Physicochemical characterisation of protein ingredients prepared from milk by ultrafiltration or microfiltration for application in formulated nutritional products

Formulated food systems are becoming more sophisticated as demand grows for the design of structural and nutritional profiles targeted at increasingly specific demographics. Milk protein is an important bio- and techno-functional component of such formulations, which include infant formula, sports supplements, clinical beverages and elderly nutrition products. This thesis outlines research into ingredients that are key to the development of these products, namely milk protein concentrate (MPC), milk protein isolate (MPI), micellar casein concentrate (MCC), β-casein concentrate (BCC) and serum protein concentrate (SPC). MPC powders ranging from 37 to 90% protein (solids basis) were studied for properties of relevance to handling and storage of powders, powder solubilisation and thermal processing of reconstituted MPCs. MPC powders with ≥80% protein were found to have very poor flowability and high compressibility; in addition, these high-protein MPCs exhibited poor wetting and dispersion characteristics during rehydration in water. Heat stability studies on unconcentrated (3.5%, 140°C) and concentrated (8.5%, 120°C) MPC suspensions, showed that suspensions prepared from high-protein MPCs coagulated much more rapidly than lower protein MPCs. β-casein ingredients were developed using membrane processing. Enrichment of β-casein from skim milk was performed at laboratory-scale using ‘cold’ microfiltration (MF) at <4°C with either 1000 kDa molecular weight cut-off or 0.1 µm pore-size membranes. At pilot-scale, a second ‘warm’ MF step at 26°C was incorporated for selective purification of micellised β-casein from whey proteins; using this approach, BCCs with β-casein purity of up to 80% (protein basis) were prepared, with the whey protein purity of the SPC co-product reaching ~90%. The BCC ingredient could prevent supersaturated solutions of calcium phosphate (CaP) from precipitating, although the amorphous CaP formed created large micelles that were less thermo-reversible than those in CaP-free systems. Another co-product of BCC manufacture, MCC powder, was shown to have superior rehydration characteristics compared to traditional MCCs. The findings presented in this thesis constitute a significant advance in the research of milk protein ingredients, in terms of optimising their preparation by membrane filtration, preventing their destabilisation during processing and facilitating their effective incorporation into nutritional formulations designed for consumers of a specific age, lifestyle or health status

Desorption isotherms and thermodynamics properties of anchovy in natura and enzymatic modified paste

The thermodynamic properties of anchovy fillets and enzymatic modified pastes in two hydrolysis degrees (3% HD and 14% HD), at 50, 60 and 70 C were evaluated. The GAB model was used to calculate the values of the monolayer moisture content and the thermodynamic properties of the samples. The enzymatic modification led to the increases of the superficial area and differential enthalpies, and decrease of the differential entropies in relation the samples in natura. The enthalpy–entropy compensation showed that the process was controlled by the enthalpy, it was only spontaneous for the samples in natura. Pore size decreased with enzymatic modification, and all samples were in the limit of region between micropores and mesopores (<2 nm) for moisture content of 15%, and mesopores (from 2 to 50 nm) to moisture content above 15%.

New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Large-Scale Controlled-Condition Experiment to Evaluate Light Weight Deflectometers for Modulus Determination and Compaction Quality Assurance of Unbound Pavement Materials

Compaction control using lightweight deflectometers (LWD) is currently being evaluated in several states and countries and fully implemented for pavement construction quality assurance (QA) by a few. Broader implementation has been hampered by the lack of a widely recognized standard for interpreting the load and deflection data obtained during construction QA testing. More specifically, reliable and practical procedures are required for relating these measurements to the fundamental material property—modulus—used in pavement design. This study presents a unique set of data and analyses for three different LWDs on a large-scale controlled-condition experiment. Three 4.5x4.5 m2 test pits were designed and constructed at target moisture and density conditions simulating acceptable and unacceptable construction quality. LWD testing was performed on the constructed layers along with static plate loading testing, conventional nuclear gauge moisture-density testing, and non-nuclear gravimetric and volumetric water content measurements. Additional material was collected for routine and exploratory tests in the laboratory. These included grain size distributions, soil classification, moisture-density relations, resilient modulus testing at optimum and field conditions, and an advanced experiment of LWD testing on top of the Proctor compaction mold. This unique large-scale controlled-condition experiment provides an excellent high quality resource of data that can be used by future researchers to find a rigorous, theoretically sound, and straightforward technique for standardizing LWD determination of modulus and construction QA for unbound pavement materials.

