A research report submitted in partial fulfilment requiremenrs of degree Master of Science tothe School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa, January 2018 / South Africa’s energy sector is vital to the development of its economy. Instability in the form of disruption in supply affects production costs, investments, and social and economic growth. Domestic sources are no longer able to meet the country’s demands. South Africa must find a local alternative fuel source in order to reclaim stability and encourage social and economic development. Biomass is one of the most abundant renewable energy sources, and has great potential as a fuel source. Currently biomass contributes 12% of the world’s energy supply, while in some developing countries it is responsible for up to 50% of the energy supply. South Africa is the highest maize producer on the African continent. Many studies carried out indicated that maize, and its residue contain valuable materials, and has the highest lower heating value in comparison to other agricultural crops. This indicates that maize can be a potential biomass for renewable energy generation in South Africa. A means for energy conversion for biomass, is the process of gasification. Gasification results in gaseous products H2, CO and CO2. Since the process of biomass gasification involves a series of complex chemical reactions involving a number of parameters, which include flow, heat transfer and mass transfer, it is very difficult to study the process of gasification by relying on experimentation only. Numerical simulation was used to provide further insight on this process, and accelerate development and application of maize gasification in a cost effective and efficient manner. The objective of this study was therefore, to verify and evaluate the feasibility of maize gasification and liquid fuels production in South Africa from an economic and energy perspective. The simulation model was developed in Aspen Plus® based on two thermodynamic models specified as Soave – Redlich – Kwong and the Peng Robinson equation of state. All binary parameters required for this simulation were available in Aspen Plus®. The gasification unit was modelled based on a modified Gibbs free energy minimization model. Gasification of maize and downstream processing in the form of Fischer-Tropsch (FT) synthesis and gas to liquids (GTL) processing for liquid fuels production was modelled in Aspen Plus®. Sensitivity analyses were carried out on the process variables: equivalence ratio (ER), steam to biomass ratio (SBR), temperature and pressure, to obtain the optimum gasification conditions. The optimum reactor conditions, which maximized syngas volume and quality was found to be an ER of 0.22 and SBR of 0.2 at a temperature of 611ºC. An increase in pressure was found to have a negative effect; therefore atmospheric conditions of 101.325 kPa were chosen, in order to maximize CO and H2 molar volumes. Based on these conditions the produced syngas consisted of 35% H2, 16% CO, 24% CO2 and 3%CH4. The results obtained from gasification, based on a modified Gibbs free energy model, show a closer agreement with experimental data, than other simulations based on the assumption that equilibrium is reached and no tar is formed. However, these results were still idealistic as it under predicted the formation of CO and CH4. Although tar was accounted for as 5.5% of the total product from the gasifier (Barman et al., 2012), it may have been an insufficient estimation resulting in the discrepancy in CO and CH4. The feasibility of maize as a feed for gasification was examined based on quality of syngas produced in relation to the requirements for FT synthesis. A H2/CO ratio of 2.20 was found, which is within range of 2.1 – 2.56 found to support greater conversions of CO with deactivation of the FT catalyst (Lillebo et al., 2017). The syngas produced from maize was found to have a higher H2/CO ratio than conventional fossil fuel feeds; implying that maize can result in a syngas feed which is both renewable and richer in CO and H2 molar volumes. Liquid fuels generation was modelled based on experimental production distributions obtained from literature for FT synthesis and hydrocracking. The liquid fuel production for 1000 kg/hr maize feed, was found to be 152 kg/hr LPG, 517 kg/hr petrol and 155 kg/hr diesel. The simulation of liquid fuels production via the Fischer-Tropsch synthesis and hydrocracking process showed fair agreement with literature. Where significant deviations were found, they could be reasonably explained and supported. This simulation was found to be a suitable means to predict liquid fuels production from maize gasification and downstream processing. The feasibility of liquid fuels production from maize in South Africa was examined based on the country’s resource capacity to support additional maize generation. It was found that based on 450 000 hectares of underutilized land found in the Homelands, an additional 1.216 billion litre/annum of synthetic fuels in the form of diesel and petrol could be produced. This has the potential to supplement South African liquid fuels demand by 6% using a renewable fuel source. This fuel generation from maize will not impact food security due to the use of underutilized arable land for maize cultivation, or impact water supply as maize does not require irrigation. In addition, fuel generation in this manner supports the Biofuels Industry Strategy (2007) by targeting the use of underutilized land, ensuring minimal impact on food security, and exceeds its primary objective of achieving a 2% blending rate from renewable sources. The economic feasibility of liquid fuels derived from maize was determined based on current economic conditions in 2016. Based on these conditions of 49 $/bbl Brent Crude, 40 $/MT coal and 6.5 $/mmBTU of natural gas at a R/$ exchange rate of R14.06 per U.S. dollar, it was found that coal, natural gas and oil processing are more economically viable feeds for fuel generation relative to maize. However, based on projected market conditions for South Africa, the R/$ exchange rate is expected to weaken further, the coal supply is expected to diminish and supply of natural gas is expected to be a continued issue for South Africa. Based on this, maize should be considered as a feed for fuel generation to reduce the dependency on non-renewable fossil fuel sources. The energy feasibility of liquid fuels produced from maize was only evaluated from a thermal energy perspective. It was found that maize gasification and FT processing requires 0.91 kg steam/kg feed. This 0.91kg of steam accounts for the raw material feed, distillation and heating required for every 1kg of maize processed. It was found that 2.56 kg steam/kg feed was generated from the reactor units. This was assumed to be in the form of 10 bar steam, as in this form it can be sent to steam turbines for electricity generation to assist with overall energy efficiency for this process. In addition, the amount of CO2 (kg/kg feed) produced, was examined for maize processing in comparison to fossil fuel feeds: natural gas and coal. The CO2 production from liquid fuels processing based on a maize feed, was found to be the highest at 0.66 kg/kg feed. However, a coal feed has higher ash and fix carbon content indicating greater solid waste generation in the gasifer. While dry reforming of natural gas is a net consumer of CO2, but had significantly higher steam requirements in order to achieve the same H2/CO ratio as maize. This indicates that although maize results in more CO2/kg feed, it is 88% more energy efficient than dry methane reforming. Additional experimental work on FT processing using syngas derived from maize is recommended. This will assist in further verification of liquid fuels quantity, quality and process energy requirements. / XL2018

