<p>The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials.</p>

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

Au Québec, lors de la période de gel et dégel, l’enrobé bitumineux, constituant le revêtement de la chaussée, est soumis à des conditions sévères qui le dégradent. Ces conditions sont : précipitations de pluie et fontes de neige générant une saturation partielle du matériau, présence de sel déverglaçant, passages de véhicule lourd sollicitant mécaniquement le matériau, variations de températures engendrant la création de déformations et de contraintes au sein du revêtement, et présence de cycles de gel-dégel.A cet effet, la revue de la littérature porte sur l’étude : des conditions sévères (sollicitations mécaniques, climatiques, hydriques et chimiques), et des caractéristiques physiques de l’enrobé qui affectent sa durabilité, ses comportements mécaniques (viscoélastique linéaire et en fatigue) et thermomécaniques (coefficient de dilatation-contraction thermique).Notamment, un programme expérimental de laboratoire a été réalisé en vue de vérifier l’influence de ces conditions sévères sur la dégradation et le comportement de l’enrobé. Premièrement, des essais thermiques, incluant des cycles de gel et dégel, ont été réalisés sur des éprouvettes d’enrobé à l’état sec et partiellement saturé en eau ou en saumures. Les éprouvettes sont instrumentées d’une jauge axiale et de deux thermocouples. L’éprouvette partiellement saturée en eau, comparativement à celles partiellement saturées en saumures, est soumise à des dilatations et des contractions nettement plus importantes lors de la formation et la fonte de la glace. De +10 à +23°C, les coefficients de dilatation linéique des éprouvettes partiellement saturées sont assez similaires, mais supérieurs à celui de l’enrobé à l’état sec, ce qui implique que l’enrobé partiellement saturé se contracte et se dilate un peu plus que celui a l’état sec à ces températures.Deuxièmement, les éprouvettes ont été soumises à des essais mécaniques, de module complexe, afin d’évaluer l’évolution de leur endommagement suite aux cycles de gel et dégel. Les résultats des essais et du modèle rhéologique 2S2P1D ont été utilisés afin de simuler le comportement de l’enrobé selon les divers états. Au fil des cycles de gel et dégel, un endommagement est observable pour l’ensemble des éprouvettes, mais nettement supérieur pour l’éprouvette partiellement saturée en eau. De plus, pour les éprouvettes partiellement saturées, un comportement distinct est observable en dessous et au-dessus de la température de solidification des liquides.Pour terminer, l’étude du comportement à la fatigue de l’enrobé suivant l’état sec et partiellement saturé en eau est réalisée. A +10°C et 10Hz, seules des diminutions légères ont été observées au niveau du module (3%) et de la résistance à la fatigue (ɛ6 de 105 vs 109ƒμdef) pour l’enrobé partiellement saturé en eau. Ces faibles diminutions sont attribuables à la faible période d’immersion des éprouvettes d’enrobé dans l’eau, à la faible température de l’eau et de l’essai, à la faible teneur en vides des éprouvettes, au bitume modifié et aux granulats de qualité utilisés / During winter and spring in the province of Quebec, hot mix asphalt (HMA) pavement could be subjected to sever conditions over their design life. These conditions are: 1) rainfall and snowmelt, which generates the partial saturation of the HMA, 2) winter maintenance requiring the presence of de-icing salt, which acting chemically on HMA, 3) traffic, which acting mechanically on HMA, and 4) temperature changes and presence of freeze-thaw cycles (FTC) creating thermal stress and deformation (thermo-mechanical coupling) within the pavement, and pressure, within the material, generated by freezing water or brines. More specifically, the literature review of this work focuses on the study of: 1) severe conditions such as climatic, chemical and mechanical solicitations, 2) physical characteristics of HMAthat affect its durability, mechanical properties (viscoelastic and fatigue) and thermomechanical properties (coefficient of thermal contraction).An experimental laboratory program was conducted to verify the influence of these severe conditions on the degradation and behavior of HMA. First, thermal testing (-18 to +23°C), including freeze-thaw cycles (FTC, -18 to +10°C) were performed on samples under dry (D)and partially saturated (PS), with water or brine, states. The samples were instrumented with an axial gauge and two thermocouples. During FTC (-18 to +10°C), sample partially saturated with water, compared to those partially saturated with brines, is subject to expansions and contractions significantly greater during formation and melting of ice. In the temperature range from +10 to +23°C, the linear coefficients of thermal contraction of partially saturated samples are quite similar, but higher than that of HMA in dry state. At such temperature range, this implies that the partially saturated HMA contracts and expands a little more than that in dry state. Secondly, the samples were subjected to mechanical testing.The complex modulus test was performed in order to evaluate the damage of samples due to FTC. The test results and rheological model 2S2P1D were used to simulate the behavior of the HMA according to the various states. Over FTC, damage is observed for all samples, butmuch higher for the PS sample with water. Moreover, for PS samples, a distinct behavior is observable below and above the solidification temperature of the liquid. Finally, the study of the fatigue behavior of HMA under PS, with water, and D states is performed. At +10°C and 10Hz, only slight decreases were observed for complex modulus (3%) and fatigue (ε6 = 105 vs 109μstrain) for HMA partially saturated with water. These small decreases are due to the low period of immersion of samples in water, lowers temperatures of water and test, low void content of the samples, modified bitumen and good aggregates used.

