Ecohydrology, evapotranspiration and hydrogeochemistry of carbonate mangrove wetlands

Coastal environments can be highly susceptible to environmental changes caused by anthropogenic pressures and natural events. Both anthropogenic and natural perturbations may directly affect the amount and the quality of water flowing through the ecosystem, both in the surface and subsurface and can subsequently, alter ecological communities and functions. The Florida Everglades and the Sian Ka'an Biosphere Reserve (Mexico) are two large ecosystems with an extensive coastal mangrove ecotone that represent a historically altered and pristine environment, respectively. Rising sea levels, climate change, increased water demand, and salt water intrusion are growing concerns in these regions and underlies the need for a better understanding of the present conditions. The goal of my research was to better understand various ecohydrological, environmental, and hydrogeochemical interactions and relationships in carbonate mangrove wetlands. A combination of aqueous geochemical analyses and visible and near-infrared reflectance data were employed to explore relationships between surface and subsurface water chemistry and spectral biophysical stress in mangroves. Optical satellite imagery and field collected meteorological data were used to estimate surface energy and evapotranspiration and measure variability associated with hurricanes and restoration efforts. Furthermore, major ionic and nutrient concentrations, and stable isotopes of hydrogen and oxygen were used to distinguish water sources and infer coastal groundwater discharge by applying the data to a combined principal component analysis-end member mixing model. Spectral reflectance measured at the field and satellite scales were successfully used to estimate surface and subsurface water chemistry and model chloride concentrations along the southern Everglades. Satellite imagery indicated that mangrove sites that have less tidal flushing and hydrogeomorphic heterogeneity tend to have more variable evapotranspiration and soil heat flux in response to storms and restoration. Lastly, water chemistry and multivariate analyses indicated two distinct fresh groundwater sources that discharge to the phosphorus-limited estuaries and bays of the Sian Ka'an Biopshere Reserve; and that coastal groundwater discharge was an important source for phosphorus. The results of the study give us a better understanding of the ecohydrological and hydrogeological processes in carbonate mangrove environments that can be then be extrapolated to similar coastal ecosystems in the Caribbean.

Radionuclides, Nd isotopes and biogenic Opal in Atlanic Ocean sediments

Reconstructing past modes of ocean circulation is an essential task in paleoclimatology and paleoceanography. To this end, we combine two sedimentary proxies, Nd isotopes (epsilon-Nd) and the 231Pa/230Th ratio, both of which are not directly involved in the global carbon cycle, but allow the reconstruction of water mass provenance and provide information about the past strength of overturning circulation, respectively. In this study, combined 231Pa/230Th and epsilon-Nd down-core profiles from six Atlantic Ocean sediment cores are presented. The data set is complemented by the two available combined data sets from the literature. From this we derive a comprehensive picture of spatial and temporal patterns and the dynamic changes of the Atlantic Meridional Overturning Circulation over the past ~25 ka. Our results provide evidence for a consistent pattern of glacial/stadial advances of Southern Sourced Water along with a northward circulation mode for all cores in the deeper (>3000 m) Atlantic. Results from shallower core sites support an active overturning cell of shoaled Northern Sourced Water during the LGM and the subsequent deglaciation. Furthermore, we report evidence for a short-lived period of intensified AMOC in the early Holocene.

Síntese e caracterização de catalisadores baseados em vermiculita modificada com ferro: aplicação em processos do tipo foto-fenton

Clays are materials with specific properties that make them promising for various studies. In this work we used the vermiculite clay as support for iron compounds, in order to obtain promising materials for application in the heterogeneous type photo-Fenton process. In all, the study included six solid, starting from the vermiculite (V0) was obtained calcined vermiculite (V0-C), the mixed material (V0/β-FeOOH) formed by vermiculite more akaganeite, exchanged vermiculite (v0t-C), vermiculite impregnated Wet (V0u-C) and V0u-CL that is the solid obtained by impregnating with a back washing. The solids of the study had their physical and chemical characteristics investigated by the following characterization techniques: X-Ray Diffraction (XRD), Infrared Spectroscopy (IR), Energy Dispersive Spectroscopy (EDS), X-Ray Fluorescence Spectroscopy (XRF), UV-Vis by Diffuse Reflectance (DR UV-Vis), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The V0 material showed three distinct phases, which are the very vermiculite, hidrobiotite and biotite, the last two phases are part of the geological of formation process vermiculite. The solids obtained after the modification showed an increase in the amount of iron present in the clay, these being quantities important for application in photocatalysis. The micrographs and EDS data, show that after treatment of addition of the metal , the iron was intercalary in structure of vermiculite for solid V0t-C and V0u-C, however, this did not occur with mixed material. In the photoFenton process, was observed a maximum removal of 88.8% of the dye methylene blue coloring for the catalyst V0/β-FeOOH, while for the other solids was obtained values between 76.8 and 62.6%, compared to 37.8% of discoloration without the presence of catalyst. Therefore, it is concluded that the vermiculite clay presents as a good catalyst and iron support for the, beyond of presenting a low cost because of its high abundance.

Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Far-infrared constraints on the contamination by dust-obscured galaxies of high-z dropout searches

The spectral energy distributions (SED) of dusty galaxies at intermediate redshift may look similar to very high-redshift galaxies in the optical/near infrared (NIR) domain. This can lead to the contamination of high-redshift galaxy searches based on broad-band optical/NIR photometry by lower redshift dusty galaxies because both kind of galaxies cannot be distinguished. The contamination rate could be as high as 50%. This work shows how the far-infrared (FIR) domain can help to recognize likely low-z interlopers in an optical/NIR search for high-z galaxies. We analyze the FIR SEDs of two galaxies that are proposed to be very high-redshift (z > 7) dropout candidates based on deep Hawk-I/VLT observations. The FIR SEDs are sampled with PACS/Herschel at 100 and 160 μm, with SPIRE/Herschel at 250, 350 and 500 μm and with LABOCA/APEX at 870 μm. We find that redshifts > 7 would imply extreme FIR SEDs (with dust temperatures >100 K and FIR luminosities >10^13 L_⊙). At z ~ 2, instead, the SEDs of both sources would be compatible with those of typical ultra luminous infrared galaxies or submillimeter galaxies. Considering all available data for these sources from visible to FIR we re-estimate the redshifts and find z ~ 1.6–2.5. Owing to the strong spectral breaks observed in these galaxies, standard templates from the literature fail to reproduce the visible-to-near-IR part of the SEDs even when additional extinction is included. These sources strongly resemble dust-obscured galaxies selected in Spitzer observations with extreme visible-to-FIR colors, and the galaxy GN10 at z = 4. Galaxies with similar SEDs could contaminate other high-redshift surveys.

Determining star formation rates for infrared galaxies

We show that measures of star formation rates (SFRs) for infrared galaxies using either single-band 24 μm or extinction-corrected Paα luminosities are consistent in the total infrared luminosity = L(TIR) ~ 10^10 L_☉ range. MIPS 24 μm photometry can yield SFRs accurately from this luminosity upward: SFR(M_☉ yr^–1) = 7.8 × 10^–10 L(24 μm, L_☉) from L(TIR) = 5× 10^9 L_☉ to 10^11 L_☉ and SFR = 7.8 × 10^–10 L(24 μm, L_☉)(7.76 × 10^–11 L(24))^0.048 for higher L(TIR). For galaxies with L(TIR) ≥ 10^10 L_☉, these new expressions should provide SFRs to within 0.2 dex. For L(TIR) ≥ 10^11 L_☉, we find that the SFR of infrared galaxies is significantly underestimated using extinction-corrected Paα (and presumably using any other optical or near-infrared recombination lines). As a part of this work, we constructed spectral energy distribution templates for eleven luminous and ultraluminous purely star forming infrared galaxies and over the spectral range 0.4 μm to 30 cm. We use these templates and the SINGS data to construct average templates from 5 μm to 30 cm for infrared galaxies with L(TIR) = 5× 10^9 to 10^13 L_☉. All of these templates are made available online.

Search for associations containing young stars (SACY). VII. New stellar and substellar candidate members in the young associations

Context. The young associations offer us one of the best opportunities to study the properties of young stellar and substellar objects and to directly image planets thanks to their proximity (<200 pc) and age (≈5−150 Myr). However, many previous works have been limited to identifying the brighter, more active members (≈1 M_⊙) owing to photometric survey sensitivities limiting the detections of lower mass objects. Aims. We search the field of view of 542 previously identified members of the young associations to identify wide or extremely wide (1000−100 000 au in physical separation) companions. Methods. We combined 2MASS near-infrared photometry (J, H, K) with proper motion values (from UCAC4, PPMXL, NOMAD) to identify companions in the field of view of known members. We collated further photometry and spectroscopy from the literature and conducted our own high-resolution spectroscopic observations for a subsample of candidate members. This complementary information allowed us to assess the efficiency of our method. Results. We identified 84 targets (45: 0.2−1.3 M_⊙, 17: 0.08−0.2 M_⊙, 22: <0.08 M_⊙) in our analysis, ten of which have been identified from spectroscopic analysis in previous young association works. For 33 of these 84, we were able to further assess their membership using a variety of properties (X-ray emission, UV excess, Hα, lithium and K I equivalent widths, radial velocities, and CaH indices). We derive a success rate of 76–88% for this technique based on the consistency of these properties. Conclusions. Once confirmed, the targets identified in this work would significantly improve our knowledge of the lower mass end of the young associations. Additionally, these targets would make an ideal new sample for the identification and study of planets around nearby young stars. Given the predicted substellar mass of the majority of these new candidate members and their proximity, high-contrast imaging techniques would facilitate the search for new low-mass planets.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials

Développement et caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse.

Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

Quantifying Aflatoxin B1 in peanut oil using fabricating fluorescence probes based on upconversion nanoparticles

Rare earth doped upconversion nanoparticles convert near-infrared excitation light into visible emission light. Compared to organic fluorophores and semiconducting nanoparticles, upconversion nanoparticles (UCNPs) offer high photochemical stability, sharp emission bandwidths, and large anti-Stokes shifts. Along with the significant light penetration depth and the absence of autofluorescence in biological samples under infrared excitation, these UCNPs have attracted more and more attention on toxin detection and biological labelling. Herein, the fluorescence probe based on UCNPs was developed for quantifying Aflatoxin B₁ (AFB₁) in peanut oil. Based on a specific immunity format, the detection limit for AFB₁ under optimal conditions was obtained as low as 0.2 ng·ml^{- 1}, and in the effective detection range 0.2 to 100 ng·ml^{- 1}, good relationship between fluorescence intensity and AFB₁ concentration was achieved under the linear ratios up to 0.90. Moreover, to check the feasibility of these probes on AFB₁ measurements in peanut oil, recovery tests have been carried out. A good accuracy rating (93.8%) was obtained in this study. Results showed that the nanoparticles can be successfully applied for sensing AFB₁ in peanut oil.

Supernova 2013fc in a circumnuclear ring of a luminous infrared galaxy: The big brother of SN 1998S

We present photometric and spectroscopic observations of SN 2013fc, a bright type II supernova (SN) in a circumnuclear star-forming ring in the luminous infrared galaxy ESO 154-G010, observed as part of the Public ESO Spectroscopic Survey of Transient Objects. SN 2013fc is both photometrically and spectroscopically similar to the well-studied type IIn SN 1998S and to the bright type II-L SN 1979C. It exhibits an initial linear decline, followed by a short plateau phase and a tail phase with a decline too fast for ⁵⁶Co decay with full γ -ray trapping. Initially, the spectrum was blue and featureless. Later on, a strong broad (~8000 km s^-1) H α emission profile became prominent. We apply a STARLIGHT stellar population model fit to the SN location (observed when the SN had faded) to estimate a high extinction of A_V = 2.9 ± 0.2 mag and an age of 10⁺³ _-2 Myr for the underlying cluster.We compare the SN to SNe 1998S and 1979C and discuss its possible progenitor star considering the similarities to these events. With a peak brightness of B = -20.46 ± 0.21 mag, SN 2013fc is 0.9 mag brighter than SN 1998S and of comparable brightness to SN 1979C.We suggest that SN 2013fc was consistent with a massive red supergiant (RSG) progenitor. Recent mass loss probably due to a strong RSG wind created the circumstellar matter illuminated through its interaction with the SN ejecta. We also observe a near-infrared excess, possibly due to newly condensed dust.