Development of ultra-high-performance concrete (UHPC) using waste glass materials ─ towards innovative eco-friendly concrete

Le béton conventionnel (BC) a de nombreux problèmes tels que la corrosion de l’acier d'armature et les faibles résistances des constructions en béton. Par conséquent, la plupart des structures fabriquées avec du BC exigent une maintenance fréquent. Le béton fibré à ultra-hautes performances (BFUP) peut être conçu pour éliminer certaines des faiblesses caractéristiques du BC. Le BFUP est défini à travers le monde comme un béton ayant des propriétés mécaniques, de ductilité et de durabilité supérieures. Le BFUP classique comprend entre 800 kg/m³ et 1000 kg/m³ de ciment, de 25 à 35% massique (%m) de fumée de silice (FS), de 0 à 40%m de poudre de quartz (PQ) et 110-140%m de sable de quartz (SQ) (les pourcentages massiques sont basés sur la masse totale en ciment des mélanges). Le BFUP contient des fibres d'acier pour améliorer sa ductilité et sa résistance aux efforts de traction. Les quantités importantes de ciment utilisées pour produire un BFUP affectent non seulement les coûts de production et la consommation de ressources naturelles comme le calcaire, l'argile, le charbon et l'énergie électrique, mais affectent également négativement les dommages sur l'environnement en raison de la production substantielle de gaz à effet de serre dont le gas carbonique (CO[indice inférieur 2]). Par ailleurs, la distribution granulométrique du ciment présente des vides microscopiques qui peuvent être remplis avec des matières plus fines telles que la FS. Par contre, une grande quantité de FS est nécessaire pour combler ces vides uniquement avec de la FS (25 à 30%m du ciment) ce qui engendre des coûts élevés puisqu’il s’agit d’une ressource limitée. Aussi, la FS diminue de manière significative l’ouvrabilité des BFUP en raison de sa surface spécifique Blaine élevée. L’utilisation du PQ et du SQ est également coûteuse et consomme des ressources naturelles importantes. D’ailleurs, les PQ et SQ sont considérés comme des obstacles pour l’utilisation des BFUP à grande échelle dans le marché du béton, car ils ne parviennent pas à satisfaire les exigences environnementales. D’ailleurs, un rapport d'Environnement Canada stipule que le quartz provoque des dommages environnementaux immédiats et à long terme en raison de son effet biologique. Le BFUP est généralement vendu sur le marché comme un produit préemballé, ce qui limite les modifications de conception par l'utilisateur. Il est normalement transporté sur de longues distances, contrairement aux composantes des BC. Ceci contribue également à la génération de gaz à effet de serre et conduit à un coût plus élevé du produit final. Par conséquent, il existe le besoin de développer d’autres matériaux disponibles localement ayant des fonctions similaires pour remplacer partiellement ou totalement la fumée de silice, le sable de quartz ou la poudre de quartz, et donc de réduire la teneur en ciment dans BFUP, tout en ayant des propriétés comparables ou meilleures. De grandes quantités de déchets verre ne peuvent pas être recyclées en raison de leur fragilité, de leur couleur, ou des coûts élevés de recyclage. La plupart des déchets de verre vont dans les sites d'enfouissement, ce qui est indésirable puisqu’il s’agit d’un matériau non biodégradable et donc moins respectueux de l'environnement. Au cours des dernières années, des études ont été réalisées afin d’utiliser des déchets de verre comme ajout cimentaire alternatif (ACA) ou comme granulats ultrafins dans le béton, en fonction de la distribution granulométrique et de la composition chimique de ceux-ci. Cette thèse présente un nouveau type de béton écologique à base de déchets de verre à ultra-hautes performances (BEVUP) développé à l'Université de Sherbrooke. Les bétons ont été conçus à l’aide de déchets verre de particules de tailles variées et de l’optimisation granulaire