Abstract There is a growing concern related to increasing energy requirement and greenhouse gas emissions. Hydrogen gas is recognised as a desirable clean fuel and may be a sustainable solution. Hydrogen gas can be directly used as an anodic fuel for Proton Exchange Membrane Fuel Cell that converts chemical energy of hydrogen into electrical energy with no environmentally harmful by-products. Chemical hydrides with high hydrogen storage capacity in terms of gravimetric and volumetric efficiencies are the most promising candidates to supply pure hydrogen at room temperature. Among them, Sodium borohydride (SBH) and Ammonia borane (AB) have drawn a lot of interest as they are stable, non-flammable, nontoxic, and have a high hydrogen storage capability. Large amount of pure hydrogen gas is released during the hydrolysis of these chemical hydrides in presence of certain catalysts. The by-products are non-toxic, environmentally safe and can be recycled. Noble catalysts like Pt and Pd, used in the past to enhance the hydrogen production rate, do not seem to be viable for industrial application considering their cost and availability. Co and Ni borides are considered as good candidates for catalyzed hydrolysis owing to their good catalytic activity, low cost and effortlessly synthesis. Transition metals with varying (metal)/(Co + metal) molar ratio were doped in Co-B catalyst and the effect of metal doping on surface morphology, electronic interaction, and catalytic efficiency of the alloy catalyst powder on hydrogen production by hydrolysis of SBH and AB were studied. On the basis of characterization results, the role of each metal species, involved in hydrolysis and enhanced catalytic performance is discussed. The stability, reusability, and durability of these catalysts have also been investigated. Nanoparticle-assembled Co-B-P thin films on Ni foam (by electroless deposition), along with supported and unsupported Co-B nanoparticles over carbon films were synthesized by Pulsed Laser Deposition and studied for catalytic hydrolysis.

Oxide-based transparent conductors constitute a novel class of materials, which finds applications in many technological fields such as photovoltaics and organic light emitting devices. They can be employed in the new generation solar cells as transparent charge collectors. The transparent and conductive oxide mostly used nowadays is indium tin oxide (ITO), however due to the high cost and scarcity of indium, other materials are under research and development as potential substitutes. Many candidates are currently under study, mainly doped-ZnO, doped-CdO, doped-SnO2, doped-TiO2. The work undertaken in this thesis is a study of the doping processes of thin films of TiO2 and ZnO, two cheap, chemically stable and non-toxic materials. Two main objectives were pursued in this work: (i) the optimization of the film deposition and doping conditions for a potential replacement of ITO and (ii) the understanding of the factors dominating the doping process as well as its limitations. The approach was to explore three doping methods of the films: intrinsic doping, extrinsic doping and, with the aim to combine the benefits of both, intrinsic-extrinsic co-doping. Since the structural defects (such as oxygen vacancies) are at the basis of the intrinsic doping, a control of their formation was searched through the variation of the growth process conditions of the ZnO and TiO2 films. Niobium was selected for the extrinsic doping of the TiO2 films. The films were grown by RF plasma sputtering in different atmospheres (Argon, Ar-O2 and Ar-H2 gas mixtures) and under different plasma power conditions and substrate temperature, onto silicon and quartz substrate. The Nb-containing films were obtained by co-sputtering of either a single composite TiO2 -Nb target or two distinct niobium and TiO2 targets. Many characterization techniques were applied to define the film structural, electronic, electrical and optical properties obtained upon doping. For chemical analysis, X-ray Photoelectron Spectroscopy (XPS) was used. The structure and morphology of the films were analyzed by X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The chemical species present in various plasmas used in deposition process were investigated by Optical Emission Spectroscopy (OES). Further, the defect structure and properties of the obtained films were studied by Positron Annihilation Spectroscopy. Analysis by this technique shed more light on the nature of the vacancies/open volume and on the effect of the latter on the electrical and structural properties of the films. A study based on a joint use of XPS and optical measurements allowed to define the electronic properties of the films (valence band edge, Fermi level position, work function, ionization potential and electron affinity). Structural analysis results revealed the formation of both anatase and rutile nanocrystalline phases for intrinsic and extrinsic doping of TiO2, while