L’objectif de cette thèse est d’arriver à mieux contraindre les paramètres qui contrôlent les processus d’altération à l’échelle d’un petit bassin versant, en se focalisant plus précisément sur le rôle de l’hydrologie. Pour ce faire, les variations temporelles et spatiales des signatures chimiques et isotopiques (U, Sr) des eaux du bassin versant du Ringelbach (Vosges, France) sont étudiées. Plusieurs sources de ce bassin versant, essentiellement composé d’un granite plus ou moins fracturé, ont été échantillonnées mensuellement sur une période de deux ans, le long d’un profil altitudinal. Ce bassin versant présente également l’avantage d’être équipé de trois forages profonds (allant jusqu’à 150 mètres de profondeur) qui ont permis de prélever à la fois les roches et les eaux profondes. Sur la base de l’interprétation géochimique des eaux, la connectivité des différents compartiments hydrologiques a été évaluée et un schéma de fonctionnement hydrogéochimique est proposé s’appuyant sur une bonne connaissance du contexte géologique. Enfin, un taux d’altération et un flux d’eau sont estimés à partir d’une modélisation de l’évolution du rapport isotopique de l’uranium (234U/238U) le long d’un trajet d’eau. L’originalité de cette étude est également de coupler cette approche de traçage géochimique avec une approche modélisatrice en utilisant le logiciel KIRMAT (Kinetic Reactions and Mass transport) qui intègre les équations des réactions géochimiques (dissolution/précipitation) et les équations de transport (1D). Il est ainsi possible de simuler le transport réactif d’une eau traversant la roche le long d’un certain trajet d’eau. Cette modélisation s’appuie sur la caractérisation minéralogique, des propriétés physiques des échantillons de roches prélevés le long des forages et sur les interprétations géochimiques des eaux. Ainsi, la modélisation de la composition chimique des eaux de sources et des eaux de forages a permis d’affiner la compréhension des processus d’altération, notamment le rôle des phases secondaires précipitées. Celle-ci permet également une meilleure compréhension des phénomènes de couplage entre les différents paramètres qui contrôlent la signature chimique des eaux à l’échelle du bassin versant. / The main goal of the present thesis is to better constrain the parameters that control weathering processes at a small catchment scale, focusing specifically on the role of hydrology. For this purpose, temporal and spatial variations of the chemical and isotopic (U, Sr) water composition of the Ringelbach catchment are studied. Several springs of this catchment whose basement is mainly composed of granite more or less fractured located along an altitudinal profile were monthly sampled over a period of two years. The additional interest of this site is that three deep boreholes (up to 150 meters deep) allow the sampling of both deep rocks and waters. The connectivity of the different hydrological compartments is evaluated based on the geochemical interpretation of water samples. A schematic hydrological functioning is proposed based on a good knowledge of the geological context. Finally, a weathering rate and a water flux are estimated from the modeling of the uranium activity ratio along a water path. The originality of this study lays also in combination of a geochemical and modeling approaches using the software KIRMAT (Kinetic Reactions and Mass transport) that integrates geochemical reactions (dissolution/precipitation) and 1D mass transport equations. It allow to simulate the reactive transport of a fluid through a rock along a given water pathway. This modeling is based on the characterization of the mineralogical and physical properties of the rock, sampled along the boreholes and the geochemical interpretation of the waters. Thus, the modeling of the chemical composition of the spring waters and borehole waters permit to improve the understanding of weathering processes including the role of precipitated secondary phases. It also allows to better understand the interplay of parameters that that control the water chemical signature at the catchment scale.