de la des matrices granulaires et cimentaires. Les BEVUP peuvent être conçus avec une quantité réduite de ciment (400 à 800 kg/m³), de FS (50 à 220 kg/m³), de PQ (0 à 400 kg/m³), et de SQ (0-1200 kg/m³), tout en intégrant divers produits de déchets de verre: du sable de verre (SV) (0-1200 kg/m³) ayant un diamètre moyen (d[indice inférieur 50]) de 275 µm, une grande quantité de poudre de verre (PV) (200-700 kg/m³) ayant un d50 de 11 µm, une teneur modérée de poudre de verre fine (PVF) (50-200 kg/m³) avec d[indice inférieur] 50 de 3,8 µm. Le BEVUP contient également des fibres d'acier (pour augmenter la résistance à la traction et améliorer la ductilité), du superplastifiants (10-60 kg/m³) ainsi qu’un rapport eau-liant (E/L) aussi bas que celui de BFUP. Le remplacement du ciment et des particules de FS avec des particules de verre non-absorbantes et lisse améliore la rhéologie des BEVUP. De plus, l’utilisation de la PVF en remplacement de la FS réduit la surface spécifique totale nette d’un mélange de FS et de PVF. Puisque la surface spécifique nette des particules diminue, la quantité d’eau nécessaire pour lubrifier les surfaces des particules est moindre, ce qui permet d’obtenir un affaissement supérieur pour un même E/L. Aussi, l'utilisation de déchets de verre dans le béton abaisse la chaleur cumulative d'hydratation, ce qui contribue à minimiser le retrait de fissuration potentiel. En fonction de la composition des BEVUP et de la température de cure, ce type de béton peut atteindre des résistances à la compression allant de 130 à 230 MPa, des résistances à la flexion supérieures à 20 MPa, des résistances à la traction supérieure à 10 MPa et un module d'élasticité supérieur à 40 GPa. Les performances mécaniques de BEVUP sont améliorées grâce à la réactivité du verre amorphe, à l'optimisation granulométrique et la densification des mélanges. Les produits de déchets de verre dans les BEVUP ont un comportement pouzzolanique et réagissent avec la portlandite générée par l'hydratation du ciment. Cependant, ceci n’est pas le cas avec le sable de quartz ni la poudre de quartz dans le BFUP classique, qui réagissent à la température élevée de 400 °C. L'addition des déchets de verre améliore la densification de l'interface entre les particules. Les particules de déchets de verre ont une grande rigidité, ce qui augmente le module d'élasticité du béton. Le BEVUP a également une très bonne durabilité. Sa porosité capillaire est très faible, et le matériau est extrêmement résistant à la pénétration d’ions chlorure (≈ 8 coulombs). Sa résistance à l'abrasion (indice de pertes volumiques) est inférieure à 1,3. Le BEVUP ne subit pratiquement aucune détérioration aux cycles de gel-dégel, même après 1000 cycles. Après une évaluation des BEVUP en laboratoire, une mise à l'échelle a été réalisée avec un malaxeur de béton industriel et une validation en chantier avec de la construction de deux passerelles. Les propriétés mécaniques supérieures des BEVUP a permis de concevoir les passerelles avec des sections réduites d’environ de 60% par rapport aux sections faites de BC. Le BEVUP offre plusieurs avantages économiques et environnementaux. Il réduit le coût de production et l’empreinte carbone des structures construites de béton fibré à ultra-hautes performances (BFUP) classique, en utilisant des matériaux disponibles localement. Il réduit les émissions de CO[indice inférieur 2] associées à la production de clinkers de ciment (50% de remplacement du ciment) et utilise efficacement les ressources naturelles. De plus, la production de BEVUP permet de réduire les quantités de déchets de verre stockés ou mis en décharge qui causent des problèmes environnementaux et pourrait permettre de sauver des millions de dollars qui pourraient être dépensés dans le traitement de ces déchets. Enfin, il offre une solution alternative aux entreprises de construction dans la production de BFUP à moindre coût.

