Sasol biological sludge, coal fine and gasification ash were the three waste streams involved in this study. The main concern is that on their own they are not suitable as growth mediums, the ash is alkaline (pH>12) with high salinity (total dissolved solids of 8000 mg ℓ-1). Fine ash is microporous (particle size diameter <250 μm) and forms cemented layers that can restrict root growth while, gasification ash in macroporous (most particle size diameter ranged between 1 and 75 mm) and has a low water holding capacity. Sludge is unstable and can inhibit gaseous exchange. However, these wastes potentially, have physical, biological and chemical attributes that make them suitable as hospitable growth medium. Sludge can promote micro-fauna activity and, provide plant available nitrogen (N) as well as phosphorus (P) the ash is poor in. On a short term bases and in the long term it can also contribute to cation exchange capacity (CEC). Fine ash can increase water holding capacity and gasification ash can improve gaseous exchange. It was hypothesized that if the ash was treated with sludge, pH will be reduced to between 5.5 and 8, and weathering will reduce salinity to less than 400 mSm-1, increase CEC and increase plant available N and P. Therefore, the main purpose of this laboratory column study was to establish combinations of these waste streams that hold promise as plant growth media, based on various chemical and physical criteria link to hospitable plant growth media, as well as the influence of weathering on the release of essential plant nutrients. A total of 51 mixtures (each weighing 2.6 kg) were formulated based on wet mass basis and divided into 6 groups based on sludge content (0, 10, 20, 30, 40 and 50%) and packed into columns, subjected to wetting and drying for 1 year (10 wetting and drying cycles) by passing through deionized water equivalent to the pore volume and allowing the mixtures to dry in between. The leachates were analysed using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and Kjeldahl procedures (for N release). Total elemental analysis was done using X-ray Fluorescence Spectroscopy (XRF) and acid digestion method. Particle size distribution was done using the sieve method. Cation exchange properties were assessed using ammonium acetate (NH4OAc), lithium chloride (LiCl) and potassium chloride (KCl) methods. Results indicated that sludge was critical for these mixtures,at a minimal content of 10% it increased the water holding capacity of the mixtures. In the mineralization of inorganic N at a lower limit of 20% sludgeenabled the production of plant available NH4+ and NO3- and less NO2-. Increasing sludge to 50% further reduced the production of NO2- in the mixtures. In terms of elemental release, mixtures without sludge were dominated by Na and the order of abundance was as follows; Na>K>Ca>Mg>P on mmol kg-1 but the introduction of sludge at a lower content limit of 10% changed the abundance of the elements as follows; P>Mg>Ca>Na>K on mmol kg-1. Sludge content as low as 10% reduced the pH of the mixtures to between 7.6 and 8 and EC to less than 400 mSm-1. However, increasing sludge to 50% increased the leachate EC dramatically and kept the EC high (415 mSm-1) till the end. Introduction of sludge at a low limit of 10 % content increased the CEC above 8 cmolc kg-1. The effects of fine ash on the water holding capacity of the mixtures were seen at the 10 % level, for example, mixture 13 with 10% fine ash had 0.3 mg kg-1, while mixture 12 with 0% fine ash had 0.27 mg kg-1. Increasing fine ash content above 40% increased pozzalanic properties, pH (>8), EC (>400 mSm-1), Na release and reduced CEC.Gasification ash is the biggest waste stream and utilizing these wastes as growth media will mean that it realistically will always dominate these mixtures. This study showed that on its own it will be a challenging environment. However, the amendent with sludge and fine ash resulted in some chemically and physically favourable changes in these media. It can be concluded that the main objective has been achieved and bio assay evalution of theses mixtures is recommended Copyright / Dissertation (MSc(Agric))--University of Pretoria, 2012. / Plant Production and Soil Science / unrestricted