Made available in DSpace on 2014-12-17T14:08:55Z (GMT). No. of bitstreams: 1 PauloECB_DISSERT.pdf: 998748 bytes, checksum: ca9ede6adc0bf3c38d53d423e9580270 (MD5) Previous issue date: 2013-04-01 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / This work aims to obtain a low-cost virtual sensor to estimate the quality of LPG. For the acquisition of data from a distillation tower, software HYSYS ? was used to simulate chemical processes. These data will be used for training and validation of an Artificial Neural Network (ANN). This network will aim to estimate from available simulated variables such as temperature, pressure and discharge flow of a distillation tower, the mole fraction of pentane present in LPG. Thus, allowing a better control of product quality / Este trabalho tem como objetivo a obten??o de um sensor virtual de baixo custo para estimar a qualidade do GLP. Para a simula??o dos dados gerados por uma torre de destila??o foi utilizado um software que simula processos qu?micos, chamado HYSYS?. Esses dados ser?o utilizados para treinamento e valida??o de uma Rede Neural Artificial (RNA). Essa rede ter? como objetivo estimar a partir de vari?veis dispon?veis em uma simula??o, como a temperatura, press?o e vaz?o de refluxo de uma torre de destila??o, a fra??o molar de pentano presente no GLP. Possibilitando, desta forma, um melhor controle de qualidade do produto final

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2018-02-07T13:54:23Z No. of bitstreams: 1 dissertação_Laura.pdf: 5408448 bytes, checksum: f3d1bfb2f5f04ffe5df9adae2d5c5946 (MD5) / Made available in DSpace on 2018-02-07T13:54:23Z (GMT). No. of bitstreams: 1 dissertação_Laura.pdf: 5408448 bytes, checksum: f3d1bfb2f5f04ffe5df9adae2d5c5946 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O material particulado em suspensão (MPS) é formado principalmente por partículas originadas do intemperismo das rochas presentes na bacia, além de partículas orgânicas. O conhecimento acerca do MPS pode fornecer informações sobre proveniência, processos e influências antrópicas. Alterações na bacia de drenagem, como as relacionadas ao uso do solo e construções de barragens, influenciam principalmente na quantidade de material transportada, enquanto a urbanização sobretudo na qualidade. O presente trabalho buscou estabelecer a contribuição de MPS da bacia do rio Piabanha (RJ) para o rio Paraíba do Sul e caracterizá-la química e mineralogicamente, além de estabelecer diferenças temporais e espaciais na bacia, qualitativa e quantitativamente. Foram feitas sete coletas ao longo do ano de 2016, em três pontos da bacia, e as amostras tiveram seus valores de concentração, carga e fluxo de MPS calculados. Foram realizadas análises químicas por fluorescência de raios X e análises mineralógicas por difração de raios X, essas últimas acrescidas de quantificação pelo método de Rietveld. Os resultados encontrados indicaram variação sazonal na quantidade de sedimentos produzida (10‒1600 ton dia⁻¹ na foz) e também variação espacial, fruto principalmente das diferenças da cobertura e uso do solo ao longo da bacia. As barragens também se mostraram importantes na retenção de sedimentos. Os minerais encontrados no MPS foram caulinita, gibbsita, goethita, illita, feldspatos, quartzo, muscovita, anatásio e weddelita, sendo esta última mais presente na região urbanizada, funcionando como um traçador de influência antrópica. A caulinita foi o mineral mais representativo do MPS em todas as amostras (28‒55%), indicando um material significativamente intemperizado. As análises químicas mostraram predominância de SiO2 (35‒46%) e Al2O3 (25‒41%). Houve maior participação de P2O5 e Fe2O3 no período seco, relacionados direta ou indiretamente à influência antrópica na bacia, como lançamento de efluentes, contudo essa diferença sazonal foi vista principalmente nas áreas urbanizadas / The suspended particulate matter (SPM) is formed mainly by particles resulted from rock weathering, but also by organic ones. The knowledge of SPM is able to provide information about provenience, processes and anthropic influences. River basin alterations, like the ones related to land use and dam constructions, can change mainly the transported load’s quantity, while urbanization is related mostly to quality. The present study aimed to determine the SPM contribution from Piabanha river basin (RJ) to Paraiba do Sul river and characterize its mineralogy and chemistry, as well as set temporal and spatial variation, qualitatively and quantitatively. Samples were collected in three points of Piabanha basin, in seven different days of 2016, and concentration, load and flow values of SPM were calculated. The samples analysis included its chemistry (X-ray fluorescence) and mineralogy (X-ray diffraction), the last one with addition of quantification by Rietveld method. The results showed seasonal (10‒1600 ton day⁻¹ in the mouth) and spatial variation in sediments yield, due to differences in cover and land use along the basin. Dams also exposed their importance in sediments retention. Minerals found in SPM were kaolinite, gibbsite, goethite, illite, feldspars, quartz, muscovite, anathase and weddellite, with the last one more present in urban areas, working as a tracer of anthropic influence. Kaolinite was the most representative mineral of SPM in all samples (28‒55%), denoting a material associated to significant weathering. The chemical analysis showed SiO2 (35‒46%) and Al2O3 (25‒41%) predominance. P2O5 and Fe2O3 were higher in the dry period, related directly or indirectly to anthropic influence, like effluents release. However, this seasonal difference was observed mainly in urban areas.

