Ever-growing discharges of various emerging chemical contaminants are imposing a great threat of pollution to the coastal environment. Adsorption by sediment plays an essential role in the transport and fate of pollutants in the aquatic system. The sorption of emerging contaminants onto sediment is believed to be largely dependent on the sediment organic matter (SOM). In the present study, laboratory experiments were carried out on the changes of the adsorption behavior of sediment during the sediment aging and diagenesis process. A few EDCs and antibiotics were selected as the model emerging compounds for the adsorption tests. The results demonstrated that both the quantity and the quality of the SOM affected the adsorption of the model pollutants, such as 17α-ethinyl estradiol (EE2) and bisphenol A (BPA), onto the marine sediment collected from Victoria Harbour, Hong Kong. The adsorption isotherms can be well described by the linear partition model. Natural and artificial sediment with a high SOM content was incubated for 4-6 months to simulate the natural diagenesis process. The most rapid degradation of labile SOM occurred in the first 1 month or so and afterward, SOM reduction became slower. Microbial activity played an important role in SOM degradation and transformation. A rapid initial bacterial growth was observed in the sediment, followed by a slow endogenous decay. The dynamics of biomass growth and decay first transformed the labile SOM into biomass and microbial byproducts. After the exhaust of readily biodegradable SOM, the biomass decay produced humic-like substances, resulting in more refractory and condensed SOM residues in the sediment. More importantly, the degradation and transformation of SOM displayed a profound impact on the adsorption behavior of the sediment. For the selected EDCs and antibiotics, including BPA, EE2, nonylphenol (NP), phenanthrene (PHE) and tetracyclines (TCs), the adsorption capacity indicated by the partition coefficient, Kd, decreased at the beginning of SOM diagenesis. The Kd values for different chemicals recovered lately to different extents as the result of the SOM condensation and humification. All of the organic matter normalized partition coefficients, KOM, of the concerned pollutants increased considerably in the late phase of SOM diagenesis. Based on the experimental results, a general conceptual model was established to describe SOM diagenesis and its impact on chemical adsorption by the sediment. According to the model prediction, the SOM profile would become more dominated by the condensed and refractory fractions during sediment diagenesis with an increasing affinity and partition capacity for organic contaminants. Moreover, the release of adsorbed contaminants from marine sediment in the simulated digestive fluids was investigated. In general, the presence of gastric pepsin and bile salts helped the desorption of hydrophobic pollutants from the sediment into the digestive solutions. The influence of the SOM diagenetic status on chemical desorption from the sediment varied between EDCs of different chemical properties. It is apparent that aged sediment could bring more emerging pollutants into the digestive system of receiving organisms, imposing a potential risk to human health through the food chain. / published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

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Currently, there is a high demand for lightweight aerospace materials, driven by the desire to provide enhanced fuel efficiency by reducing vehicular weight. Aluminum alloys are attractive due to their excellent mechanical properties and high strength to weight ratios. Powder metallurgy (PM), which converts metal powder into a high performance product, presents an alternative to traditional forming techniques, which are often unable to provide adequate dimensional tolerances. The challenge is to determine if aluminum PM alloys and technologies can be successfully employed within aerospace applications. This research focuses on the PM processing technologies (die compaction, cold isostatic pressing (CIP), and spark plasma sintering (SPS)) of two alloys, PM2024 and PM7075. Processing parameters were assessed using attributes such as density, hardness, and tensile properties. Both powders showed comparable densities and tensile properties to their wrought equivalents. Ultimately, the groundwork was laid for future research into these alloys and their processing methods.

Titanium is well known for its excellent properties, such as high strength-to-weight ratio and outstanding corrosion resistance. However the high cost of this metal has confined its applications to those mostly within the aerospace and military industries. The high purchase price of titanium is primarily driven by the need for intricate metal extraction processes, as well as the sensitivity towards conventional metal working operations. Among the potential solutions, powder metallurgy (P/M) technology provides an economical approach to bring down the price of finished titanium products. However, there are still many problems, such as the residual porosity in the sintered body, that need to be overcome. In this thesis, a fundamental study was carried out focusing on the P/M press-and-sinter technique, using commercially pure titanium (CP Ti) as well as two binary titanium alloys, namely Ti-Ni and Ti-Sn. The influence of several processing parameters including compaction pressure, lubricant type/concentration, sintering time/temperature were performed on both the CP and binary systems. The principal tools utilized for mechanical characterization were hardness and tensile testing, whereas optical microscopy, x-ray diffraction (XRD), and scanning electron microscopy were employed to identify the microstructural features present. Press-and-sinter P/M strategies were successfully developed for all of the blends studied. For CP-Ti, a maximum tensile strength >750MPa and near full theoretical density (~99%) were achieved. Transitions in the size and the size distribution of pores and ?-Ti grains were also observed and quantified. It was found these transitions, as well as the powder impurities present (i.e. oxygen and carbon), greatly influenced the final mechanical properties. In the case of the binary alloys, it was shown that liquid phase sintering (LPS) significantly improved the sintered density for the Ti-10%Ni composition, when sintered at l100°C. A eutectic microstructure (CP-Ti + Ti2Ni), coupled with grains of CP-Ti, were identified as the principal phases present. On the other hand, the Ti-Sn alloys only showed a modest increase in sintered density compared to the CP-Ti, owing to the high solubility of Sn in Ti. In terms of crystal structure, XRD highlighted that the Sn containing samples were fully CP-Ti.

