La carbonatation minérale est une technique alternative de capture et stockage du CO2 anthropique. L'abondance des matériaux carbonatables sur terre en fait une solution à fort potentiel. En particulier, la carbonatation directe en voie aqueuse a été présentée dans la littérature comme la voie la plus intéressante d'un point de vue énergétique pour la carbonatation minérale ex-situ, à la condition que les cinétiques naturellement lentes de dissolution des silicates magnésiens en phase aqueuse puissent être accélérées de plusieurs ordres de grandeur. Cette thèse étudie en détail les verrous et mécanismes de cette réaction en présence d'additifs organiques tels que l'oxalate, connus pour leur capacité à accélérer la dissolution des silicates magnésiens. Dans un premier temps, la carbonatation en voie aqueuse sans additif d'une olivine modèle est étudiée de manière à mettre en évidence la nature des phénomènes limitants. Ensuite le travail se concentre sur l'étude du rôle de l'additif oxalate à travers des essais spécifiques et une analyse fine de la phase solide. Il est démontré que pour différentes concentrations de suspension et sous 20 bar de CO2, cet additif conduit à la formation de complexes aqueux stables du magnésium avec l'oxalate et à la précipitation de MgC2O4,2H2O (glushinskite), qui empêchent toute précipitation quantitative de magnésite. La simulation géochimique complète du système a été réalisée et a permis d'expliquer les résultats des essais par un mécanisme de dissolution à grain rétrécissant. L'extension de l'étude à un autre silicate (harzburgite) et à d'autres ligands organiques accélérateurs de la dissolution des silicates tels que le citrate et l'EDTA n'a pas non plus permis d'obtenir la formation quantitative de carbonate, à cause d'une forte complexation en phase aqueuse du Mg extrait du minerai. Ces travaux remettent en doute la perspective de développement d'un procédé industrialisable de minéralisation du CO2 en présence d'additifs organiques. / Mineral carbonation is an interesting option for mitigation of anthropogenic CO2 emissions. Direct aqueous mineral carbonation has been presented by many as a promising strategy for ex-situ mineral carbonation, on the basis that organic additives such as oxalate increase the rate and extent of dissolution of magnesium silicates several folds. This thesis discusses and extends the current understanding of this process through geochemical modelling and detailed solid characterization. First, mineral carbonation is investigated in water alone, without additives, in order to understand and quantify the actual limitations of the process with specific magnesium silicate ores. Dissolution kinetics being critical with this process, the role of disodium oxalate as a dissolution accelerating agent is thoroughly examined with olivine, through dedicated experiments and comprehensive analysis of both solid and liquid phases. Under 20 bar of CO2, and irrespective of the conditions used, it is found that the formation of strong oxalate-magnesium complexes in solution and precipitation of MgC2O4,2H2O (glushinskite) impede any chance of precipitating significant amounts of magnesium carbonate. Geochemical modelling permits successful simulation of the dissolution kinetics of magnesium silicate using a shrinking particle model. Other promising ligands from a dissolution perspective, namely citrate and EDTA, were also investigated. Contrary to oxalate, these do not form any solid by-products with magnesium, and yet they do not produce better carbonation results. The results and findings from this work cast strong doubts about the possibility of developing a viable direct aqueous mineral carbonation process using organic salts.

Dans le domaine de la valorisation des dérivés de la biomasse, les réactions de transestérification suscitent un grand intérêt en raison de leur importance pour transformer des molécules plateformes biobasées. L'étude des paramètres clés régissant une réaction de transestérification modèle, catalysée par des solides de type silicate de magnésium, a été menée. L'ensemble des données expérimentales (XRD, XPS, DRIFTS, RMN) a démontré qu'une phase de silicate de magnésium hydraté (MSH) est présente à la surface des catalyseurs les plus actifs. Cette phase, possédant une structure proche de celle d'une argile mais avec des défauts et présentant des propriétés acido-basiques spécifiques, est capable d'activer à la fois l'alcool (sur des sites basiques) et l'ester (sur des sites acides). Ce résultat est confirmé par l'étude cinétique qui met en évidence un mécanisme Langmuir-Hinshelwood. En outre, il a été montré que l'eau coordonnée au magnésium situé sur le bord des feuillets des particules ou dans les défauts présents à la surface des silicates engendre des sites acides particuliers.Par ailleurs, une série de phyllosilicates de magnésium, a été testée dans la réaction de transestérification modèle. Le rôle de la taille des particules a été mis en évidence et les meilleurs résultats catalytiques ont été obtenus avec le talc et la laponite possédant des tailles de feuillet nanométriques. De plus, l'étude cinétique indique que la réaction de transestérification catalysée par la laponite, n’ayant seulement que des sites basiques, implique un mécanisme Eley-Rideal. Enfin, dans le cas de la laponite la dissociation de l’eau sur les sites basiques empoissonne la réaction. / In the field of biomass derivatives valorisation, transesterification reactions have attracted numerous interest due to its importance to transform platform molecules. A study of the parameters governing the reactivity of magnesium silicate based catalyst in a model transesterification reaction was thoroughly undertaken. The set of experimental data (XRD, XPS, DRIFTS, NMR) demonstrated that a magnesium silicate hydrate (MSH) phase is formed at the surface of the