Search

The results of an existing one-dimensional diagnostic model that calculates the fugacity of CO 2 (fCO 2 ) in the surface layer of the southern ocean were compared with in situ observations from different ocean sectors and seasons. Our model is based on the translation of monthly variations of constraints fields into surface water fCO 2 variations, and was used to assess the CO 2 uptake of the southern ocean. In situ observations are useful to verify the model results and were here applied to improve the estimation of the CO 2 uptake of the southern ocean south of 50 S. The model reproduces the fCO 2 distribution in both Pacific and Indian sectors of the southern ocean satisfactorily, the mean deviation being only 5 μatm. This diserepancy requires only a minor modification of the CO 2 uptake calculated by the model for that area. By contrast, the model strongly underestimates the fCO 2 levels in carly spring and early winter in the Weddell gyre. This indicates that the CO 2 uptake by the Atlantic sector of the southern ocean as calculated by the model, amounting to 0.47 GtC yr -1 . should be reduced, possibly by about half of this value. The reason for this mismatch lies in the use of climatological physical constraints by the model, that do not sufficiently well describe reality. Partly, the mismatch is also caused by a difference of seasonal stage between the model which reflects climatological conditions and the real ocean which is affected by interannual variability. Based on this study it is concluded that the CO 2 uptake of the southern ocean south of 50 S is likely to lie somewhere between 0.6 and 0.7 GtC yr -1 for the 1990s, which is a high value compared to estimates from other investigations.

Foraminifera are the most important source of information for oceanographic and climatic reconstruction on glacial–interglacial as well as on much longer time-scales. The information is contained in the chemical composition, especially the isotopic ratios, of the calcitic shells (e.g., δ 11 B , δ 13 C , δ 18 O ). Based on the assumption that our understanding of the major parameters controlling stable isotope incorporation is complete, these geochemical proxies have been used to reconstruct glacial ice volumes, sea surface and deep water temperatures, ocean circulation changes and shifts between carbon reservoirs. However, recent laboratory experiments have demonstrated that the δ 13 C and δ 18 O are not only strongly dependent on the carbonate chemistry of the culture medium but that the so-called `vital-effects' are probably mediated via perturbations of the local carbonate system. These findings have an important impact on the interpretation of isotope data. For instance, the carbonate system of the glacial ocean was quite different from that of the Holocene and since the onset of the industrial revolution the carbonate chemistry of the surface water must have changed drastically. As a first step towards a better understanding of the isotopic fractionation processes we present results of a diffusion-reaction model of the carbonate system (CO2, HCO3−, CO32−, H+, OH−, B(OH)3, B(OH)4−) in the microenvironment (the diffusive boundary layer) of living planktic foraminifera. The carbon fluxes associated with the main life processes (calcification, respiration and symbiont photosynthesis) lead to substantial perturbations in pH and significant shifts in the concentrations of CO2, CO32− and other components in the vicinity of the foraminifer. Consequently, the carbonate chemistry of the ambient environment is quite different from that of the bulk sea water. Comparison with pH-microelectrode measurements confirm our numerical results. Our results further demonstrate that the symbionts must use bicarbonate as an additional carbon source for photosynthesis as the calculated CO2 fluxes are not sufficient to support measured rates of oxygen evolution. The simulations also show that for the fast calcification of Globigerinoides sacculifer the supply of carbonate ions is insufficient and therefore use of bicarbonate or an internal pool for carbon is required, whereas no such pool is necessary for the much slower calcification in Orbulina universa.

International audience; Antarctic and Southern Ocean (ASO) marine ecosystems have been changing for at least the last 30 years, including in response to increasing ocean temperatures and changes in the extent and seasonality of sea-ice; the magnitude and direction of these changes differ between regions around Antarctica that could see populations of the same species changing differently in different regions. This paper reviews current and expected changes in ASO physical habitats in response to climate change. It then reviews how these changes may impact the autecology of marine biota of this polar region: microbes, zooplankton, salps, Antarctic krill, fish, cephalopods, marine mammals, seabirds, and benthos. The general prognosis for ASO marine habitats is for an overall warming and freshening, strengthening of westerly winds, with a potential pole-ward movement of those winds and the frontal systems, and an increase in ocean eddy activity. Many habitat parameters will have regionally specific changes, particularly relating to sea-ice characteristics and seasonal dynamics. Lower trophic levels are expected to move south as the ocean conditions in which they are currently found move pole-ward. For Antarctic krill and finfish, the latitudinal breadth of their range will depend on their tolerance of warming oceans and changes to productivity. Ocean acidification is a concern not only for calcifying organisms, but also for crustaceans such as Antarctic krill; it is also likely to be the most important change in benthic habitats over the coming century. For marine mammals and birds, the expected changes primarily relate to their flexibility in moving to alternative locations for food and the energetic cost of longer or more complex foraging trips for those that are bound to breeding colonies. Few species are sufficiently well studied to make comprehensive species-specific vulnerability assessments possible. Priorities for future work are discussed. This article is protected by copyright. All rights reserved.

