Phytoplankton composition derived from CHEMTAX along 10°E during POLARSTERN cruise ANT-XXVIII/3, Jan-March 2012

Phytoplankton community structure and their physiological response in the vicinity of the Antarctic Polar Front (APF; 44°S to 53°S, centred at 10°E) were investigated as part of the ANT-XXVIII/3 Eddy-Pump cruise conducted in austral summer 2012. Our results show that under iron-limited (< 0.3 µmol/m**3) conditions, high total chlorophyll-a (TChl-a) concentrations (> 0.6 mg/m**3) can be observed at stations with deep mixed layer (> 60 m) across the APF. In contrast, light was excessive at stations with shallower mixed layer and phytoplankton were producing higher amounts of photoprotective pigments, diadinoxanthin (DD) and diatoxanthin (DT), at the expense of TChl-a, resulting in higher ratios of (DD+DT)/ TChl-a. North of the APF, significantly lower silicic acid (Si(OH)4) concentrations (< 2 mmol/m**3) lead to the domination of nanophytoplankton consisting mostly of haptophytes, which produced higher ratios of (DD+DT)/TChl-a under relatively low irradiance conditions. The Si(OH)4 replete (> 5 mmol/m**3) region south of the APF, on the contrary, was dominated by microphytoplankton (diatoms and dinoflagellates) with lower ratios of (DD+DT)/TChl-a, despite having been exposed to higher levels of irradiance. The significant correlation between nanophytoplankton and (DD+DT)/TChl-a indicates that differences in taxon-specific response to light are also influencing TChl-a concentration in the APF during summer. Our results reveal that provided mixing is deep and Si(OH)4 is replete, TChl-a concentrations higher than 0.6 mg/m**3 are achievable in the iron-limited APF waters during summer.

Middle Miocene evolution and stable isotope ratios of Globorotalia (Fohsella) in the western equatorial Pacific

Evolution of the planktic foraminiferal lineage Globorotalia (Fohsella) occurred during the Miocene between 23.7 and 11.8 Ma and forms the basis for stratigraphic subdivision of the early middle Miocene (Zones N 10 through N 12). Important morphologic changes within the G. (Fohsella) lineage included a marked increase in test size, a transition from a rounded to an acute periphery, and the development of a keel in later forms. We found that the most rapid changes in morphology of G. (Fohsella) occurred between 13 and 12.7 Ma and coincided with an abrupt increase in the delta18O ratios of shell calcite. Comparison of isotopic results of G. (Fohsella) with other planktic foraminifers indicate that delta18O values of the lineage diverge from surface-dwelling species and approach deep-dwelling species after 13.0 Ma, indicating a change in depth habitat from the surface mixed layer to intermediate depth near the thermocline. Isotopic and faunal evidence suggests that this change in depth stratification was associated with an expansion of the thermocline in the western equatorial Pacific. After adapting to a deeper water habitat at 13.0 Ma, the G. (Fohsella) lineage became extinct abruptly at 11.8 Ma during a period when isotopic and faunal evidence suggest a shoaling of the thermocline. Following the extinction of G. (Fohsella), the ecologic niche of the lineage was filled by the Globorotalia (Menardella) group, which began as a deep-water form and later evolved to an intermediate-water habitat. We suggest that the evolution of G. (Fohsella) and G. (Menardella) were tightly linked to changes in the structure of the thermocline in the western equatorial Pacific.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

Evidence for methane production by the marine algae Emiliania huxleyi

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g−1 d−1, or 30 ng g−1 POC h−1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.

Evidence for methane production by the marine algae Emiliania huxleyi

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g−1 d−1, or 30 ng g−1 POC h−1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.