most active silicates. It is thus concluded that this active phase, presented a clay-like structure with defects and specific acido-basic properties, is able to activate together the alcohol (over base sites) and the ester (over acid sites). This result fits with the kinetic study that implies the Langmuir-Hinshelwood mechanism. Moreover, the acid sites were revealed that are created from the water coordinated to magnesium located on the edge of the clay-like particles or in the defects present in the silicate layer.Besides, a series of phyllosilicates having the similar structure with MSH, were tested in the model transesterification reaction. The influence of the particles size was investigated and the best catalytic performances were obtained with talc and laponite with nanosheets. In addition, kinetic study indicates that the transesterification reaction on the laponite, with purely basic sites, undergoes Eley-Rideal mechanism. Finally, unlike the positive role of water on the formation of acid sites in MSH, on laponite, the dissociation of the water on basic sites poisons the reaction.

Le talc naturel est utilisé en tant que charge de haute performance des matrices polymères, car il permet d'améliorer leurs propriétés mécaniques. Pour cela, la dispersion de la charge dans la matrice doit être de qualité, ce qui implique que les particules soient nanométriques. Or, obtenir des particules nanométriques par broyage s'avère coûteux énergétiquement et économiquement. L'étude d'une opération de précipitation a conduit à la synthèse de silicate de magnésium amorphe constitué de particules primaires nanométriques. L'analyse de surface du solide par chromatographie gazeuse inverse a été employée afin de prédire les interactions entre le solide et la matrice polymère. La constante d'équilibre du solide amorphe et les vitesses de cristallisation ont pu être identifiées après modélisation des équilibres chimiques. / Natural talc is used as an high performance filler in polymer matrices because it enables to improve mechanical properties. In order to improve these properties, a good-quality dispersion of the filler in the polymer matrix is necessary, that involves particles being nano-sized. However, getting nano-sized particles by milling processes is expensive and very energetic. The study of a precipitation operation has led to the synthesis of amorphous magnesium silicate whose primary particles are nano-sized. Solid surface analysis by inverse gas chromatography has been made in order to predict interactions between solid and polymer matrix. Equilibrium constant of amorphous solid and crystallization rates have been identified after modelling of chemical equilibria.

Made available in DSpace on 2014-06-11T19:23:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-07-27Bitstream added on 2014-06-13T19:06:35Z : No. of bitstreams: 1 fonseca_im_me_jabo.pdf: 2300678 bytes, checksum: 7d716e8445017c177b67dfa0bf9efb53 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação para o Desenvolvimento da UNESP (FUNDUNESP) / A escória de siderurgia é constituída basicamente por silicato de cálcio e magnésio, sendo considerada como material corretivo da acidez do solo e como fonte de nutrientes e de silício para as plantas. Diante disso, objetivou-se avaliar os efeitos da escória de siderurgia como fonte de silício e material corretivo na presença de doses de nitrogênio nos atributos químicos do solo, no estado nutricional, no crescimento e na produção de massa seca do capim-marandu. Desenvolveu-se o estudo em casa de vegetação, na FCAV/Unesp, Campus Jaboticabal-SP, no período de dezembro/05 a julho/06, realizando dois cortes. O delineamento experimental utilizado foi o de blocos ao acaso, em esquema fatorial 2x3x3 + 1, sendo duas fontes de material corretivo, três doses de material corretivo (1,61, 3,22 e 6,44 t ha-1 de ECaCO3), três doses de nitrogênio, sendo a metade, a dose e duas vezes a dose recomendada (200 mg dm-3) aplicados nos dois cortes das plantas, e uma testemunha absoluta, com quatro repetições. A unidade experimental foi constituída por um vaso preenchido com 4 dm3 de terra de um Latossolo Vermelho distrófico textura média, e quatro plantas. Verificouse que as doses de escória aumentaram as concentrações de Si no solo e na planta, diminuindo, porém, o acúmulo de N no capim. A adubação nitrogenada associada à escória incrementou a produção de massa seca e a absorção de Si pelo capimmarandu. O uso da escória de siderurgia mostra-se adequado ao cultivo da forrageira como material corretivo da acidez do solo e fonte de silício para o capim-marandu. / The slag is constituted basically by calcium and magnesium silicate, being considered as neutralizing material of the soil acidity and as source of nutrients and of silicon for the plants. This research was carried out in greenhouse conditions with the objective to evaluate the effects of the slag plus nitrogen on the chemical attributes of the soil, nutritional state, growth and dry matter production of the marandu palisadegrass (Brachiaria brizantha). The experiment was conducted in São Paulo State University - UNESP, Brazil, during December/05 the July/06 period, when the grasses were cut twice. The experimental design was a randomized blocks with treatments organized in 2x3x3+1 in factorial scheme (two types of corrective material, tree corrective material rates, tree nitrogen rates plus a control treatment), with four replications. The experimental units were pots filled with 4 dm3 of medium texture Oxissol with four plants. The slag rates increased the soil and plant silicon contents. However, decreased the plant nitrogen contents. The nitrogen fertilization plus slag increased dry matter production and plant silicon contents. The slag was adequate as corrective material of the acidity of the soil and as silicon source to marandu palisadegrass.

