Increasing nitrate concentration in ground water from improper disposal of sewage and excessive use of fertilizers is deleterious to human health as ingestion of nitrate contaminated water can cause methaemoglobinemia in infants and possibly cancer in adults. The permissible limit for nitrate in potable water is 45 mg/L. Unacceptable levels of nitrate in groundwater is an important environmental issue as nearly 80 % of Indian rural population depends on groundwater as source of drinking water. Though numerous technologies such as reverse osmosis, ion exchange, electro-dialysis, permeable reactive barriers using zero-valent iron exists, nitrate removal from water using affordable, sustainable technology, continues to be a challenging issue as nitrate ion is not amenable to precipitation or removable by mineral adsorbents. Tapping the denitrification potential of soil denitrifiers which are inherently available in the soil matrix is a possible sustainable approach to remove nitrate from contaminated drinking water. Insitu denitrification is a useful process to remove NO3–N from water and wastewater. In biological denitrification, nitrate ions function as terminal electron acceptor instead of oxygen; the carbon source serve as electron donor and the energy generated in the redox process is utilized for microbial cell growth and maintenance. In this process, microorganisms first reduce nitrate to nitrite and then produce nitric oxide, nitrous oxide, and nitrogen gas. The pathway for nitrate reduction can be written as: NO3-→ NO2-→ NO → N2O → N2. (i) Insitu denitrification process occurring in soil environments that utilizes indigenous soil microbes is the chosen technique for nitrate removal from drinking water in this thesis. As presence of clay in soil promotes bacterial activity, bentonite clay was mixed with natural sand and this mix, referred as bentonite enhanced sand (BES) acted as the habitat for the denitrifying bacteria. Nitrate reduction experiments were carried out in batch studies using laboratory prepared nitrate contaminated water spiked with ethanol; the batch studies examined the mechanisms, kinetics and parameters influencing the heterotrophic denitrification process. Optimum conditions for effective nitrate removal by sand and bentonite enhanced sand (BES) were evaluated. Heterotrophic denitrification reactors were constructed with sand and BES as porous media and the efficiency of these reactors in removing nitrate from contaminated water was studied. Batch experiments were performed at 40°C with sand and bentonite enhanced sand specimens that were wetted with nutrient solution containing 22.6 mg of nitrate-nitrogen and ethanol to give C/N ratio of 3. The moist sand and BES specimens were incubated for periods ranging from 0 to 48 h. During nitrate reduction, nitrite ions were formed as intermediate by-product and were converted to gaseous nitrogen. There was little formation of ammonium ions in the soil–water extract during reduction of nitrate ions. Hence it was inferred that nitrate reduction occurred by denitrification than through dissimilatory nitrate reduction to ammonium (DNRA). The reduction in nitrate concentration with time was fitted into rate equations and was observed to follow first order kinetics with a rate constant of 0.118 h-1 at 40°C. Results of batch studies also showed that the first order rate constant for nitrate reduction decreased to 5.3x10-2 h-1 for sand and 4.3 x10-2 h-1 for bentonite-enhanced sand (BES) at 25°C. Changes in pH, redox potential and dissolved oxygen in the soil-solution extract served as indicators of nitrate reduction process. The nitrate reduction process was associated with increasing pH and decreasing redox potential. The oxygen depletion process followed first order kinetics with a rate constant of 0.26 h-1. From the first order rate equation of oxygen depletion process, the nitrate reduction lag time was computed to be 12.8 h for bentonite enhanced sand specimens. Ethanol added as an electron donor formed acetate ions as an intermediate by-product that converted to bicarbonate ions; one mole of nitrate reduction generated 1.93 moles of bicarbonate ions that increased the pH of the soil-solution extract. The alkaline pH of BES specimen (8.78) rendered it an ideal substrate for soil denitrification process. In addition, the ability of bentonite to stimulate respiration by maintaining adequate levels of pH for sustained bacterial growth and protected bacteria in its microsites against the effect of hypertonic osmotic pressures, promoting the rate of denitrification. Buffering capacity of bentonite was mainly due to high cation exchange capacity of the clay. The presence of small pores in BES specimens increased the water retention capacity that aided in quick onset of anaerobiosis within the soil microsites. The biochemical process of nitrate reduction was affected by physical parameters such as bentonite content, water content, and temperature and chemical parameters such as C/N ratio, initial nitrate concentration and presence of indigenous micro-organisms in contaminated water. The rate of nitrate reduction process progressively increased with bentonite content but the presence of bentonite retarded the conversion of nitrite ions to nitrogen gas, hence there was significant accumulation of nitrite ions with increase in bentonite content. The dependence of nitrate reduction process on water content was