Concentrations of major and minor constituents of samples from the lower end of the cores from the eastern Mediterranean Sea (Table 2)

The pore water chemistry of mud volcanoes from the Olimpi Mud Volcano Field and the Anaximander Mountains in the eastern Mediterranean Sea have been studied for three major purposes: (1) modes and velocities of fluid transport were derived to assess the role of (upward) advection, and bioirrigation for benthic fluxes. (2) Differences in the fluid chemistry at sites of Milano mud volcano (Olimpi area) were compiled in a map to illustrate the spatial heterogeneity reflecting differences in fluid origin and transport in discrete conduits in near proximity. (3) Formation water temperatures of seeping fluids were calculated from theoretical geothermometers to predict the depth of fluid origin and geochemical reactions in the deeper subsurface. No indications for downward advection as required for convection cells have been found. Instead, measured pore water profiles have been simulated successfully by accounting for upward advection and bioirrigation. Advective flow velocities are found to be generally moderate (3-50 cm/y) compared to other cold seep areas. Depth-integrated rates of bioirrigation are 1-2 orders of magnitude higher than advective flow velocities documenting the importance of bioirrigation for flux considerations in surface sediments. Calculated formation water temperatures from the Anaximander Mountains are in the range of 80 to 145 °C suggesting a fluid origin from a depth zone associated with the seismic decollement. It is proposed that at that depth clay mineral dehydration leads to the formation and advection of fluids reduced in salinity relative to sea water. This explains the ubiquitous pore water freshening observed in surface sediments of the Anaximander Mountain area. Multiple fluid sources and formation water temperatures of 55 to 80 °C were derived for expelled fluids of the Olimpi area.

Shell flux and oxygen isotope data of North Atlantic foraminifera

We present an almost 3 year long time series of shell fluxes and oxygen isotopes of left-coiling Neogloboquadrina pachyderma and Turborotalita quinqueloba from sediment traps moored in the deep central Irminger Sea. We determined their response to the seasonal change from a deeply mixed water column with occasional deep convection in winter to a thermally stratified water column with a surface mixed layer (SML) of around 50 m in summer. Both species display very low fluxes during winter with a remnant summer population holding out until replaced by a vital population that seeds the subsequent blooms. This annual population overturning is marked by a 0.7 per mill increase in d18O in both species. The shell flux of N. pachyderma peaks during the spring bloom and in late summer, when stratification is close to its minimum and maximum, respectively. Both export periods contribute about equally and account for >95% of the total annual flux. Shell fluxes of T. quinqueloba show only a single broad pulse in summer, thus following the seasonal stratification cycle. The d18O of N. pachyderma reflects temperatures just below the base of the seasonal SML without offset from isotopic equilibrium. The d18O pattern of T. quinqueloba shows a nearly identical amplitude and correlates highly with the d18O of N. pachyderma. Therefore T. quinqueloba also reflects temperature near the base of the SML but with a positive offset from isotopic equilibrium. These offsets contrast with observations elsewhere and suggest a variable offset from equilibrium calcification for both species. In the Irminger Sea the species consistently show a contrast in their flux timings. Their flux-weighted delta d18O will thus dominantly be determined by seasonal temperature differences at the base of the SML rather than by differences in their depth habitat. Consequently, their sedimentary delta d18O may be used to infer the seasonal contrast in temperature at the base of the SML.

Physical oceanography during cruise SUBPOLAR with RV THALASSA in the subpolar North Atlantic in June-July 2005

In 2003 and in 2005, hydrographic data provided sufficient spatial coverage in the Labrador Sea to infer basin wide changes in the water mass characteristic of the Upper Labrador Sea Water (ULSW). The ULSW was considerably saltier and warmer in 2005 than in 2003. Although convection in the Labrador Sea leads to mixing with salinity-poor surface water and is opposed to the observed salinity trend, the increased vertical homogeneity of the CTD profiles, the increase in the ULSW thickness and the intensification of the potential vorticity minimum for the isopycnals sigma-theta = 27.700-27.734 kg/m**3 in 2005 point to convection in winter 2005 which ventilated at least about 20% of the Labrador Sea region.