Orientador: Renato de Mello Prado / Banca: José Carlos Barbosa / Banca: Takashi Muraoka / Resumo: A escória de siderurgia é constituída basicamente por silicato de cálcio e magnésio, sendo considerada como material corretivo da acidez do solo e como fonte de nutrientes e de silício para as plantas. Diante disso, objetivou-se avaliar os efeitos da escória de siderurgia como fonte de silício e material corretivo na presença de doses de nitrogênio nos atributos químicos do solo, no estado nutricional, no crescimento e na produção de massa seca do capim-marandu. Desenvolveu-se o estudo em casa de vegetação, na FCAV/Unesp, Campus Jaboticabal-SP, no período de dezembro/05 a julho/06, realizando dois cortes. O delineamento experimental utilizado foi o de blocos ao acaso, em esquema fatorial 2x3x3 + 1, sendo duas fontes de material corretivo, três doses de material corretivo (1,61, 3,22 e 6,44 t ha-1 de ECaCO3), três doses de nitrogênio, sendo a metade, a dose e duas vezes a dose recomendada (200 mg dm-3) aplicados nos dois cortes das plantas, e uma testemunha absoluta, com quatro repetições. A unidade experimental foi constituída por um vaso preenchido com 4 dm3 de terra de um Latossolo Vermelho distrófico textura média, e quatro plantas. Verificouse que as doses de escória aumentaram as concentrações de Si no solo e na planta, diminuindo, porém, o acúmulo de N no capim. A adubação nitrogenada associada à escória incrementou a produção de massa seca e a absorção de Si pelo capimmarandu. O uso da escória de siderurgia mostra-se adequado ao cultivo da forrageira como material corretivo da acidez do solo e fonte de silício para o capim-marandu. / Abstract: The slag is constituted basically by calcium and magnesium silicate, being considered as neutralizing material of the soil acidity and as source of nutrients and of silicon for the plants. This research was carried out in greenhouse conditions with the objective to evaluate the effects of the slag plus nitrogen on the chemical attributes of the soil, nutritional state, growth and dry matter production of the marandu palisadegrass (Brachiaria brizantha). The experiment was conducted in São Paulo State University - UNESP, Brazil, during December/05 the July/06 period, when the grasses were cut twice. The experimental design was a randomized blocks with treatments organized in 2x3x3+1 in factorial scheme (two types of corrective material, tree corrective material rates, tree nitrogen rates plus a control treatment), with four replications. The experimental units were pots filled with 4 dm3 of medium texture Oxissol with four plants. The slag rates increased the soil and plant silicon contents. However, decreased the plant nitrogen contents. The nitrogen fertilization plus slag increased dry matter production and plant silicon contents. The slag was adequate as corrective material of the acidity of the soil and as silicon source to marandu palisadegrass. / Mestre

O silício (Si) é benéfico ao desenvolvimento das plantas por proporcionar aumento na capacidade de defesa contra o ataque de pragas e de doenças, além de garantir porte ereto das plantas, o que aumenta a capacidade fotossintética dos vegetais. Fontes silicatadas, como silicatos de cálcio e de magnésio, fornecem Si ao solo e podem funcionar como corretivos de acidez. O acúmulo de resíduos vegetais e fertilizantes, mesmo no sistema semeadura direta (SSD), acelera o processo de acidificação do solo em curto prazo, principalmente em sua camada mais superficial. Esse processo é contínuo em solos tropicais úmidos e tem por consequência a baixa disponibilidade de nutrientes e elevados teores tóxicos de Al+3. Assim como no sistema convencional de manejo do solo, o SSD também demanda a aplicação de insumos, especialmente materiais corretivos de acidez. A aplicação de silicato pode interferir na disponibilidade de Si às plantas e nas formas desse elemento na solução do solo. O ácido silícico (H4SiO4) é a espécie de Si predominante em solos ácidos; e o aumento do pH pode