with the co-doping method only anatase phase was obtained, a phase known to be favorable for Nb incorporation in TiO2 lattice. The intrinsic doping of TiO2 films showed high transparency in the visible range, but resulted in still high resistivity values (101-103 ï —xcm). The latter could be lowered by using Ar-H2 gas mixtures during film deposition. The same trend was observed in the case of intrinsically-doped ZnO films, an increase in the electrical conductivity was observed when the concentration of defects was increased. The lowest resistivity was achieved with niobium doping of TiO2, 5x10-3 ï —xcm, with an optical absorption coefficient in the visible range of ~1x104 cm-1, however the combination of the internal defects and Nb, in co-doping, did not improve the conductivity. Nonetheless, it was found that co-doping method strongly modified the electronic properties of the TiO2 films, allowing a control of the work function, an important parameter for transparent electrodes. Low cost transparent conductive oxides were obtained when niobium was successfully incorporated in TiO2 lattice. By optimization of the deposition process of the films (dopant concentration, RF power, atmosphere, and annealing temperature) the electronic, electrical and optical properties of doped- TiO2 films can be improved. The obtained results can contribute to the development of transparent electrodes and charge collectors by RF sputtering, a suitable technique for coating on large area substrates.

The development of new materials represents the recent frontier in hydrogen storage technologies. In the last few decades the preparation of nanostructured materials has had an increasing interest, because the hydrogen storage capacity is closely linked to the material dimensions, and increases considerably with the reduction of the particles sizes. The chemical synthesis plays an important role in the development of new materials for hydrogen absorption because it allows a good control of the hydride phase sizing, and thus of the kinetics/ thermodynamics of such materials. The aim of the work concerns the synthesis by chemical techniques of metals nanoparticles. Nanostractured metals embedded into a polymeric matrix are prepared. The polymer was used for achieving nanoparticles with tailored properties.

Cu2ZnSnS4 (CZTS) quaternary compound has attracted much attention in the last years as new abundant, low cost and non-toxic material, with desirable properties for thin film photovoltaic (PV) applications. In this work, CZTS thin films were grown using two different processes, based on vacuum deposition of precursors, followed by a heat treatment in sulphur atmosphere. The precursors were deposited using two different approaches: (i) electron-beam evaporation of multiple stacks made of ZnS, Sn and Cu and (ii) co-sputtering deposition of the three binary sulphides CuS, SnS and ZnS. All the materials were characterized both as isolated films and as absorber layer in solar cells, produced using the typical structure Mo/CZTS/CdS/i:Zno/AZO. Both growth processes were found to give good quality kesterite films, showing CZTS as the main phase, large grains and suitable properties for PV application, but higher homogeneity and stoichiometry control were achieved using the co-sputtering route. A detailed investigation on CZTS optical properties, microstructure, intrinsic defect density and their correlation with the material composition is presented. A strong effect of the tin content on the bandgap energy, sub-gap absorption coefficient, crystalline domain and grain size is shown and a model based on the increase of the intrinsic defect density induced by a reduced tin content is proposed. These studies suggested a correlation between the increase of the bandgap energy and the improvement of the material quality, which was also confirmed by the performances of the final devices. CZTS thin films were then assembled into the solar cells and their properties as absorber layer were optimized by varying both composition and thickness. CZTS samples produced from stacked evaporated precursors allowed achieving a maximum efficiency of 3.2%, but reproducibility limits of the evaporation process made difficult to obtain further and rapid efficiency improvements. The co-sputtering route was demonstrated to be a more successful strategy, assuring a fine-control of the film composition with good process reproducibility. A fast improvement of solar cell efficiency was obtained using this approach and a maximum efficiency of 5.7% was achieved. The relationship between the absorber layer stoichiometry and the device performances was investigated: the effect of the Zn enrichment and a possible influence of the Cu/Sn ratio on the device performances are discussed. Investigation on CZTS/CdS and CZTS/MoS2 interfaces revealed that the optimization of both buffer-layer and back-contact technology is a primary need for further improvement of CZTS solar cells.