Modeling of burden distribution in the blast furnace

The blast furnace is the main ironmaking production unit in the world which converts iron ore with coke and hot blast into liquid iron, hot metal, which is used for steelmaking. The furnace acts as a counter-current reactor charged with layers of raw material of very different gas permeability. The arrangement of these layers, or burden distribution, is the most important factor influencing the gas flow conditions inside the furnace, which dictate the efficiency of the heat transfer and reduction processes. For proper control the furnace operators should know the overall conditions in the furnace and be able to predict how control actions affect the state of the furnace. However, due to high temperatures and pressure, hostile atmosphere and mechanical wear it is very difficult to measure internal variables. Instead, the operators have to rely extensively on measurements obtained at the boundaries of the furnace and make their decisions on the basis of heuristic rules and results from mathematical models. It is particularly difficult to understand the distribution of the burden materials because of the complex behavior of the particulate materials during charging. The aim of this doctoral thesis is to clarify some aspects of burden distribution and to develop tools that can aid the decision-making process in the control of the burden and gas distribution in the blast furnace. A relatively simple mathematical model was created for simulation of the distribution of the burden material with a bell-less top charging system. The model developed is fast and it can therefore be used by the operators to gain understanding of the formation of layers for different charging programs. The results were verified by findings from charging experiments using a small-scale charging rig at the laboratory. A basic gas flow model was developed which utilized the results of the burden distribution model to estimate the gas permeability of the upper part of the blast furnace. This combined formulation for gas and burden distribution made it possible to implement a search for the best combination of charging parameters to achieve a target gas temperature distribution. As this mathematical task is discontinuous and non-differentiable, a genetic algorithm was applied to solve the optimization problem. It was demonstrated that the method was able to evolve optimal charging programs that fulfilled the target conditions. Even though the burden distribution model provides information about the layer structure, it neglects some effects which influence the results, such as mixed layer formation and coke collapse. A more accurate numerical method for studying particle mechanics, the Discrete Element Method (DEM), was used to study some aspects of the charging process more closely. Model charging programs were simulated using DEM and compared with the results from small-scale experiments. The mixed layer was defined and the voidage of mixed layers was estimated. The mixed layer was found to have about 12% less voidage than layers of the individual burden components. Finally, a model for predicting the extent of coke collapse when heavier pellets are charged over a layer of lighter coke particles was formulated based on slope stability theory, and was used to update the coke layer distribution after charging in the mathematical model. In designing this revision, results from DEM simulations and charging experiments for some charging programs were used. The findings from the coke collapse analysis can be used to design charging programs with more stable coke layers.

Optimizing PAT data transmission: assessing the accuracy of temperature summary data to estimate environmental conditions

Pop-up archival tags (PAT) provide summary and high-resolution time series data at predefined temporal intervals. The limited battery capabilities of PATs often restrict the transmission success and thus temporal coverage of both data products. While summary data are usually less affected by this problem, as a result of its lower size, it might be less informative. We here investigate the accuracy and feasibility of using temperature at depth summary data provided by PATs to describe encountered oceanographic conditions. Interpolated temperature at depth summary data was found to provide accurate estimates of three major thermal water column structure indicators: thermocline depth, stratification and ocean heat content. Such indicators are useful for the interpretation of the tagged animal's horizontal and vertical behaviour. The accuracy of these indicators was found to be particularly sensitive to the number of data points available in the first 100 m, which in turn depends on the vertical behaviour of the tagged animal. Based on our results, we recommend the use of temperature at depth summary data as opposed to temperature time series data for PAT studies; doing so during the tag programming will help to maximize the amount of transmitted time series data for other key data types such as light levels and depth.

Mean structure of the North Atlantic subtropical permanent pycnocline from in-situ observations

In the north Atlantic subtropical gyre, the oceanic vertical structure of density is characterized by a region of rapid increase with depth. This layer is called the permanent pycnocline. The permanent pycnocline is found below a surface mode water ,which are ventilated every winter when penetrated locally by the mixed layer. Assessing the structure and variability of the permanent pycnocline is of a major interest in the understanding of the climate system because the pycnocline layer delimits important heat and anthropogenic reservoir. Moreover, the heat content structure translate into changes in the large scale stratification feature, such as the permanent pycnocline. We developed a new objective algorithm for the characterization of the large scale structure of the permanent pycnocline (OAC-P). Argo data have been used with OAC-P to provide a detailed description of the mean structure of the North-Atlantic subtropical pycnocline (e.g.: depth, thickness, temperature, salinity, density, potential vorticity). Results reveal a surprisingly complex structure with inhomogeneous properties. While the classical bowl shape of the pycnocline depth is captured, much more complex pycnocline structure emerges at the regional scale. In the southern recirculation gyre of the Gulf Stream Extension, the pycnocline is deep, thick, the maximum of stratification is found in the middle on the layer and follow an isopycnal surface. But local processes influence and modify this textbook description and the pycnocline is characterized by a vertically asymmetric structure and gradients in thermohaline properties. T/S distribution along the permanent pycnocline depth is complex and reveals a diversity of water masses resulting from mixing of different source waters. We will present the observed mean structure of the North-Atlantic subtropical permanent pycnocline and relate it to physical processes that constraint it.