causar sua desprotonação, gerando o ânion silicato (H3SiO4-). Estudos ligados ao Si em solos sob SSD são escassos, principalmente em experimentos de longa duração conduzidos sob condições de clima tropical úmido. Desde 2002 está sendo conduzido experimento de campo em um Latossolo Vermelho distroférrico sob SSD que recebeu aplicação superficial de calcário e de silicato de cálcio e de magnésio. Foram determinados os teores disponíveis de macronutrientes e silício, pH, soma de bases, saturação por bases, capacidade de troca catiônica, matéria orgânica, H+Al e Al3+, minerais silicatados e óxidos de Fe e Al, 24 meses após a reaplicação superficial dos corretivos. Foi feita especiação iônica de Al, Ca, Mg e Si em extrato aquoso e realizada a quantificação de Al por espectroscopia de ressonância magnética nuclear (27Al-NMR). Os principais óxidos encontrados foram a gibbsita, goethita e hematita. Diferentemente do Ca e do Mg, o Al não estava presente, em sua maioria, na forma livre Al3+, mas formando complexos com o carbono orgânico dissolvido. O silício estava quase que totalmente na forma de H4SiO4, sendo que a atividade dessa espécie foi semelhante à sua concentração em solução. A análise quantitativa de 27Al-NMR forneceu somente picos do complexo de alumínio hexa-hidratado ([Al(H2O)6]3+), não havendo espécies de alumínio complexadas com ácidos orgânicos. Amostras com teores moderados a alto de Al (27Al-NMR) se correlacionaram com as concentrações totais de Al provenientes da análise de espectroscopia de emissão atômica (ICP-AES). / Silicon (Si) is an element which is beneficial to plant development in that it provides a line of defense against attack by pests and disease as well, as ensure a plant posture that is more erect that increases their photosynthetic capacity. Silicon sources such as calciummagnesium silicates provide Si to the soil and act as acidity correctives. The accumulation of plant residues and fertilizers, even under a no-till system (NT), accelerates the process of soil acidification in the short term, especially in the uppermost surface layer. This process is continuous in moist tropical soils and results in a low level of nutrients and a high level of Al3+. As is the case under the conventional system of soil management, NT also requires the application of additives, especially acidity corrective materials. The application of silicate can interfere with the availability of Si to plants and the forms in which this element is found in soil solution. Silicic acid (H4SiO4) is the predominant form of Si found in acidic soils; and increases in the pH can cause deprotonation, which generates silicate anions (H3SiO4-). Studies related to Si in soils under NT are scarce, especially long-term experiments carried out under humid tropical conditions. Since 2002, a field experiment has been conducted on a dystroferric Oxisol under NT, where lime and calcium-magnesium silicate were surface applied. The contents of macronutrients and silicon available, as well as pH, basis total and basis saturation, cationic exchange capacity, organic matter, H+Al and Al3+, silicate minerals and Fe and Al oxides, were all determined 24 months after the correctives were applied. The ionic speciation of Al, Ca, Mg and Si took place in aqueous extract as well as the quantification of Al by nuclear magnetic resonance spectroscopy (27Al-NMR). The main oxides found were gibbsite, goethite and hematite. Unlike Ca and Mg, Al was not, for the most part, present in its free form Al3+ but complexed with dissolved organic carbon. Silicon was almost entirely in the form of H4SiO4, and its activity was similar to the concentration of this specie in solution. Quantitative analysis of 27Al-NMR has provided only peaks of Hexaaquaaluminium complex ([Al(H2O) 6]3+), with no species of organic-aluminum complexes. Samples with moderate to high levels of Al (27Al-NMR) were positively correlated with the total concentration of Al derived from the atomic emission spectroscopy analysis (ICP-AES).