Thesis (MScIng)--Stellenbosch University, 2008. / ENGLISH ABSTRACT: Conventional pulse oximetry has limited accuracy in measuring blood oxygen saturation in low saturation and perfusion scenarios. This limits the application of pulse oximetry in patients su ering from peripheral vascular a ictions. A novel pulse oximetry system is presented in this study which proposes solutions to these low saturation and perfusion issues. The presented system was designed to overcome the low perfusion issues by inducing an arti cial pulse in the detected photoplethysmograph. A novel arterio-venous hypothesis was formulated to extract arterial and venous saturation data from this arti cial photoplethysmograph using arterial-to-venous compliance ratios. Sensor wavelengths were selected to provide high and low saturation accuracy, followed by an in vitro sensor calibration procedure. System performance was validated by means of in vivo human studies. In vivo results indicate good accuracy for high saturation, with limited accuracy in low saturation scenarios. The arterio-venous hypothesis was validated, indicating that venous saturation information can be extracted from the arti cial PPG. Although inconclusive, results indicate that the proposed system might be able to accurately monitor arterial and venous saturation in severe hypoperfusion scenarios with recommended hardware and calibration modi cations. It is recommended that further studies into the presented system's performance are conducted. / AFRIKAANSE OPSOMMING: Konvensionele 'pulse oximetry' sisteme het beperkte akkuraatheid tydens die meting van bloed suurstof saturasie in lae saturasie en perfusie gevalle. Dit beperk die bruikbaarheid van 'pulse oximetry' in pasiënte wat ly aan perifere vaskulêre siektes. 'n Nuwe 'pulse oximetry' sisteem, wat oplossings vir hierdie lae saturasie en perfusie beperkings voorstel, word in hierdie studie aangebied. Die voorgestelde sisteem is ontwerp om die lae perfusie beperkings te oorkom deur 'n kunsmatige polsslag in die 'photoplethysmograph' te induseer. 'n Nuwe arterio-veneuse hipotese is geformuleer om arteriële en veneuse saturasie inligting uit hierdie kunsmatige polsslag te onttrek deur middel van 'n arteriële-teenoor-veneuse styfheids verhouding. Die gol engtes wat gebruik is in die sensors, is spesi ek gekies om hoë en lae saturasie akkuraatheid te verskaf. 'n In vitro kalibrasie prosedure is gevolg om die sensors vir hoë en lae saturasie te kalibreer, waarna die werkverrigting van die sisteem getoets is deur middel van 'n in vivo validasie prosedure. Die in vivo resultate toon goeie akkuraatheid vir hoë saturasie, met beperkte akkuraatheid vir lae saturasie. Die arterio-veneuse hipotese is gevalideer, wat aandui dat veneuse saturasie wel uit die kunsmatige 'photoplethysmograph' onttrek kan word. Alhoewel die resultate wat in hierdie studie aangebied word nie omvattend of beslissend is nie, dui dit egter aan dat die voorgestelde sisteem dalk in staat kan wees om arteriële en veneuse saturasie in uiters lae perfusie gevalle te meet. Verbeteringe sal egter aan die sisteem aangebring moet word in terme van hardeware en kalibrasie, om 'n meer gestandardiseerde metings metode te verseker. Verdere navorsing oor die werkverrigting van die voorgestelde sisteem word ook voorgestel.