Investigação experimental das propriedades termofísicas e da convecção forçada de nanofluido de grafeno

This work presents an experimental investigation of thermal hydraulic performance of the nanofluid composed by graphene nanoparticles dispersed in a mixture of water and ethylene glycol at a ratio of 70:30% by volume. The tests were carried out under forced convection inside a circular tube with uniform heat flux on the wall for the laminar-turbulent transition regime. The mass flow rate ranged from 40 to 70 g/s corresponding to Reynolds numbers between 3000 and 7500. The heat flux was maintained constant at values of 11, 16 and 21 kW/m², as well as the inlet temperature of 15, 20 and 25°C. Three samples were produced with the nanofluid volumetric concentration of 0.05%, 0.10% and 0.15%. Thermophysical properties were experimentaly measured for all samples that were critically compared and discussed with theoretical models most commonly used in the literature. Initially, experiments with distilled water confirmed the validity of the experimental equipment for the thermo-hydraulic tests. Therefore, nanofluid samples that showed the highest thermal conductivity, corresponding to the volumetric concentrations of 0.15% and 0.10%, were subjected to the tests. The thermal-hydraulic performance for both samples was unsatisfactory. The heat transfer coefficients for convection of nanofluids reduced 21% in average, for the sample with = 0.15% and 26% and for =0.10%. The pressure drop of the samples was higher than the base fluid. Finally, the pressure drop and heat transfer coefficient by convection of both samples were also compared to theoretical models. The models used for pressure drop showed an excellent agreement with experimental results, which is remarkable considering the transitional flow.

Mechanistic Models of Anti-HIV Microbicide Drug Delivery

A new modality for preventing HIV transmission is emerging in the form of topical microbicides. Some clinical trials have shown some promising results of these methods of protection while other trials have failed to show efficacy. Due to the relatively novel nature of microbicide drug transport, a rigorous, deterministic analysis of that transport can help improve the design of microbicide vehicles and understand results from clinical trials. This type of analysis can aid microbicide product design by helping understand and organize the determinants of drug transport and the potential efficacies of candidate microbicide products.

Microbicide drug transport is modeled as a diffusion process with convection and reaction effects in appropriate compartments. This is applied here to vaginal gels and rings and a rectal enema, all delivering the microbicide drug Tenofovir. Although the focus here is on Tenofovir, the methods established in this dissertation can readily be adapted to other drugs, given knowledge of their physical and chemical properties, such as the diffusion coefficient, partition coefficient, and reaction kinetics. Other dosage forms such as tablets and fiber meshes can also be modeled using the perspective and methods developed here.

The analyses here include convective details of intravaginal flows by both ambient fluid and spreading gels with different rheological properties and applied volumes. These are input to the overall conservation equations for drug mass transport in different compartments. The results are Tenofovir concentration distributions in time and space for a variety of microbicide products and conditions. The Tenofovir concentrations in the vaginal and rectal mucosal stroma are converted, via a coupled reaction equation, to concentrations of Tenofovir diphosphate, which is the active form of the drug that functions as a reverse transcriptase inhibitor against HIV. Key model outputs are related to concentrations measured in experimental pharmacokinetic (PK) studies, e.g. concentrations in biopsies and blood. A new measure of microbicide prophylactic functionality, the Percent Protected, is calculated. This is the time dependent volume of the entire stroma (and thus fraction of host cells therein) in which Tenofovir diphosphate concentrations equal or exceed a target prophylactic value, e.g. an EC50.

Results show the prophylactic potentials of the studied microbicide vehicles against HIV infections. Key design parameters for each are addressed in application of the models. For a vaginal gel, fast spreading at small volume is more effective than slower spreading at high volume. Vaginal rings are shown to be most effective if inserted and retained as close to the fornix as possible. Because of the long half-life of Tenofovir diphosphate, temporary removal of the vaginal ring (after achieving steady state) for up to 24h does not appreciably diminish Percent Protected. However, full steady state (for the entire stromal volume) is not achieved until several days after ring insertion. Delivery of Tenofovir to the rectal mucosa by an enema is dominated by surface area of coated mucosa and whether the interiors of rectal crypts are filled with the enema fluid. For the enema 100% Percent Protected is achieved much more rapidly than for vaginal products, primarily because of the much thinner epithelial layer of the mucosa. For example, 100% Percent Protected can be achieved with a one minute enema application, and 15 minute wait time.