controlled by the degree of saturation of the soil specimens. The rate of nitrate reduction process increased with water content until the specimens were saturated. The threshold water content for nitrate reduction process for sand and bentonite enhanced sand specimens was observed to be 50 %. The rate of nitrate reduction linearly increased with C/N ratio till steady state was attained. The optimum C/N ratio was 3 for sand and bentonite enhanced sand specimens. The activation energy (Ea) for this biochemical reaction was 35.72 and 47.12 kJmol-1 for sand and BES specimen respectively. The temperature coefficient (Q10) is a measure of the rate of change of a biological or chemical system as a consequence of increasing the temperature by 10°C. The temperature coefficient of sand and BES specimen was 2.0 and 2.05 respectively in the 15–25°C range; the temperature coefficients of sand and BES specimens were 1.62 and 1.77 respectively in the 25–40°C range. The rate of nitrate reduction linearly decreased with increase in initial nitrate concentration. The biochemical process of nitrate reduction was unaffected by presence of co-ions and nutrients such as phosphorus but was influenced by presence of pathogenic bacteria. Since nitrate leaching from agricultural lands is the main source of nitrate contamination in ground water, batch experiments were performed to examine the role of vadose (unsaturated soil) zone in the nitrate mitigation by employing sand and BES specimens with varying degree of soil saturation and C/N ratio as controlling parameters. Batch studies with sand and BES specimens showed that the incubation period required to reduce nitrate concentrations below 45 mg/L (t45) strongly depends on degree of saturation when there is inadequate carbon source available to support denitrifying bacteria; once optimum C/N ratio is provided, the rate of denitrification becomes independent of degree of soil saturation. The theoretical lag time (lag time refers to the period that is required for denitrification to commence) for nitrate reduction for sand specimens at Sr= 81 and 90%, C/N ratio = 3 and temperature = 40ºC corresponded to 24.4 h and 23.1 h respectively. The lag time for BES specimens at Sr = 84 and 100%, C/N ratio = 3 and temperature = 40ºC corresponded to 13.9 h and 12.8 h respectively. Though the theoretically computed nitrate reduction lag time for BES specimens was nearly half of sand specimens, it was experimentally observed that nitrate reduction proceeds immediately without any lag phase in sand and BES specimens suggesting the simultaneous occurrence of anaerobic microsites in both. Denitrification soil columns (height = 5 cm and diameter = 8.2 cm) were constructed using sand and bentonite-enhanced sand as porous reactor media. The columns were permeated with nitrate spiked solutions (100 mg/L) and the outflow was monitored for various chemical parameters. The sand denitrification column (packing density of 1.3 Mg/m3) showed low nitrate removal efficiency because of low hydraulic residence time (1.32 h) and absence of carbon source. A modified sand denitrification column constructed with higher packing density (1.52 Mg/m3) and ethanol addition to the influent nitrate solution improved the reactor performance such that near complete nitrate removal was achieved after passage of 50 pore volumes. In comparison, the BES denitrification column achieved 87.3% nitrate removal after the passage of 28.9 pore volumes, corresponding to 86 h of operation of the BES reactor. This period represents the maturation period of bentonite enhanced sand bed containing 10 % bentonite content. Though nitrate reduction is favored by sand bed containing 10 % bentonite, the low flow rate (20-25 cm3/h) impedes its use for large scale removal of nitrate from drinking water. Hence new reactor was designed using lower bentonite content of 5 % that required maturation period of 9.6 h. The 5 and 10 % bentonite-enhanced sand reactors bed required shorter maturation period than sand reactor as presence of bentonite contributes to increase in hydraulic retention time of nitrate within the reactor. On continued operation of the BES reactors, reduction in flow rate from blocking of pores by microbial growth on soil particles and accumulation of gas molecules was observed that was resolved by backwashing the reactors.

Author´s name: Bc. Stanislav Klimek School: Brno University of Technology, Faculty of Mechanical Engineering, Energy institute Title: Determining the life storage of a carbon steel cask Consultant: Prof. Ing. Oldřich Matal, CSc. Number of pages: 70 Year: 2009 The assignment of this diploma thesis is to estimate the lifetime of spent fuel container made from carbon steel grade. This container is designed for deep geological disposal of spent nuclear fuel. Basic mechanism of corrosion are described in detail in the first part. Further on, this work deals with the other specific phenomena and influences, which affect at corrosion of steel in conditions of a deep geological repository. Heat, radiation and surroundings are considered of particular importance. In the following part an estimate of the lifetime of model container is introduced, which is affected by temperature and radiation. Here recommendations for protection of container are introduced, arising from the model calculation. Finally, the relevancy of incidence of particular parameters is evaluated, which affect the corrosion.