O silício (Si) é benéfico ao desenvolvimento das plantas por proporcionar aumento na capacidade de defesa contra o ataque de pragas e de doenças, além de garantir porte ereto das plantas, o que aumenta a capacidade fotossintética dos vegetais. Fontes silicatadas, como silicatos de cálcio e de magnésio, fornecem Si ao solo e podem funcionar como corretivos de acidez. O acúmulo de resíduos vegetais e fertilizantes, mesmo no sistema semeadura direta (SSD), acelera o processo de acidificação do solo em curto prazo, principalmente em sua camada mais superficial. Esse processo é contínuo em solos tropicais úmidos e tem por consequência a baixa disponibilidade de nutrientes e elevados teores tóxicos de Al+3. Assim como no sistema convencional de manejo do solo, o SSD também demanda a aplicação de insumos, especialmente materiais corretivos de acidez. A aplicação de silicato pode interferir na disponibilidade de Si às plantas e nas formas desse elemento na solução do solo. O ácido silícico (H4SiO4) é a espécie de Si predominante em solos ácidos; e o aumento do pH pode causar sua desprotonação, gerando o ânion silicato (H3SiO4-). Estudos ligados ao Si em solos sob SSD são escassos, principalmente em experimentos de longa duração conduzidos sob condições de clima tropical úmido. Desde 2002 está sendo conduzido experimento de campo em um Latossolo Vermelho distroférrico sob SSD que recebeu aplicação superficial de calcário e de silicato de cálcio e de magnésio. Foram determinados os teores disponíveis de macronutrientes e silício, pH, soma de bases, saturação por bases, capacidade de troca catiônica, matéria orgânica, H+Al e Al3+, minerais silicatados e óxidos de Fe e Al, 24 meses após a reaplicação superficial dos corretivos. Foi feita especiação iônica de Al, Ca, Mg e Si em extrato aquoso e realizada a quantificação de Al por espectroscopia de ressonância magnética nuclear (27Al-NMR). Os principais óxidos encontrados foram a gibbsita, goethita e hematita. Diferentemente do Ca e do Mg, o Al não estava presente, em sua maioria, na forma livre Al3+, mas formando complexos com o carbono orgânico dissolvido. O silício estava quase que totalmente na forma de H4SiO4, sendo que a atividade dessa espécie foi semelhante à sua concentração em solução. A análise quantitativa de 27Al-NMR forneceu somente picos do complexo de alumínio hexa-hidratado ([Al(H2O)6]3+), não havendo espécies de alumínio complexadas com ácidos orgânicos. Amostras com teores moderados a alto de Al (27Al-NMR) se correlacionaram com as concentrações totais de Al provenientes da análise de espectroscopia de emissão atômica (ICP-AES). / Silicon (Si) is an element which is beneficial to plant development in that it provides a line of defense against attack by pests and disease as well, as ensure a plant posture that is more erect that increases their photosynthetic capacity. Silicon sources such as calciummagnesium silicates provide Si to the soil and act as acidity correctives. The accumulation of plant residues and fertilizers, even under a no-till system (NT), accelerates the process of soil acidification in the short term, especially in the uppermost surface layer. This process is continuous in moist tropical soils and results in a low level of nutrients and a high level of Al3+. As is the case under the conventional system of soil management, NT also requires the application of additives, especially acidity corrective materials. The application of silicate can interfere with the availability of Si to plants and the forms in which this element is found in soil solution. Silicic acid (H4SiO4) is the predominant form of Si found in acidic soils; and increases in the pH can cause deprotonation, which generates silicate anions (H3SiO4-). Studies related to Si in soils under NT are scarce, especially long-term experiments carried out under humid tropical conditions. Since 2002, a field experiment has been conducted on a dystroferric Oxisol under NT, where lime and calcium-magnesium silicate were surface applied. The contents of macronutrients and silicon available, as well as pH, basis total and basis saturation, cationic exchange capacity, organic matter, H+Al and Al3+, silicate minerals and Fe and Al oxides, were all determined 24 months after the correctives were applied. The ionic speciation of Al, Ca, Mg and Si took place in aqueous extract as well as the quantification of Al by nuclear magnetic resonance spectroscopy (27Al-NMR). The main oxides found were gibbsite, goethite and hematite. Unlike Ca and Mg, Al was not, for the most part, present in its free form Al3+ but complexed with dissolved organic carbon. Silicon was almost entirely in the form of H4SiO4, and its activity was similar to the concentration of this specie in solution. Quantitative analysis of 27Al-NMR has provided only peaks of Hexaaquaaluminium complex ([Al(H2O) 6]3+), with no species of organic-aluminum complexes. Samples with moderate to high levels of Al (27Al-NMR) were positively correlated with the total concentration of Al derived from the atomic emission spectroscopy analysis (ICP-AES).