Over the last four decades, different hypotheses of Ca(2+) and dissolved inorganic carbon transport to the intracellular site of calcite precipitation have been put forth for Emiliania huxleyi (Lohmann) HayMohler. The objective of this study was to assess these hypotheses by means of mathematical models. It is shown that a vesicle-based Ca(2+) transport would require very high intravesicular Ca(2+) concentrations, high vesicle fusion frequencies as well as a fast membrane recycling inside the cell. Furthermore, a kinetic model for the calcification compartment is presented that describes the internal chemical environment in terms of carbonate chemistry including calcite precipitation. Substrates for calcite precipitation are transported with different stoichiometries across the compartment membrane. As a result, the carbonate chemistry inside the compartment changes and hence influences the calcification rate. Moreover, the effect of carbonic anhydrase (CA) activity within the compartment is analyzed. One very promising model version is based on a Ca(2+) /H(+) antiport, CO2 diffusion, and a CA inside the calcification compartment. Another promising model version is based on an import of Ca(2+) and HCO3 (-) and an export of H(+) .

[1] 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.

Assmy, Philipp ... et. al.-- 6 pages, 4 figures, Diatoms of the iron-replete continental margins and North Atlantic are key exporters of organic carbon. In contrast, diatoms of the iron-limited Antarctic Circumpolar Current sequester silicon, but comparatively little carbon, in the underlying deep ocean and sediments. Because the Southern Ocean is the major hub of oceanic nutrient distribution, selective silicon sequestration there limits diatom blooms elsewhere and consequently the biotic carbon sequestration potential of the entire ocean. We investigated this paradox in an in situ iron fertilization experiment by comparing accumulation and sinking of diatom populations inside and outside the iron-fertilized patch over 5 wk. A bloom comprising various thin- and thick-shelled diatom species developed inside the patch despite the presence of large grazer populations. After the third week, most of the thinner-shelled diatom species underwent mass mortality, formed large, mucous aggregates, and sank out en masse (carbon sinkers). In contrast, thicker-shelled species, in particular Fragilariopsis kerguelensis, persisted in the surface layers, sank mainly empty shells continuously, and reduced silicate concentrations to similar levels both inside and outside the patch (silica sinkers). These patterns imply that thick-shelled, hence grazer-protected, diatom species evolved in response to heavy copepod grazing pressure in the presence of an abundant silicate supply. The ecology of these silica-sinking species decouples silicon and carbon cycles in the iron-limited Southern Ocean, whereas carbon- sinking species, when stimulated by iron fertilization, export more carbon per silicon. Our results suggest that large-scale iron fertilization of the silicate-rich Southern Ocean will not change silicon sequestration but will add carbon to the sinking silica flux, P.A. was supported through Deutsche Forschungsgemeinschaft–Cluster of Excellence “The Ocean in the Earth System” and the Centre for Ice, Climate and Ecosystems at the Norwegian Polar Institute

A predictive model of carbon isotope fractionation (sigma p) and abundance (delta13C phyto) is presented under circumstances where photosynthesis is strictly based on CO2(aq) that passively diffuses into marine phytoplankton cells. Similar to other recent models, the one presented here is based on a formulation where the expression of intracellular enzymatic isotope fractionation relative to that imposed by CO2(aq) transport is scaled by the ratio of intracellular to external [CO2(aq)], ci/ce. Unlike previous models, an explicit calculation of ci is made that is dependent on ce as well as cell radius, cell growth rate, cell membrane permeability to CO2(aq), temperature, and, to a limited extent, pH and salinity. This allows direct scaling of ci/ce to each of these factors, and thus a direct prediction of sigma p and delta13C phyto responses to changes in each of these variables. These responses are described, and, where possible, compared to recent experimental and previous modeling results.