The objective of this research was to design aluminum powder metallurgy (PM) alloys and processing strategies that yielded sintered products with thermal properties that rivaled those of the cast and wrought aluminum alloys traditionally employed in heat sink manufacture. Research has emphasized PM alloys within the Al-Mg-Sn system. In one sub-theme of research the general processing response of each PM alloy was investigated through a combination of sintering trials, sintered density measurements, and microstructural assessments. In a second, the thermal properties of sintered products were studied. Thermal conductivity was first determined using a calculated approach through discrete measurements of specific heat capacity, thermal diffusivity and density and subsequently verified using a transient plane source technique on larger specimens. Experimental PM alloys achieved >99% theoretical density and exhibited thermal conductivity that ranged from 179 Wm-1K-1 to 225 Wm-1K-1. Thermal performance was largely dominated by the amount of magnesium present within the aluminum grains and in turn, bulk alloy chemistry. Data confirmed that the novel PM alloys were highly competitive with even the most advanced heat sink materials such as wrought 6063 and 6061. Two methods of thermal analysis were employed in order to determine the thermal conductivity of each alloy. This first consisted of individual analysis of the specific heat capacity (Cp), thermal diffusivity (?) and density (?) as a function of temperature for each alloy. The thermal conductivity (K) was subsequently determined through the relationship: K=C_p ??. The second means of thermal analysis was a direct thermal conductivity measure using a transient plane source (TPS). The thermal diffusivity and density of samples were both found to decrease with temperature in a linear fashion. Conversely, the specific heat capacity was found to increase with temperature. The only measured thermal property that appeared to be influenced by the alloy chemistry was the thermal diffusivity (and subsequently the calculated thermal conductivity). Both means of thermal analysis showed high thermal conductivity in alloys with low concentrations of magnesium, demonstrating the significance of having alloying elements in solid solution with aluminum. Overall, several alloys were developed using a press and sinter approach that produced higher levels of thermal conductivity than conventional aluminum heat sink materials. The highest thermal conductivity was achieved by alloy Al-0.6Mg-1.5Sn with a calculated value of 225.4 Wm-1K-1. This novel aluminum PM alloy was found to exceed both wrought 6061 and 6063 (195 and 217 Wm-1K-1 respectively). Furthermore, PM alloy Al-0.6Mg-1.5Sn was found to have a significant advantage over die-cast A390 (142 Wm-1K-1).

In metal powder compaction, density non-uniformity due to friction can be a source of flaws. Currently in industry, uniform density distribution is achieved by the optimization of punch motions through trial and error. This method is both costly and time consuming. Over the last decade, the finite element (FE) method has received significant attention as an alternative to the trial and error method; however, there is still lack of an accurate and robust material model for the simulation of metal powder compaction. In this study, Cam-clay and Drucker-Prager cap (DPC) material models were implemented into the commercial FE software ABAQUS/Explicit using the user-subroutine VUMAT. The Cam-clay model was shown to be appropriate for simple geometries. The DPC model is a pressure-dependent, non-smooth, multi-yield surface material model with a high curvature in the cap yield surface. This high curvature tends to result in instability issues; a sub-increment technique was implemented to address this instability problem. The DPC model also shows instability problems at the intersection of the yield surfaces; this problem was solved using the corner region in DPC material models for soils. The computational efficiency of the DPC material model was improved using a novel technique to solve the constitutive equations. In a case study it was shown that the numerical technique leads to a 30% decrease in computational cost, while degrading the accuracy of the analysis by only 0.4%. The forward Euler method was shown to be accurate in the integration of the constitutive equations using an error control scheme. Experimental tests were conducted where cylindrical-shaped parts were compacted from Distaloy AE iron based powder to a final density of 7.0 g/cm3. To measure local density, metallography and image processing was used. The FE results were compared to experimental results and it was shown that the FE analysis predicted local relative density within 2% of the actual experimental density. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2010-09-23 12:15:27.371