On the Movements of the North Atlantic Subpolar Front in the Preinstrumental Past*

Three sediment records of sea surface temperature (SST) are analyzed that originate from distant locations in the North Atlantic, have centennial-to-multicentennial resolution, are based on the same reconstruction method and chronological assumptions, and span the past 15 000 yr. Using recursive least squares techniques, an estimate of the time-dependent North Atlantic SST field over the last 15 kyr is sought that is consistent with both the SST records and a surface ocean circulation model, given estimates of their respective error (co)variances. Under the authors' assumptions about data and model errors, it is found that the 10 degrees C mixed layer isotherm, which approximately traces the modern Subpolar Front, would have moved by ~15 degrees of latitude southward (northward) in the eastern North Atlantic at the onset (termination) of the Younger Dryas cold interval (YD), a result significant at the level of two standard deviations in the isotherm position. In contrast, meridional movements of the isotherm in the Newfoundland basin are estimated to be small and not significant. Thus, the isotherm would have pivoted twice around a region southeast of the Grand Banks, with a southwest-northeast orientation during the warm intervals of the Bolling-Allerod and the Holocene and a more zonal orientation and southerly position during the cold interval of the YD. This study provides an assessment of the significance of similar previous inferences and illustrates the potential of recursive least squares in paleoceanography.

Dating of sediments in the Biscay bay: Implication for pollution chronology

Important historical informations on the temporal changes of anthropogenic pollution in marine environment can be assessed using sediment analysis. Dating is a crucial prerequisite to reconstruct pollution events, to calculate fluxes, and thus to allow comparison between different sites. This work presents estimates of accumulation rates of sediments in the Bay of Biscay. Fives cores were collected during RIKEAU 2002 cruise on board o/v Thalia in order to study temporal changes in PAH and organohalogens compounds content of sediment. We compare chronostratigraphic estimates on cores derived from the natural radionuclide 210Pb in excess with estimates from the known times of introduction of the artificial radionuclide 137Cs to the environment. 210Pb, 226Ra and 137Cs were measured directly by non-destructive gamma spectrometry using a well type γ-detector. Total 210Pb and 226Ra activities vary from 30 to 150 mBq g-1, and 20 to 36 mBq g-1 respectively; 137Cs presents lower levels (< 5 mBq g-1). Profiles of 210Pb in three cores present a well mixed layer, from 2-3 to 10 cm, in the uppermost sediments, followed by an exponential decrease of activities, suitable for the determination of sedimentation rates. Under constant flux and sedimentation rate assumptions, vertical accretion rates derived from 210Pb present a large range from nearly 0.1 cm yr-1 up to almost 0.3 cm yr-1. Differences are mainly due to relative position of studied cores regarding the muddy patch. Although the moderate level of 137Cs limits the accuracy of this dating method, profiles of 137Cs with depth strengthen mean rates derived from 210Pb data. The implication of this dating on pollutant inputs in sediments of the Bay of Biscay is briefly discussed.

Characterizing, modelling and understanding the climate variability of the deep water formation in the North-Western Mediterranean Sea

Observing, modelling and understanding the climate-scale variability of the deep water formation (DWF) in the North-Western Mediterranean Sea remains today very challenging. In this study, we first characterize the interannual variability of this phenomenon by a thorough reanalysis of observations in order to establish reference time series. These quantitative indicators include 31 observed years for the yearly maximum mixed layer depth over the period 1980–2013 and a detailed multi-indicator description of the period 2007–2013. Then a 1980–2013 hindcast simulation is performed with a fully-coupled regional climate system model including the high-resolution representation of the regional atmosphere, ocean, land-surface and rivers. The simulation reproduces quantitatively well the mean behaviour and the large interannual variability of the DWF phenomenon. The model shows convection deeper than 1000 m in 2/3 of the modelled winters, a mean DWF rate equal to 0.35 Sv with maximum values of 1.7 (resp. 1.6) Sv in 2013 (resp. 2005). Using the model results, the winter-integrated buoyancy loss over the Gulf of Lions is identified as the primary driving factor of the DWF interannual variability and explains, alone, around 50 % of its variance. It is itself explained by the occurrence of few stormy days during winter. At daily scale, the Atlantic ridge weather regime is identified as favourable to strong buoyancy losses and therefore DWF, whereas the positive phase of the North Atlantic oscillation is unfavourable. The driving role of the vertical stratification in autumn, a measure of the water column inhibition to mixing, has also been analyzed. Combining both driving factors allows to explain more than 70 % of the interannual variance of the phenomenon and in particular the occurrence of the five strongest convective years of the model (1981, 1999, 2005, 2009, 2013). The model simulates qualitatively well the trends in the deep waters (warming, saltening, increase in the dense water volume, increase in the bottom water density) despite an underestimation of the salinity and density trends. These deep trends come from a heat and salt accumulation during the 1980s and the 1990s in the surface and intermediate layers of the Gulf of Lions before being transferred stepwise towards the deep layers when very convective years occur in 1999 and later. The salinity increase in the near Atlantic Ocean surface layers seems to be the external forcing that finally leads to these deep trends. In the future, our results may allow to better understand the behaviour of the DWF phenomenon in Mediterranean Sea simulations in hindcast, forecast, reanalysis or future climate change scenario modes. The robustness of the obtained results must be however confirmed in multi-model studies.