Philosophiae Doctor - PhD / The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials. / South Africa

Embora a indústria da carne utilize a marinação em larga escala, o comportamento da penetração da salmoura em bifes massageados de carne bovina é pouco conhecido. O músculo Biceps femoris tem sido considerado pouco macio e suculento e apresentado grande variação de maciez intermuscular. Desta forma, o objetivo deste estudo foi avaliar o efeito da marinação com adição de proteína hidrolisada de soja sobre a estrutura muscular de porções distintas do Biceps femoris e suas implicações sobre a qualidade de carne. No Capítulo 2, 3 e 4, seis músculos bovinos foram submetidos aos tratamentos: CONTROLE (bifes não massageados), CS (bifes massageados com salmoura) e SPHS (bifes massageados com salmoura adicionada de proteína hidrolisada de soja). No capítulo 2, os músculos foram divididos em duas porções: Origem (PO) e Inserção (PI), e os tempos de massageamento foram 30 e 60 min. No capítulo 3 e 4, os músculos foram divididos em três porções: Origem (PO), Inserção 1 (PI1) e Inserção 2 (PI2), e os bifes destas porções foram armazenados por 1 e 12 dias após equalização da salmoura, exceto os bifes CONTROLE que foram armazenados somente por 1 dia. As análises realizadas foram: mensuração da penetração da salmoura, determinação do melhor tempo de massageamento, pH, rendimento (REND), colágeno total (CT), composição centesimal, perdas por gotejamento (PPG), perdas por cocção (PPC), força de cisalhamento (FC), microscopia eletrônica de varredura (MEV), análises microbiológicas e sensoriais. O delineamento experimental utilizado foi em blocos inteiramente casualizados, onde cada músculo representou um bloco. A análise de mensuração da penetração da salmoura demonstrou que os bifes SPHS, massageados por maior tempo (60 min), obtiveram maior absorção e retenção de salmoura ao longo da profundidade dos bifes. A PI2 apresentou menor quantidade de CT em comparação às demais, para o CONTROLE. Já os bifes CS e SPHS da PO e PI1 obtiveram menores quantidades de CT em comparação aos bifes destes mesmos tratamentos da PI2. Os bifes massageados não sofreram efeito de tempo de armazenamento e foram mais macios, suculentos e melhor pontuados para impressão global em comparação ao CONTROLE. O pH dos bifes se elevou com os tratamentos CS e SPHS e pareceu influenciar sobre o REND das porções de forma que, a PO obteve menor pH e maior REND, enquanto a PI resultou em maior pH e menor REND. Menores PPG, PPC e FC foram observados para os bifes CS e SPHS e o período de 12 dias de armazenamento permitiu que as PPC e FC diminuíssem. Respostas similares entre a maciez sensorial e objetiva foram observadas nas porções do músculo de forma que, as PIs foram mais macias do que a PO. A analise MEV demonstrou inchaço das fibras e diminuição dos espaços interfibrilares nos bifes massageados CS e SPHS. / Although meat industry uses marination in large-scale, the brine penetration behavior in tumbled steaks from bovines is little known. The Biceps femoris muscle has been considered little tender and juicy, and presented large range of intramuscular tenderness. Therefore, the objective of this work was to evaluate the effect of marination added of hydrolyzed soy protein on the muscular structure of different portions from the Biceps femoris and its implication on beef quality. In Chapter 2, 3 and 4, steaks from six bovine muscles were submitted to the treatments: CONTROL (no tumbling or addition of brine), WTB (with tumbling and addition of brine), and WTB/HSP (with tumbling and addition of brine plus hydrolyzed soy protein). In Chapter 2, the muscles were divided in two portions: Origin (OP) and Insertion (IP), and the tumbling times were 30 and 60 min. In Chapter 3 and 4, the muscles were divided in three portions: Origin (OP), Insertion 1 (IP1) and Insertion 2 (IP2), and their steaks were stored for 1 and 12 days after equalization of brine, except to the CONTROL steaks that were only stored for 1 day. The analyses performed were: monitoring of brine penetration, pH, yield (YIE), total collagen (TC), proximate composition, drip loss (DL), cooking loss (CL), shear force (SF), scanning electron microscopy (SEM), microbiologic and sensory. The experimental design was completely randomized blocks, where each muscle represented one block. The analysis of monitoring of the brine penetration showed that the WTB/HSP steaks, tumbled for largest time (60 min), had higher absorption and retention of brine along the depth of the steaks. The IP2 presented lower TC amount in relation to other portions, in CONTROL steaks. However, the WTB and WTB/HSP steaks from OP and IP1 had lower TC amount when compared to IP2, in these same treatments. The tumbled steaks were not affected by storing time and were tender, juicier and better scored for overall satisfaction with regard to CONTROL steaks. The pH of the steaks was elevated with the WTB and WTB/HSP treatments and appeared to influence the YIE of the portions, where OP had lower pH and higher YIE, while IP resulted in higher pH and lower YIE. Lower DL, CL and SF were observed for WTB and WTB/HSP steaks and the storing time of 12 days allowed that the CL and SF declined. Similar responses between sensory tenderness and SF were observed in the muscle portions, which IPs were tender than OP. The SEM analysis showed swelling of fibers and decrease of spaces between fibrils in tumbled WTB and WTB/HSP steaks