International audience; Fertilization of the ocean by adding iron compounds has induced diatom-dominated phytoplankton blooms accompanied by considerable carbon dioxide drawdown in the ocean surface layer. However, because the fate of bloom biomass could not be adequately resolved in these experiments, the timescales of carbon sequestration from the atmosphere are uncertain. Here we report the results of a five-week experiment carried out in the closed core of a vertically coherent, mesoscale eddy of the Antarctic Circumpolar Current, during which we tracked sinking particles from the surface to the deep-sea floor. A large diatom bloom peaked in the fourth week after fertilization. This was followed by mass mortality of several diatom species that formed rapidly sinking, mucilaginous aggregates of entangled cells and chains. Taken together, multiple lines of evidence--although each with important uncertainties--lead us to conclude that at least half the bloom biomass sank far below a depth of 1,000 metres and that a substantial portion is likely to have reached the sea floor. Thus, iron-fertilized diatom blooms may sequester carbon for timescales of centuries in ocean bottom water and for longer in the sediments.

Photosynthesis, respiration, N(2) fixation and ammonium release were studied directly in Nodularia spumigena during a bloom in the Baltic Sea using a combination of microsensors, stable isotope tracer experiments combined with nanoscale secondary ion mass spectrometry (nanoSIMS) and fluorometry. Cell-specific net C- and N(2)-fixation rates by N. spumigena were 81.6±6.7 and 11.4±0.9 fmol N per cell per h, respectively. During light, the net C:N fixation ratio was 8.0±0.8. During darkness, carbon fixation was not detectable, but N(2) fixation was 5.4±0.4 fmol N per cell per h. Net photosynthesis varied between 0.34 and 250 nmol O(2) h(-1) in colonies with diameters ranging between 0.13 and 5.0 mm, and it reached the theoretical upper limit set by diffusion of dissolved inorganic carbon to colonies (1 mm). Dark respiration of the same colonies varied between 0.038 and 87 nmol O(2) h(-1), and it reached the limit set by O(2) diffusion from the surrounding water to colonies (1 mm). N(2) fixation associated with N. spumigena colonies (1 mm) comprised on average 18% of the total N(2) fixation in the bulk water. Net NH(4)(+) release in colonies equaled 8-33% of the estimated gross N(2) fixation during photosynthesis. NH(4)(+) concentrations within light-exposed colonies, modeled from measured net NH(4)(+) release rates, were 60-fold higher than that of the bulk. Hence, N. spumigena colonies comprise highly productive microenvironments and an attractive NH(4)(+) microenvironment to be utilized by other (micro)organisms in the Baltic Sea where dissolved inorganic nitrogen is limiting growth.

Schuiling et al. (1) question our conclusion (2) that the annual dissolution rate of olivine is limited by the saturation of waters with silicic acid (H4SiO4), which is one product of the dissolution reaction of olivine. In support of this point they discuss findings of CO2 sequestration in a mine in Yukon, Canada, claiming that a minimum of 1,700 g C m−2 y−1 was sequestered between 1978 and 2004 by silicate weathering and precipitation of (mainly) magnesium carbonates (3). This value is approximately …

International audience; 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 biogeochemi-cal 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 depo-Correspondence to: Y. Ye (ying.ye@awi.de) sition 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.