Scaffolds porosos à base de fosfatos de cálcio para regeneração óssea

Graças ao aumento da esperança média de vida do ser humano, a engenharia de tecidos tem sido uma área alvo de enorme investigação. A utilização de estruturas tridimensionais porosas e biodegradáveis, denominadas de scaffolds, como matriz para a adesão e proliferação celular tem sido amplamente investigada. Existem atualmente diversas técnicas para a produção destas estruturas mas o grau de exigência tem vindo a aumentar, existindo ainda lacunas que necessitam ser preenchidas. A técnica de robocasting consiste numa deposição camada a camada de uma pasta coloidal, seguindo um modelo computorizado (CAD) e permite a produção de scaffolds com porosidade tamanho de poro e fração de porosidade controlados, boa reprodutibilidade, e com formas variadas, as quais podem ser idênticas às dos defeitos ósseos a preencher. O presente estudo teve como objetivo produzir scaffolds porosos à base de fosfatos de cálcio através de robocasting. Para tal, foram estudadas duas composições de pós à base de β-TCP, uma pura e outra co-dopada com estrôncio, zinco e manganês. Inicialmente os pós foram sintetizados pelo método de precipitação química por via húmida. Após a síntese, estes foram filtrados, secos, calcinados a 1000ºC e posteriormente moídos até possuírem um tamanho médio de partícula de cerca de 1,5 μm. Os pós foram depois peneirados com uma malha de 40μm e caracterizados. Posteriormente foram preparadas várias suspensões e avaliado o seu comportamento reológico, utilizando Targon 1128 como dispersante, Hidroxipropilmetilcelulose (HPMC) como ligante e polietilenimina (PEI) como agente floculante. Por fim, e escolhida a melhor composição para a formação da pasta, foram produzidos scaffolds com diferentes porosidades, num equipamento de deposição robótica (3D Inks, LLC). Os scaffolds obtidos foram secos à temperatura ambiente durante 48 horas, sinterizados a 1100ºC e posteriormente caracterizados por microscopia eletrónica de varrimento (SEM), avaliação dos tamanhos de poro, porosidade total e testes mecânicos. Ambas as composições estudadas puderam ser transformadas em pastas extrudíveis, mas a pasta da composição pura apresentou uma consistência mais próxima do ideal, tendo originado scaffolds de melhor qualidade em termos de microestrutura e de propriedades mecânicas.

Immunogenicity of Outer Membrane Proteins VirB9-1 and VirB9-2, a Novel Nanovaccine against Anaplasma marginale

Anaplasma marginale is the most prevalent tick-borne livestock pathogen and poses a significant threat to cattle industry. In contrast to currently available live blood-derived vaccines against A. marginale, alternative safer and better-defined subunit vaccines will be of great significance. Two proteins (VirB9-1 and VirB9-2) from the Type IV secretion system of A. marginale have been shown to induce humoral and cellular immunity. In this study, Escherichia coli were used to express VirB9-1 and VirB9-2 proteins. Silica vesicles having a thin wall of 6 nm and pore size of 5.8 nm were used as the carrier and adjuvant to deliver these two antigens both as individual or mixed nano-formulations. High loading capacity was achieved for both proteins, and the mouse immunisation trial with individual as well as mixed nano-formulations showed high levels of antibody titres over 107 and strong T-cell responses. The mixed nano-formulation also stimulated high-level recall responses in bovine T-cell proliferation assays. These results open a promising path towards the development of efficient A. marginale vaccines and provide better understanding on the role of silica vesicles to deliver multivalent vaccines as mixed nano-formulations able to activate both B-cell and T-cell immunity, for improved animal health.