The first and foremost goal of the present work was to develop novel theoretical and computational methods and use state-of-the-art techniques in electronic structure theory to interpret a specific set of physical problems mainly related, but not limited to, materials science. Our guiding principle was to relate information obtained from scattering experiments with the numerical solution of the multichannel dynamics of many-body systems, shedding light on the origin of electronic and optical properties of a variety of systems. The general approach adopted in this thesis was not to present separate chapters for theory, rather we introduced methods along with the experiments. In particular, we focused on the modeling of both ground and excited states of materials, on vibrational, core and valence electron spectroscopy of condensed matter systems using computational methods at different level of accuracy and complexity to interpret a number of experimental data. While these methods have been devised for this scope, their applicability, notably the treatment of the continuum states through multichannel scattering formalism, is totally general and can be applied to describe several different experiments, performed with a variety of apparently distant techniques. In particular, the Fano--Fesbach discrete-continuum interaction provides a common framework suitable to this task. Within this scheme, thus, the calculation of the spectral lineshapes measured by XPS, Auger, NEXAFS, and EEL spectroscopy can be reconciled on the same theoretical grounds with the investigation of the properties of ultra-cold Fermi gases at unitarity, or of the electronic capture and decay rate in ultra-hot plasma found in stellar environments or, finally, with the study of the epitaxial growth of nanostructured materials. Crossing the borders between several computational, theoretical and experimental techniques, this thesis should be of interest to a broad community, including those interested in aspects of atomic and molecular physics, electronic structure calculations, experimental and theoretical spectroscopy, astrophysics and scattering theorists in a broad sense.

Photovoltaic technology in the field of renewable energy has reached a high commercial interest over the past decade. The traditional silicon photovoltaic systems that is currently the most widespread, mainly due to government subsidies, have a low energy production. The wide use of material and the low efficiency of the silicon modules required the research and development of photovoltaic systems more efficient. The most promising technology is the photovoltaic concentration that increases the efficiency of the modules by reducing the area of the PV cell. The concentration photovoltaic has had considerable technological progress related to the development of multi-junction PV cells with high efficiency. Another approach is the technology of photovoltaic concentration with the spectral separation, so using the interference filters the solar spectrum is splitted into different optical bands. In this research was designed and built a CPV prototype system with spectral separation. The interference filters such as anti-reflection and dichroic mirror are made up of silicon dioxide and titanium dioxide. These oxides have been realized by means of physical vapor deposition reactive magnetron sputtering technique. The PVD technique allows to deposit thin films with a homogeneous process reproducible and reliable. In the first part of the work, the characterization of individual layers of oxide materials have allowed to extrapolate the optical constants. This is necessary for the design of the optical multilayer. The characterization has nvolved various analyzes such as atomic force microscopy (AFM) to determine the thickness and the roughness, compositional analysis Rutherforf backscattering spectrometry (RBS), and optical analysis UV-Vis-NIR. These analyzes were necesary to calibrate the deposition system in order to subsequently to realize the multilayer optics. The as deposited optical multilayers not confirm the optical design, and it was necessary to carry out an annealing at 350°C. In the second part of the work, there were also micro structural characterizations for evaluating the phase variation of the titanium dioxide with the annealing treatment. The Fourier transform infrared (FT-IR) analysis has checked the absorption peak of the Ti-O-Ti of the crystalline phase. In addition, X-ray diffraction (XRD) analysis verified the phase variation of titanium dioxide from purely amorphous phase with