We studied the evolution of the isotopic composition of dissolved Si (d30SiDSi) and biogenic Si (d30SiBSi) during a diatom bloom induced by an iron fertilization experiment in a Southern Ocean (SO) eddy. Dissolved Si (DSi) consumption was clearly boosted as a result of iron addition. We estimate an apparent Si isotopic fractionation factor of -1.36 parts per thousand +/- 0.11 parts per thousand, not significantly different from estimates based on in vitro incubations under Fe-replete conditions and in agreement with previous SO studies under Fe-depleted conditions. The temporal variations of the d30Si are best reconstructed considering the fertilized surface waters as an open system, i.e., DSi is continuously supplied from the winter water. Using vertical diffusivity, we estimate a supply of 6.7 +/- 1.2 mmol Si m-2 d-1 representing 30% +/- 5% of total DSi demand. We estimate biogenic silica (BSi) production at 22.1 +/- 1.8 mmol Si m-2 d-1, similar to BSi production under natural conditions in the SO. The DSi use preceding the start of the fertilization was conservatively estimated at 49% +/- 4%, and as a result of the Fe-fertilization, a further 31% +/- 4% of the initial DSi reservoir was consumed. The BSi export was estimated to be 17.4 +/- 1.7 mmol Si m-2 d-1. Our results suggest that for this study three main processes were acting significantly on d30Si signatures, biological uptake, Si supply from subsurface, and export of BSi, and that the magnitude of production and export in such a Fe-fertilized experiment are similar to those for natural diatom blooms occurring in the Southern Ocean.

The numerical modelling community is an important user group of ocean observations requiring data of global coverage for model parameterisation and evaluation. Dynamic Green Ocean Models (DGOMs) are a class of ocean biogeochemistry models that represent various types of plankton with distinct functions in food webs and biogeochemical cycles. DGOMs are used to study the feedbacks between climate and ocean biogeochemistry, particularly those mediated by ecosystem dynamics that influence CO2, DMS, and N2O fluxes to and from the atmosphere. DGOMs require experimental data for the parameterization of plankton growth and loss rates and of ecological interactions, and a range of observations for their evaluation. The most urgent data needs are: (1) decadal trends in surface ocean pCO2 and subsurface O2, (2) biomass (in carbon concentration) and (3) growth rates as a function of temperature for the important plankton types, and (4) sinking flux of particulate organic carbon. A global coverage is essential to evaluate the model mean state. Repeated measurements for all seasons are most useful to evaluate the model response to environmental change. These data can be obtained by a combination of platforms, including remote sensing, repeat sections and gliders, and oceanic and atmospheric time-series stations.

Seawater carbonate chemistry is typically calculated from two measured parameters. Depending on the choice of these input parameters, discrepancies in calculated pCO2 have been recognized by marine chemists, but the significance of this phenomenon for CO2 perturbation experiments has so far not been determined. To mimic different pCO2 scenarios, two common perturbation methods for seawater carbonate chemistry (changing either DIC or TA) were applied using state-of-the-art protocols and equipment. The carbonate system was over-constrained by measuring DIC, TA, pH, and pCO2. Calculated pCO2 matched measured pCO2 if pH and TA or pH and DIC were chosen as input parameters, whereas pCO2 calculated from TA and DIC was considerably lower than measured values. This has important implications for CO2 perturbation experiments. First, calculated pCO2 values may not be comparable if different input parameters were used. Second, responses of organisms to acidification may be overestimated when using TA and DIC for calculations. This is especially troublesome for experiments with calcifiers, as carbonate ion concentration and thus calcite or aragonite saturation state are overestimated. We suggest refraining from measuring TA and DIC only and rather include pH as input parameter for carbonate chemistry calculations.

In this laboratory study, we monitored the buildup of biomass and concomitant shift in seawater carbonate chemistry over the course of a Trichodesmium bloom under different phosphorus (P) availability. During exponential growth, dissolved inorganic carbon (DIC) decreased, while pH increased until maximum cell densities were reached. Once P became depleted, DIC decreased even further and total alkalinity (TA) dropped, accompanied by precipitation of aragonite. Under P-replete conditions, DIC increased and TA remained constant in the postbloom phase. A diffusion-reaction model was employed to estimate changes in carbonate chemistry of the diffusive boundary layer. This study demonstrates that Trichodesmium can induce precipitation of aragonite from seawater and further provides possible explanations about underlying mechanisms.

Lattice-gas cellular automaton (LGCA) and lattice Boltzmann (LB) models are promising models for studying emergent behaviour of transport and interaction processes in biological systems. In this chapter, we will emphasise the use of LGCA/LB models and the derivation and analysis of LGCA models ranging from the classical example dynamics of fluid flow to clotting phenomena in cerebral aneurysms and the invasion of tumour cells.

Geoengineering is a proposed action to manipulate Earth’s climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO 2 sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of p H values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1–5 Pg of C per year for the 21st century by this technique.

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.

