explaining the abundance of organic Fe-binding ligands by modelling their origin and fate. The vertical distribution of different particle classes in the model shows high sensitivity to changing aggregation rates. Using the aggregation rates from the sensitivity study in this work, modelled particle fluxes are close to observations, with dust particles dominating near the surface and aggregates deeper in the water column. POC export at 1000 m is a little higher than regional sediment trap measurements, suggesting further improvement of modelling particle aggregation, sinking or remineralisation. Modelled strong ligands have a high abundance near the surface and decline rapidly below the deep chlorophyll maximum, showing qualitative similarity to observations. Without production of strong ligands, phytoplankton concentration falls to 0 within the first 2 years in the model integration, caused by strong Fe-limitation. A nudging of total weak ligands towards a constant value is required for reproducing the observed nutrient-like profiles, assuming a decay time of 7 years for weak ligands. This indicates that weak ligands have a longer decay time and therefore cannot be modelled adequately in a one-dimensional model. The modelled DFe profile is strongly influenced by particle concentration and vertical distribution, because the most important removal of DFe in deeper waters is colloid formation and aggregation. Redissolution of particulate iron is required to reproduce an observed DFe profile at TENATSO site. Assuming colloidal iron is mainly composed of inorganic colloids, the modelled colloidal to soluble iron ratio is lower that observations, indicating the importance of organic colloids.

Description: Stratospheric ozone depletion and emission of greenhouse gases lead to a trend of the southern annular mode (SAM) toward its high-index polarity. The positive phase of the SAM is characterized by stronger than usual westerly winds that induce changes in the physical carbon transport. Changes in the natural carbon budget of the upper 100 m of the Southern Ocean in response to a positive SAM phase are explored with a coupled ecosystem-general circulation model and regression analysis. Previously overlooked processes that are important for the upper ocean carbon budget during a positive SAM period are identified, namely, export production and downward transport of carbon north of the polar front (PF) as large as the upwelling in the south. The limiting micronutrient iron is brought into the surface layer by upwelling and stimulates phytoplankton growth and export production but only in summer. This leads to a drawdown of carbon and less summertime outgassing (or more uptake) of natural CO2. In winter, biological mechanisms are inactive, and the surface ocean equilibrates with the atmosphere by releasing CO2. In the annual mean, the upper ocean region south of the PF loses more carbon by additional export production than by the release of CO2 into the atmosphere, highlighting the role of the biological carbon pump in response to a positive SAM event.

Description: We combined data sets of measured sedimentary calcium carbonate (CaCO3) and satellite-derived pelagic primary production to parameterize the relation between CaCO3 content on the Antarctic shelves and primary production in the overlying water column. CaCO3 content predicted in this way was in good agreement with the measured data. The parameterization was then used to chart CaCO3 content on the Antarctic shelves all around the Antarctic, using the satellite-derived primary production. The total inventory of CaCO3 in the bioturbated layer of Antarctic shelf sediments was estimated to be 0.5 Pg C. This quantity is comparable to the total CO2 uptake by the Southern Ocean in only one to a few years (dependent on the uptake estimate and area considered), indicating that the dissolution of these carbonates will neither delay ocean acidification in this area nor augment the Southern Ocean CO2 uptake capacity.

Description: The major part of dissolved iron (DFe) in seawater is bound to organic matter, which prevents iron from adsorptive removal by sinking particles and essentially regulates the residence time of DFe and its availability for marine biota. Characteristics of iron‐binding ligands highly depend on their biological origin and physico‐chemical properties of seawater which may intensely alter under ongoing climate change. To understand environmental controls on the iron binding, we applied a function of pH and dissolved organic carbon (DOC) to describe changes in the binding strength of organic ligands in a global biogeochemical model (REcoM). This function was derived based on calculations using a thermodynamic chemical speciation model NICA. This parameterization considerably improved the modeled DFe distribution, particularly in the surface Pacific and the global mesopelagic and deep waters, compared to our previous model simulations with a constant ligand or one prognostic ligand. This indicates that the organic binding of iron is apparently controlled by seawater pH in addition to its link to organic matter. We tested further the response of this control to environmental changes in a simulation with future pH of a high emission scenario. The response of the binding potential shows a complex pattern in different regions and is regulated by factors that have opposite effects on the binding potential. The relative contributions of these factors can change over time by a continual change of environmental conditions. A dynamic feedback system therefore needs to be considered to predict the marine iron cycle under ongoing climate change.