Results of these models have good agreement with experimental pharmacokinetic data, in animals and clinical trials. They also improve upon traditional, empirical PK modeling, and this is illustrated here. Our deterministic approach can inform design of sampling in clinical trials by indicating time periods during which significant changes in drug concentrations occur in different compartments. More fundamentally, the work here helps delineate the determinants of microbicide drug delivery. This information can be the key to improved, rational design of microbicide products and their dosage regimens.

Design of Latent Thermal Energy Storage Systems

This dissertation documents the results of a theoretical and numerical study of time dependent storage of energy by melting a phase change material. The heating is provided along invading lines, which change from single-line invasion to tree-shaped invasion. Chapter 2 identifies the special design feature of distributing energy storage in time-dependent fashion on a territory, when the energy flows by fluid flow from a concentrated source to points (users) distributed equidistantly on the area. The challenge in this chapter is to determine the architecture of distributed energy storage. The chief conclusion is that the finite amount of storage material should be distributed proportionally with the distribution of the flow rate of heating agent arriving on the area. The total time needed by the source stream to ‘invade’ the area is cumulative (the sum of the storage times required at each storage site), and depends on the energy distribution paths and the sequence in which the users are served by the source stream. Chapter 3 shows theoretically that the melting process consists of two phases: “invasion” thermal diffusion along the invading line, which is followed by “consolidation” as heat diffuses perpendicularly to the invading line. This chapter also reports the duration of both phases and the evolution of the melt layer around the invading line during the two-dimensional and three-dimensional invasion. It also shows that the amount of melted material increases in time according to a curve shaped as an S. These theoretical predictions are validated by means of numerical simulations in chapter 4. This chapter also shows that the heat transfer rate density increases (i.e., the S curve becomes steeper) as the complexity and number of degrees of freedom of the structure are increased, in accord with the constructal law. The optimal geometric features of the tree structure are detailed in this chapter. Chapter 5 documents a numerical study of time-dependent melting where the heat transfer is convection dominated, unlike in chapter 3 and 4 where the melting is ruled by pure conduction. In accord with constructal design, the search is for effective heat-flow architectures. The volume-constrained improvement of the designs for heat flow begins with assuming the simplest structure, where a single line serves as heat source. Next, the heat source is endowed with freedom to change its shape as it grows. The objective of the numerical simulations is to discover the geometric features that lead to the fastest melting process. The results show that the heat transfer rate density increases as the complexity and number of degrees of freedom of the structure are increased. Furthermore, the angles between heat invasion lines have a minor effect on the global performance compared to other degrees of freedom: number of branching levels, stem length, and branch lengths. The effect of natural convection in the melt zone is documented.

Mechanisms Governing the Eyewall Replacement Cycle in Numerical Simulations of Tropical Cyclones