[1] We report on the discovery of the mineral ikaite (CaCO3·6H2O) in sea-ice from the Southern Ocean. The precipitation of CaCO3 during the freezing of seawater has previously been predicted from thermodynamic modelling, indirect measurements, and has been documented in artificial sea ice during laboratory experiments but has not been reported for natural sea-ice. It is assumed that CaCO3 formation in sea ice may be important for a sea ice-driven carbon pump in ice-covered oceanic waters. Without direct evidence of CaCO3 precipitation in sea ice, its role in this and other processes has remained speculative. The discovery of CaCO3·6H2O crystals in natural sea ice provides the necessary evidence for the evaluation of previous assumptions and lays the foundation for further studies to help elucidate the role of ikaite in the carbon cycle of the seasonally sea ice-covered regions

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.

Blooms of the coccolithophorid Emiliania huxleyi can be infected by viruses, which can lead to bloom-termination. This pilot study used an expressed sequence tag (EST) approach to get a first view of gene-expression changes that occur during viral infection of E. huxleyi. cDNA libraries were constructed from uninfected cultures and 6, 12, and 24 h after infection with E. huxleyi-specific virus 86 (EhV-86). From each library 60-90 ESTs were randomly selected and annotated manually with PhyloGena. Viral genes were identified using BLAST-Search of the known viral genome. The data of this study show, that 6 h after viral infection the algal transcriptome changed significantly although few viral transcripts were present. At this point, changes mainly concerned transcripts related to photosynthesis and protein metabolism. However, after 24 h viral transcripts were most abundant. Viral transcripts found at this stage of viral infection encode proteins involved in protein degradation, nucleic acid degradation, transcription and replication.

By means of numerical modeling, we analyze the cycling of iron between its various physical (dissolved, colloidal, particulate) and chemical (redox state and organic complexation) forms in the upper mixed layer. With our proposed model it is possible to obtain a first quantitative assessment of how this cycling influences iron uptake by phytoplankton and its loss via particle export. The model is forced with observed dust deposition rates, mixed layer depths, and solar radiation at the site of the Bermuda Atlantic Time-series Study (BATS). It contains an objectively optimized ecosystem model which yields results close to the observational data from BATS that has been used for the data-assimilation procedure. It is shown that the mixed layer cycle strongly influences the cycling of iron between its various forms. This is mainly due to the light dependency of photoreductive processes, and to the seasonality of primary production. The daily photochemical cycle is driven mainly by the production of superoxide, and its amplitude depends on the concentration and speciation of dissolved copper. Model results are almost insensitive to the dominant form of dissolved iron within dust deposition, and also to the form of iron that is taken up directly during algal growth. In our model solutions, the role of the colloidal pumping mechanism depends strongly on assumptions on the colloid aggregation and photoreduction rate.

Ecosystem processes are important determinants of the biogeochemistry of the ocean, and they can be profoundly affected by changes in climate. Ocean models currently express ecosystem processes through empirically derived parameterizations that tightly link key geochemical tracers to ocean physics. The explicit inclusion of ecosystem processes in models will permit ecological changes to be taken into account, and will allow us to address several important questions, including the causes of observed glacial-interglacial changes in atmospheric trace gases and aerosols, and how the oceanic uptake of CO2 is likely to change in the future. There is an urgent need to assess our mechanistic understanding of the environmental factors that exert control over marine ecosystems, and to represent their natural complexity based on theoretical understanding. We present a prototype design for a Dynamic Green Ocean Model (DGOM) based on the identification of (a) key plankton functional types that need to be simulated explicitly to capture important biogeochemical processes in the ocean; (b) key processes controlling the growth and mortality of these functional types and hence their interactions; and (c) sources of information necessary to parameterize each of these processes within a modeling framework. We also develop a strategy for model evaluation, based on simulation of both past and present mean state and variability, and identify potential sources of validation data for each. Finally, we present a DGOM-based strategy for addressing key questions in ocean biogeochemistry. This paper thus presents ongoing work in ocean biogeochemical modeling, which, it is hoped will motivate international collaborations to improve our understanding of the role of the ocean in the climate system.