Orientador: Flávio Dutra de Resende / Banca: Danilo Domingues Millen / Banca: Laura Franco Prados / Banca: Ivanna Moraes de Oliveira / Banca: Ricardo Andrade Reis / Resumo: O objetivo no trabalho foi avaliar o desempenho e as características de carcaça e carne de bovinos Nelore em confinamento, com utilização de monensina sódica como modulador de consumo de matéria seca. Foram utilizados 250 bovinos da raça Nelore, com peso médio de 363 kg. Os animais foram alojados em 35 baias coletivas equipadas com seis metros lineares de cocho de alimentação de concreto e bebedouros de 1500L de água. Os animais foram blocados através do peso, assim ficou disposto de forma que cada baia alojava 7 animais, sendo que o último bloco (5 baias finais) estava alojado 8 animais. De cada baia foi sorteado dois animais no início do experimento, afim de classificar os animais que seria feito coletas de sangue e coleta de dados no abate comercial, totalizando 70 animais para tais coletas. O experimentou foi de 148/156 dias no total, dividido em período de adaptação e terminação. Foram utilizadas três dietas, como os mesmos ingredientes, bagaço de cana-de-açúcar, milho grão, polpa cítrica, farelo de algodão e núcleo mineral, mas com relação a proporção de volumoso:concentrado diferente, sendo que a adaptação era 22:78; transição 17:83 e terminação 12:88 O fornecimento era feito pela manhã e durante a tarde, sendo dois fornecimentos de 50% cada um. Em todas as dietas era acrescido no núcleo mineral 25 mg/kg MS de virginiamicina e de acordo com os tratamentos era adicionado monensina sódica na dose de 20 mg/kg MS. Foram avaliados cinco tratamentos: VM - Uso de virginiamici... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim was evaluation the performance and the characteristics of the carcass of Nelore beef in feedlot, with the use of sodium monensin as a modulator of dry matter intake. A total of 250 Nellore cattle were used, with a mean weight of 363 kg. The animals were housed in 35 collective pens equipped with six linear meters of concrete feeding trough and water troughs of 1500L. The animals were blocked by weight, so they were arranged so that each pen 7 animals, and the last block (5 final pens) housed 8 animals. From each pen, 2 animals were randomly selected at the beginning of the experiment, in order to separate the animals that carried out blood collection and data collection in slaughterhouse, totaling 70 animals for such collections. The experiment was 148/156 days in total, in the period of adaptation and termination. The types of diet, such as the ingredients themselves, sugar cane bagasse, corn grain, citrus pulp, cottonseed meal and mineral, but with regard to a proportion of bulky: a different, being a 22:78 adaptation; transition 17:83 and termination 12:88 The supply was made in the morning and during the afternoon, two supplies of 50% each. In all diets, 25 mg/kg MS of virginiamycin was added to the mineral core and according to treatments sodium monensin was added at a dose of 20 mg/kg DM. Five treatments were applied: VM - Use of virginiamycin throughout the experimental period, without addition of sodium monesin in the diet (Control); 34d - Use sodium monesin f... (Complete abstract click electronic access below) / Doutor

A dissertation submitted to the faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfillment of the requirements for the degree of Master of Science in Engineering. 21 November 2016 / In this work a comprehensive exergy analysis and heat integration study was carried out on a coal based oxy-combustion power plant simulated using ASPEN plus. This is an extension on the work of Fu and Gundersen (2013). Several of the assumptions made in their work have been relaxed here. Their impact was found to be negligible with the results here matching closely with those in the original work. The thermal efficiency penalty was found to be 9.24% whilst that in the original work was 9.4%. The theoretical minimum efficiency penalty was determined to be 3% whilst that in the original work was 3.4%. Integrating the compression processes and the steam cycle was determined to have the potential to increase net thermal efficiency by 0.679%. This was close to the 0.72% potential reported in the original work for the same action. / MT2017