Eyewall replacement cycle (ERC) is frequently observed during the evolution of intensifying Tropical Cyclones (TCs). Although intensely studied in recent years, the underlying mechanisms of ERC are still poorly understood, and the forecast of ERC remains a great challenge. To advance our understanding of ERC and provide insights in improvement of numerical forecast of ERC, a series of numerical simulations is performed to investigate ERCs in TC-like vortices on a f-plane. The simulated ERCs possess key features similar to those observed in real TCs including the formation of a secondary tangential wind maximum associated with the outer eyewall. The Sawyer-Eliassen equation and tangential momentum budget analyses are performed to diagnose the mechanisms underlying the secondary eyewall formation (SEF) and ERC. Our diagnoses reveal crucial roles of outer rainband heating in governing the formation and development of the secondary tangential wind maximum and demonstrate that the outer rainband convection must reach a critical strength relative to the eyewall before SEF and the subsequent ERC can occur. A positive feedback among low-level convection, acceleration of tangential winds in the boundary layer, and surface evaporation that leads to the development of ERC and a mechanism for the demise of inner eyewall that involves interaction between the transverse circulations induced by eyewall and outer rainband convection are proposed. The tangential momentum budget indicates that the net tendency of tangential wind is a small residual resultant from a large cancellation between tendencies induced by the resolved and sub-grid scale (SGS) processes. The large SGS contribution to the tangential wind budget explains different characteristics of ERC shown in previous numerical studies and poses a great challenge for a timely correct forecast of ERC. The sensitivity experiments show that ERCs are strongly subjected to model physics, vortex radial structure and background wind. The impact of model physics on ERC can be well understood with the interaction among eyewall/outer rainband heating, radilal inflow in the boundary layer, surface layer turbulent processes, and shallow convection in the moat. However, further investigations are needed to fully understand the exhibited sensitivities of ERC to vortex radial structure and background wind.

Stable isotope record, foraminifera and susceptibility determination of sediment core ENAM93-21

A high-resolution piston core, ENAM93-21, from a water depth of 1020 m near the Faeroe-Shetland Channel is investigated for variations in magnetic susceptibility, surface oxygen isotopes, grain size distribution, content of ice-rafted detritus (IRD), and distribution of planktonic and benthic foraminifera. The core, covering the last 58,000 years, is correlated with the Greenland ice cores and compared with paleorecords from the Norwegian Sea and the North Atlantic Ocean. All fifteen Dansgaard-Oeschger climatic cycles recognized from the investigated time period in the Greenland ice cores have been identified in the ENAM93-21 core. Each cycle is subdivided into three intervals on the basis of characteristic benthic and planktonic faunas. Interstadial intervals contain a relatively warm planktonic fauna and a benthic fauna similar to the modern fauna in the Norwegian Sea. This indicates thermohaline convection as at present, with a significant contribution of deep water to the North Atlantic Deep Water (NADW). Transitional cooling intervals are characterized by more cold water planktonic foraminfera and ice-related benthic species. The benthic fauna signifies restricted bottom water conditions and a reduced contribution to the NADW. The peak abundance of N. pachyderma (s.) and the coldest surface water conditions are found in the stadial intervals. The benthic fauna is dominated by species with an association to Atlantic Intermediate Water, suggesting an increased Atlantic influence in the Norwegian Sea, and there was probably no contribution to the NADW through the Faeroe-Shetland Channel. The three different modes of circulation can be correlated to paleoceanographic events in the Norwegian Sea and the North Atlantic Ocean.

Smear slide analysis of sediment core GeoB5836-2

Laminated sediments spanning the last 20,000 years (though not continuously) in the Shaban Deep, a brine-filled basin in the northern Red Sea, were analyzed microscopically and with backscattered electron imagery in order to determine laminae composition with emphasis on the diatomaceous component. Based on this detailed study, we present schematic models to propose paleoflux scenarios for laminae formation at different time-slices. The investigated core (GeoB 5836-2; 26°12.61'N, 35°21.56'E; water depth 1475 m) shows light and dark alternating laminae that are easily distinguishable in the mid-Holocene and at the end of the deglaciation (13-15 ka) period. Light layers are mainly composed of coccoliths, terrigenous material and diatom fragments, while dark layers consist almost exclusively of diatom frustules (monospecific or mixed assemblages). The regularity in the occurrence of coccolith/diatom couplets points to an annual deposition cycle where contrasting seasons and associated plankton blooms are represented (diatoms-fall/winter deposition, coccoliths-summer signal). We propose that, for the past ~15,000 years, the laminations represent two-season annual varves. Strong dissolution of carbonate, with the concomitant loss of the coccolith-rich layer in sediments older than 15 ka, prevents us from presenting a schematic model of annual deposition. However, the diatomaceous component reveals a marked switch in species composition between Last Glacial Maximum (LGM) sediments (dominated by Chaetoceros resting spores) and sediments somewhat younger (18-19 ka; dominated by Rhizosolenia). We propose that different diatom assemblages reflect changing conditions in stratification in the northern Red Sea: Strong stratification conditions, such as during two meltwater pulses at 14.5 and 11.4 ka, are reflected in the sediment by Rhizosolenia layers, while Chaetoceros-dominated assemblages represent deep convection conditions.