Glass is a common form of trace evidence found at many scenes of crimes in the form of small fragments. These glass fragments can transfer to surrounding objects and/or persons and may provide forensic investigators valuable information to link a suspect to the scene of a crime. Since the elemental composition of different glass sources can be very similar, a highly discriminating technique is required to distinguish between fragments that have originated from different sources. The research presented here demonstrates that Laser Induced Breakdown Spectroscopy (LIBS) is a viable analytical technique for the association and discrimination of glass fragments. The first part of this research describes the optimization of the LIBS experiments including the use of different laser wavelengths to investigate laser-material interaction. The use of a 266 nm excitation laser provided the best analytical figures of merit with minimal damage to the sample. The resulting analytical figures of merit are presented. The second part of this research evaluated the sensitivity of LIBS to associate or discriminate float glass samples originating from the same manufacturing plants and produced at approximately the same time period. Two different sample sets were analyzed ranging in manufacturing dates from days to years apart. Eighteen (18) atomic emission lines corresponding to the elements Sr, K, Fe, Ca, Al, Ba, Na, Mg and Ti, were chosen because of their detection above the method detection limits and for presenting differences between the samples. Ten elemental ratios producing the most discrimination were selected for each set. When all the ratios are combined in a comparison, 99% of the possible pairs were discriminated using the optimized LIBS method generating typical analytical precisions of ~5% RSD. The final study consisted of the development of a new approach for the use of LIBS as a quantitative analysis of ultra-low volume solution analysis using aerosols and microdrops. Laser induced breakdown spectroscopy demonstrated to be an effective technique for the analysis of as low as 90 pL for microdrop LIBS with 1 pg absolute LOD and 20 µL for aerosol LIBS with an absolute LOD of ~100 fg.

Cotton is the most abundant natural fiber in the world. Many countries are involved in the growing, importation, exportation and production of this commodity. Paper documentation claiming geographic origin is the current method employed at U.S. ports for identifying cotton sources and enforcing tariffs. Because customs documentation can be easily falsified, it is necessary to develop a robust method for authenticating or refuting the source of the cotton commodities. This work presents, for the first time, a comprehensive approach to the chemical characterization of unprocessed cotton in order to provide an independent tool to establish geographic origin. Elemental and stable isotope ratio analysis of unprocessed cotton provides a means to increase the ability to distinguish cotton in addition to any physical and morphological examinations that could be, and are currently performed. Elemental analysis has been conducted using LA-ICP-MS, LA-ICP-OES and LIBS in order to offer a direct comparison of the analytical performance of each technique and determine the utility of each technique for this purpose. Multivariate predictive modeling approaches are used to determine the potential of elemental and stable isotopic information to aide in the geographic provenancing of unprocessed cotton of both domestic and foreign origin. These approaches assess the stability of the profiles to temporal and spatial variation to determine the feasibility of this application. This dissertation also evaluates plasma conditions and ablation processes so as to improve the quality of analytical measurements made using atomic emission spectroscopy techniques. These interactions, in LIBS particularly, are assessed to determine any potential simplification of the instrumental design and method development phases. This is accomplished through the analysis of several matrices representing different physical substrates to determine the potential of adopting universal LIBS parameters for 532 nm and 1064 nm LIBS for some important operating parameters. A novel approach to evaluate both ablation processes and plasma conditions using a single measurement was developed and utilized to determine the “useful ablation efficiency” for different materials. The work presented here demonstrates the potential for an a priori prediction of some probable laser parameters important in analytical LIBS measurement.