Description: The influence of the overturning circulation on the anthropogenic carbon sink in the North Atlantic is investigated with a simple box model. The net air-sea flux of anthropogenic carbon in the North Atlantic is the result of two opposing fluxes: The first is the uptake caused by the disequilibrium between the rapidly rising atmospheric pCO2 and the dissolved carbon content in the ocean, depending mainly on the water exchange rate between mixed layer and interior North Atlantic ocean. Superimposed is a second flux, related to the northward transport of heat within the Atlantic basin, that is directed out of the ocean, contrary to conventional wisdom. It is caused by a latitudinal gradient in the ratio of seawater alkalinity to total dissolved inorganic carbon that in turn is related to the cooling and freshening of surface water on its way north. This flux depends strongly on the vertical structure of the upper branch of the overturning circulation and on the distribution of undersaturation and supersaturation of CO2 in Atlantic surface waters. A data-based estimate of anthropogenic carbon inventory in the North Atlantic is consistent with a dominance of the disequilibrium flux over the heat-flux-related outgassing at the present time, but, in our model, does not place a strong constraint on the net anthropogenic air-sea flux. Stabilization of the atmospheric pCO2 on a higher level will change the relative role of the two opposing fluxes, making the North Atlantic a source of anthropogenic carbon to the atmosphere. We discuss implications for the interpretation of numerical carbon cycle models.

Description: Mineral dust aerosol constitutes an important component of the Earth's climate system, not only on short timescales due to direct and indirect influences on the radiation budget but also on long timescales by acting as a fertilizer for the biosphere and thus affecting the global carbon cycle. For a quantitative assessment of its impact on the global climate, state-of-the-art atmospheric and aerosol models can be utilized. In this study, we use the ECHAM6.3-HAM2.3 model to perform global simulations of the mineral dust cycle for present-day (PD), pre-industrial (PI), and last glacial maximum (LGM) climate conditions. The intercomparison with marine sediment and ice core data, as well as other modeling studies, shows that the obtained annual dust emissions of 1221, 923, and 5159 Tg for PD, PI, and LGM, respectively, generally agree well with previous findings. Our analyses focusing on the Southern Hemisphere suggest that over 90 % of the mineral dust deposited over Antarctica are of Australian or South American origin during both PI and LGM. However, contrary to previous studies, we find that Australia contributes a higher proportion during the LGM, which is mainly caused by changes in the precipitation patterns. Obtained increased particle radii during the LGM can be traced back to increased sulfate condensation on the particle surfaces as a consequence of longer particle lifetimes. The meridional transport of mineral dust from its source regions to the South Pole takes place at different altitudes depending on the grain size of the dust particles. We find a trend of generally lower transport heights during the LGM compared to PI as a consequence of reduced convection due to colder surfaces, indicating a vertically less extensive Polar cell.

Description: Among mechanisms accounting for atmospheric pCO2 drawdown during glacial periods, processes operating in the North Atlantic (NA) and Southern Ocean (SO) have been proposed to be critical. Their individual and synergic effects during a course of glaciation, however, remain enigmatic. We conducted simulations to examine these effects at idealized glacial stages. Under early-glacial-like conditions, cooling in the SO can trigger an initial pCO2 drawdown while the associated sea ice expansion has little impact on air-sea gas exchange. Under later glacial-like conditions, further cooling in the NA enhances ocean carbon uptake due to a stronger solubility pump, and the SO-induced stronger deep stratification prevents carbon exchange between the deep and upper ocean. Meanwhile, strengthened dust deposition increases the SO contribution to the global biological pump, and CO2 outgassing is suppressed by fully extended sea ice cover. More carbon is then stored in the deep Pacific, acting as a passive reservoir.

Description: In this paper we describe the implementation of the carbon isotopes 13C and 14C (radiocarbon) into the marine biogeochemistry model REcoM3. The implementation is tested in long-term equilibrium simulations where REcoM3 is coupled with the ocean general circulation model FESOM2.1, applying a low-resolution configuration and idealized climate forcing. Focusing on the carbon-isotopic composition of dissolved inorganic carbon (δ13CDIC and Δ14CDIC), our model results are largely consistent with reconstructions for the pre-anthropogenic period. Our simulations also exhibit discrepancies, e.g. in upwelling regions and the interior of the North Pacific. Some of these differences are due to the limitations of our ocean circulation model setup, which results in a rather shallow meridional overturning circulation. We additionally study the accuracy of two simplified modelling approaches for dissolved inorganic 14C, which are faster (15 % and about a factor of five, respectively) than the complete consideration of the marine radiocarbon cycle. The accuracy of both simplified approaches is better than 5 %, which should be sufficient for most studies of Δ14CDIC.