A petrographic investigation into the durability of common replacement sandstones to the crystallisation of de-icing salts

Scottish sandstone buildings are now suffering the long-term effects of salt-crystallisation damage, owing in part to the repeated deposition of de-icing salts during winter months. The use of de-icing salts is necessary in order to maintain safe road and pavement conditions during cold weather, but their use comes at a price. Sodium chloride (NaCl), which is used as the primary de-icing salt throughout the country, is a salt known to be damaging to sandstone masonry. However, there remains a range of alternative, commercially available de-icing salts. It is unknown however, what effect these salts have on porous building materials, such as sandstone. In order to protect our built heritage against salt-induced decay, it is vital to understand the effects of these different salts on the range of sandstone types that we see within the historic buildings of Scotland. Eleven common types of sandstone were characterised using a suite of methods in order to understand their mineralogy, pore structure and their response to moisture movement, which are vital properties that govern a stone’s response to weathering and decay. Sandstones were then placed through a range of durability tests designed to measure their resistance to various weathering processes. Three salt crystallisation tests were undertaken on the sandstones over a range of 16 to 50 cycles, which tested their durability to NaCl, CaCl2, MgCl2 and a chloride blend salt. Samples were primarily analysed by measuring their dry weight loss after each cycle, visually after each cycle and by other complimentary methods in order to understand their changing response to moisture uptake after salt treatment. Salt crystallisation was identified as the primary mechanism of decay across each salt, with the extent of damage in each sandstone influenced by environmental conditions and pore-grain properties of the stone. Damage recorded in salt crystallisation tests was ultimately caused by the generation of high crystallisation pressures within the confined pore networks of each stone. Stone and test-specific parameters controlled the location and magnitude of damage, with the amount of micro-pores, their spatial distribution, the water absorption coefficient and the drying efficiency of each stone being identified as the most important stone-specific properties influencing salt-induced decay. Strong correlations were found between the dry weight loss of NaCl treated samples and the proportion of pores <1µm in diameter. Crystallisation pressures are known to scale inversely with pore size, while the spatial distribution of these micro-pores is thought to influence the rate, overall extent and type of decay within the stone by concentrating crystallisation pressures in specific regions of the stone. The water absorption determines the total amount of moisture entering into the stone, which represents the total amount of void space for salt crystallisation. The drying parameters on the other hand, ultimately control the distribution of salt crystallisation. Those stones that were characterised by a combination of a high proportion of micro-pores, high water absorption values and slow drying kinetics were shown to be most vulnerable to NaCl-induced decay. CaCl2 and MgCl2 are shown to have similar crystallisation behaviour, forming thin crystalline sheets under low relative humidity and/or high temperature conditions. Distinct differences in their behaviour that are influenced by test specific criteria were identified. The location of MgCl2 crystallisation close to the stone surface, as influenced by prolonged drying under moderate temperature drying conditions, was identified as the main factor that caused substantial dry weight loss in specific stone types. CaCl2 solutions remained unaffected under these conditions and only crystallised under high temperatures. Homogeneous crystallisation of CaCl2 throughout the stone produced greater internal change, with little dry weight loss recorded. NaCl formed distinctive isometric hopper crystals that caused damage through the non-equilibrium growth of salts in trapped regions of the stone. Damage was sustained as granular decay and contour scaling across most stone types. The pore network and hydric properties of the stones continually evolve in response to salt crystallisation, creating a dynamic system whereby the initial, known properties of clean quarried stone will not continually govern the processes of salt crystallisation, nor indeed can they continually predict the behaviour of stone to salt-induced decay.