Indiana University-Purdue University Indianapolis (IUPUI) / The reaction between elemental sulfur and sulfide is a lynchpin in the biotic and abiotic cycling of sulfur. This dissertation is focused on the reactivity of elemental sulfur nanoparticles (S8weimarn, S8raffo) among other forms of elemental sulfur (S8aq, S8aq-surfactant, α-S8), and how the variation of their surface area, character and coatings reflect on the analytical, physical-chemical and geochemical processes involving sulfur cycling. A comprehensive electrochemical investigation utilizing mercury-surface electrodes showed that elemental sulfur compounds are represented by three main voltammetric signals, corresponding to potentials at -1.2V, -0.8V, and -0.6V in the absence of organics at circumneutral pH. Dissolved S8aq-surfactant signals can be found from -0.3V up to -1.0V, depending on the surfactant in the system. Variations in current response resulted from differences in electron transfer efficiency among the forms of S8, due to their molecular structural variability. Based on this observation a new reaction pathway between S8 and Hg-surface electrodes is proposed, involving an amalgam-forming intermediate step. The kinetics of the nucleophilic dissolution of S8nano by sulfide, forming polysulfides, were investigated under varying surface area, surface character and presence or absence of surfactant coatings on S8nano. Hydrophobic S8weimarn and hydrophilic S8raffo show kinetic rate laws of 𝑟𝑆8𝑤𝑒𝑖𝑚𝑎𝑟𝑛 = 10−11.33 (𝑒 −700.65 𝑅𝑇 ) (Molar(S8)/second/dm-1) and𝑟𝑆8𝑟𝑎𝑓𝑓𝑜 = 10−4.11 𝑖−0.35 (𝑒 −615.77 𝑅𝑇 ) (Molar(S8)/second), respectively. The presence of surfactant molecules can influence the reaction pathways by dissolving S8nano and releasing S8aqsurfactant, evolving the rate-limiting step as a function of the degree of the solubilization of S8nano. The reaction rate of S8biological can be compared with those of S8raffo and S8weimarn in circumneutral pH values and T=50oC, making the forms of S8nano successful abiotic analogue models of microbially produced S8biological. Field observations and geochemical kinetic modeling in the geothermal features of Yellowstone indicate that the nucleophilic dissolution reaction appears to be a key abiotic pathway for the cycling of sulfur species and the enhancement of elemental sulfur bioavailability. Furthermore, in situ and ex situ voltammetry in the same geothermal waters disclosed chaotic variability in chemical gradients of sulfide (observed over small temporal and spatial scales) which can be considered as an ecological stressor capable of influencing single cell physiology and microbial community adaptation.

Can a house be a product? This thesis sets out to form a set of basic elements for a minimum house in light of this question that is both functional and aesthetic. The goal is to develop an efficient prefabricated system of construction analogous to a chart of chemical elements. The modular system is then applied to the most basic footprint for a house - a 400 square foot Accessory Dwelling Unit (ADU). Through studying the fundamental parts of a house, a level of understanding emerges, which allows for a projection of the idea as a whole. The ideal of prefabrication posits the possibility of architecture as a system. This idea has attracted architects for decades, despite what appears to be an inherent tension between architecture as a system and the poetic iconicity of the house as a type. A study of the systemic introduced by considerations of prefabrication can offer a deeper understanding of the complex nature of architecture. Finally, can the essence of architecture endure amidst the necessary limitations of factory production and manufacturing in our post-industrial age? / Master of Architecture / This thesis consists of a system-generated 400 square foot prefabricated house, a catalog of the house's elements, an expanded catalog of small houses, and a series of studies conducted while traveling through Europe and upon return. The system utilizes a series of functional pods and frames the 'served' with panelized elemental compounds such as walls, floors, and roofs to meet the programmatic requirements of a house. By applying this limited catalog, the feasibility of production can be explored through an expanded catalog. Ultimately, the whole must be greater than the sum of its parts; through tectonic articulation, functional clarity and an additive approach, this can be achieved while meeting the strict constraints that prefabrication demands.

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Laser-induced breakdown spectroscopy (LIBS) is an advanced data analysis technique for spectral analysis based on the direct measurement of the spectrum of optical emission from a laser-induced plasma. Assignment of different atomic and ionic lines, which are signatures of a particular element, is the basis of a qualitative identification of the species present in plasma. The relative intensities of these atomic and ionic lines can be used for the quantitative determination of the corresponding elements present in different samples. Calibration curve based on absolute intensity is the statistical method of determining concentrations of elements in different samples. Since we need an exact knowledge of the sample composition to build the proper calibration curve, this method has some limitations in the case of samples of unknown composition. The current research is to investigate the usefulness of ANN for the determination of the element concentrations from spectral data. From the study it is shown that neural networks predict elemental concentrations that are at least as good as the results obtained from traditional analysis. Also by automating the analysis process, we have achieved a vast saving in the time required for the data analysis.

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No description available.

"A significant work of architecture is never the product of a single individual. It is always a collaboration with history and tradition, with the silent wisdom of the discipline of architecture. An architect who understands the essence of his craft accepts his role as a builder of a tradition, and he places his work in the context of this continuum with combined humility and pride." Juhani Pallasmaa. / Master of Architecture