Supramolecular chemists can be thought of as architects, who combine individual non-covalently bonded molecular building blocks, designed to be held together by intermolecular forces to create functional architectures. Perhaps the most important assets of a supramolecular chemist, however, are imagination and creativity, which have given rise to a wide range of beautiful and functional systems. For years, analytical chemistry has taken advantage of supramolecular assemblies in the development of new analytical methods. The role of synthetic supramolecular chemistry has proven to be a key component in this multidisciplinary research. As such, the demand for synthetic receptors is rapidly increasing within the analytical sciences. The field “supramolecular analytical chemistry” involves analytical applications of synthetic organic and inorganic chemical structures that display molecular recognition properties and self-assembly but also signal these events. Chapter 1 presents an introduction to the background literature relevant to the central themes of the research presented in this thesis. The nonthermal production of visible light by a chemical reaction leads to the term “cool light”, and the process is called chemiluminescence. Although chemiluminescent reactions are not rare, the production of “cool light” holds such fascination for both chemists and nonchemists that demonstrations of chemiluminescent reactions are always well received. A glow assay technology for the detection of a chemical warfare simulant is presented in Chapter 2, which is based on modulating the peroxyoxalate chemiluminescence pathway by way of utilizing an oximate super nucleophile that gives an off-on glow response. As an alternative to highly analyte-specific synthetic receptors, trends in chemical sensing have shifted to the design of new materials and devices that rely on a series of chemo- or biosensors. The research relevant to Chapter 3 focuses on investigating the use of a single receptor, for sensing two different analytes; thiols and metal ions, utilizing a squaraine as the receptor in a sensor array format. The data is interpreted with principal component analysis. Finally Chapter 4 discusses an attempt to design and synthesize a chemosensor based on the luminophore-spacer-receptor format by incorporating the two concepts photoinduced electron transfer and peroxyoxalate chemiluminescence. / text

Methane (CH4) is one of the most important greenhouse gases after water vapor and carbon dioxide due to its high concentration and global warming potential 25 times than that of CO2 (based on a 100 year time horizon). Its atmospheric concentration has more than doubled from the preindustrial era due to anthropogenic activities such as rice cultivation, biomass burning, and fossil fuel production. However, the rate of increase of atmospheric CH4 (or the growth rate) slowed from 1980 until present. The main reason for this trend is a slowdown in the trend of CH4 sources. Measuring stable isotopes of atmospheric CH4 can constrain changes of CH4 sources. The main goal of this work is to interpret the CH4 trend from 1978-2010 in terms of its sources using measurements of CH4 mixing ratio and its isotopes. The current work presents the measurements and analysis of CH4 and its isotopes (δ13C and δD) of four air archive sample sets collected by the Oregon Graduate Institute (OGI). CH4 isotope ratios (δ13C and δD) were measured by a continuous flow isotope ratio mass spectrometer technique developed at PSU. The first set is for Cape Meares, Oregon which is the oldest and longest set and spans 1977-1999. The integrity of this sample set was evaluated by comparing between our measured CH4 mixing ratio values with those measured values by OGI and was found to be stable. Resulting CH4 seasonal cycle was evaluated from the Cape Meares data. The CH4 seasonal cycle shows a broad maximum during October-April and a minimum between July and August. The seasonal cycles of δ13C and δD have maximum values in May for δ13C and in July for δD and minimum values between September-October for δ13C and in October for δD. These results indicate a CH4 source that is more enriched January-May (e.g. biomass burning) and a source that is more depleted August-October (e.g. microbial). In addition to Cape Meares, air archive sets were analyzed from: South Pole (SPO), Samoa (SMO), Mauna Loa (MLO) 1992-1996. The presented δD measurements are unique measured values during these time periods at these stations. To obtain the long-term in isotopic CH4 from 1978-2010, other datasets of Northern Hemisphere mid-latitude sites are included with Cape Meares. These sites are Olympic Peninsula, Washington; Montaña de Oro, California; and Niwot Ridge, Colorado. The seasonal cycles of CH4 and its isotopes from the composite dataset have the same phase and amplitudes as the Cape Meares site. CH4 growth rate shows a decrease over time 1978-2010 with three main spikes in 1992, 1998, and 2003 consistent with the literature from the global trend. CH4 lifetime is estimated to 9.7 yrs. The δ13C trend in the composite data shows a slow increase from 1978-1987, a more rapid rate of change 1987-2005, and a gradual depletion during 2005-2010. The δD trend in the composite data shows a gradual increase during 1978-2001 and decrease from 2001-2005. From these results, the global CH4 emissions are estimated and show a leveling off sources 1982-2010 with two large peak anomalies in 1998 and 2003. The global average δ13C and δD of CH4 sources are estimated from measured values. The results of these calculations indicate that there is more than one source which controls the decrease in the global CH4 trend. From 1982-2001, δ13C and δD of CH4 sources becomes more depleted due to a decrease in fossil and/or biomass burning sources relative to microbial sources. From 2005-2010, δ13C of CH4 sources returns to its 1981 value. There are two significant peaks in δ13C and δD of CH4 sources in 1998 and 2003 due to the wildfire emissions in boreal areas and in Europe.

