Carbon dioxide hydrates were synthesized in a 0.10m I.D. and 1.22m tall bubble column equipped with a cooling jacket for heat removal. Visual observations at different driving forces (pressures between 2.75 and 3.60 MPa and temperatures between 0 and 8ºC) were recorded with a digital camera through a sight glass of 118.8 by 15.6 mm. The superficial gas velocity was varied from 20 to 50 mm/s to attain different levels of turbulence in the liquid. The growth rate was found to be dependent on the sequence/method used to reach the operating temperature and pressure. A greater supersaturation was obtained when the system temperature and pressure were reached with very low or no bubble-induced mixing. As a result, hydrates nucleated and grew immediately when starting the gas flow with the reactor volume being quickly filled with hydrates. Moreover, the hydrate growth rate and solution final density were higher when operating conditions partially condensed CO2 resulting in greater interphase mass transfer rates. In parallel, since hydrate formation is an exothermic process and the reaction is often limited by the rate of heat removal, heat transfer measurements were achieved in a simulated hydrate environment. The instantaneous heat transfer coefficient and related statistics gave insight on the role of bubbles on heat transfer and hydrodynamics.

Slurry walls have been widely used for more than 25 years to control the migration of contaminants in the subsurface. In the USA, vertical barriers are mostly constructed of soil-bentonite using the slurry trench method of construction. In this method, sodium bentonite is mixed with water to form a viscous slurry that is pumped into a trench during excavation to maintain the trench stability. The stable trench is then backfilled with a mixture of soil and slurry having a consistency of high slump concrete. These barriers have been designed primarily for low permeability, generally less than 10&minus / 9 m/s. Some investigations have pointed toward improved performance using admixtures that would provide low permeability. In this study, Soma thermal power plant fly ash, granulated blast furnace slag, lime, and steel slag are used as admixture to improve the performance of slurry walls. Permeability, compressive strength, slump, compressibility properties of the mixtures were found and checked for the minimum requirements. According to the findings of this study, granulated blast furnace slag (GGBS), fly ash and steel slag can be used at certain percentages and curing periods as additive in cement-bentonite barrier wall construction. Permeability of specimens having fly ash decreases by increasing fly ash content. Mixtures having 50 % of GGBS type I with 5 % of lime and 9% bentonite content gave acceptable results in 28 days of curing time. Specimens including 50 % of GGBS type II with 5 % of lime and 9% bentonite content gave the higher permeability value in 28 days of curing time with respect to GGBS type I. In addition, most of the mixtures prepared by steel slag gave the acceptable permeability values in 28 days of curing period. Unconfined compressive strength of all mixtures increase by increasing curing time. Cc, Cr, Cv, kcon values were found from consolidation test results. Permeability values found from consolidation tests are 10 times to 100 times higher than flexible wall k results for the same effective stress of 150 kPa. Generally, mv values are decreasing with increasing curing time. As mv decreases, D increases.

Carbon dioxide hydrates were synthesized in a 0.10m I.D. and 1.22m tall bubble column equipped with a cooling jacket for heat removal. Visual observations at different driving forces (pressures between 2.75 and 3.60 MPa and temperatures between 0 and 8ºC) were recorded with a digital camera through a sight glass of 118.8 by 15.6 mm. The superficial gas velocity was varied from 20 to 50 mm/s to attain different levels of turbulence in the liquid. The growth rate was found to be dependent on the sequence/method used to reach the operating temperature and pressure. A greater supersaturation was obtained when the system temperature and pressure were reached with very low or no bubble-induced mixing. As a result, hydrates nucleated and grew immediately when starting the gas flow with the reactor volume being quickly filled with hydrates. Moreover, the hydrate growth rate and solution final density were higher when operating conditions partially condensed CO2 resulting in greater interphase mass transfer rates. In parallel, since hydrate formation is an exothermic process and the reaction is often limited by the rate of heat removal, heat transfer measurements were achieved in a simulated hydrate environment. The instantaneous heat transfer coefficient and related statistics gave insight on the role of bubbles on heat transfer and hydrodynamics.