MENVSC / Department of Ecology and Resource Management / See the attached abstract below

Abandoned mines present considerable environmental risks through the release of toxic metals, particularly into adjacent water bodies. The implementation of reliable geotechnical cut-off walls containing bentonite stands as a crucial strategy in mitigating environmental groundwater contamination. This study evaluates the viability of employing the methylene blue titration method to quantify bentonite content in till samples, with the objective of verifying the assumed bentonite content (3.5%) and exploring the impact of sample preparation on bentonite content determined through titrations. Bentonite, known for its swelling properties and high cation exchange capacity, was introduced into till samples both in laboratory settings and on-site. The methylene blue titration method was utilized to measure bentonite content in these samples. Laboratory results indicated significant variations in bentonite content depending on the sample preparation method, with methods employing soil homogenization proving more effective in quantifying bentonite accurately. The study's findings support the hypothesis that the methylene blue method can reliably quantify bentonite in till soil samples with the correct preparation in a laboratory environment. On-site analysis exhibited larger variations and deviations in bentonite content quantifications compared to laboratory-based incorporations. Additionally, on-site incorporated samples demonstrated a statistically significant difference in bentonite content compared to laboratory-incorporated samples, highlighting the method's sensitivity and need for future research. This research contributes valuable insights into leveraging methylene blue titration for quantifying bentonite in till soils, crucial for establishing geotechnical barriers to control toxic metal output from mines.

This thesis focuses on the synthesis and characterisation of organoclays. X-ray diffraction has been used to study the changes in the basal spacings of montmorillonite clay and surfactant-intercalated organoclays. Variation in the d-spacing was found to be a step function of the surfactant concentration. Three different molecular environments for surfactant octadecyltrimethylammonium bromide (ODTMA) within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. High-resolution thermogravimetric analysis (HRTG) shows that the thermal decomposition of montmorillonite modified with ODTMA takes place in four steps attributing to dehydration of adsorbed water, dehydration of water hydrating metal cations, loss of surfactant and the loss of OH units respectively. In addition, it has shown that the decomposition procedure of DODMA and TOMA modified clays are very different from that of ODTMA modified ones. The surfactant decomposition takes place in several steps in the DODMA and TOMA modified clays while for ODTMA modified clays, it shows only one step for the decomposition of surfactant. Also TG was proved to be a useful tool to estimate the amount of surfactant within the organoclays. A model is proposed in which, up to 0.4 CEC, a surfactant monolayer is formed between the montmorillonite clay layers; up to 0.8 CEC, a lateral-bilayer arrangement is formed; and above 1.5 CEC, a pseudotrimolecular layer is formed, with excess surfactant adsorbed on the clay surface. While for dimethyldioctadecylammonium bromide (DODMA) and trioctadecylmethylammonium bromide (TOMA) modified clays, since the larger sizes of the surfactants, some layers of montmorillonite are kept unaltered because of steric effects. The configurations of surfactant within these organoclays usually take paraffin type layers. Thermal analysis also provides an indication of the thermal stability of the organoclay as shown by different starting decomposition temperatures. FTIR was used as a guide to determine the phase state of the organoclay interlayers as determined from the CH asymmetric stretching vibration of the surfactants to provide more information on surfactant configurations. It was used to study the changes in the spectra of the surfactant ODTMA upon intercalation into a sodium montmorillonite. Surfaces of montmorillonites were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant ODTMA. Changes in the surfaces and structure were characterized using electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Both XRD patterns and TEM images demonstrate that SWy-2-Namontmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant will reduce the clay particle aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Fundamentally this thesis has increased the knowledge base of the structural and morphological properties of organo-montmorillonite clays. The configurations of surfactant in the organoclays have been further investigated and three different molecular environments for surfactant ODTMA within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Changes in the spectra of the surfactant upon intercalation into clay have been investigated in details. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic contaminants from aqueous media and for the removal of hydrocarbon spills on roads.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-06T20:35:55Z No. of bitstreams: 1 ILIANA DE OLIVEIRA GUIMARÃES - TESE PPG-CEMat 2014..pdf: 50160837 bytes, checksum: 767ec5c57ef7319ccbd6b2d10571ff53 (MD5) / Made available in DSpace on 2018-04-06T20:35:55Z (GMT). No. of bitstreams: 1 ILIANA DE OLIVEIRA GUIMARÃES - TESE PPG-CEMat 2014..pdf: 50160837 bytes, checksum: 767ec5c57ef7319ccbd6b2d10571ff53 (MD5) Previous issue date: 2014-08-29 / Capes / O processo Bayer, utilizado para a obtenção de alumina, usa bauxita como matériaprima. Este processo abrange quatro estágios: digestão, clarificação, precipitação e calcinação. O resíduo gerado na etapa de calcinação é um produto com pequeno tamanho de partícula, conhecido como ESP dust. Esta pesquisa teve como objetivo desenvolver membranas cerâmicas tubulares utilizando em sua composição o ESP dust, um pó de alumina do precipitador eletrostático, e uma argila bentonítica. Inicialmente, foi realizada a caracterização dos precursores. Foram analisadas duas amostras do resíduo, uma do resíduo bruto e outra do resíduo calcinado a 1200°C. Essas amostras apresentaram um alto teor de alumina nas suas composições químicas. As fases gibbsita e α-alumina foram identificadas no resíduo bruto e, após sua calcinação, a gibbsita foi totalmente transformada em α-alumina. Observou-se que não houve alterações significativas no tamanho e morfologia das partículas após a calcinação, mas durante este processo, as partículas tornaram-se porosas, provavelmente devido às mudanças de fase cristalina da alumina e a saída de água dos cristais. Dentre vinte formulações diferentes testadas para produzir membranas cerâmicas, quatro composições apresentaram os melhores resultados com relação ao processamento por extrusão: duas composições com o resíduo bruto e duas com o resíduo calcinado. Neste trabalho, as membranas tubulares compostas pelo resíduo de alumina e pela argila bentonítica foram produzidas por extrusão e foram sinterizadas a 900, 1000 e 1100°C. Foi observado que as membranas produzidas apresentaram superfícies com poros distribuídos. A porosidade aparente variou entre 47,70% (composição com 60% de resíduo calcinado e 40% de argila bentonítica sinterizada a 1000°C) e 58,40% (composição com 70% de resíduo bruto e 30% de argila bentonítica sinterizada a 1000°C). Foram realizados ensaios de fluxo tangencial com água deionizada em pressões de 1,0; 1,5 e 2,0 Bar. O maior fluxo permeado (909,24L/h.m2) foi observado para as membranas feitas da composição contendo 70% de resíduo bruto e 30% de argila bentonítica sinterizadas a 1100°C, aplicando pressão de 1 Bar. / The Bayer process uses bauxite as raw material to obtain alumina. This process includes four stages: digestion, clarification, precipitation and calcination. The waste generated during the calcination step is a product with small particle size, known as ESP dust. This research aimed to develop tubular ceramic membranes using in its composition the ESP dust, an alumina powder from electrostatic precipitator, and a bentonite clay. Initially, the characterization of the precursors was performed. Two samples were studied, one from crude residue and other from calcined residue at 1200°C. These samples showed a high content of alumina in chemical compositions. The gibbsite and α-alumina phases were identified in crude residue and after calcination gibbsite was completely transformed into α-alumina. Were observed no significant changes in particles size and morphology after calcination, but during this process, the particles become porous, probable due changes in crystalline phase of alumina and the water outlet of crystals. Among twenty different formulations tested to produce ceramic membranes, four compositions showed better results with regard to the extrusion processing: two compositions with crude residue and two with calcined residue. In this paper, tubular membranes produced from alumina residue and bentonite clay were sintered at 900, 1000 and 1100°C. It was observed that the produced membranes had surfaces with distributed pores. The apparent porosity was between 47.70% (composition with 60% of calcined residue and 40% of bentonite clay sintered at 1000°C) and 58.40% (composition with 70% of crude residue and 30% of bentonite clay sintered at 1000°C). Tangential flow tests were performed with deionized water at pressures of 1.0; 1.5 and 2.0 Bar. Higher permeate flow rate (909,24L/h.m2) was observed for membranes made of a composition containing crude residue (70%) and bentonite clay (30%) sintered at 1100°C, applying pressure of 1 bar.