a slight presence of rutile to the anatase phase. Through the optical analysis it was possible to extrapolate the new optical constants corresponding to the phase of anatase. In the third part of the work, the ray tracing design of optical splitting of the CPV prototype was carry out. The CPV system is designed by coupling a concentration Fresnel a dichroic mirror. The focus of the radiation on the PV cell, is simulated by two ideal detector. The optical optimization as function of the f-number of the lens has allowed to define the layout for the prototyping phase. A further optimization is to insert a secondary optics element (SOE) of homogenization. The secondary optics will also limits the optical losses due to a misalignment of the CPV prototype. In the last part of this thesis is devoted to the preparation and the characterization of the CPV prototype. Were performed measures of solar radiation, which combined with the characteristic I-V-P curves of the solar cells have enable to evaluate the efficiency of the prototype system. The efficiency of the spectral separation system was compared with concentration multi-junction PV cells. Daily measurement were performed to compare the spectral separation technology than to the multi-junction technology. The results show that the separation system maintains a more constant performance during the day. Finally, thermal measurements were conducted on the component of the CPV prototype separation system. The experimental results allows to guarantee that the spectral separation is also a selective filter of temperature. This allows the solar cells to maximize the photovoltaic conversion and to reduce the overheating.

In this thesis work nanoscrystalline optical properties of diamond and two recent new NCD functionalisation techniques involving UV light (one step method and photochemical oxidation) have been investigated. Firstly the oxidation of diamond surface caused by the irradiation of the surface with UV-light in oxygen atmosphere was considered. Two different experiments in situ were realized in order to understand the physic-chemistry of this method. The chemical bonds between oxygen and surface carbon atoms were investigated by firstly performing an annealing treatment in ultra hight vacuum of a oxidized UV surface and then comparing the obtained result with annealing treatments of two different oxygenated diamond surfaces using other two techniques: plasma oxidation and piranha solution oxidation. An other interesting aspect on which clarity has to be made deal with amination process of diamond surface. As a first fundamental step, the efficiency on hydrogenated diamond surface was investigate. Successively the role of oxygen in the chemistry of amination process was studied performing in situ experiments using different terminated diamond surface (hydrogenated, chemically oxidized, UV oxidized) and different gaese (pure NH3 or NH3 + O2).

No description available.

El cártamo es un cultivo oleaginoso poco difundido en Argentina con potencial de desarrollo en regiones semiáridas de la región pampeana. Las características requeridas por la industria y los productores agropecuarios son la base de los objetivos del mejoramiento. El ideotipo para el sudoeste bonaerense presenta alto contenido de aceite alto oleico, alto rendimiento, precocidad, adaptación a siembras de otoño-invierno y al ambiente en general. El objetivo principal de la presente tesis fue el desarrollo de criterios de selección para la obtención de líneas avanzadas para el mercado o para futuros planes de mejoramiento. Además, se buscó una herramienta molecular para seleccionar por el perfil acídico de la materia grasa (MG) y generar nuevas herramientas moleculares para cártamo a través del mapeo de QTLs en una población biparental. A partir de germoplasma F3 proveniente de un plan de mejoramiento del USDA (Pullman, Washington), se llevó a cabo un plan de selección a campo con el fin de obtener líneas avanzadas promisorias. En generaciones tempranas (F3- F4) se utilizaron variables fácilmente medibles como herramientas de selección indirecta del contenido de materia grasa (MG). La selección en F3 se realizó por adaptación, precocidad y bajo espesor de pericarpio, y en F4 se realizó por contenido de cáscara, altura de planta, granos por capítulo y las dimensiones del grano. En generaciones avanzadas (F5-F6), la evaluación a campo en ensayos comparativos en cuatro ambientes representativos del sudoeste bonaerense permitió seleccionar de forma directa por el rendimiento de MG y su estabilidad. L62, L6 y L69 