Os revestimentos curáveis por radiação ultravioleta (UV) ou feixe de elétrons (EB) são sistemas líquidos reativos compostos por resinas, diluentes (monômero) e aditivos, capazes de formar compostos poliméricos termorrígidos por reações de polimerização e reticulação induzidas por radiação. Esta tecnologia tem sido empregada como alternativa aos processos convencionais no desenvolvimento de uma variada gama de produtos. Um dos grandes desafios da aplicação da tecnologia de cura UV/EB em produtos a serem submetidos ao intemperismo é a manutenção de suas propriedades físicas e de sua aparência. Este trabalho apresenta informações sobre o comportamento de quatro vernizes com e sem aditivos estabilizantes à luz-curados por radiação UV ou EB quando submetidos ao processo de envelhecimento acelerado. Os vernizes foram caracterizados por técnicas termoanalíticas como termogravimetria (TG), calorimetria exploratória diferencial (DSC) e fotocalorimetria diferencial (foto-DSC); espectroscopia de absorção no infravermelho e no ultravioleta, e propriedades mecânicas. Os vernizes sob a forma de filmes de 50 µm de espessura foram curados com diferentes doses de radiação UV ou EB. A cura por radiação UV foi conduzida em túnel de luz, provido de uma lâmpada de mercúrio de média pressão e esteira rolante com velocidade variável. As diferentes doses de radiação UV de 50 a 1500 mJ cm-2 foram obtidas variando-se a velocidade da esteira. A cura por EB foi realizada utilizando-se acelerador de elétrons de energia de 1,5 MeV, sob atmosfera de nitrogênio, aplicando-se doses no intervalo de 1,6 a 300 kGy. O grau de cura dos diferentes filmes foi calculado por meio dos valores das entalpias de reação da cura residual obtidos por DSC. Os testes de envelhecimento acelerado dos filmes curados foram feitos em câmara de envelhecimento do tipo Weather-Ometer por períodos de exposição de 100 a 3000 horas. Os dados obtidos experimentalmente foram avaliados em função da composição dos vernizes, da dose e do tipo de radiação empregada na cura e do tempo de permanência na câmara de envelhecimento. Os resultados indicam que os filmes curados por EB apresentam maior durabilidade frente ao intemperismo do que os seus pares curados por radiação UV. Os filmes não estabilizados (sem aditivos) apresentam grande instabilidade nas condições do teste de envelhecimento. O efeito do envelhecimento foi observado por meio de dados de dureza, brilho, rugosidade, índice de amarelecimento e alteração das bandas de absorção dos espectros FTIR. / The materials curable by ultraviolet (UV) or electron beam (EB) radiation such as inks, adhesives and coatings are reactive compounds made up of resin, monomer, photoinitiator and additives which undergo polymerization and crosslinking under irradiation producing thermoset products. This technology has been used in a great variety of industrial applications, replacing the conventional curing process in the development of new products. One of the challenging applications has been to design weatherable radiation cured coating which maintain their desirable physical properties and aesthetic appearance. This research reports information about the behavior of four UV and EB curable clear coatings -with or without light stabilizer additives- under accelerated weathering. Thermogravinietry, differential scanning calorimetry, differential photocalorimetry, infrared and ultraviolet spectroscopy and tensile properties were used to evaluate these formulations. Clear coating 50 µm thick films were cured with UV and EB radiation at different doses. The UV curing process was carried out at room temperature using an UV tunnel, with a medium pressure mercury lamp and a transport belt with variable speed. The ultraviolet radiation doses were in the range of 50 to 1500 mJ cm-2. The EB curing process was performed under N2 atmosphere, with doses in the range from 1,6 to 300 kGy using the IPEN-CNEN/SP Dynamitron electron beam accelerator with energy of 1.5 MeV. The cure degree was determined by means of the residual reaction heat of the undercured samples obtained from photo-DSC or DSC measurements. The accelerated aging tests were carried out using a Weather-Ometer chamber with exposition times in the range of 100 to 3000 hours. The experimental data obtained from the photo-aged samples were evaluated and correlated to the formulation composition, type of radiation - UV or EB, radiation dose and residence time in the aging chamber. The results have shown that the EB cured films have a better resistance to photoinduced weathering effects than UV cured ones. UV/EB films with light stabilizers have shown larger stability than those counterparts with no additives. The aging effects were evaluated by parameters such as hardness, gloss, surface roughness, yellowness index and changes in the FTIR absorption bands.