Hafnium and neodymium in surface waters of the Atlantic sector of the Southern Ocean

Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANT-XXIV/3 and ANT-XXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (<0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labelled by terrigenous inputs. Near South Africa Nd isotope values as low as epsilon-Nd = -18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to epsilon-Hf = 6.1 and epsilon-Nd = -4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (epsilon-Nd ~ -8 to -8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Pasage. The Hf isotope compositions in the entire study area only show a small range between epsilon-Hf = +6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from epsilon-Nd = -18.9 to -4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.

Sediment and pore water data of five cores from the continental slope off Uruguay

Assessing frequency and extent of mass movement at continental margins is crucial to evaluate risks for offshore constructions and coastal areas. A multidisciplinary approach including geophysical, sedimentological, geotechnical, and geochemical methods was applied to investigate multistage mass transport deposits (MTDs) off Uruguay, on top of which no surficial hemipelagic drape was detected based on echosounder data. Nonsteady state pore water conditions are evidenced by a distinct gradient change in the sulfate (SO4**2-) profile at 2.8 m depth. A sharp sedimentological contact at 2.43 m coincides with an abrupt downward increase in shear strength from approx. 10 to >20 kPa. This boundary is interpreted as a paleosurface (and top of an older MTD) that has recently been covered by a sediment package during a younger landslide event. This youngest MTD supposedly originated from an upslope position and carried its initial pore water signature downward. The kink in the SO4**2- profile approx. 35 cm below the sedimentological and geotechnical contact indicates that bioirrigation affected the paleosurface before deposition of the youngest MTD. Based on modeling of the diffusive re-equilibration of SO4**2- the age of the most recent MTD is estimated to be <30 years. The mass movement was possibly related to an earthquake in 1988 (approx. 70 km southwest of the core location). Probabilistic slope stability back analysis of general landslide structures in the study area reveals that slope failure initiation requires additional ground accelerations. Therefore, we consider the earthquake as a reasonable trigger if additional weakening processes (e.g., erosion by previous retrogressive failure events or excess pore pressures) preconditioned the slope for failure. Our study reveals the necessity of multidisciplinary approaches to accurately recognize and date recent slope failures in complex settings such as the investigated area.

Distinguishing tectonically-and gravity-driven synsedimentary deformation structures along the Apulian platform margin (Gargano Promontory, southern Italy)

Acknowledgements This work has been supported by Reservoir Characterisation Project (www.rechproject.com) and FAR Project 2014 "Characterisation and modelling of natural reservoirs of geofluids in fractured carbonate rocks", funded by the University of Camerino, coordinator Emanuele Tondi.

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.

C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.

Continuously measured 222Rn activity concentrations (daily means) in near surface air at Neumayer Station in the period 1995 through 2011

We report on continuously measured 222Rn activity concentrations in near-surface air at Neumayer Station in the period 1995-2011. This 17-year record showed no long-term trend and has overall mean ± standard deviation of (0.019 ± 0.012) Bq/m**3. A distinct and persistent seasonality could be distinguished with maximum values of (0.028 ± 0.013) Bq/m**3 from January to March and minimum values of (0.015 ± 0.009) Bq/m**3 from May to October. Elevated 222Rn activity concentrations were typically associated with air mass transport from the Antarctic Plateau. Our results do not support a relation between enhanced 222Rn activity concentrations at Neumayer and cyclonic activity or long-range transport from South America. The impact of oceanic 222Rn emissions could not be properly assessed but we tentatively identified regional sea ice extent (SIE) variability as a significant driver of the annual 222Rn cycle.

CoO nanoparticles embedded in three-dimensional nitrogen/sulfur co-doped carbon nanofiber networks as a bifunctional catalyst for oxygen reduction/evolution reactions

High-performance and low-cost bifunctional electrocatalysts play crucial roles in oxygen reduction and evolution reactions. Herein, a novel three-dimensional (3D) bifunctional electrocatalyst was prepared by embedding CoO nanoparticles into nitrogen and sulfur co-doped carbon nanofiber networks (denoted as CoO@N/S-CNF) through a facile approach. The carbon nanofiber networks were derived from a nanostructured biological material which provided abundant functional groups to nucleate and anchor nanoparticles while retaining its interconnected 3D porous structure. The composite possesses a high specific surface area and graphitization degree, which favors both mass transport and charge transfer for electrochemical reaction. The CoO@N/S-CNF not only exhibits highly efficient catalytic activity towards oxygen reduction reaction (ORR) in alkaline media with an onset potential of about 0.84 V, but also shows better stability and stronger resistance to methanol than Pt/C. Furthermore, it only needs an overpotential of 1.55 V to achieve a current density of 10 mA cm^-2, suggesting that it is an efficient electrocatalyst for oxygen evolution reaction (OER). The ΔE value (oxygen electrode activity parameter) of CoO@N/S-CNF is calculated to be 0.828 V, which demonstrates that the composite could be a promising bifunctional electrocatalyst for both ORR and OER.

Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilos

Dutra, R. P. S.; Varela,M. L.; Nascimento, R. M. ; Gomes, U. U. ; Martinelli1, A. E. ; Paskocimas, C. A. Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilosa. Cerâmica [online]. 2009, vol.55, n.333, pp. 100-105. ISSN 0366-6913. doi:Disponivem em: . Acesso em: 04 out. 2010.

Study of the oceanographic conditions in the Caribbean in 2003

[EN]A meridional hydrographic section was made in October 2003 at 66ºW from the coast of Venezuela to Puerto Rico. In this report, we concentrate from surface to 1700 m depth in the Caribbean. The data show two distinct water masses with different origins: Caribbean Surface Water, with salinity values less that 35.5, and Subtropical Underwater (SUW), with subsurface salinity higher than 37, with their source in the North Atlantic and subtropics respectively, as previously observed. Different velocity patterns in the water masses from Atlantic Ocean to the Caribbean are observed. Mass transport through the section is westward and about 30 Sv that matches the transport of the Florida Current.

Séquestration géologique du CO2 par carbonatation minérale dans les résidus miniers

La carbonatation minérale dans les résidus miniers est un moyen sûr et permanent de séquestrer le CO2 atmosphérique. C’est un processus naturel et passif qui ne nécessite aucun traitement particulier et donc avantageux d’un point de vue économique. Bien que la quantité de CO2 qu’il soit possible de séquestrer selon ce processus est faible à l’échelle globale, dans le cadre d’un marché du carbone, les entreprises minières pourraient obtenir des crédits et ainsi revaloriser leurs résidus. À l’heure actuelle, il y a peu d’informations pour quantifier le potentiel de séquestration du CO2 de façon naturelle et passive dans les piles de résidus miniers. Il est donc nécessaire d’étudier le phénomène pour comprendre comment évolue la réaction à travers le temps et estimer la quantité de CO2 qui peut être séquestrée naturellement dans les piles de résidus. Plusieurs travaux de recherche se sont intéressés aux résidus miniers de Thetford Mines (Québec, Canada), avec une approche principalement expérimentale en laboratoire. Ces travaux ont permis d’améliorer la compréhension du processus de carbonatation, mais ils nécessitent une validation à plus grande échelle sous des conditions atmosphériques réelles. L’objectif général de cette étude est de quantifier le processus de carbonatation minérale des résidus miniers sous des conditions naturelles, afin d’estimer la quantité de CO2 pouvant être piégée par ce processus. La méthodologie utilisée repose sur la construction de deux parcelles expérimentales de résidus miniers situées dans l’enceinte de la mine Black Lake (Thetford Mines). Les résidus miniers sont principalement constitués de grains et de fibres de chrysotile et lizardite mal triés, avec de petites quantités d’antigorite, de brucite et de magnétite. Des observations spatiales et temporelles ont été effectuées dans les parcelles concernant la composition et la pression des gaz, la température des résidus, la teneur en eau volumique, la composition minérale des résidus ainsi que la chimie de l’eau des précipitations et des lixiviats provenant des parcelles. Ces travaux ont permis d’observer un appauvrissement notable du CO2 dans les gaz des parcelles (< 50 ppm) ainsi que la précipitation d’hydromagnésite dans les résidus, ce qui suggère que la carbonatation minérale naturelle et passive est un processus potentiellement important dans les résidus miniers. Après 4 ans d’observations, le taux de séquestration du CO2 dans les parcelles expérimentales a été estimé entre 3,5 et 4 kg/m3/an. Ces observations ont permis de développer un modèle conceptuel de la carbonatation minérale naturelle et passive dans les parcelles expérimentales. Dans ce modèle conceptuel, le CO2 atmosphérique (~ 400 ppm) se dissout dans l’eau hygroscopique contenue dans les parcelles, où l’altération des silicates de magnésium forme des carbonates de magnésium. La saturation en eau dans les cellules est relativement stable dans le temps et varie entre 0,4 et 0,65, ce qui est plus élevé que les valeurs de saturation optimales proposées dans la littérature, réduisant ainsi le transport de CO2 dans la zone non saturée. Les concentrations de CO2 en phase gazeuse, ainsi que des mesures de la vitesse d’écoulement du gaz dans les cellules suggèrent que la réaction est plus active près de la surface et que la diffusion du CO2 est le mécanisme de transport dominant dans les résidus. Un modèle numérique a été utilisé pour simuler ces processus couplés et valider le modèle conceptuel avec les observations de terrain. Le modèle de transport réactif multiphase et multicomposant MIN3P a été utilisé pour réaliser des simulations en 1D qui comprennent l’infiltration d’eau à travers le milieu partiellement saturé, la diffusion du gaz, et le transport de masse réactif par advection et dispersion. Même si les écoulements et le contenu du lixivat simulés sont assez proches des observations de terrain, le taux de séquestration simulé est 22 fois plus faible que celui mesuré. Dans les simulations, les carbonates précipitent principalement dans la partie supérieure de la parcelle, près de la surface, alors qu’ils ont été observés dans toute la parcelle. Cette différence importante pourrait être expliquée par un apport insuffisant de CO2 dans la parcelle, qui serait le facteur limitant la carbonatation. En effet, l’advection des gaz n’a pas été considérée dans les simulations et seule la diffusion moléculaire a été simulée. En effet, la mobilité des gaz engendrée par les fluctuations de pression barométrique et l’infiltration de l’eau, ainsi que l’effet du vent doivent jouer un rôle conséquent pour alimenter les parcelles en CO2.

Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilos

Dutra, R. P. S.; Varela,M. L.; Nascimento, R. M. ; Gomes, U. U. ; Martinelli1, A. E. ; Paskocimas, C. A. Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilosa. Cerâmica [online]. 2009, vol.55, n.333, pp. 100-105. ISSN 0366-6913. doi:Disponivem em: . Acesso em: 04 out. 2010.

Sea-level control on the connection between shelf-edge deltas and the Bourcart canyon head (western Mediterranean) during the last glacial/interglacial cycle

A dense grid of high- and very high resolution seismic data, together with piston cores and borehole data providing time constraints, enables us to reconstruct the history of the Bourcart canyon head in the western Mediterranean Sea during the last glacial/interglacial cycle. The canyon fill is composed of confined channel–levee systems fed by a series of successively active shelf fluvial systems, originating from the west and north. Most of the preserved infill corresponds to the interval between Marine Isotope Stage (MIS) 3 and the early deglacial (19 cal ka BP). Its deposition was strongly controlled by a relative sea level that impacted the direct fluvial/canyon connection. During a period of around 100 kyr between MIS 6 and MIS 2, the canyon “prograded” by about 3 km. More precisely, several parasequences can be identified within the canyon fill. They correspond to forced-regressed parasequences (linked to punctuated sea-level falls) topped by a progradational-aggradational parasequence (linked to a hypothetical 19-ka meltwater pulse (MWP)). The bounding surfaces between forced-regressed parasequences are condensed intervals formed during intervals of relative sediment starvation due to flooding episodes. The meandering pattern of the axial incision visible within the canyon head, which can be traced landward up to the Agly paleo-river, is interpreted as the result of hyperpycnal flows initiated in the river mouth in a context of increased rainfall and mountain glacier flushing during the early deglacial.

Integrated micro fuel cells with on-board hydride reactors and autonomous control schemes

Miniaturization of power generators to the MEMS scale, based on the hydrogen-air fuel cell, is the object of this research. The micro fuel cell approach has been adopted for advantages of both high power and energy densities. On-board hydrogen production/storage and an efficient control scheme that facilitates integration with a fuel cell membrane electrode assembly (MEA) are key elements for micro energy conversion. Millimeter-scale reactors (ca. 10 µL) have been developed, for hydrogen production through hydrolysis of CaH2 and LiAlH4, to yield volumetric energy densities of the order of 200 Whr/L. Passive microfluidic control schemes have been implemented in order to facilitate delivery, self-regulation, and at the same time eliminate bulky auxiliaries that run on parasitic power. One technique uses surface tension to pump water in a microchannel for hydrolysis and is self-regulated, based on load, by back pressure from accumulated hydrogen acting on a gas-liquid microvalve. This control scheme improves uniformity of power delivery during long periods of lower power demand, with fast switching to mass transport regime on the order of seconds, thus providing peak power density of up to 391.85 W/L. Another method takes advantage of water recovery by backward transport through the MEA, of water vapor that is generated at the cathode half-cell reaction. This regulation-free scheme increases available reactor volume to yield energy density of 313 Whr/L, and provides peak power density of 104 W/L. Prototype devices have been tested for a range of duty periods from 2-24 hours, with multiple switching of power demand in order to establish operation across multiple regimes. Issues identified as critical to the realization of the integrated power MEMS include effects of water transport and byproduct hydrate swelling on hydrogen production in the micro reactor, and ambient relative humidity on fuel cell performance.