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-28T21:49:04Z No. of bitstreams: 1 KARINE CASTRO NÓBREGA – DISSERTAÇÃO (UAEMa) 2015.pdf: 1849613 bytes, checksum: c5a145f0dd677d54aab0ed55f6ccc4e9 (MD5) / Made available in DSpace on 2018-06-28T21:49:04Z (GMT). No. of bitstreams: 1 KARINE CASTRO NÓBREGA – DISSERTAÇÃO (UAEMa) 2015.pdf: 1849613 bytes, checksum: c5a145f0dd677d54aab0ed55f6ccc4e9 (MD5) Previous issue date: 2015-02-23 / CNPq / A perfuração de poços de petróleo pode danificar fortemente a formação, incluindo a região de interesse: o reservatório. Perfurar sem que se danifique o reservatório caracteriza-se como um grande desafio, e por isso, tem sido estimulado o desenvolvimento de tecnologias de fluidos e otimização de processos de perfuração, incluindo, por exemplo, o uso de fluidos argilosos com vistas à minimização de perdas excessivas de filtrado para as formações permeáveis. Desta forma, este trabalho teve como objetivo avaliar a influência dos aditivos carboximetilcelulose (CMC) e calcita (CaCO3) e suas interações nas propriedades de filtração de fluidos de perfuração argilosos. Para tanto, foi utilizada uma amostra de argila bentonítica, comercialmente conhecida por Volclay, duas amostras de CMC com diferentes massas molares (CMC 1 (9,0 x 104g/mol) e CMC 2 (2,5 x 105g/mol)) e mesmo grau de substituição (DS = 0,7) e, duas amostras de calcita (CaCO3), com diferentes diâmetros médios de partículas e curvas de distribuição em tamanho. Foram realizadas a caracterização física e mineralógica da amostra de argila e a caracterização granulométrica das amostras de calcita, em seguida determinadas as propriedades reológicas (viscosidades aparente (VA) e plástica (VP), limite de escoamento (LE) e força gel (FG)) e de filtração (volume de filtrado (VF), volume de filtrado corrigido (VFcorr), spurt loss (SPL), espessura (h) e permeabilidade (k) do reboco e poder de retenção (R)) dos fluidos argilosos estudados. Os resultados evidenciaram que os fluidos estudados apresentaram comportamento pseudoplástico e os fluidos argilosos preparados com elevada concentração de CMC 2 (2g/350mL de água) apresentaram melhores valores de propriedades reológicas, pois estas propriedades são fortemente influenciadas pelo grau médio de polimerização dos aditivos poliméricos. A aditivação de fluidos argilosos com carboximetilcelulose de baixa massa molar e com calcita de granulometria fina conferiu aos fluidos melhor desempenho na melhoria das propriedades de filtração. Isto aconteceu, porque no meio aquoso a CMC 1 em elevada concentração associada a calcita 1 conduziu a menores valores de VF, h e k e, elevados valores de R. / The drilling of oil wells can greatly damage the formation, including the region of interest: the reservoir. Drilling without damaging the reservoir is characterized as a big challenge, and therefore, has been stimulated the development of fluid technologies and optimization of drilling processes, including, for example, the clay fluids use aiming at minimization excessive losses of the filtrate into the permeable formations. Thus, this study aimed to evaluate the influence of additives carboxymethylcellulose (CMC) and calcite (CaCO3) and their interactions in the filtration properties of clay drilling fluids. For this, it was used a sample of bentonite clay, commercially known by Volclay, two samples of CMC with different molecular weight (CMC 1 (9,0 x 104g/mol) and CMC 2 (2,5 x 105g/mol) ) and the same degree of substitution (DS = 0,7) and two samples of calcite (CaCO3) with different average diameters of particles and size distribution curves. It was done the physical and mineralogical characterization of the clay sample and the particle size characterization of the calcite samples it was also determined the rheological properties (apparent viscosity (AV) and plastic (PV), yield limit (YL) and gel strength (GS)) and of filtration (filtrate volume (FV), filtrate volume corrected (FVcorr), spurt loss (SPL), cake thickness (h) and permeability (k) and retaining power (R)) of the studied clay fluids. The results showed that the studied fluids showed pseudoplastic behavior and clay fluids prepared with high concentration of CMC 2 (2g/350mL of water) showed better values of rheological properties, because these properties are strongly influenced by the average degree of polymerization of polymeric additives. The additived clay fluids with low molecular weight carboxymethylcellulose and with fine granulometry calcite gave the fluids best performance in improving the filtration properties. This happened because in the aqueous medium the CMC 1 in high concentration associated at calcite 1 led at lower values of FV, h and k and high values of R.

In my work, I dealt with the development of building technology project for multi-functional building in Olomouc Tabulový Vrch. The goal is to select and develop appropriate design of the building in terms of financial, time and technical requirements based on the technical documentation provided by the designer. Building technology project includes a study of implementation of main technological stages, object, time and financial plan, drawings site equipment, site equipment technical report, technical regulations, inspection and test plan, financial budget for the construction of the technological steps, the schedule, the draft report and not machine prescription number for safety in the implementation of reinforced concrete monolithic skeleton including security risks.