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-19T16:19:47Z No. of bitstreams: 1 DISSERTJULIANAGRODRIGUES.pdf: 4883356 bytes, checksum: 5706faa288cd5541e1bfe8cc446e591b (MD5) / Made available in DSpace on 2016-04-19T16:19:47Z (GMT). No. of bitstreams: 1 DISSERTJULIANAGRODRIGUES.pdf: 4883356 bytes, checksum: 5706faa288cd5541e1bfe8cc446e591b (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / Em janeiro de 2011, a região serrana do Estado do Rio de Janeiro foi atingida por inúmeros movimentos de massa em um evento denominado de “Megadesastre”. A ocorrência de movimentos de massa depende da disponibilidade de material a ser mobilizado, e essa disponibilidade está relacionada com o intemperismo. Dessa forma, essa dissertação buscou avaliar as transformações geoquímicas e mineralógicas em dois perfis de intemperismo desenvolvidos sobre rocha granítica, na bacia do Córrego do Príncipe (Teresópolis/RJ), e a relação com a ocorrência de movimentos de massa. Nas análises químicas empregaram-se os métodos de ativação neutrônica (AAN) e fluorescência de raios-X (FRX). Já na mineralogia utilizou-se petrografia, observação em lupa e difração de raios-X (DRX), e na granulometria, peneiramento e difratometria a laser. A análise estatística multivariada indicou a separação de quatro grupos: G1 - apresenta o maior grau de dissimilaridade e é formado por material ferro-manganoso; G2 - amostras com menor grau de alteração, onde foi verificada a presença de plagioclásio e a escassez de minerais secundários, além da presença de material rochoso (corestones) menos alterado e material inconsolidado com textura grossa; G3 e G4 - apesar de apresentarem fortes similaridades, estão em estágios de alteração diferentes, sendo a principal diferença a mineralogia das frações finas (silte/argila): em G3, há plagioclásio, caulinita e gibbsita, enquanto que em G4 verificou-se a ausência de feldspatos e presença desses minerais secundários, indicando que as amostras em G3 estão em menor estágio de alteração do que as de G4. Quanto ao comportamento dos elementos químicos, houve um empobrecimento em K2O, Na2O, CaO, Rb, Ba e ETR, relacionado principalmente com a alteração dos felspatos, e enriquecimento em SiO2 e Al2O3 (relacionado aos minerais detríticos e neoformados), Fe2O3, TiO2 e MgO, referente a alteração da biotita. O estudo permitiu elaborar um modelo de transformação geoquímica, mineralógica e textural, a partir do qual se pode concluir que a formação de corestones juntamente com a mobilização e reconcentração de elementos e argilominerais, atuaram como heterogeneidades dentro desses perfis de alteração. Estes processos tornaram os perfis susceptíveis a movimentos de massa, mostrando assim uma inter-relação entre o estudo da evolução geoquímica e mineralógica, e a estabilidade mecânica do material / On January 2011, the mountainous region of Rio de Janeiro state was affected by a great number of landslides. This event was called "Megadisaster". The occurrence of landslide depends on the presence of material to be mobilized due to weathering processes. This work aims to assess the geochemical and mineralogical changes in two granite weathering profiles in Córrego do Príncipe watershed (Teresópolis / RJ) related to landslides. Instrumental Neutron Activation Analysis (INAA) and X-ray fluorescence (XRF) were used to quantify the chemical compositions of weathering profile samples. Mineralogy was done by X-ray diffraction analysis (XRD) and by petrography. Particle size analysis was done by sieving and laser diffraction. A multivariate statistical analysis of the data showed four groups: G1 is quite different from the other groups and is characterized by an iron-manganous material; G2 represents the material with the lower degree of weathering. The presence of plagioclase, the lack of secondary minerals, the corestones and the coarse grain size of the unconsolidated samples explain this group; G3 and G4 are fairly homogeneous. They are the most weathered samples of both profiles consisting of secondary minerals and little or no plagioclase present. The main difference between these groups is silt and clay mineralogy. The elements mobility during weathering process showed a depletion of K2O, Na2O, CaO, Rb, Ba and REE (mainly due to feldspar weathering), while SiO2, Al2O3 (due to detrital and secondary mineral growth) Fe2O3, TiO2 and MgO (due to biotite weathering) increase. This study allowed the elaboration of a geochemical, mineralogical and particle size weathering model. The production of corestones, the mobilization and concentration of elements and clay minerals acted as heterogeneities within these profiles, leaving them susceptible to landslides

