A laboratory process exists for the extraction of kafirin protein from sorghum grain in order to form kafirin encapsulating microparticles. This laboratory process extracts approximately 2 g of protein and takes in excess of 60 hours from start to finish. A scaled-up extraction process based on the current laboratory process, consisting of a 100 L extraction vessel, was established in order to extract large volumes of kafirin protein from sorghum grain. Approximately 2.5 kg of kafirin protein, which contained approximately 80 % protein after defatting, was extracted from red sorghum grain. This blended kafirin protein, which was the product of combining 9 batches done on the up-scaled process, was needed in order to obtain a consistent base raw material for further experimentation. The blended kafirin was used to investigate the formation of kafirin encapsulating microparticles. This was achieved by means of the solvent phase separation technique with acetic acid as the solvent phase. A series of experiments, selected from a partial factorial design, were used to screen how the formation of microparticles was affected by various parameters. The parameters investigated were solvent to protein ratio, stirring speed, water addition rate and number of water droplets. The morphology of the various microparticles produced was analysed by means of light microscopy, FTIR and particle size analysis, and the different formed microparticles characterised. From the screening partial factorial experimental design, it was determined that the acetic acid concentration was crucial for the formation of microparticles. Microparticles did not form at a low mass ratio (2.3) of glacial acetic acid solvent to protein. Water addition rate and stirring rate also affected microparticle formation while the number of water droplets was insignificant. Therefore, using a high solvent to protein mass ratio (6.8), additional refined partial factorial experiments were conducted. These experiments focused on the effect of water addition rate and stirring speed on the final kafirin microparticle size. Ultimately, a polynomial model was developed to predict the final kafirin microparticle size using only the water addition rate and stirring speed as inputs. The model had an R2 value of 0.986 and was found to relatively accurate during validation. The model also identified that three distinct regions existed within the workspace: _ A region containing large particles due to protein mass agglomeration and crosslinking, which occurs at low stirring speeds (< 400 rpm) and high water addition rates (> 5 mL/min) _ A region where only small individual microparticles exist, which occurs at high stirring speeds (< 800 rpm) and low water addition rates (> 2 mL/min) _ A region where moderate particles existed as uniform agglomerates of the microparticles, which occurs at moderate stirring speeds (+- 600 rpm) and moderate water addition rates (+- 3.5 mL/min) Ultimately these kafirin microparticles, prepared from protein extracted in an up scaled process, were used to form qualitative microparticle films. The microparticle films were made without plasticiser and without dewatering the microparticles. Furthermore these films were made from microparticles in the regions identified in the model. This qualitative film formation showed that agglomerated microparticles can form films. This could be beneficial for the feasibility of a commercialised process for kafirin microparticle films since the production time would be shorter and less energy intensive. / Dissertation (MEng)--University of Pretoria, 2016. / Chemical Engineering / MEng / Unrestricted

The specific surface area, determined by the BET method, is a parameter often used to scale results of mineral studies of surface reactions in terms of rate and capacity to the field scale. Such extrapolations of results from small-scale laboratory experiments to the field-scale are important within many environmental applications. An example of this is for the prediction of radionuclide retention in the bedrock surrounding a deep repository for radioactive waste, following failure of the engineered barriers, where radionuclides may sorb onto minerals constituting the geological environment. As a first step, the approach used in this work is to study the relationship between specific surface area and the particle size (0.075-8 mm) and to approach the field scale via measurements on large, centimetre-sized pieces, for seven natural minerals commonly found in granite: apatite, biotite, chlorite, K-feldspar, hornblende, labradorite and magnetite. The underlying assumption is that sorption of radionuclides can be related to specific surface area of a particular mineral in a continuation of this project.The results show that the phyllosilicates biotite and chlorite have a specific surface area that is about 10 times larger than the other minerals. Over the range of particle size fractions studied, the specific surface area varies between 0.1 and 1.2 m2g-1 for biotite and chlorite. The other studied minerals have specific surface areas varying between 0.01 m2g-1 for the largest fraction and up to 0.06 - 0.12 m2g-1 for the smallest. Results show linear relationships between the specific surface area and the inverse of the particle size for all studied minerals for small particle sizes, as expected. For some minerals, however, the data seemingly can be divided in two linear trends, where a change in internal surface area, surface roughness and/or particle geometry as the particle size decreases may explain this behaviour. Interestingly, for larger particles, there is a deviation from the linearity observed for small particles. Tentatively, this behaviour is attributed to a disturbed zone, created by the mechanical treatment of the material during particle size reduction, extending throughout small particles, but not altering an undisturbed core of the larger particles. In agreement with this, measurements on large pieces show a surface area 5 to 150 times lower than expected from the linear trends observed for the crushed material, implying an overestimation of the surface area and possibly also of the sorption capacities of the rock material from simple extrapolations of experimental results employing finely crushed material to the field situation. / QC 20110929 / Äspö Radionuclide sorption