Deep slurry injection is a process of solid waste disposal that involves grinding the solid waste to a relatively fine-grained consistency, mixing the ground waste with water and/or other liquids to form slurry, and disposing of the slurry by pumping it down a well at a high enough pressure that fractures are created within the target formation. This thesis describes the site assessment criteria involved in selecting a suitable target reservoir for deep slurry injection. The main goals of this study are the follows: <ul> <li>Identify the geological parameters important for a prospective injection site</li> <li>Recognize the role of each parameter</li> <li>Determine the relationships among different parameters</li> <li>Design and develop a model which can assemble all the parameters into a semi-quantitative evaluation process that could allow site ranking and elimination of sites that are not suitable</li> <li>Evaluate the model against several real slurry injection cases and several prospective cases where slurry injection may take place in future</li> </ul> The quantitative and qualitative parameters that are recognized as important for making a decision regarding a target reservoir for deep slurry injection operations are permeability, porosity, depth, areal extent, thickness, mechanical strength, and compressibility of a reservoir; thickness and flow properties of the cap rock; geographical distance between an injection well and a waste source or collection centre; and, regional and detailed structural and tectonic setup of an area. Additional factors affecting the security level of a site include the details of the lithostratigraphic column overlying the target reservoir and the presence of overlying fracture blunting horizons. Each parameter is discussed in detail to determine its role in site assessment and also its relationship with other parameters. A geological assessment model is developed and is divided into two components; a decision tree and a numerical calculation system. The decision tree deals with the most critical parameters, those that render a site unsuitable or suitable, but of unspecified quality. The numerical calculation gives a score to a prospective injection site based on the rank numbers and weighting factors for the various parameters. The score for a particular site shows its favourability for the injection operation, and allows a direct comparison with other available sites. Three categories have been defined for this purpose, i. e. average, below average, and above average. A score range of 85 to 99 of 125 places a site in the ?average? category; a site will be unsuitable for injection if it belongs to the ?below average? category, i. e. if the total score is less than 85, and the best sites will generally have scores that are in the ?above average? category, with a score of 100 or higher. One may assume that for sites that fall in the ?average? category there will have to be more detailed tests and assessments. The geological assessment model is evaluated using original geological data from North America and Indonesia for sites that already have undergone deep slurry injection operations and also for some possible prospective sites. The results obtained from the model are satisfactory as they are in agreement with the empirical observations. Areas for future work consist of the writing of a computer program for the geological model, and further evaluation of the model using original data from more areas representing more diverse geology from around the world.

Slurry infiltrated fiber concrete (SIFCON) was first produced in 1979 in the USA, by incorporating large amounts of steel fiber in molds to form very dense network of fibers. The network is then infiltrated by a fine liquid cement-based slurry or mortar. The steel fiber content can be as high as 30 % by volume. This percentage usually does not exceed 2 % in normal fiber reinforced concrete (FRC) for reasons related to mixing and workability. Due to its high fiber content, SIFCON demonstrates unique and superior mechanical properties in the areas of both strength and ductility. Most of previous research work on SIFCON has focused mainly on investigating the mechanical properties of this material. On the other hand, the studies carried out in the field of durability of SIFCON are quite limited. v Therefore, it seemed that it would be worth to study the various durability aspects of SIFCON. In view of the above, the objectives of this study are to investigate and provide information about durability of SIFCON, mainly permeability, resistance to chloride penetration, freezing and thawing and drying shrinkage. This information will help in providing the necessary database and knowledge about the ability of SIFCON to withstand the conditions for which it has been designed without deterioration, especially when it is intended to be used in aggressive environments The investigations included studying the effects of the following on durability of SIFCON: (i) matrix type (slurry or mortar), (ii) fiber contents (7%, 9.5%, and 12% by volume), and (iii) steel fiber geometry (hooked or crimped). The results obtained indicated that SIFCON, especially when prepared using mortar not slurry, has shown good durability characteristics in spite of its apparent high water absorption. The SIFCON made with the highest possible fiber volume fractions showed the best results. However, it was concluded that SIFCON needs to be protected with suitable low permeability overlays to ensure ideal improved performance by protecting the steel fibers exposed on the surfaces especially against chloride attack.