Ce travail porte sur l'utilisation des déséquilibres radioactifs dans les échantillons de sols totaux, et des fractions minérales séparées. Les objectifs étaient d'évaluer : 1) l'impact d'un changement de végétation et de la granulométrie de la roche mère dans les sols sur les déséquilibres, 2) les phases minérales secondaires capables d'enregistrer des informations temporelles, et leur séparation chimique et 3) l’information temporelle portée par les minéraux primaires. Ce travail a mis en évidence sur le site de Breuil-Chenue que les couches les plus profondes du sol (< 40cm) ne montrent pas d’impact de la végétation ou de la granulométrie de la roche mère sur les déséquilibres radioactifs. Les faibles vitesses de production du sol (~1-2 mm/ka) obtenues reflètent la très faible érosion physique affectant ce site situé sur un plateau. La seconde partie de ce travail a permis d'identifier un protocole permettant d’extraire les oxydes de fer sans création de fractionnement chimique. Enfin, l'analyse de biotites d’un profil du même site a montré que les déséquilibres U/Th permettaient de déterminer de façon indépendante les vitesses d’altération in situ des minéraux dans les sols. / The aim of the present study was to evaluate weathering and soil formation rates using U-Th disequilibria in bulk soil or separated minerals. The specific objectives of this work were to evaluate the use of U-Th chronometric tools 1) regarding the impact of a land cover change and the bedrock characteristics 2) in selected secondary mineral phases and 3) in primary minerals. On the Breuil-Chenue (Morvan) site, no vegetation effect neither a grain size effect was observed on the U-Th series in the deepest soil layers (< 40cm). The low soil production rate (1-2 mm/ka) is therefore more affected by regional geomorphology than by the underlying bedrock texture. In the second part of this work, based on a thorough evaluation of different technics, a procedure was retained to extract Fe-oxides without chemical fractionation. Finally, the analysis of biotites hand-picked from one of the studied soil profile showed that U- series disequilibria allow to independently determinate the field-weathering-rate of minerals.

This work deals with the influence of atmospheric corrosion on high-cycle fatigue properties of a weathering steel ATMOFIX B. New experimental data on fatigue strength of a steel exposed for 20 years to an atmospheric corrosion were compared to those characterizing the base material. Reduction of the fatigue lifetime of the exposed material compared with the base material was predicted on the basic of fractographic examination of fracture surfaces and the influence of surface notches on fatigue strength. The predicted results agree well with the experimental results.

This thesis is focused on prominent uranium deposits in Czech Republic and their secondary uranium mineralization. Main goal of this thesis is to analyze collected minerals and to determine their ages. Next step is to prove or disprove hypothesis that this secondary uranium minerals are products of Quaternary glacier weathering. As a suitable analytical method, an alpha spectrometry was used and the age was calculated by 230 Th/234 U ratio. Firstly, chosen methodology was verified with admixture of reference material PU1 (Přibram uraninite) in secular equilibrium and internal standard, both with known activity. Analyzed spectra confirmed that some of the samples lay on the very edge of datability, especially in case of PL1 and GF1, both samples are very young, so they easily could be products of anthropogenic activity (changed environment due to mining works). On the other hand, in case of sample GF3, the age was successfully determined, although it is also quite young phase. In case of samples ME3, ME4 and ME6 was used threshold dating method, because they were considered to be too old for age calculation. The rest of the samples chosen for age determination was analyzed without further complications. Based on the age and geological setting, samples GF3 (3 725 ± 845 years), JE1 (10 655 ± 1 795...