mostraron un alto y estable rendimiento de MG, pero sin alcanzar el contenido de MG que rige la norma (33%). LFM3 y L3 exhibieron buena adaptación al sudoeste bonaerense, alto rendimiento de MG, alto contenido de MG, alto contenido de ácido oleico y mayor precocidad que el testigo comercial CW99-OL. El desarrollo de nuevos cultivares se acompañó con la generación de una norma de manejo en cuanto a la fecha de siembra. La evaluación de fechas de siembra en dos ambientes permitió concluir que la siembra entre fines de mayo e inicio de junio optimiza el rendimiento del cultivo. El perfil de ácidos grasos es el carácter cualitativo más importantes del cártamo, para el cuál existe gran variabilidad genética y determina las características industriales del aceite. Las nuevas tecnologías de secuenciación generan una rápida y económica identificación de marcadores moleculares e impulsaron la selección asistida por marcadores. En este trabajo se utilizó la tecnología KASP (kompetitive allele specific PCR) para validar un marcador basado en la secuencia del gen responsable en la determinación del perfil acídico del aceite. La secuenciación de última generación aplicada al genotipado por secuenciación permite descubrir millones de SNPs (polimorfismos de un solo nucleótido) en una población de mapeo. La integración de densos mapas genéticos con datos fenotípicos permite la identificación de loci de caracteres cuantitativos (QTLs). A través del genotipado de una población F2, se identificaron 673 marcadores polimórficos, se generó un mapa de ligamiento, y sobre éste, se mapearon 31 QTLs: siete QTLs asociados a características de la cascara, cinco a arquitectura, morfología y rendimiento de planta, ocho a dimensiones de grano y capítulo, y 11 a características asociadas al tamaño de grano. Los marcadores flanqueantes a estas regiones genómicas representan un nuevo recurso para el mejoramiento, y son un punto de partida para el mapeo fino de las regiones involucradas. Esta tesis es el primer estudio genómico de cártamo realizado en Argentina y el primer plan de selección llevado a cabo en el sudoeste de Buenos Aires con la finalidad de obtener nuevos genotipos adaptados, generando a su vez una recomendación de fecha de siembra óptima para la región en cuestión / Safflower is an alternative oilseed crop in Argentina, potentially adapted to the semiarid “Pampa” region. Crop characteristics required by the industry and farmers like yield, oil content or oil quality are the target traits for breeding programs. Safflower ideotype for the southwest of the Buenos Aires province should be high yielding with high oil content and high oleic acid content. Earliness and adaptation to fall sowing are also required. The aims of this thesis were the development of new advanced breeding lines to be registered or as a source of initial germplasm for future breeding programs; the development of a molecular tool for selecting the high oleic allele and QTL mapping of yield and oil content related traits in a biparental population obtained from the hybridization of contrasting varieties. Safflower F3 germplasm from one of the USDA (Pullman, Washington) breeding programs was the initial material for the field selection plan. In early breeding lines (F3-F4), selection was carried out through simple traits, that were used as indirect selection tools for a complex trait like oil content. Selection was done through adaptation, earliness and hull thickness in F3 generation, and through hull content, plant height, number of grains per capitulum and grain dimensions in F4. After the two selection cycles, 16 promising F5 breeding lines were obtained. In advanced generations (F5-F6), selection for high oil yield and stability was accomplished through field evaluation in multi environmental trials. L62, L6 and L69 showed high and stable oil yield, but an oil content below the commercial base. L3 and LFM3 were the best adapted and high yielding breeding material, with high oleic oil content and an earlier development the commercial check CW 99 OL. The development of new genotypes was integrated with the exploration of optimum sowing dates. From the evaluation of six sowing dates in two environments it was concluded that sowings during late May and early June have the highest and more stable grain yield. The fatty acid profile is the most important qualitative trait of safflower since it determines the oil industrial quality and is genetically diverse across the germplasm. The new sequencing technologies applied to molecular marker discovery have promoted marker assisted