International audience; Marine diatoms take up silicic acid for the buildup of their opaline shells and discriminate against the heavier silicon isotope. For the first time, the overall oceanic distribution of silicon isotopes has been estimated by integration of the Hamburg Model of the Ocean Carbon Cycle, version 4 (HAMOCC4). It is shown that the relationship between the silicic acid concentration and its silicon isotope composition is not a simple Rayleigh distillation curve. Only the Southern Ocean and the equatorial Pacific show a clear functional dependency similar to the Rayleigh distillation curve. Model results can be used to predict opal silicon isotope compositions in the sediment and constrain the use of silicon isotopes as a proxy for silicic acid utilization. Owing to the structure of the Pacific current system, it might be valid to apply a relationship between surface silicic acid concentrations and the silicon isotope signal in the equatorial Pacific sediments.

The stable boron isotope composition (δ11B) of fossil foraminiferal shells is used as a paleo-pH recorder and is therefore one of the most promising paleocarbonate chemistry proxies (“paleoacidimetry”). One crucial question regarding this proxy is whether foraminifera record the pH of the bulk seawater or the pH of the microenvironment (diffusive boundary layer, ∼500 μm), which is strongly influenced by life processes. Here we present a novel theoretical approach to address this question by using a diffusion-reaction model. Model results indicate that the δ11B in planktonic foraminifera is primarily controlled by the pH of the microenvironment. We therefore predict that the δ11B of different species (e.g., symbiont-bearing versus symbiont-barren) or of foraminifera grown in the dark and in the light should be offset from the δ11B of inorganic calcite. This theoretical prediction was experimentally confirmed while this paper was written [Honisch et al., 2003]. Most importantly, the model predicts that this offset is constant over a wide pH range. Thus the use of δ11B as a paleo-pH indicator is not compromised through vital effects as modeled here.

Biotic and abiotic processes, climate change, regional and global environmental issues, greenhouse gas emission, stratospheric ozone depletion, loss of biodiversity, desertification, freshwater availability, and air quality are all inter-linked. Understanding the driving forces and feedback mechanisms of these processes is essential for understanding the evolution and future of the earth, the environment, and society. It is important to realize that the ocean's carbon cycle plays an important role in the global element fluxes. In the following, we look at two major processes representing a sink for carbon in the ocean: 1) sedimentation of biogenic carbonate from productive surface waters, and 2) carbon sequestration by methane oxidation above gashydrate and other sites of methane seepage. We point out the necessity to monitor and understand the submarine environments at the interface between the geo- and biosphere.

THE supply of dissolved inorganic carbon (DIC) is not considered to limit oceanic primary productivity1, as its concentration in sea water exceeds that of other plant macronutrients such as nitrate and phosphate by two and three orders of magnitude, respectively. But the bulk of oceanic new production2 and a major fraction of vertical carbon flux is mediated by a few diatom genera whose ability to use DIG components other than CO2, which comprises < 1% of total DIC3, is unknown4. Here we show that under optimal light and nutrient conditions, diatom growth rate can in fact be limited by the supply of CO2. The doubling in surface water pCO2 levels since the last glaciation from 180 to 355 p.p.m.5,6 could therefore have stimulated marine productivity, thereby increasing oceanic carbon sequestration by the biological pump.

Fossil foraminiferal shells are utilized in paleoceanography to extract information about environmental conditions of the past ocean. Based on several assumptions, the ratio of 13 C and 12 C preserved in their shells is used to reconstruct, for example, the paleoproductivity or the oceanic pCO2. Metabolism of the living organism and the sea water chemistry, however, can influence the incorporation of carbon isotopes during calcification such that the signal of the shells differ from the signal of the sea water. These effects occur because the chemical microenvironment of the foraminifer (boundary layer thickness ∼500 μm) differs from the bulk sea water. Here, we present a numerical model that calculates the δ 13 C of the foraminiferal shell as a function of the sea water chemistry and the magnitude of vital effects. Concentration profiles of the chemical species of the carbonate system within the microenvironment of foraminifera are obtained by solving diffusion-reaction equations. The compounds of dissolved forms of carbon dioxide containing either the stable carbon isotope 13 C or 12 C are considered separately. Spherical symmetry of the foraminifer is assumed. The model outcome is compared to results from culture experiments with the planktonic foraminifer Orbulina universa. Model results indicate that the interaction between vital effects of the foraminifer and the sea water chemistry can account for changes in the δ 13 C of foraminiferal calcite of 0.3–0.4‰ when glacial and interglacial sea water conditions are compared. These effects occur even though the δ 13 C of the total dissolved inorganic carbon is kept constant. Thus, changes in sea water chemistry should be distinguished from events which changed the δ 13 C of the inorganic carbon of the sea water.