Studies on the behavior of steel fiber reinforced concrete (SFRC) and slurry infiltrated fibrous concrete (SIFCON) to impact loading have started in recent years. Using these relatively new materials, higher values of tensile and compressive strength can be obtained with greater fracture toughness and energy absorption capacity, and therefore they carry a considerable importance in the design of protective structures. In this thesis, computational analyses concerning impact loading effect on concrete, steel fiber reinforced concrete (SFRC) and slurry infiltrated fibrous concrete (SIFCON) are conducted by the aid of ANSYS AUTODYN 11.0.0 software. In the simulations, the importance of the concrete compressive and tensile strengths, and the fracture energy, together with the target and projectile erosion parameters, were investigated on the response of concrete target and projectile residual velocity. The obtained results of the simulation trials on concrete, SFRC and SIFCON have been compared with the experimental outcomes of three concrete, two SFRC and two SIFCON specimens in terms of deformed target crater radius, depth volume and striking projectile residual velocities. The simulation analyses have shown that, compressive as well as tensile strengths of the concrete, SFRC and SIFCON specimens are of great importance on the crater volume while erosion parameters have a significant effect on the projectile residual velocity. Simulation outcomes possess a higher accuracy for concrete simulations when comparisons are made with available experimental results. This accuracy deteriorates for SFRC and SIFCON specimens. It was further concluded that related material tests of the specimens must be available in order to obtain higher accuracy.

Le but de cette étude est de mieux comprendre l’effet d’une fertilisation en lisier de porc sur la productivité d’une plantation de saule tout en évaluant les risques d’impact négatif sur l’environnement. Nous avons évalué la réponse des plants à des quantités croissantes de lisiers en plus de la comparer à celle d’une fertilisation minérale. Nous avons aussi vérifié l’impact du lisier sur les teneurs nutritionnelles du sol ainsi que sur les concentrations en nitrates et phosphore de la solution du sol. Bien que l’azote du lisier soit moins efficace que celui des engrais minéraux, les résultats de notre étude montrent que le lisier est un bon engrais pour les plantations de saules. En effet, les rendements sur deux ans des parcelles ayant reçu les quantités croissantes de lisier étaient de l’ordre de 30,3 à 32,9 t/ha. Nous avons observé l’augmentation des teneurs en nitrate, cuivre et zinc dans le sol en fonction des apports croissants de lisier. Ces teneurs ont d’ailleurs diminué lors de la deuxième saison de croissance, ce qui pourrait être dû au prélèvement par les saules. Les concentrations printanières des eaux de lysimètres indiquent que la quantité maximale de lisier telle que testée lors de nos essais comporte un certain facteur de risque de lessivage des nitrates. Nous n’avons pas analysé la solution du sol des parcelles fertilisées avec des quantités plus faibles de lisier, mais nous pouvons croire qu’elles auraient induit des concentrations en nitrate comportant moins de risque de lessivage tout en assurant une productivité considérable. / The aim of this study is to investigate the effect of the use of pig slurry as fertilizer on the productivity of a willow plantation, while evaluating the risk of a negative impact on the environment. We evaluated plant response to increasing slurry amounts and compared this response to the effect of mineral fertilization. We also verified the impact of slurry on soil nutritional content as well as on nitrate and phosphorus concentrations in the soil. Although slurry nitrogen was less efficient than mineral fertilizer, the results of our study show that slurry constitutes an effective fertilizer for willow plantations. In fact, yields over two years on plots that received increasing amounts of slurry were on the order of 30.0 to 32.9 t/ha. We observed an increase in soil levels of nitrates, copper and zinc as a function of increasing slurry amounts. These levels actually decreased during the second growing season, possibly due to uptake by the willows. Springtime concentrations of water in lysimeters indicated that the maximum amount of slurry tested in our experiments was accompanied by a certain risk of nitrates leaching into the soil. We did not analyze the soil solution of plots fertilized with lower amounts of slurry, but it seems likely that these nitrate concentrations would have had a lower risk of leaching while still ensuring considerable productivity.