Die Delamination beschreibt einen glaskorrosiven Angriff, bei welchem dünne, plättchenförmige Partikel im angreifenden Medium vorhanden sind. Ziel dieser Arbeit ist die Analyse der zu Grunde liegenden Reaktionsmechanismen. Nahezu jedes der untersuchten silikatischen Glassysteme zeigt Delamination. Notwendige Bedingungen sind das Vorhandensein von Magnesiumionen sowie eine ausreichende Auflösung des Glasnetzwerkes zur Bereitstellung der Reaktionspartner. Es kommt zur Bildung einer magnesiumreichen Schicht auf der Glasoberfläche, welche sich ablöst. Die Delaminationsprodukte sind teilweise kristallin. Als Hauptphase wird das Magnesiumsilikat-Hydrat Talk nachgewiesen. Es wirken weitere Elemente delaminationsfördernd, darunter die Erdalkalimetalle höherer Ordnungszahl, außerdem Eisen und Mangan sowie Lithium. Eine hemmende Wirkung besitzen die Elemente der dritten Haupt- und Nebengruppe des Periodensystems, insbesondere Bor, Aluminium und Yttrium sowie Beryllium. Die Delamination ist nur einer von zahlreichen Teilschritten der Glaskorrosion mit Phasenneubildung.

Made available in DSpace on 2015-03-26T13:39:47Z (GMT). No. of bitstreams: 1 texto completo.pdf: 739809 bytes, checksum: 69524346956f11b5bb2a849577857347 (MD5) Previous issue date: 2012-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The competitive ability of crops and weeds is related to the efficient use of environmental resources. However, it may also be related to the associations of these species with soil microbiota and the ability to change it to minimize interference. The objective of this study was to evaluate the effects of the interference of five weeds in dry matter accumulation of corn plants and in the relative content of nutrients, as well as evaluate the biomass and microbial activity associated with weeds and corn in monoculture and in competition, in soils with diferent fertility managements. The experiment was conducted in a protected environment, considering four soil fertility managements (with calcium and magnesium silicate and fertilization; with limestone and fertilization; without correction of acidity, but with fertilization; without correction of acidity and without fertilization) and five arrangements competition between Zea mays and the weeds Brachiaria brizantha, Ipomoea grandifolia, Conyza canadensis, Bidens pilosa and Hyptis suaveolens, addition of species in monoculture and soils without plants. The coexistence of corn with weeds caused average reductions of 43.9%, 39.8% and 41.9% in dry matter of shoot, root and total culture, respectively. Under interference of B. brizantha, the corn had reductions exceeding 50% in the content of all macronutrients, being this weed the most damaging to the culture. Additionally, B. brizantha and B. pilosa in competition with corn stood out among the other weeds and has high ability to extract and use macronutrients in the four soil conditions. There was a tendency of reduction of microbial biomass carbon (MBC) in soils that receive were not correction acidity. B. pilosa and the arrangement formed by Z. mays and B. brizantha, showed high values of MBC, regardless of soil management. Low biological activity was observed in soil without acidity correction and without fertilization. In soil with calcium and magnesium silicate and maize plants in monoculture, the metabolic quotient (qCO2) was higher than the value observed with the weeds in monoculture and in competition arrangements, suggesting greater susceptibility of this system for carbon losses. Z. mays in competition with H. suaveolens was the arrangement that had greater preservation of organic matter (<qCO2) in the four soils. The weeds showed different competitive abilities causing reductions in the dry matter and nutrients accumulation in the corn plants, and showed distinct potential for nutrient cycling, depending on soil condition. Calcium and magnesium silicate and limestone did not differ in the weed interference on the dry biomass of corn plants, being the influence of these sources variable on nutrient accumulation by plants in monoculture or under interference. The microbial biomass and activity were altered by plant species, interference and managements of soil fertility. The manipulation of soil microorganisms may be a strategy used by corn and, or the weeds to minimize the competition in a given soil. / A habilidade competitiva das culturas e das plantas daninhas está relacionada à utilização eficiente dos recursos do meio na qual se encontram. No entanto, pode também estar relacionada com as associações dessas espécies com a microbiota do solo e a capacidade de alterá-la para minimizar a interferência. Objetivou-se com este trabalho avaliar os efeitos da interferência de cinco plantas daninhas no acúmulo de matéria seca e no conteúdo relativo de macronutrientes de plantas de milho, bem como a biomassa e a atividade microbiana associada às plantas daninhas e de milho em monocultivo e em competição, em solos com diferentes manejos de fertilidade. O