Diatoms have evolved a multitude of morphologies, including highly elongated cells and cell chains. Elongation and chain formation have many possible functions, such as grazing protection or effects on sinking. Here, a model of diffusive and advective nutrient transport is used to predict impacts of cell shape and chain length on potential nutrient supply and uptake in a turbulent environment. Rigid, contiguous, prolate spheroids thereby represent the shapes of simple chains and solitary cells. Ar scales larger than a few centimeters, turbulent water motions produce a more or less homogeneous nutrient distribution. At the much smaller scale of diatom cells, however, turbulence creates a roughly linear shear and nutrients can locally become strongly depleted because of nutrient uptake by phytoplankton cells. The potential diffusive nutrient supply is greater for elongated than for spherically shaped cells of similar volume but lower for chains than for solitary cells. Although the relative increase in nutrient transport due to turbulence is greater for chains, single cells still enjoy a greater total nutrient supply in turbulent environments, Only chains with specialized structures, such as spaces between the cells, can overcome this disadvantage and even obtain a higher nutrient supply than do solitary cells. The model results are compared to laboratory measurements of nutrient uptake under turbulent conditions and to effects of sinking.

Ongoing global warming induced by anthropogenic emissions has opened the debate as to whether geoengineering is a 'quick fix' option. Here we analyse the intended and unintended effects of one specific geoengineering approach, which is enhanced weathering via the open ocean dissolution of the silicate-containing mineral olivine. This approach would not only reduce atmospheric CO2 and oppose surface ocean acidification, but would also impact on marine biology. If dissolved in the surface ocean, olivine sequesters 0.28 g carbon per g of olivine dissolved, similar to land-based enhanced weathering. Silicic acid input, a byproduct of the olivine dissolution, alters marine biology because silicate is in certain areas the limiting nutrient for diatoms. As a consequence, our model predicts a shift in phytoplankton species composition towards diatoms, altering the biological carbon pumps. Enhanced olivine dissolution, both on land and in the ocean, therefore needs to be considered as ocean fertilization. From dissolution kinetics we calculate that only olivine particles with a grain size of the order of 1 μm sink slowly enough to enable a nearly complete dissolution. The energy consumption for grinding to this small size might reduce the carbon sequestration efficiency by ~30%.

[1] 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.

The results of an existing one-dimensional diagnostic model that calculates the fugacity of CO 2 ( f CO 2 ) in the surface layer of the southern ocean were compared with in situ observations from diVerent ocean sectors and seasons. Our model is based on the translation of monthly variations of constraints fields into surface water f CO 2 variations, and was used to assess the CO 2 uptake of the southern ocean. In situ observations are useful to verify the model results and were here applied to improve the estimation of the CO 2 uptake of the southern ocean south of 50°S. The model reproduces the f CO 2 distribution in both Pacific and Indian sectors of the southern ocean satisfactorily, the mean deviation being only 5 μatm. This discrepancy requires only a minor modification of the CO 2 uptake calculated by the model for that area. By contrast, the model strongly underestimates the f CO 2 levels in early spring and early winter in the Weddell gyre. This indicates that the CO 2 uptake by the Atlantic sector of the southern ocean as calculated by the model, amounting to 0.47 GtC yr −1 , should be reduced, possibly by about half of this value. The reason for this mismatch lies in the use of climatological physical constraints by the model, that do not sufficiently well describe reality. Partly, the mismatch is also caused by a difference of seasonal stage between the model which reflects climatological conditions and the real ocean which is affected by interannual variability. Based on this study it is concluded that the CO 2 uptake of the southern ocean south of 50°S is likely to lie somewhere between 0.6 and 0.7 GtC yr −1 for the 1990s, which is a high value compared to estimates from other investigations. DOI: 10.1034/j.1600-0889.1999.00029.x