A study was conducted to test the effects that different high fibre sources and their varying inclusion levels had on the characteristics of the excreta (faeces, urine and the slurry), and on odour from the slurry of growing pigs. Faeces and urine characteristics were tested from 52 pigs fed rations containing grass hay (GH), lucerne hay (LH), maize cobs (MC), maize stover (MS) and sunflower husk (SH) diets at inclusion levels up to 400 g/kg as fed basis. Faecal output, faecal consistency and nitrogen were influenced by fibre type (P <0.01) and inclusion level (P <0.01). Nitrogen content in faeces and urine was also affected by dietary fibre inclusion. Increasing fibre inclusion levelled to a reduction in urinary nitrogen content, indicating nitrogen repartitioning from urine to faeces, thereby minimizing nitrogen volatilization. The slurry from pigs fed on LH, MC and SH at levels up to 160 g/kg was tested for chemical composition and odour offensiveness. The slurry was incubated for 16 days. The pH and nitrogen content varied among fibre types and incubation period (P <0.05). Isobutyrate and butyrate concentrations varied with fibre type and the incubation period tested (P <0.01). Using panellists, the SH containing rations resulted in low odour offensiveness score. Maize cob-containing diets resulted in the largest odour scores, with (mean rank of 2.2 and 4.3 for SH and MC, respectively). To reduce odour offensiveness from piggeries, sunflower husk was recommended as an alternative feed ingredient for growing pigs. / Thesis (M.Sc.Agric.)-University of KwaZulu-Natal, Pietermaritzburg, 2012.

Carbon dioxide hydrates were synthesized in a 0.10m I.D. and 1.22m tall bubble column equipped with a cooling jacket for heat removal. Visual observations at different driving forces (pressures between 2.75 and 3.60 MPa and temperatures between 0 and 8ºC) were recorded with a digital camera through a sight glass of 118.8 by 15.6 mm. The superficial gas velocity was varied from 20 to 50 mm/s to attain different levels of turbulence in the liquid. The growth rate was found to be dependent on the sequence/method used to reach the operating temperature and pressure. A greater supersaturation was obtained when the system temperature and pressure were reached with very low or no bubble-induced mixing. As a result, hydrates nucleated and grew immediately when starting the gas flow with the reactor volume being quickly filled with hydrates. Moreover, the hydrate growth rate and solution final density were higher when operating conditions partially condensed CO2 resulting in greater interphase mass transfer rates. In parallel, since hydrate formation is an exothermic process and the reaction is often limited by the rate of heat removal, heat transfer measurements were achieved in a simulated hydrate environment. The instantaneous heat transfer coefficient and related statistics gave insight on the role of bubbles on heat transfer and hydrodynamics.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Soils subjected to successive pig slurry (PS) amendments present zinc (Zn) and copper (Cu) increases, mostly on soil surface layer. The continuous application of PS causes accumulation of these heavy metals (HM) in soil, increasing risks for environmental contamination. Therefore, development of methods to estimate Zn and Cu accumulation in surface layer and their movement in soil is very important for the management planning of PS and of the agricultural soils amended with these residues. The main objective of this work was to model the vertical transport of Zn and Cu in profile of agricultural soils receiving successive application of PS at high, moderate and low doses, evaluating the effects of soil tillage and water absorption by roots on the movement of these HM. We also aimed to predict the long-term accumulation of HM in soil surface and their transport into groundwater, comparing estimated results with the threshold values established for agricultural soils and groundwater by the Conselho Nacional do Meio Ambiente (CONAMA). Two studies were performed on field experiments composed by different PS doses, the first located on an Alfisol in Santa Maria RS, and the second on an Oxisol in Campos Novos SC. Hydro-physical and chemical characteristics of these soils were measured and, accompanied by atmospheric and PS application data sets, were introduced into HYDRUS-1D for parameterization of the two-site model used. In the first study, simulations for next 100 years were performed under scenarios combining two PS doses and four time intervals between