Philosophiae Doctor - PhD / Coal combustion accounts for 95% of electricity generation in South Africa while globally coal combustion for energy generation stands at 42%. It has been predicted that coal utilization for energy generation will continue due to its low cost and availability in huge quantities in different parts of the world. Additionally brine and gaseous emissions are produced in the power generation and coal combustion processes. In fact, it has been established that CO2 emissions from power plants are the main cause of the green-house effect leading to global warming. Mitigation of the effects of disposal of fly ash, brine and CO2 emissions is critical for sustainable energy generation from coal and environmental protection. The study investigated whether South African coal fly ash could be used for brine remediation and CO2 capture using fly ash based hydrotalcites and zeolites. Four main objectives were investigated. These were; firstly, to compare the natural CO2 capture potential of a power station ash dam with an accelerated ex-situ mineral carbonation process. Secondly, to probe the effect of accelerated ex-situ mineral carbonation on brine quality with regards to major, minor and trace elements concentration. Furthermore, the study investigated the feasibility of synthesizing hydrotalcites from fly ash by optimizing the synthesis parameters such as acid concentration, aging time, aging temperature, pH during aging, crystallization time and crystallization temperature. Finally the study compared the CO2 adsorption capacities of the fly ash based hydrotalcites with fly ash based zeolites NaA, and NaX. The natural carbonation potential of the wet disposed ash dam at Secunda was investigated by coring a 20 year old dam. Three cores (SI, S2 and S3) were obtained by air flush coring the dam along a geophysical line and establishing the geophysical profile of the three cores. The surface of the three cores was of medium resistivity with values between 9.3 and 12.2 nm while the midsections were of low resistivity with values ranging between 4 and 7 nm. The base section of core SI had a resistivity of 28.3 nm, that of S2 was between 16.2 and 21.4 nm and that of S3 between 12.2 and 16.2 nm; implying that SI had the lowest salt load while S3 had the highest salt content. Moisture content was observed to be high deeper down the profiles of S2 and S3 with samples appearing water logged while SI had the highest moisture content at the surface showing the inhomogeneity of the ash dam. The morphology of fresh fly ash taken from the ash collection hoppers at Secunda was observed to be spherical. Weathered ash from the ash dam showed irregularly agglomerated particles while accelerated ex-situ mineral carbonation resulted in the formation of acicular particles of calcite. Fresh ash, weathered ash and the accelerated carbonated ash were all class F with a sum total of silica, alumina and iron oxide totaling more than 70%. A reduction in silica and alumina content with instability of fly ash. Dumping of spent iron catalyst (resulting from the petrochemical operations as Sasol) on the ash dam led to an increase in Fe203 content of the weathered ash. Enrichment of Nb, Sr, Y, Th, Na, Cl, S04, K and S with natural carbonation as well as during accelerated ex-situ mineral carbonation was observed and was due to the contact of ash with brine during these two processes. Reduction of Zr, Rb, Pb, Ni, Co and V content of ash was observed with weathering. Mineralogically, all the ash samples had main phases of mullite, quartz, magnetite and hematite, with weathered and accelerated carbonated ash having additional phases of calcite. The aluminosilicious nature of the three ashes was identified by structural evaluation using Fourier transform infrared analysis which revealed that, bands associated with C-O in-plane and out of plane bending of carbonates was only visible in weathered and carbonated ash.