Sedimentology of sites 14-141, 41-366, 47-397 and 79-544B

Along the N-S-transect of DSDP-Sites 5446, 397, 141, and 366, oxygen and carbon isotopes, flux rates of calcium carbonate, terrigenous matter, and biogenic opal, clay minerals and the size distribution of terrigenous partictes were determined in order to assess the ties between atmospheric and oceanic surface and deep-water circulation off northwest Africa during the late Neogene. During the last 9 m.y., both the paleoceanography in the eastern Atlantic and west African paleodimates were intimately correlated with the evolution of the polar ice sheets as reflected in the benthos d18O curves of the 4 DSDP-Sites. These records make it possible to distinguish six major time intervals which were charaterized by long-term persistent regimes of climatic stability or climatic change. Short-term, "Milankovitch"-type cycles superimpose the long-term climatic evolution and may reflect the chronostratigraphic control fluctuations of the solar insolation persisting back to pre-Pleistocene times. Relatively stable, warm climates prevailed during the late Tortonian/early Messinean, 9 to 6 m.y., and the early Pliocene, 4.5 to 3.5 m.y. ago. Based on d18O curves, the amplitudes of short-term climatic variation were generally low, and the ice sheets were smaller than during peak Holocene time. Oceanic circulation and resulting paleoproductivity in upwelling zones were insignificant. The strength of dust supplying meridional trade winds was low (3 to 5 m/s), interglacial-style zonal winds near the ITCZ were dominant, as indicated by the high abundance of kaolinite. Phases of fluvial sediment supply were common. Humidity was characteristic of the climate in northwest Africa for the major part of this time. Major episodes of climatic deterioration in the subtropics occurred in the latest Miocene/early Pliocene, between some 5.6 and 5.2 and between 4.9 and 4.6 m.y. ago, in the late Pliocene, between 3.2 and 2.4 m.y. ago, and again in the Quaternary, near 1 m.y. ago. The episodes were correlated with marked increases of the global ice volume, as revealed by drastic increases of d18O values. They suggest sea-level falls of up to 70 m below the present sea level in the latest Miocene and earliest Pliocene and of 145 m in the latest Pliocene and Quaternary. The climatic changes resulted in strongly enhanced meridional trade winds as suggested by coarser terrigenous grain-sizes, increased mass accumulation rates of eolian dust, and changes in clay-mineral composition from dominantly kaolinite to illite and chlorite. The meridional trade winds reached speeds of 8 to 10 m/s with a maximum near 15 m/s. The enhanced winds probably led t o intensified coastal upwelling as shown by the contemporaneous local increase i n the deposition of biogenic silica and the local depletion of 13C at Site 397. The most drastic environmental changes near 2.4 and 1 m.y. ago coincide with hiatuses which may indicate phases of general erosion due to strongly enhanced deep-water circulation in the northeast At1antic along the northwest African continental margin. The occasional occurrence of quartz grains coarser than 250 µm may suggest ice-rafted debris in sediments off Morocco. During these time intervals the climate in NW-Africa was dominantly arid. Nevertheless, fluvial runoff (and humidity) continued to be important during intermittent warm phases of the short-term climatic cycles. During the end and the beginning of (inter-) glacial times, fluvial supply of nutrients seems to be the dominant factor, controling phases of enhanced paleoproductivity observed off northwest Africa, whereas during phases of glacial maximum strenger fertility of (increased) coastal upwelling becomes more important. A long-term evolution of paleoenvironments during the last 40 m.y. is depicted in the sediments of Site 366 and is clearly controlled by the plate tectonic route of this Site. During Oligocene times, Site 366 lay in the center of the equatorial upwelling, as shown by the high content of biogenic silica contributing up to 100 % of the carbonate-free sediment fraction >6 µm. The influence of equatorial upwelling abruptly terminated near 15 m.y. ago, a change in the record exaggerated by a hiatus of about 2 m.y. Prior to 25 m.y., the terrigenous input at the paleolatitude of Site 366 was restricted t o eolian sediment supply from South Africa by southeasterly trade winds, as shown by dominantly illite and chlorite in the clay fraction and extremely fine-grained terrigenous matter. Near the Oligocene/Miocene boundary, Site 366 drifted across the equator into the belt of the northeasterly trade winds, which is inferred from the increased content of kaolinite and coarser grain sizes of the terrigenous sediment fraction. The clay-mineral and grain-size compositions of Site 366 do not reflect a noteworthy northward shift of the ITCZ during late Miocene and early Pliocene times, i.e. no marked global circulation asymmetry due to the possible absence of a major Northern Hemisphere glaciation (Flohn 1981). This lack of a more northerly position of the ITCZ may result from a bipolar glaciation already existing during late Miocene times, such as also suggested by the evidence of tillites on Iceland and in southern Alaska during those intervals (e.g., Denton & Amstrong 1969, Mudie & Helgason 1983).

Using Surface Spectroscopy to Help Interpret STM Images of Chemisorbed Molecules: Application to the Study of the Hydrogenation of Ketones and a-Ketoesters on Pt

Depuis que la haute énantiopureté est nécessaire dans l’industrie pharmaceutique, les études visant à découvrir les mécanismes pour l’hydrogénation énantiosélective de cétones ou céto-esters sur les surfaces, et à rechercher de nouveaux et plus performants catalyseurs asymétriques, sont d’une grande importance. La microscopie à effet tunnel (STM), la spectroscopie infrarouge de réflexion-absorption, la spectroscopie de désorption à température programmée et la spectrométrie de photoélectrons induits par rayons X sont des méthodes performantes facilitant la compréhension des mécanismes de réaction. En plus de nous permettre de comprendre les mécanismes réactionnels, les études peuvent fournir des informations sur la dynamique des réactions en catalyse hétérogène ainsi que sur le développement de la théorie de la fonctionnelle de la densité (DFT) afin de calculer des interactions faibles dans les processus de surface. D’autres parts, les calculs DFT fournissent une aide essentielle à l’interprétation des données de STM et spectroscopie de surface. Dans cette thèse, certains cétones et céto-esters sur la surface de platine sont étudiées par les techniques sophistiquées mentionnées ci-dessus. Mes études démontrent que la combinaison de l’utilisation de la spectroscopie de routine, des nanotechnologies et de nombreux calculs élaborés, est une méthode efficace pour étudier les réactions à la surface car ces techniques explorent les différents aspects de la surface ainsi que s’entraident mutuellement lors de certaines interprétations.