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There is evidence that soil compaction, through the use of mechanised equipment, causes detrimental effects to soil quality and reduces long-term productivity of soils. For economic reasons, farmers need to purchase larger, heavier machinery in order to cultivate larger areas under crops, resulting in larger forces on the soil. The severity of soil compaction is governed by various soil and vehicle properties and normally causes an increase in the soil's bulk density and a decrease in the air filled porosity. These changes in soil properties have negative effects on crop production and environmental sustainability. The aim of this study was to investigate and develop a model based decision support system for soil compaction management and research. Soil compaction occurs during the transfer of stresses from the tyre interface into the soil. Numerically, it has been modelled using both mechanistic and empirical models, which attempt to simulate the stress propagation and also sometimes the consequent damage to the soil. The SOCOMO soil compaction model is described and this model computes the stress at a point in the soil for any given horizontal and vertical stress distribution at the soil / tyre interface. It has been successfully used in the Netherlands and in Sweden to map the impact on the soil. The SOCOMO model was tested and verified at a forestry site in Richmond, KwaZulu- Natal. Relationships to determine bulk density were also tested and verified. The SOCOMO model performs satisfactory (RMSE = 47.9 kPa), although it tends to overestimate the pressures within the soil. This could be as a result of the high organic carbon content in the particular soil. Models predicting bulk density also performed satisfactory (RMSE = 69.9 kg.m" ), but resultant densities in the soil are generally underestimated. Future research is needed to find better relationships to estimate changes in dry bulk density and to test the model on a wider range of soils. If the model performs satisfactory it could provide a useful tool to determine the impact of soil compaction on crop yield. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, 2006.

Fibroblast growth factor 2 (FGF2) is a multifunctional protein translated as CUG-initiated, high molecular weight (hi FGF2) or AUG-initiated, low molecular weight (lo FGF2) isoforms with potentially distinct functions. Previous work showed that overexpression of hi- but not lo FGF2 elicited chromatin compaction resulting in cell death, by an intracrine route. A series of studies were undertaken aimed at extending our understanding of the intracrine action of Hi FGF2. Major findings are as follows: a. Hi FGF2 overexpression induces apoptotic cell death, as indicated by increased TUNEL staining, and mitochondrial participation (cytochrome c release to cytosol, rescue of the hi FGF2 phenotype by the anti-apoptotic protein Bcl-2. b. Increased expression of pro-survival signals/proteins that are known to upregulate Bcl-2, such as nuclear Akt; the PIM-1 kinase; and the heat shock protein hsp70, also rescued the hi FGF2-induced phenotype. c. The hi-FGF2 effect was associated with sustained, intracrine, activation of ERK, and was blocked by ERK inhibitors. d. FGF2 isoform specific affinity chromatography followed by mass spectroscopy identified several proteins as potentially interacting with hi FGF2; of these, the p68 RNA helicase and the hsp70 were further confirmed as interacting partners, by co-immunoprecipitation. e. Increased nuclear co-localization, and possibly interaction, between hi FGF2 and overexpressed hsp70 correlated with rescue from hi FGF2 induced cell death. f. Factors associated with cardiac pathology (isoproterenol, angiotensin II, endothelin I) also upregulated endogenous hi FGF2 in cardiac cells in culture. Adriamycin-induced cardiotoxicity in the rat, known to be linked to increased incidence of apoptosis, was also associated with increased endogenous hi FGF2. g. Hi FGF2 is expressed in the human heart (atria) and localizes in both cytosol and nuclei, suggesting a participation in human heart physiology and pathophysiology. Work presented here is consistent with the notion that endogenous hi FGF2 up-regulation may play a role in promoting cell death during prolonged tissue stress and dysfunction. It follows that processes related to hi FGF2 upregulation, hi FGF2-nuclear protein interactions and mechanisms of hi FGF2 induced cell death, represent potential therapeutic targets for modulating cell death.

Strip mining in Kentucky has left large areas of land that could potentially be used for business and housing developments. However, the mine spoils underlying these areas are prone to severe differential settlement due to a variety of factors. Mine spoil from the Gateway Business Park in Jenkins, Kentucky was used for a series of laboratory tests to develop relationships between shear wave velocity, confining stress, compaction energy, and dry unit weight to develop a method to assess settlement potential. It was found that a stress-corrected shear wave velocity of greater than 275 ft/s/psi0.25 typically indicated dry mine spoil, and less than 275 ft/s/psi0.25 typically indicated wet mine spoil. Equations were developed to predict the amount of settlement of a mine spoil profile based on the load, the mine spoil lithology, and the shear wave velocity of the mine spoil. With regards to compaction, it was found that if the mine spoil was compacted to at least 120 pcf (18.8 kN/m3), or a void ratio of 0.45 or less, the mine spoil would suffer little to no volume change when wetted. The results provided herein form the basis of a methodology for screening mine spoil sites for development based on settlement potential.