selection procedures. In this work, KASP (kompetitive allele specific PCR) technology was used to validate a molecular marker based on the sequence of ctFAD2-1 gene, involved in the oleic acid content of safflower oil. Next-generation sequencing technologies applied to genotyping by sequencing allow fast and massive SNP discovery in a mapping population. The integration of dense genetic maps with phenotypic data is used in QTL (quantitative trait loci) mapping. In this study, an F2 population was genotyped by Dartseq method and almost 700 polymorphic markers were identified and a linkage map was constructed. Thirty-one (31) QTLs were mapped: seven of them were related to hull characteristics, five to architecture and morphology of the plant, eight to grain and capitulum dimensions, and 11 to grain size. Molecular markers flanking these genomic regions represent a new genetic resource for breeding and are starting points for further studies like fine mapping of the involved regions. This thesis represents the first genomic approach in safflower of Argentina, and the first attempt of breeding by selection in the southwest of Buenos Aires province with the objective of developing new adapted genotypes and providing a basic management tool of sowing date / TEXTO PARCIAL en período de teletrabajo

El rol de la materia orgánica disuelta (DOM) en el ambiente marino como fuente o sumidero global de carbono es comprendido sólo parcialmente. Si bien la DOM representa una cantidad de carbono aproximadamente diez veces mayor que la materia orgánica particulada (POM), su estudio ha sido frecuentemente relegado por dificultades metodológicas. Sin embargo el avance en las técnicas y metodologías ha permitido el estudio de su distribución y fuentes en diferentes ambientes, y recientemente, se ha comenzado a conocer cuál es la distribución y rol de la DOM en la plataforma Argentina. El objetivo general de esta tesis es profundizar en el conocimiento del origen y la composición de la DOM en el ambiente pelágico del Mar Argentino, en particular en sectores de alta producción biológica nueva o regenerada o influenciados por aportes continentales, con gradientes espaciales que cubren diferentes estados tróficos de aguas estuarinas y oceánicas como lo son las zonas de El Rincón y estuarios fríos de la Patagonia Atlántica. Durante el desarrollo de la tesis doctoral, fue un punto de particular importancia la caracterización química y de patrones de fluorescencia de la DOM con la determinación de aminoácidos, carbohidratos y propiedades ópticas en ambas regiones de muestreo, utilizando métodos de separación y cuantificación como HPLC y espectrometría. Se utilizaron técnicas de biología molecular para estudiar la estructura de la comunidad bacteriana como hibridación in situ con sondas fluorescentes y adicionalmente, determinación de isótopos estables de nitrógeno con el propósito de determinar las fuentes de la DOM y posible dinámica de la zona. Tras efectuar estas investigaciones, en la zona de El Rincón y transición, se llevó a cabo el estudio de la correlación de la estructura de la comunidad bacteriana y la abundancia del fitoplancton con cambios en la composición química de la materia orgánica disuelta. Se ha encontrado que el principal componente de la fracción químicamente caracterizada está constituido por los aminoácidos, en primavera y carbohidratos en otoño; en ambas estaciones del año la fracción no caracterizada de la DOM contiene una alta proporción de carbono indicando una posible acumulación del mismo con características refractarias en una zona regenerativa como El Rincón. Esto es apoyado por las propiedades de la DOM fluorescente (FDOM) e índices derivados que nos indica un predominio de DOM con propiedades húmicas, especialmente en la zona de El Rincón. Mediante la aplicación de métodos estadísticos multivariados y correlaciones entre variables se estableció la relación entre la composición química y fluorescente de DOM, con la comunidad planctónica y aportes alóctonos, ya que se observó una afinidad de las betaproteobacterias por la DOM alóctona con características refractarias y la asociación de DOM autóctona de propiedades proteínicas con las alproteobacterias y citófagas/flavobaterias. Estos patrones sugieren un primer camino de origen, transformación y remineralización de la metería orgánica disuelta en el área de El Rincón. Finalmente, en el extremo sur de la plataforma argentina, las señales biogeoquímicas investigadas en la conexión del Pacífico-Atlántico presentan las siguientes tendencias. Entre los componentes disueltos, el