Desenvolvimento e caracterização de micropartículas de amido reticuladas com agente fosfatado e avaliação da adsorção do azul de metileno

Starch has properties that make it one of the most studied biopolymers today. It is biodegradable, biocompatible, stable and non-toxic. This work has synthesis of starch and tapioca microparticles, through chemical modification by crosslinking with sodium tripolyphosphate agent in concentrations 7.5 and 15% (m / m). The amylose content was measured for starch and commercial cassava starch at 21.8% and 28.6%, respectively. According to the solubility index, processing in basic medium does not change the solubility of the material, but the addition of crosslinking agent increases this index, which changed from 12.8% for the control unprocessed, to 22.4% for the A5R15 sample. Soluble starch-based materials had a significant increase in the crosslinking density by increasing the concentration of crosslinker, from 1.4 in A5R7,5 sample, to 1.9 in A5R15. The cassava starch-based materials exhibited an opposite behavior: to increase the concentration of crosslinker crosslinking density decreased significantly in F5R7.5 from 2.9, to 1.9 in F5R15 sample. The point of zero charge (PZC) shows that below pH 4 the surface is positively charged. The surface area data is between 3,04 and 1,15 m2.g-1. The pore volume between 2.94 and 1.33 cm3.g-1 and pore size around 1.5 nm. The SEM indicates uneven distribution of microparticles, which are smooth, with no ridges. The maximum adsorption capacity of the materials were tested at pH 7.7 and for A5R15 and CA sample, at pH 2, 5, 6 and 9. It is noted that the processing in basic medium reduces the adsorption capacity of CA and CF in respect fo A and F. The adsorption in A5R15 sample has great dependency on the pH, reaching a value of 587 μg.g-1 in pH 7.7. The samples A5R15 and F5R7,5 adsorbed similar amounts, according to the statistical analysis, and significantly higher than their respective controls and showed lower desorption, indicating that the modification process was effective to control the release of methylene blue. The infrared spectra not show the characteristic bands of the phosphate bonds to the material formed, however, developments in hydroxyl characteristic band suggest modification in the way this group was linked after the reaction. After adsorption, the infrared spectra show different format in the band of hydroxyl. PCA analysis shows that the greatest changes observed in the IR spectra are observed in the region of 3500 cm-1. Thermal analysis showed three thermal events related to dehydration and material degradation. It is observed that the processing increases the temperature to the first mass loss, fixed at 12%, but not observed increased stability due to the presence of crosslinker or process.

Design of passive methane oxidation biosystems considering their response to the presence of capillary barrier effect