Diploma thesis deals with searching of the most appropriate solution of air mass cooling to clear away contained solvents. The solution is based on real and operated pharmaceutical unit. The cooling system is solved as systém of three tubular heat exchangers. In the first heat exchanger the air mass is cooled down by water, in the second by ice-cold water and brine R32 is used for cooling in the third heat exchanger. Heat exchanger system is solved for cooling the air mass which results in condensation of contained solvent – acetone.

The overall objective of this thesis is to develop methods for fault detection and diagnosis for ground source heat pumps that can be used by servicemen to assist them to accurately detect and diagnose faults during the operation of the heat pump. The aim of this thesis is focused to develop two fault detection and diagnosis methods, sensitivity ratio and data-driven using principle component analysis. For the sensitivity ratio method model, two semi-empirical models for heat pump unit were built to simulate fault free and faulty conditions in the heat pump. Both models have been cross-validated by fault free experimental data. The fault free model is used as a reference. Then, fault trend analysis is performed in order to select a pair of uniquely sensitive and insensitive parameters to calculate the sensitivity ratio for each fault. When a sensitivity ratio value for a certain fault drops below a predefined value, that fault is diagnosed and an alarm message with that fault appears. The simulated faults data is used to test the model and the model successfully detected and diagnosed the faults types that were tested for different operation conditions. In the second method, principle component analysis is used to drive linear correlations of the original variables and calculate the principle components to reduce the dimensionality of the system. Then simple clustering technique is used for operation conditions classification and fault detection and diagnosis process. Each fault is represented by four clusters connected with three lines where each cluster represents different fault intensity level. The fault detection is performed by measuring the shortest orthogonal distance between the test point and the lines connecting the faults’ clusters. Simulated fault free and faulty data are used to train the model. Then, a new set of simulated faults data is used to test the model and the model successfully detected and diagnosed all faults type and intensity level of the tested faults for different operation conditions. Both models used simple seven temperature measurements, two pressure measurements (from which the condensation and evaporation temperatures are calculated) and the electrical power, as an input to the fault detection and diagnosis model. This is to reduce the cost and make it more convenient to implement. Finally, for each models, a user friendly graphical user interface is built to facilitate the model operation by the serviceman.

One of the major remaining question about Mars is its habitability - if the requirements necessary to allow for life are presently fulfilled. One of the most relevant ingredients for life, as we know it, is water. Indirect evidence of transient liquid water on Mars has been retrieved from both rover [Martín-Torres et al., 2015] and orbiter [Ojha et al., 2015]. [Martín-Torres et al., 2015] inferred the existence of an active water cycle, driven by chlorate and perchlorate salts, which are commonly found on the Martian surface, and absorb atmospheric water to form stable hydrated compounds and liquid solutions. This happens through a process called deliquescence (absorption of moisture from the atmosphere by the salts and dissolving into a liquid solution). One of the goals of HABIT is to confirm the hypothesis about the water cycle on Mars. HABIT will record the behavior of a selection of salts on Mars, and will also record Martian environmental conditions (UVdose, air and ground temperatures). The Field-Site Prototype for HABIT (FSP-HABIT) was the first prototype of HABIT deployed during field-site campaigns. Three campaigns took place during summer 2016: First, a short preparatory campaign in Abisko, Sweden, was carried out. The second campaign took place in Iceland, within the EU COST Action TD1308 ORIGINS (Origins and evolution of life on Earth and in the Universe), and the third campaign was conducted within the NASA Spaceward Bound India Program in Ladakh. After providing the corresponding background on the mission framework and the scientific background, this document covers the mechanical, electrical, and software design of the instrument. Afterwards, the steps taken to test the instrument and their results are covered, followed by a rating of the instrument and ideas for future improvements. Instruments like FSP-HABIT will enable the characterization of hygroscopic salts by their conductivity as liquid brines are good conductors, hydrated salts are poor conductors, and dehydrated salts are insulators. During the field-site campaigns, the measurements of FSP-HABIT were used to characterize the near surface environment by its temperature, pressure and relative humidity. Now, these measurements are available for comparison with microbiological studies of the water, ice and soils to characterize the habitability of the explored site. The lessons learned while designing and building FSP-HABIT can be used to inform the development of further prototypes for space missions such as HABIT. / Habitability, Brines, Irradition and Temperature (HABIT)