carbono orgánico con características terrestres y la concentración de amonio mostraron una distribución espacial muy influenciada por la entrada de agua dulce del SE del Pacífico a través de la conexión con el Atlántico por la corriente del Cabo de Hornos, canal Beagle y probablemente también de fuentes continentales de Tierra del Fuego. A su vez, la distribución de nitrato, fosfato y silicato en la región mostró una fuerte influencia de la contribución de las aguas ricas en nutrientes de la Corriente Circumpolar Antártica. Además se pudo establecer que los valores positivos de δ15N en el sector estudiado parecen excluir la entrada significativa de amonio al Atlántico por medio de la deposición húmeda en el SE del Pacífico, favoreciendo más bien la contribución de este nutriente por escorrentía continental. / Only partially is understood the roll of Dissolved Organic Matter (DOM) in the marine environment as a global source or sink for carbon, even having in mind that it contributes in approximately ten times more of carbon´s content than the particulate form (POM), its study was frequently relegated for methodological reasons. Improvements in techniques and methodologies have conducted to a better knowledge on its distribution and sources in different environments, and recently in the Argentine Continental Shelf. The general aim of this thesis work was to access the origin and composition of the Dissolved Organic Matter in the pelagic environment in the Argentinian Sea, particularly in regions of high biological production – both new and regenerated - or land-derived sources, having spatial concentration gradients and including diverse trophic states of estuarine and oceanic waters as El Rincon zone and cold estuarine regions of the Atlantic Patagonia. An important focal point in the development of this work was the chemical characterization and the identification of fluorescence patterns of DOM, with the determination of amino acids, carbohydrates and optical properties in both sampling areas, by using separation and quantification methods as HPLC and spectrometry. Molecular biology techniques were applied to the sltudy of the bacterial community structure, such as in situ hybridation with fluorescent probes and additionally nitrogen stable isotopes determination with de aim of access on the sources and possible dynamics of DOM in the area. After this studies, in the El Rincón and Transition zones, the bacterial community structure and phytoplankton abundance were correlated with changes in the chemical composition of dissolved organic matter. In this sense, it was defined that the principal component of the chemically characterized fraction was amino acids contents in spring and carbohydrates in autumn. During both seasons the non-characterized fraction of DOM contains a high proportion of carbon, indicating, a possible accumulation of refractory forms in a regenerative region as El Rincon. This is in agreement with fluorescent (FDOM) properties of DOM and derived index showing a dominance of organic matter having humic properties in such a region. By application of multivariate statistical methods and correlation among variables, it was established a relationship between chemical and fluorescence composition of DOM and planktonic community, and allochthonous sources, through an affinity of betaproteobacteriae and allochthonous DOM with refractary characteristics and also by the association of authocthonous DOM with proteinic properties and alproteobacteriae and citofagues/flavobacteriae. These kind of patterns suggest a first way about origin, transformation and remineralization of dissolved organic matter in the El Rincón area. Finally, in the southermost part of the Argentinian shelf, studied biogeochemical signals in the Pacific-Atlantic connection show the following trends: Among dissolved components, organic carbon with terrestrial characteristics and ammonia concentrations show a spatial distribution with a dominance of freshwater arriving from de Ocean through the Cape Horn current, the Beagle Channel and may be by runoff of continental sources in Tierra del Fuego island. By the other side, nitrate, phosphate and silicate distribution in the region presents a strong influence of the nutrient rich waters of the Circumpolar Antartic Current. Furthermore, it was established that positive values in δ15N in the studied sector seems to exclude a significant arrival of ammonia to the Atlantic through wet deposition in the South-East Pacific, favouring instead the contribution of this nutrient by continental surface runoff.