La construction des biosystèmes d’oxydation passive du méthane (BOPM) est une option économique et durable pour réduire les émissions de méthane des sites d’enfouissement de déchets et des effets subséquents du réchauffement climatique. Les BOPM sont constitués de deux couches principales: la couche d'oxydation du méthane (MOL) et la couche de distribution du gaz (GDL). L'oxydation du méthane se produit dans la MOL par les réactions biochimiques des bactéries méthanotrophes, et la GDL est construite sous la MOL pour intercepter et distribuer les émissions fugitives de biogaz à la base de la MOL. Fondamentalement, l'efficacité d'un BOPM est définie en fonction de l'efficacité d'oxydation du méthane dans la MOL. Par conséquent, il est indispensable de fournir des conditions adéquates pour les activités bactériennes des méthanotrophes. En plus des paramètres environnementaux, l'intensité et la distribution du biogaz influencent l'efficacité des BOPM, et ils peuvent rendre le matériau de la MOL - avec une grande capacité d'accueillir les activités bactériennes - inutilisables en termes d'oxydation du méthane sur place. L'effet de barrière capillaire le long de l'interface entre la GDL et la MOL peut provoquer des émissions localisées de méthane, due à la restriction ou la distribution non uniforme de l’écoulement ascendant du biogaz à la base de la MOL. L'objectif principal de cette étude est d'incorporer le comportement hydraulique non saturé des BOPM dans la conception des BOPM, afin d’assurer la facilité et la distribution adéquates de l'écoulement du biogaz à la base de la MOL. Les fonctions de perméabilité à l'air des matériaux utilisés pour construire la MOL des BOPM expérimentaux au site d’enfouissement des déchets de St Nicéphore (Québec, Canada), ainsi que celles d'autres de la littérature technique, ont été étudiés pour évaluer le comportement d'écoulement non saturé du gaz dans les matériaux et pour identifier le seuil de migration sans restriction du gaz. Ce dernier seuil a été introduit en tant que un paramètre de conception avec lequel le critère de conception recommandé ici, c’est à dire la longueur de la migration sans restriction de gaz (LMSG), a été défini. La LMSG est considérée comme la longueur le long de l'interface entre la GDL et la MOL où le biogaz peut migrer à travers la MOL sans restriction. En réalisant des simulations numériques avec SEEP/W, les effets de la pente de l'interface, des paramètres définissant la courbe de rétention d'eau, de la fonction de la conductivité hydraulique du matériau de la MOL sur la valeur de la LMSG (représentant la facilité d'écoulement du biogaz à l'interface) et de la distribution de l'humidité (et par conséquent celle du biogaz) ont été évalués. Selon les résultats des simulations, la conductivité hydraulique saturée et la distribution des tailles de pores du matériau de la MOL sont les paramètres les plus importants sur la distribution de l'humidité le long de l'interface. Ce dernier paramètre influe également sur la valeur du degré de saturation et donc la facilité du biogaz à la base de la MOL. La densité sèche du matériau de MOL est un autre paramètre qui contrôle la facilité d'écoulement ascendant du biogaz. Les limitations principales de la présente étude sont associées au nombre de matériaux de MOL testés et à l'incapacité de SEEP/W de considérer l'évapotranspiration. Toutefois, compte tenu des hypothèses raisonnables dans les simulations et en utilisant les données de la littérature, on a essayé de réduire ces limitations. En utilisant les résultats des expériences et des simulations numériques, des étapes et des considérations de conception pour la sélection du matériau de MOL et de la pente d'interface ont été proposées. En effet,le comportement hydraulique non saturé des matériaux serait intégré dans les nécessités de conception pour un BOPM efficace, de sorte que la capacité maximale possible d'oxydation du méthane du matériau de la MOL soit exploitée.

Alteration of cell-wall porosity is involved in osmotic stress-induced enhancement of aluminium resistance in common bean (Phaseolus vulgaris L.)

Aluminium (Al) toxicity and drought are the two major abiotic stress factors limiting common bean production in the tropics. Using hydroponics, the short-term effects of combined Al toxicity and drought stress on root growth and Al uptake into the root apex were investigated. In the presence of Al stress, PEG 6000 (polyethylene glycol)-induced osmotic (drought) stress led to the amelioration of Al-induced inhibition of root elongation in the Al-sensitive genotype VAX 1. PEG 6000 (>> PEG 1000) treatment greatly decreased Al accumulation in the 1 cm root apices even when the roots were physically separated from the PEG solution using dialysis membrane tubes. Upon removal of PEG from the treatment solution, the root tips recovered from osmotic stress and the Al accumulation capacity was quickly restored. The PEG-induced reduction of Al accumulation was not due to a lower phytotoxic Al concentration in the treatment solution, reduced negativity of the root apoplast, or to enhanced citrate exudation. Also cell-wall (CW) material isolated from PEG-treated roots showed a low Al-binding capacity which, however, was restored after destroying the physical structure of the CW. The comparison of the Al(3+), La(3+), Sr(2+), and Rb(+) binding capacity of the intact root tips and the isolated CW revealed the specificity of the PEG 6000 effect for Al. This could be due to the higher hydrated ionic radius of Al(3+) compared with other cations (Al(3+) >> La(3+) > Sr(2+) > Rb(+)). In conclusion, the results provide circumstantial evidence that the osmotic stress-inhibited Al accumulation in root apices and thus reduced Al-induced inhibition of root elongation in the Al-sensitive genotype VAX 1 is related to the alteration of CW porosity resulting from PEG 6000-induced dehydration of the root apoplast.