An arterialblood gas analysis which is conducted in critical care areas contributes to the assessment of a patient's ventilatory status and acid -base balance. The purpose of this research was to determine the relationship of time delays and temperature on the result of a blood gas analysis. The objective was to either accept or refute the null hypothesis, that there is no relationship between temperature and time delays and an arterial blood gas result Fifteen subjects were randomly selected. The researcher drew three samples of arterial blood from each subject. Ethical principles were observed. An inferential non-parametric statistic was used. The chi-squared test was used to test the hypothesis and the Friedman and the Wilcoxon signed ranks test were used to test the differences between the means. The results revealed that there was a relationship between time delays, temperature and the arterial blood gas result. The null hypothesis was rejected. / Health Stusies / M.A. (Health Studies)

Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017. / Cataloged from PDF version of thesis. / Includes bibliographical references (pages 185-213). / In this thesis, I use coastal measurements of dissolved O₂ and inert gases to provide insight into the chemical, biological, and physical processes that impact the oceanic cycles of carbon and dissolved gases. Dissolved O₂ concentration and triple isotopic composition trace net and gross biological productivity. The saturation states of inert gases trace physical processes, such as air-water gas exchange, temperature change, and mixing, that affect all gases. First, I developed a field-deployable system that measures Ne, Ar, Kr, and Xe gas ratios in water. It has precision and accuracy of 1 % or better, enables near-continuous measurements, and has much lower cost compared to existing laboratory-based methods. The system will increase the scientific community's access to use dissolved noble gases as environmental tracers. Second, I measured O₂ and five noble gases during a cruise in Monterey Bay, California. I developed a vertical model and found that accurately parameterizing bubble-mediated gas exchange was necessary to accurately simulate the He and Ne measurements. I present the first comparison of multiple gas tracer, incubation, and sediment trap-based productivity estimates in the coastal ocean. Net community production estimated from ¹⁵NO₃⁻ uptake and 02 /Ar gave equivalent results at steady state. Underway O₂/Ar measurements revealed submesoscale variability that was not apparent from daily incubations. Third, I quantified productivity by O₂ mass balance and air-water gas exchange by dual tracer (³He/SF₆ ) release during ice melt in the Bras d'Or Lakes, a Canadian estuary. The gas transfer velocity at >90 % ice cover was 6 % of the rate for nearly ice-free conditions. Rates of volumetric gross primary production were similar when the estuary was completely ice-covered and ice-free, and the ecosystem was on average net autotrophic during ice melt and net heterotrophic following ice melt. I present a method for incorporating the isotopic composition of H₂O into the O₂ isotope-based productivity calculations, which increases the estimated gross primary production in this study by 46-97 %. In summary, I describe a new noble gas analysis system and apply O₂ and inert gas observations in new ways to study chemical, biological, and physical processes in coastal waters. / by Cara Charlotte Marie Manning. / Ph. D.

An arterialblood gas analysis which is conducted in critical care areas contributes to the assessment of a patient's ventilatory status and acid -base balance. The purpose of this research was to determine the relationship of time delays and temperature on the result of a blood gas analysis. The objective was to either accept or refute the null hypothesis, that there is no relationship between temperature and time delays and an arterial blood gas result Fifteen subjects were randomly selected. The researcher drew three samples of arterial blood from each subject. Ethical principles were observed. An inferential non-parametric statistic was used. The chi-squared test was used to test the hypothesis and the Friedman and the Wilcoxon signed ranks test were used to test the differences between the means. The results revealed that there was a relationship between time delays, temperature and the arterial blood gas result. The null hypothesis was rejected. / Health Stusies / M.A. (Health Studies)

Concentrations of CO, CO₂, and O₂ in woodstove flue gases are some of the measured inputs required by algorithms used to calculate woodstove efficiency by the stack loss method. Since these algorithms have been shown to be very sensitive to small errors in these input values, it was necessary to determine whether measurements of these compounds are subject to interference. Concentrations of CO, CO₂, and O₂ in a series of flue gas samples were measured using a variety of independent measurement techniques for each compound. The concentrations indicated by each of the measurement techniques for each compound and sample were compared to check for agreement. Disagreement among the measurement techniques for a given compound could indicate interference if some trend could be established. Tests were conducted on four samples taken randomly during each of three stove firings. / M.S.