soil tillage of the arable layer. The solute transport model used on these simulations was already validated for this local soil in another study. In the second study, the validation of a solute transport model was carried out primarily, following the same approaches used for the Alfisol. Afterwards, root water uptake and root growth modules were introduced to the model. The future scenarios were simulated using applications of different PS doses during the next 50 years. The solute transport model previously validated for the Alfisol was also validated for the Oxisol, and the introduction of the root modules in HYDRUS-1D produced even better results. This increased the usefulness of the model for its use in simulations related to Zn and Cu transport on other contaminated soils. Future scenarios exhibit a great accumulation of these two HM in soil surface layer during the simulated times. Moreover, when soils are submitted to high PS annual doses, its Cu concentrations reached the maximum values established by CONAMA for agricultural soils in approximately 94 years on the Alfisol and in 29 years on the Oxisol. Reduction in PS doses and sporadic soil tillage are strategies that slow the increase of these HM concentrations in soil surface layer, decreasing so the environmental risks and making PS additions on agricultural soils viable for longer time. / Solos submetidos a sucessivas aplicações de dejeto líquido de suínos (DLS) apresentam incrementos nos seus teores de zinco (Zn) e cobre (Cu), principalmente na camada superficial. A continuidade dessa prática faz com que esses metais pesados (MP) se acumulem no solo, aumentando o potencial de contaminação do ambiente. Dessa forma, o desenvolvimento de métodos que estimem o acúmulo superficial e o movimento de Zn e Cu no solo é de extrema importância no planejamento do manejo dos DLS e dos solos agrícolas que recebem esses resíduos. O trabalho objetivou modelar o transporte vertical de Zn e Cu no perfil de solos agrícolas contaminados por aplicações sucessivas de altas, moderadas e baixas doses de DLS, avaliando o efeito do revolvimento do solo e da absorção de água pelas raízes no movimento desses MP, prevendo, no longo prazo, seus acúmulos na camada superficial do solo e suas transferências rumo ao lençol freático, confrontando os resultados estimados com os respectivos limites de concentração para solos agrícolas e águas subterrâneas estabelecidos pelo Conselho Nacional do Meio Ambiente (CONAMA). Foram realizados dois estudos em experimentos de campo com diferentes doses de DLS, o primeiro localizado sobre um Argissolo, em Santa Maria RS, e o segundo sobre um Latossolo, em Campos Novos SC. Diversas características físico-hídricas e químicas foram determinadas nesses solos para, juntamente com os dados atmosféricos e do histórico de aplicação de DLS nessas áreas, serem introduzidos no HYDRUS-1D para parametrização do modelo químico de dois sítios utilizado. No primeiro estudo foram realizadas simulações para os próximos 100 anos, considerando cenários combinando duas doses de DLS e quatro intervalos de tempo entre revolvimentos periódicos da camada arável do solo. O modelo de transporte de solutos utilizado nessas simulações já havia sido validado para o solo deste local em outro trabalho. No segundo estudo foi feita a validação de um modelo de transporte de solutos, seguindo as mesmas premissas do modelo utilizado no Argissolo. Posteriormente, módulos de absorção de água e crescimento de raízes foram incorporados ao modelo. Realizaram-se então simulações futuras de cenários considerando aplicações de diferentes doses de DLS durante os próximos 50 anos. O modelo de transporte de solutos validado previamente no Argissolo foi validado também no Latossolo, apresentando resultados ainda melhores quando os módulos de raízes foram introduzidos no HYDRUS-1D. Isso aumenta a abrangência desse modelo para simular o transporte de Zn e Cu em outros solos contaminados. Os cenários futuros mostram que ocorre grande acúmulo desses MP na camada superficial do solo durante os períodos simulados. Além disso, quando os solos são submetidos a altas doses anuais de DLS, as suas concentrações de Cu atingem os valores máximos estipulados pelo CONAMA, para solos agrícolas, em aproximadamente 94 anos no Argissolo e 29 anos no Latossolo. Reduzir as doses de DLS e revolver o solo esporadicamente são alternativas que retardam o aumento da concentração desses MP na camada superficial do solo, diminuindo o potencial de impacto ao ambiente e tornando a adição de DLS em áreas agrícolas viável por mais tempo.