The role of the Indian Ocean sector and sea surface salinity for prediction of the coupled Indo-Pacific system

The purpose of this dissertation is to evaluate the potential downstream influence of the Indian Ocean (IO) on El Niño/Southern Oscillation (ENSO) forecasts through the oceanic pathway of the Indonesian Throughflow (ITF), atmospheric teleconnections between the IO and Pacific, and assimilation of IO observations. Also the impact of sea surface salinity (SSS) in the Indo-Pacific region is assessed to try to address known problems with operational coupled model precipitation forecasts. The ITF normally drains warm fresh water from the Pacific reducing the mixed layer depths (MLD). A shallower MLD amplifies large-scale oceanic Kelvin/Rossby waves thus giving ~10% larger response and more realistic ENSO sea surface temperature (SST) variability compared to observed when the ITF is open. In order to isolate the impact of the IO sector atmospheric teleconnections to ENSO, experiments are contrasted that selectively couple/decouple the interannual forcing in the IO. The interannual variability of IO SST forcing is responsible for 3 month lagged widespread downwelling in the Pacific, assisted by off-equatorial curl, leading to warmer NINO3 SST anomaly and improved ENSO validation (significant from 3-9 months). Isolating the impact of observations in the IO sector using regional assimilation identifies large-scale warming in the IO that acts to intensify the easterlies of the Walker circulation and increases pervasive upwelling across the Pacific, cooling the eastern Pacific, and improving ENSO validation (r ~ 0.05, RMS~0.08C). Lastly, the positive impact of more accurate fresh water forcing is demonstrated to address inadequate precipitation forecasts in operational coupled models. Aquarius SSS assimilation improves the mixed layer density and enhances mixing, setting off upwelling that eventually cools the eastern Pacific after 6 months, counteracting the pervasive warming of most coupled models and significantly improving ENSO validation from 5-11 months. In summary, the ITF oceanic pathway, the atmospheric teleconnection, the impact of observations in the IO, and improved Indo-Pacific SSS are all responsible for ENSO forecast improvements, and so each aspect of this study contributes to a better overall understanding of ENSO. Therefore, the upstream influence of the IO should be thought of as integral to the functioning of ENSO phenomenon.

A comparison between vertical mixing parameterizations in the Levantine Sea

The goal of this thesis was the study of an optimal vertical mixing parameterization scheme in a mesoscale dominated field characterized from a strong vorticity and the presence of a layer of colder, less saline water at about 100 m depth (Atlantic Waters); in these conditions we compared six different experiments, that differ by the turbulent closure schemes, the presence or not of an enhanced diffusion parameterization and the presence or not of a double diffusion mixing parameterization. To evaluate the performance of the experiments and the model we compared the simulations with the ARGO observations of temperature and salinity available in our domain, in our period of interest. The conclusions were the following: • the increase of the resolution gives better results in terms of temperature in all the considered cases, and in terms of salinity. • The comparisons between the Pacanovski-Philander and the TKE turbulent closure schemes don’t show significant differences when the simulations are compared to the observations. • The removing of the enhanced diffusion parameterization in presence of the TKE turbulent closure submodel doesn’t give positive results, and show limitations in the resolving of gravitational instabilities near the surface • The k-ϵ turbulent closure model utilized in all the GLS experiments, is the best performing closure model among the three considered, with positive results in all the salinity comparison with the in situ observation and in most of the temperature comparisons. • The double mixing parameterization utilized in the k-ϵ closure submodel improves the results of the experiments improving both the temperature and salinity in comparison with the ARGO data.