Undersampled Critical Branching Processes on Small-World and Random Networks Fail to Reproduce the Statistics of Spike Avalanches

The power-law size distributions obtained experimentally for neuronal avalanches are an important evidence of criticality in the brain. This evidence is supported by the fact that a critical branching process exhibits the same exponent t~3=2. Models at criticality have been employed to mimic avalanche propagation and explain the statistics observed experimentally. However, a crucial aspect of neuronal recordings has been almost completely neglected in the models: undersampling. While in a typical multielectrode array hundreds of neurons are recorded, in the same area of neuronal tissue tens of thousands of neurons can be found. Here we investigate the consequences of undersampling in models with three different topologies (two-dimensional, small-world and random network) and three different dynamical regimes (subcritical, critical and supercritical). We found that undersampling modifies avalanche size distributions, extinguishing the power laws observed in critical systems. Distributions from subcritical systems are also modified, but the shape of the undersampled distributions is more similar to that of a fully sampled system. Undersampled supercritical systems can recover the general characteristics of the fully sampled version, provided that enough neurons are measured. Undersampling in two-dimensional and small-world networks leads to similar effects, while the random network is insensitive to sampling density due to the lack of a well-defined neighborhood. We conjecture that neuronal avalanches recorded from local field potentials avoid undersampling effects due to the nature of this signal, but the same does not hold for spike avalanches. We conclude that undersampled branching-process-like models in these topologies fail to reproduce the statistics of spike avalanches.

Sea otter predation and the distribution of bivalve prey in the Elkhorn Slough National Estuarine Research Reserve

The California sea otter population is gradually expanding in size and geographic range and is consequently invading new feeding grounds, including bays and estuaries that are home to extensive populations of bivalve prey. One such area is the Elkhorn Slough, where otters have apparently established a spring and summer communal feeding and resting area. In anticipation of future otter foraging in the slough, an extensive baseline database on bivalve densities, size distributions, biomasses, and burrow depths has been established for three potential bivalve prey species, Saxidomus nuttalli, Tresus nutallii, and Zirphaea pilsbryi. In 1986, the Elkhorn Slough otters were foraging predominately at two areas immediately east and west of the Highway 1 bridge (Skipper's and the PG&E Outfall). Extensive subtidal populations of Saxidomus nuttalli and Tresus nuttallii occur in these areas. Shell records collected at these study areas indicated that sea otters were foraging selectively on Saxidomus over Tresus. The reason for this apparent preference was not clear. At the Skipper's study site, 51% of the shell record was composed of Saxidomus, yet this species accounted for only 16% of the in situ biomass, and only 39% of the available clams. Tresus represented 49% of the shell record at Skipper's, yet this species accounted for 84% of the in situ biomass and 61% of the available clams. There was no difference in mean burrow depth between the two species at this site so availability does not explain the disparity in consumption. At the PG&E Outfall, Saxidomus represents 66% of the in situ biomass and 81% of the available clams, while Tresus accounts for 34% of the in situ biomass and 19% of the available clams. Saxidomus accounts for 96% of the shell record at this site vs. 4% for Tresus, again indicating that the otters were preying on Saxidomus out of proportion to their density or biomass. High densities and biomasses of a third species, Zirphaea pilsbryi, occur in areas where sea otters were observed to be foraging, yet no cast-off Zirphaea shells were found. Although it is possible this species was not represented in the shell record because the otters were simply chewing up the shells, it is more likely this species is avoided by sea otters. There were relatively few sea otters in the Elkhorn Slough in 1986 compared to the previous two years. This, coupled with high bivalve densities, precluded any quantitative comparison of bivalve densities before and after the 1986 sea otter occupation. Qualitative observations made during the course of this study, and quantitative observations from previous studies indicate that, after 3 years, sea otters are not yet significantly affecting bivalve densities in the Elkhorn Slough.

Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2