L’altération chimique et l’érosion physique de la croûte continentale mobilisent de grandes quantités de matière sous formes solide et dissoute. Première productrice de sédiments sur le globe, la chaîne Himalayenne délivre ~1 Gt/a de sédiments aux océans. L'importance des différents facteurs qui contrôlent les flux érodés et celle des processus d’érosion (glaciers, glissements de terrain, sols) sont pourtant encore mal définies. Il en va ainsi des facteurs climatiques, en particulier de leur impact au cours des transitions climatiques. Afin de répondre à ces questions, ce travail s’attache à comparer la composition géochimique des produits de l’érosion à celles des sédiments actuels de rivière et des archives sédimentaires de la plaine du Gange. Un premier bilan des processus d’érosion a été établi petite échelle dans le bassin Haut-Himalayan de la Khudi. L’érosion actuelle conséquente de ce bassin de ~3mm/a se produit lors de la mousson, correspond pour l'essentiel à l’érosion des sols et surtout à l'intense activité d'une zone de glissement de terrain. Grâce au développement d'une nouvelle méthode de destruction de la matière organique, la mesure de l’hydratation des silicates a pu être utilisée comme traceur inédit des sols. Sur cette base, l’inversion des compositions des sédiments de la rivière démontre que l’érosion physique est dominée à ~80% par le glissement de terrain, l’érosion de sols étant mineure et comparable aux taux d’érosion des autres bassins alentours. L’érosion chimique qui conduit à un flux d'éléments dissous de 7.9 kt/a (soit une érosion équivalente de 0.02 mm/a) semble dériver de l’altération profonde du substrat rocheux. Néanmoins les flux d'éléments dissous dessinent également une relation marquée avec les flux particulaires durant la mousson, suggérant une altération additionnelle des sédiments au cours du transport fluvial. Une approche similaire a ensuite été menée à l’échelle plus vaste du bassin de la Narayani drainant l’ensemble du Népal central. Grâce à des mesures de courant par ADCP combinées à l’échantillonnage de sédiments en profondeur, un modèle de transport sédimentaire a été utilisé pour intégrer les flux sédimentaires en profondeur et ainsi réviser le taux d’érosion moyen sur le bassin versant à une valeur de ~1.7 mm/a, proche des taux d'érosion long-terme. Un système géochimique associant la mesure du δD des silicates associée aux concentrations en carbonate s’est révélé un traceur diagnostique de l’érosion glaciaire dans le Nord du bassin, tandis que la teneur en matière organique du sédiment a pu être utilisée comme traceur des sols. L’analyse temporelle des flux de sédiments, de leur composition et du signal granulométrique, a ainsi permis d’établir que seule une faible fraction des sédiments (<20%) provenait de l’érosion par les glaciers et les sols. À l'échelle du Népal central, l’érosion physique semble donc également dominée par les glissements déclenchés lors de la période de mousson. Le grand cône alluvial de la Narayani-Gandak, situé au débouché de cette rivière dans la plaine du Ganges, a enregistré l’histoire récente de l’érosion du Népal central. Trois forages réalisés dans ce méga-cône permettent ainsi d'étudier l'évolution de l'altération et de l'érosion en Himalaya au cours du tardi-Pléistocène. Ces dépôts sédimentaires révèlent une étonnante stabilité depuis ~45 ka de la géochimie, des provenances et du degré d’altération des sédiments. Seule l’intensité de l’érosion mesurée par isotopes cosmogéniques semble augmenter au cours de l’Holocène. Par contraste, l’évolution très récente de la distribution de l’érosion dans la chaîne est marquée par un accroissement (x3) de la proportion de matériel des régions basses et plus peuplées de l'Himalaya, montrant que les activités anthropiques, via notamment une forte croissance du réseau routier durant la dernière décennie, [...] / Chemical weathering and physical erosion of the continental crust mobilise huge amounts of both solid and dissolved material. As the first sediment generator on the Earth, the Himalayan range releases around 1 Gt/y of sediment into the ocean. The relative influence of the different factors that control the eroded fluxes and the importance of the erosion processes (such as landslides, glaciers, soils) are as yet poorly understood. The same is true of the climatic factors, especially regarding their impact during climatic transition periods. In order to address those questions, this work focuses on comparing the geochemical composition of erosion products to the composition of present river sediment and of sedimentary records in the Ganga Plain. A first budget of the erosion processes was done on a small scale in the Khudi catchment