experimento foi realizado em casa de vegetação, considerando-se como primeiro fator quatro manejos de fertilidade do solo (com silicato de cálcio e magnésio e adubação; com calcário e adubação; sem correção de acidez, mas com adubação; sem correção de acidez e sem adubação) e como segundo fator cinco arranjos de competição entre Zea mays e as plantas daninhas Brachiaria brizantha, Ipomoea grandifolia, Conyza canadensis, Hyptis suaveolens e Bidens pilosa, acrescido das seis espécies em monocultivo e de solo sem cultivo. A convivência do milho com plantas daninhas provocou reduções médias de 43,9%, 39,8% e 41,9% na massa da matéria seca da parte aérea, do sistema radicular e total da cultura, respectivamente. Sob interferência de B. brizantha, o milho apresentou reduções superiores a 50% no conteúdo de todos os macronutrientes, sendo esta a planta daninha mais danosa a cultura. Adicionalmente, B. brizantha e B. pilosa em competição com o milho se destacaram entre as demais plantas daninhas, apresentando elevada habilidade de extração e utilização de macronutrientes nas quatro condições de solo. Observou-se tendência de redução do carbono da biomassa microbina (CBM) nos solos que não tiveram correção de acidez. B. pilosa e o arranjo formado por Z. mays e B. brinzantha, independente do solo, apresentaram elevados valores de CBM. Baixa atividade biológica foi verificada no solo sem correção de acidez e sem adubação. No solo corrigido com silicato de cálcio e magnésio e cultivado com milho livre de interferência, o quociente metabólico (qCO2) foi maior do que com as plantas daninhas em monocultivo e arranjos de competição, sugerindo maior suscetibilidade desse sistema a perdas de carbono. Z. mays em competição com H. suaveolens mostrou ser o sistema misto mais conservativo da matéria orgânica (<qCO2) nos quatro manejos de fertilidade do solo. As plantas daninhas apresentaram não só habilidades competitivas distintas, provocando reduções consideráveis no acúmulo de matéria seca e nutrientes das plantas de milho, como também potencial diferenciado para ciclagem dos nutrientes estudados, a depender da condição de solo. Silicato de cálcio e magnésio e calcário não diferiram quanto à interferência das plantas daninhas sobre o acúmulo de biomassa seca das plantas de milho, sendo variável a influência dessas fontes sobre o acúmulo de nutrientes pelas plantas em monocultivo ou sob interferência. A biomassa e atividade microbiana foram alteradas pelas espécies de plantas, pela convivência e pelos manejos de fertilidade do solo, e a manipulação dos microrganismos do solo pode ser uma estratégia utilizada pela cultura do milho e, ou pelas plantas daninhas para minimizar a competição em determinado ambiente.

Les différentes options envisagées par la France et la Suisse pour le stockage de déchets radioactifs en couches géologiques profondes argileuses prévoient l’utilisation d’importants volumes de matériaux cimentaires. Les liants dits bas-pH ont été développés afin de limiter la perturbation de la roche encaissante par le panache alcalin. Les études expérimentales menées sur les interfaces béton bas-pH-argile mettent systématiquement en évidence la formation de phases silico-magnésiennes, potentiellement de silicate de magnésium hydraté (M-S-H), mal modélisées à cause de données thermodynamiques limitées. Cette étude a pour objectif de caractériser ces phases en température, en présence d’aluminium, calcium et d’alcalins pour alimenter les bases de données thermodynamiques et améliorer les calculs sur les évolutions physico-chimiques des bétons bas pH et éventuellement des bétons de Portland. Des suspensions de M-S-H ont été synthétisées à partir d'oxyde de magnésium et de fumée de silice à différentes températures, à différents temps de réaction et différents rapports Mg/Si. Un panel de techniques d’analyses de chimie du solide et des mesures en suspensions couplées à des analyses des phases liquides a été utilisé pour caractériser les phases synthétisées. Initialement, et quel que soit le Mg/Si total choisi pour la synthèse, un M-S-H avec un rapport Mg/Si ~1 précipite en présence de brucite et de silice amorphe. Lorsque l’équilibre du système est atteint, 2 à 3 ans à 20 °C ou 1 an à 50 et 70 °C, le Mg/Si varie de ~0,8 à ~1,4. La température a peu d'influence sur le M-S-H formé même si le M-S-H se forme plus rapidement et qu’il est légèrement moins stable thermodynamiquement lorsque la température augmente. A l'équilibre, sa structure mal définie est comparable à des nano-cristallites de phyllosilicates hydratés avec une surface spécifique supérieure à 200 m2/g. Un modèle de solution solide pour le M-S-H a été calculé et ajouté à la base de données.Dans un second temps, les travaux ont été focalisés sur la formation de M-S-H à partir de silicate de calcium hydraté (C-S-H) avec un faible Ca/Si (= 0,8) et de magnésium. Le C-S-H n’est pas stable à des pH avoisinant un pH = 10, ce qui favorise la précipitation de M-S-H. Des recherches détaillées montrent que du calcium peut