The assessment of direct effects of anthropogenic CO 2 increase on the marine biota has received relatively little attention compared to the intense research on CO 2 -related responses of the terrestrial biosphere. Yet, due to the rapid air–sea gas exchange, the observed past and predicted future rise in atmospheric CO 2 causes a corresponding increase in seawater CO 2 concentrations, [CO 2 ], in upper ocean waters. Increasing [CO 2 ] leads to considerable changes in the surface ocean carbonate system, resulting in decreases in pH and the carbonate concentration, [CO 2 −3 ]. These changes can be shown to have strong impacts on the marine biota. Here we will distinguish between CO 2 -related responses of the marine biota which (a) potentially affect the ocean's biological carbon pumps and (b) are relevant to the interpretation of diagnostic tools (proxies) used to assess climate change on geological times scales. With regard to the former, three direct effects of increasing [CO 2 ] on marine plankton have been recognized: enhanced phytoplankton growth rate, changing elemental composition of primary produced organic matter, and reduced biogenic calcification. Although quantitative estimates of their impacts on the oceanic carbon cycle are not yet feasible, all three effects increase the ocean's capacity to take up and store atmospheric CO 2 and hence, can serve as negative feedbacks to anthropogenic CO 2 increase. With respect to proxies used in palaeo-reconstructions, CO 2 -sensitivity is found in carbon isotope fractionation by phytoplankton and foraminifera. While CO 2 - dependent isotope fractionation by phytoplankton may be of potential use in reconstructing surface ocean p CO 2 at ancient times, CO 2 -related effects on the isotopic composition of foraminiferal shells confounds the use of the difference in isotopic signals between planktonic and benthic shells as a measure for the strength of marine primary production. The latter effect also offers an alternative explanation for the large negative swings in δ 13 C of foraminiferal calcite between glacial and interglacial periods. Changes in [CO 2 −3 ] affect the δ 18 O in foraminiferal shells. Taking this into account brings sea surface temperature estimates for the glacial tropics closer to those obtained from other geochemical proxies. DOI: 10.1034/j.1600-0889.1999.00023.x

A numerical model is proposed for investigatingthe potential of calcium carbonatedissolution in copepod guts. A sensitivityanalysis is performed to reveal criticalparameters. Gut clearance rate is dependent ontemperature and grazing rate and determines thetime scale on which ingested calcite is subjectto dissolution. Highest dissolution isobtained when the individual zooplankton isalternating between grazing and non-grazing and feedingis restricted to the night-time period. Model resultsshow that up to 70% of the ingested carbonate may bedissolved in the guts, considering reingestion of faecalpellets in the absence of a phytoplanktonbloom, while approximately15% dissolution is to be expectedin a bloom situation. An estimate is made for the contributionof calcite dissolution in copepod guts to the proposed globalcalcite loss in the water column.

Lake eutrophication is a pervasive problem globally, particularly serious in agricultural and densely populated areas. Whenever nutrients nitrogen and phosphorus do not limit phytoplankton growth directly, high growth rates will rapidly lead to biomass increases causing self-shading and light-limitation, and eventually CO2 depletion. The paradigm of phytoplankton limitation by nutrients and light is so pervasively established, that the lack of nutrient limitation is ordinarily interpreted as sufficient evidence for the condition of light limitation, without considering the possibility of limitation by inorganic carbon. Here, we firstly evaluated how frequently CO2 undersaturation occurs in a set of eutrophic lakes in the Pampa plains. Our results confirm that conditions of CO2 undersaturation develop much more frequently (yearly 34%, summer 44%) in these agriculturally impacted lakes than in deep, temperate lakes in forested watersheds. Secondly, we used Generalized Additive Models to fit trends in CO2 concentration considering three drivers: total incident irradiance, chlorophyll a concentration, and lake depth; in eight multi-year datasets from eutrophic lakes from Europe, North and South America, Asia and New Zealand. CO2 depletion was more often observed at high irradiance levels, and shallow water. CO2 depletion also occurred at high chlorophyll concentration. Finally, we identified occurrences of light- and carbon-limitation at the whole-lake scale. The different responses of chlorophyll a and CO2 allowed us to develop criteria for detecting conditions of CO2 limitation. For the first time, we provided whole-lake evidence of carbon limitation of phytoplankton biomass. CO2 increases and eutrophication represent two major and converging environmental problems that have additive and contrasting effects, promoting phytoplankton, and also leading to carbon depletion. Their interactions deserve further exploration and imaginative approaches to deal with their effects.