of Higher Himalaya. The total present-day erosion is considerable, at around 3 mm/y and takes place during the monsoon. It is mainly linked to the soils erosion and more importantly to the intense activity of a landsliding area. The development of a new method for the destruction of organic matter enabled the use of silicates hydration as a tracer for soils. Based on this method, a mathematical inversion of the sediment compositions was performed. It highlights that the landslide is responsible for ~80% of the overall physical erosion. The soil erosion is minor and is comparable to the erosion rates measured in the neighbouring catchments. The chemical erosion leads to a dissolved flux of 7.9 kt/y (corresponding to an erosion rate of 0.02mm/y) and seems to come from the bedrock deep weathering. Nevertheless, the dissolved fluxes also appear to be linked with the particles fluxes during the monsoon. This suggests an additional weathering of the sediment during the fluvial transport. A similar approach was used on a larger scale in the Narayani catchment that drains the whole of Central Nepal. Through ADCP-based current measurements combined with deep sediment sampling, a model for sedimentary transport was used to integrate the deep sediment fluxes. The average catchment-scale erosion rate was then corrected to a value of ~1.7 mm/y, close to the long-term erosion rates. A geochemical system that combines the measurement of the δD of silicates and the concentrations of carbonates was found to be a diagnosis tracer for glacial erosion in the northern part of the catchment. The organic matter ratio was used as a tracer for soils. The temporal analysis of sediment fluxes, as well as the sediment composition and granulometry showed that only a small fraction (< 20%) of the sediment comes from glacial and soils erosion. Over the whole Central Nepal, the physical erosion seems also to be dominated by the landslides that are triggered during the monsoon. The large Narayani-Gandak alluvial fan is located at the river mouth and can be used as a record of the recent history of Central Nepal erosion. Three drillings were done in this fan to enable the study of the evolution of Himalayan weathering and erosion during the Late Pleistocene. The sedimentary deposits display a surprising stability in their geochemistry, their sources and their weathering stage for the last ~45 ky. The erosion intensity derived from cosmogenic nuclides is the only feature that seems to have risen during Holocene. However, the very recent evolution of the erosion distribution in the range is characterised by an increase (x3) of the proportion of products coming from the lower, more densely populated areas. This shows that the anthropogenic activities have had a larger impact on the erosion than the last Pleistocene-Holocene transition, especially through the rapid growth of the road network during the last decade.

Les nanomatériaux manufacturés (comme les nanoparticules d’oxydes métalliques, les nanotubes de carbone, les nanofibres etc.) possèdent des propriétés remarquables qui leur confèrent des applications industrielles innovantes. Néanmoins, ces nouveaux matériaux soulèvent des inquiétudes vis à vis de leurs potentiels risques. Ces nanomatériaux manufacturés connaissent une production et une commercialisation croissantes. Par conséquent, de plus en plus de personnes sont potentiellement exposées à ces nanomatériaux (aussi bien les consommateurs que les opérateurs) à travers les aérosols qui pourraient être émis au cours du cycle de vie du matériau. L’une des approches possibles de réduction de risque serait la prévention de l’émission qui consisterait en une conception réfléchie du matériau avec un compromis performance/sûreté. La thèse présentée ici suit cette approche. Il s’agit de comprendre le phénomène et les mécanismes d’émission des nanomatériaux manufacturés à l’aide d’outils théoriques et expérimentaux. Le dispositif expérimental développé au cours de cette étude vise (i) à reproduire à l’échelle laboratoire des activités en conditions réelles, (ii) à identifier les mécanismes d’émission, et (iii) à mener simultanément des analyses qualitatives et quantitatives* des nanomatériaux manufacturés émis. Pour la sollicitation mécanique, le procédé d’abrasion a été choisi ; quant au vieillissement environnemental, le choix s’est porté sur un procédé d’exposition accélérée aux rayons d’UV en présence d’humidité et de chaleur. Les résultats suggèrent que les entités microscopiques présentes à la surface d’un matériau (appelées aspérités ou rugosités) subissent globalement 4 types de mécanismes d’enlèvement pendant l’abrasion, suivant la variation de 18 paramètres (liés au matériau