être faiblement incorporé dans le M-S-H (Ca/Si ≤ 0,10), et des solutions solides contenant du calcium ont été ajoutés à la base de données. Pour des pH supérieurs à 10-10,5, les C-S-H et M-S-H coexistent. L’observation par MEB-EDS d’une interface en cellule de diffusion entre C-S-H (Ca/Si=0,8 représentant un liant bas pH) et M-S-H (Mg/Si=0,8), couplée à la modélisation de celle-ci en transport réactif, sur la base des nouvelles données thermodynamiques dérivées des expériences précédentes, montrent la détérioration rapide du C-S-H et la précipitation de M-S-H dans le disque C-S-H, ainsi qu’une absorption homogène du calcium dans le disque de M-S-H.L’augmentation du pH en solution favorise la sorption de cations. Des M-S-H présentant une sorption de sodium jusqu'à Na/Si ~ 0,20 en absence de brucite ont été observés à des pH avoisinants 12,5. La sorption sur le M-S-H est favorisée dans l'ordre Na+ < Mg2+ < Ca2+. Enfin, l'aluminium s’incorpore dans le M-S-H pour former du M-A-S-H. Un rapport Al/Si jusqu’à 0,2 est observé dans des suspensions synthétisées en présence d’aluminate de sodium ou de métakaolin. Les données de RMN de l’aluminium ont montré que celui-ci est présent dans les sites tétraédriques et octaédriques du M-A-S-H. La phase formée a une structure similaire à celle du M-S-H avec un degré de polymérisation des silicates et une charge effective de surface comparables. / The various options to store radioactive wastes in deep geological strata considered in France or Switzerland include the use of large volumes of cementitious materials for infrastructure in contact with argillaceous rocks. So-called low-pH binders were developed to minimize disruption to the surrounding rock by the alkaline plume. Studies conducted on the interaction zone between concrete and clay systematically highlighted the formation of magnesium silicate phases including magnesium silicate hydrate (M-S-H) at the interfaces, which can presently be modeled only partially due to incomplete thermodynamic data. The purpose of this study was to characterize these phases in temperature, aluminum, calcium, and alkali conditions in order to provide the thermodynamic data and improve the calculations on physicochemical evolutions of low-pH concretes and possibly Portland concretes.M-S-H phases were synthesized from magnesium oxide and silica fume in batch experiments at different temperatures, for various times and varying Mg/Si. A large number of different techniques such as chemical solid characterizations coupled with suspension investigations and liquid analyses were used to characterize the phases synthesized. Initially a M-S-H phase with Mg/Si equal to 1 was precipitated in addition to amorphous silica and brucite whatever the total Mg/Si used for the synthesis. After long equilibration times, 2 to 3 years at 20°C or 1 year at 50 and 70°C, the Mg/Si in M-S-H ranged from ~0.8 to ~1.4. The temperature had little influence on the M-S-H formed even if the M-S-H formation occurred faster and M-S-H was thermodynamically slightly less stable when the temperature was increased. At or near to equilibrium, M-S-H phases were characterized with ill-defined structure comparable to nano-crystallite, hydrated phyllosilicates with a surface area greater than 200 m2/g. A M-S-H solid-solution model was calculated and implemented in the thermodynamic database.It was observed that M-S-H also form from calcium silicate hydrate (C-S-H) with a Ca/Si = 0.8 in the presence of additional magnesium. In batch experiments, a low pH of the suspensions (pH ≤ 10) destabilized C-S-H or prevented its formation and favored the precipitation of M-S-H. Detailed investigations showed that small amounts of calcium could be incorporated in M-S-H (Ca/Si ≤0.10), such that also calcium containing end-members were added to the M-S-H solid-solution. At pH ≥ 10-10.5, two separate silicate phases coexist: C-S-H and M-S-H. The interface between a simplified “low-pH” binder mimicked by C-S-H with Ca/Si = 0.8 and a magnesium-rich environment mimicked by M-S-H with Mg/Si = 0.8 confirmed these phenomena. SEM-EDS observations and reactive transport modelling using the thermodynamic data derived in the batch experiments showed the fast deterioration of the C-S-H and the precipitation of M-S-H in the C-S-H disk at the interface and a homogeneous uptake of calcium in the M-S-H disk.The increase of pH favors the sorption. M-S-H with a sodium uptake up to Na/Si ~ 0.20 and without brucite formation were observed at high pH (12.5). The sorption on M-S-H was favored in the order Na+ < Mg2+ < Ca2+. Finally, aluminum was incorporated into M-S-H to form magnesium alumino-silicate hydrate (M-A-S-H). An Al/Si ratio up to 0.2 was observed in presence of sodium aluminate or metakaolin. 27Al MAS NMR data showed that aluminum was present in both tetrahedral and octahedral sites of M-(A-)S-H. The M-(A-)S-H formed had a similar structure as M-S-H with a comparable polymerization degree of the tetrahedral silicates and a similar surface charge.