Chlorophyll-a, primary production rates, carbon concentrations and cell counts of coccolithophores, diatoms and microzooplankton measured in water samples from the North Atlantic during the M87/1 cruise in April 2012

The Deep Convection cruise repeatedly sampled two locations in the North Atlantic, sited in the Iceland and Norwegian Basins, onboard the RV Meteor (19 March - 2 May 2012). Samples were collected from multiple casts of a conductivity-temperature-depth (CTD) - Niskin rosette at each station. Water samples for primary production rates, community structure, chlorophyll a [Chl a], calcite [PIC], particulate organic carbon [POC] and biogenic silicic acid [BSi] were collected from predawn casts from six light depths (55%, 20%, 14%, 7%, 5% and 1% of incident PAR). Additional samples for community structure and ancillary parameters were collected from a second cast. Carbon fixation rates were determined using the 13C stable isotope method. Water samples for diatom and micro zooplankton counts, collected from the predawn casts, were preserved with acidic Lugol's solution (2% final solution) and counted using an inverted light microscope. Water samples for coccolithophore counts were collected onto cellulose nitrate filters and counted using polarising light microscopy. Water samples for Chl a analysis were filtered onto MF300 and polycarbonate filters and extracted in 90% acetone. PIC and BSi samples were filtered onto polycarbonate filters and analysed using an inductively coupled plasma emission optical spectrometer and a SEAL QuAAtro autoanalyser respectively.

(Table 1) Nd isotope ratios of ODP Leg 208 samples

We present new Nd isotope records from Walvis Ridge Ocean Drilling Program (ODP) sites 1262-1264 (southeastern Atlantic) spanning the past 24 Ma to investigate the Neogene evolution of Atlantic thermohaline circulation. The new data indicate that deepwater epsilon-Nd(t) values from ODP Site 1262 decrease from -11.0 at 10.6 Ma to -12.5 by 7.3 Ma. This decrease parallels the Nd isotope trends contained in Fe-Mn crust records from the northwestern Atlantic; however, the shift at ODP Site 1262 (4755 m water depth) occurred up to ~6 Ma earlier than the corresponding changes in crust records from the Atlantic and earlier than any Atlantic site shallower than 2700 m paleowater depth. Recent interpretations of the rapid decrease in Fe-Mn crust Nd epsilon-Nd(t)ss values invoke changes in weathering inputs to the Labrador Sea region rather than a fundamental change in deepwater convection in the Labrador Sea. However, the new evidence for significant depth stratification of the Nd isotope signal in the southeastern Atlantic between 10.6 and 7.3 Ma suggests that the onset of deepwater convection in the Labrador Sea may have played a role in the deepwater decrease in Nd isotopic composition. Climatic conditions during the middle to late Miocene likely favored an increase in the importance of glacially induced mechanical weathering, while at the same time promoting deep convection in the Labrador Sea.

(Table 1) Age determination of sediment cores F2-92-P3 and F2-92-P40

Although climate records from several locations around the world show nearly synchronous and abrupt changes, the nature of the inferred teleconnection is still poorly understood. On the basis of preserved laminations and molybdenum enrichments in open margin sediments we demonstrate that the oxygen content of northeast Pacific waters at 800 m depth during the Bölling-Alleröd warm period (15-13 kyr) was greatly reduced. Existing oxygen isotopic records of benthic and planktonic foraminifera suggest that this was probably due to suppressed ventilation at higher latitudes of the North Pacific. Comparison with ventilation records for the North Atlantic indicates an antiphased pattern of convection relative to the North Pacific over the past 22 kyr, perhaps due to variations in water vapor transport across Central America.