et au procédé). Ces mécanismes déterminent la forme, la taille et le nombre de particules de l’aérosol émis. De plus, dans le cas des échantillons testés dans les conditions expérimentales données, il a été observé, lors des essais mécaniques seuls, la génération d’aérosols dans lesquels sont retrouvées des nanomatériaux manufacturés liées à leur matrice. Il s’agit de particules nanométriques et micrométriques. Cependant, dans le cas du couplage abrasion/vieillissement environnemental, après un temps donné de détérioration, il est constaté l’émission de nanomatériaux manufacturés libres, en plus des nanomatériaux manufacturés liés à leur matrice. Les résultats expérimentaux relatifs aux sollicitations mécaniques ont été mis en corrélation avec des lois de mécanique classique utilisant des modèles analytiques. Le modèle utilise en partie des relations semi-empiriques ; après ajustement, on observe une très bonne convergence modèle-expérience. Ce modèle a été utilisé pour réaliser une étude de sensibilité sur les 18 paramètres évoqués précédemment, et ce pour une variation de 25% pour chaque paramètre. Ceci permet d'illustrer la capacité du modèle à hiérarchiser l'influence des différents paramètres sur l'émission de particules, pour des conditions données. Ainsi, ce travail a permis de développer un ensemble constitué d’une part d’outils expérimentaux et d’autre part d’un modèle. Si cet ensemble est largement perfectible, il permet toutefois d’ores et déjà d’entamer une conception “nanosafe by design”. / Engineering nanomaterials (ENM) like metal oxide nanoparticles, carbon nanotubes, nanofibers, etc. possess various innovative properties and their industrial use creates new opportunities. However, they also present new risks and uncertainties. There is an ever growing production and use of the products containing these ENM, like nanocomposites or nanocoatings, which result in an increasing number of workers and consumers exposed to ENM upon their emission (in the form of aerosols) from the products containing them. One of the most favored approaches, to minimize this emission, would be a preventive one which would focus on altering the product’s material properties during its design phase itself without compromising with any of its added benefits.This thesis advocates this approach. It attempts to understand the ENM emission phenomenon and its yielding mechanisms on the basis of combined experimental and theoretical approaches. The experimental set-up, developed during this thesis, is equipped with the necessary elements which can (i) seek to reproduce the real life activities on a laboratory scale (ii) identify the emission mechanism (iii) carry out both qualitative as well as quantitative*analysis of the emitted ENM simultaneously. Whilst the mean chosen for applying the mechanical solicitation or stress is an abrasion process, for the environmental weathering, it is an accelerated UV exposure process in the presence of humidity and heat. The results suggest that depending upon 18 material and process properties/parameters, the microscopic entities present on the surface of a product, called asperities, undergo mainly 4 types of removal mechanisms during abrasion. It is these mechanisms that decide the shape, size and the number of the aerosol particles emitted. Moreover, for the given test samples and experimental conditions studied during the thesis, application of the mechanical stresses alone was found to generate the emitted ENM aerosols in which ENM is always embedded inside the product matrix, thus, a representative product element. In such a case, the emitted aerosols comprise of both nanoparticles as well as microparticles. But if the mechanical stresses are coupled with the environmental weathering, then the eventual deterioration of the product, after a certain weathering duration, may lead to the emission of the free ENM aerosols too. All these experimental findings, pertaining to the effect of the mechanical stresses alone, have also been put into the perspective with classical material and mechanics state laws using a predictive analytical model. A close agreement** of the estimated results of this model with the experimentally measured ones has validated its functioning. This model was used to perform a sensitivity analysis on the aforementioned 18 parameters to rank the influence of a25% variation in each of their values on the particle emission for the given conditions.Thus, during the present thesis, both experimental and theoretical approaches have been developed to study the emission. Despite the fact that these approaches are perfectible, they can still be used during product design phase for the product to be “nanosafe by design”.