In this dissertation the effects of different types of Pulverized Fuel Ash (PF A)-types on the workability of cementitious pastes containing relative large amounts of PF A were investigated. The different types of PF A were produced at the same source thus they were chemically similar but differed in terms of average particle size and size distribution (grading). By using a two-point measurement technique based on flow through a J-shaped tube it was possible to detect relative small differences in workability between pastes. It was found and concluded that the different types of PFA had a significant effect on the workability of pastes containing cement and PFA as well as PF A alone. The physical differences between the PF A-types were quantified and their effects on workability investigated. It was concluded that PF A with a broader particle size distribution range produced pastes with higher workability at constant water content. It was found that compressive strength as measured after 28 days were solely a function of the water/cementitious ratio for the curing regime employed. It was concluded that for curing conditions used the type of PF A used could have a significant effect on compressive strength when constant workability is required. / Dissertation (MSc (Transportation))--University of Pretoria, 2006. / Civil Engineering / unrestricted

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has risen to among the top tier techniques for the direct analysis of solid samples. However, significant problems remain that must be solved to achieve the full analytical potential of LA-ICP-MS. Inefficient conversion of aerosol to ions within the ICP or transmission through the MS interface may decrease precision, sensitivity, and/or accuracy. Although fundamental mechanisms that govern ion production and transmission have been studied extensively in solution-nebulization (SN) ICP-MS instruments, significant gaps in our understanding remain. Furthermore, it is unclear to what extent differences between the aerosols generated during SN and LA influence either ion production or transmission. In this work, I initially investigated differences in the spatial distributions of Ca, Ba, and Sc ions generated by LA and SN using high-resolution LIF imaging. Ions formed from aerosol generated by LA at low fluence were distributed over much greater axial and narrower radial distances than SN aerosol. Additionally, I investigated the effects of solvent, laser fluence, and ablation atmosphere (He vs Ar) on ion distributions in the ICP. Unlike solvent, changing laser fluence and ablation atmosphere produced considerable changes in the ion signal intensity and spatial distribution during LA. At greater laser fluence, the radial distance over which ions were distributed dramatically increased. Surprisingly, when helium was mixed with argon as carrier gas, ion signals decreased. Many of these effects were assumed to be related to changes in the number and size of particles generated during LA. In a follow-up study, relative contributions to ion densities in the ICP from particles of different sizes were investigated. LIF images were recorded while filtering particles above a threshold size on-line. Micron-sized particles contributed the majority of ions formed in the ICP. For Ba, Ca, and Sc, differences in the axial position where nanometer- and micron-sized particles vaporized were 2, 1, and less than 1 mm, respectively. I also performed experiments to identify changes in the ion signal related to changing ablation conditions vs. changing ICP conditions associated with helium additions to the carrier gas. LIF images were recorded during different combinations of He/Ar added upstream and/or downstream of the ablation cell. Changes in the ion signal during ablation in helium vs argon did not always match expectations based on changes in particle numbers and sizes measured with SEM. The results force re-examination of some of the fundamental assumptions about the effect of carrier gas composition on the performance of LA-ICP-MS. The research described in this dissertation provides valuable insight into fundamental aspects of key ICP processes related to LA generated aerosol.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24184号 / 理博第4875号 / 新制||理||1698(附属図書館) / 京都大学大学院理学研究科生物科学専攻 / (主査)准教授 半谷 吾郎, 准教授 Huffman Michael Alan, 教授 今井 啓雄 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Pacific salmon has been a staple resource for residents of British Columbia for over seven thousand years. Archaeological evidence obtained from a shell midden at Namu, B.C., provides detailed information about the diets of the First Peoples living at Namu over the past seven thousand years. Pacific salmon was the most prevalent species of fish uncovered within the midden, excluding herring. Pink, chum and sockeye species were consumed in the greatest quantities. Pink was particularly favored because of its ability to store over winter months without spoiling. Evidence from the shell midden also reveals fluctuations within the pink salmon fishery from ~3800 until 1900 cal year BP. The paleoenvironmental conditions within Namu Lake during the time of the pink collapse have never before been explored. There is also little evidence pertaining to what may have contributed to the collapse of the pink fishery. Sediment cores collected from Namu Lake, B.C. provide evidence for paleoenvironmental conditions that may have contributed to fluctuations in the pink salmon population. Particle size analyses of lake sediment cores indicate changes in river discharge as well as erosional intensity within the Namu basin. Particle size, coupled with radiocarbon dating, reveal a transitional period within the basin from ~ 3200 to 2200 cal year BP. A decrease in elemental ratios/Al, particularly Ca, Na, Ba, and Sr, provides evidence for a decline in erosional intensity and a relatively drier period within the basin. The decrease in erosional intensity could be due to consistently drier conditions at Namu. A resulting reduction in the flow of the Namu River would have caused an increase in finer particles within the pink salmon spawning grounds. Average C/N ratios for NC1 are 26.28, indicating that organic matter within the lake is mainly terrestrial in origin. These results, combined with the particle size and trace metal analysis, reveal that river discharge and slope wash had declined during this period causing fine material to remain in the Namu River (outflowing), which is the spawning grounds for the pink salmon, rather than being transported out into the bay. The results of this study reveal that a shift in moisture, towards relatively dry conditions, negatively impacted spawning pink salmon at Namu Lake. This study provides insight into the sensitivity of Pacific salmon to climate and the effects future climate change may have on the species. The ability of environmental data to supplement and enhance archaeological information and interpretations of prehistoric conditions is illustrated throughout this study. The cores collected at Namu Lake also reveal the need for site specific climatic data in order to accurately interpret archaeological contexts and conditions. / Thesis / Master of Science (MSc)

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