The geology and mining industries rely heavily on reliable quantitative data on the elemental composition of various rocks and minerals. The analytical accuracy of the best measurement systems are, however, limited to the accuracy with which the composition of a generally accepted reference sample is known, which serves to calibrate an instrument or validate a method. Thus, there is an established market for well-characterised reference materials which trade internationally as value added commodities. International organisations prepare strict procedures for the preparation and certification of these reference materials. ISO/REMCO is the ISO Committee on Reference Materials that carries out and encourages a broad international effort for the harmonisation and promotion of reference materials, their production and their application. In view of recent developments in ISO/REMCO related to updated guides and changes in definitions, SARM 1 to 6 (the NIMROCs) are in danger of losing their status as certified reference materials (CRMs). Due to the continued popularity of the NIMROCs and the availability of bulk sample, the National Metrology Institute of South Africa (NMISA) embarked on a project to re-certify three materials from the suite of six igneous rock samples, i.e. SARM 2 (Syenite), SARM 3 (Lujavrite) and SARM 4 (Norite). The aim of the re-certification project was to re-certify the materials with a single primary reference measurement procedure in a single laboratory to comply with one of the possible routes to the establishment of metrological traceability as described in ISO Guide 34. Eight elements (Ba, Sr, Cd, Mo, Cu, Ni, Pb and Zn) of SARM 2, SARM 3 and SARM 4 were value assigned during this study to ensure that they comply with the ISO Guide 30 and ISO GUM requirements for traceability and measurement uncertainty. Traceability to the SI units of mass and amount of substance at the highest level of accuracy was established by employing the definitive technique of double isotope dilution ICP-MS, with primary assay standards traceable to the NIST SRM 3100 series and gravimetrically prepared samples. For the first time assigned values with uncertainty statements for these elements in these reference materials were calculated according to the ISO GUM and CITAC/EURACHEM guidelines for expression of the uncertainty of measurement. The uncertainties of the assigned values for all elements were within the target of 5% relative set during the development of the methodology, except for elements in concentrations below 10 mg.kg-1. The ID-ICP-MS results are supported by good comparability with results reported in the literature since 1978, as well as the original certified values published in 1978. The results from this study for all elements in these reference materials have the potential to become new certified values in accordance with the requirements of ISO Guides 34 and 35. This will improve the usefulness of these reference materials to the South African and international geology and mining communities for the purposes of analytical quality control and method validation in exploration and geochemical analysis. Confirmation of the homogeneity and stability of the remaining units of the reference materials is considered necessary to complete the re-certification project. / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

Moderate or Intense Low-oxygen Dilution (MILD) combustion is one of combustion technologies which can improve efficiency and reduce emissions simultaneously. This combustion type is characterised by the highly preheated reactant temperature and the relatively small temperature rise during combustion due to the intense dilution of the reactant mixture. These unique combustion conditions give MILD combustion very attractive features such as high combustion efficiency, reduction of pollutant emissions, attenuation of combustion instabilities and flexibility of the flow field. However, our understanding of MILD combustion is not enough to employ the MILD combustion technology further for modern combustion devices. In this thesis, Direct Numerical Simulation (DNS) has been carried out for turbulent MILD combustion under four MILD and classical premixed conditions. A two-phase strategy is employed in the DNS to include the effect of imperfect mixing between fresh and exhaust gases before intense chemical reactions start. In the simulated instantaneous MILD reaction rate fields, both thin and distributed reaction zones are observed. Thin reaction zones having flamelet like characteristics propagate until colliding with other thin reaction zones to produce distributed reaction zones. Also, the effect of such interacting reaction zones on scalar gradient has to be taken into account in flamelet approaches. Morphological features of MILD reaction zones are investigated by employing Minkowski functionals and shapefinders. Although a few local reaction zones are classified as thin shape, the majority of local reaction zones have pancake or tube-like shapes. The representative scales computed by the shapefinders also show a typical volume where intense reactions appear. Given high temperature and existence of radicals in the diluted reactants, both reaction dominated and flame-propagation dominated regions are locally observed. These two phenomena are closely entangled under a high dilution condition. The favourable conditions for these phenomena are investigated by focusing on scalar fluxes and reaction rate. A conditional Probability Density Function (PDF) is proposed to investigate flamelet/non-flamelet characteristics of MILD combustion. The PDF can be obtained by both numerically and experimentally. The PDF shows that MILD combustion still has the direct relationship between reaction rate and scalar gradient, although the tendency is statistically weak due to the distributed nature of MILD reaction zones. Finally, based on the physical aspects of MILD combustion explained in this work, a representative model reactor for MILD combustion is developed. The model reactor is also used in conjunction with the presumed PDF for a mean and filtered reaction rate closure. The results show a good agreement between the modelled reaction rate and the DNS results.

Objectifs : valider des équations prédictives de la teneur en eau totale (TBW) chez le chien vigile de race beagle par bioimpédancemétrie monofréquence à 50 kHz, en comparaison avec la méthode de référence de dilution au deutérium. Ces équations seront ensuite appliquées à différentes races de chiens afin de vérifier leur validité chez tous les formats de chiens.Animaux : 26 chiens de laboratoire de race beagle et 13 chiens de propriétaires de diverses races. Méthodes : TBW est déterminée par la méthode de référence de dilution à l’eau deutérée et indirectement par l’utilisation d’équations prédictives établies à partir de mesures morphologiques et des mesures électriques (résistance et réactance) obtenues au moyen d’un bioimpédancemètre. Résultats : Les données obtenues chez 16 des 26 beagle a permis d’établir, par régression linéaire, deux équations prédictives de la teneur en eau totale suivantes : TBW1 = –0.019(BL2/R) + –0.199(RC + AC) + 0.996W + 0.081H + 12.31; et TBW2 = 0.048(BL2/R) + –0.144(RC +AC) + 0.777W + 0.066H + 0.031X + 7.47, où AC est le périmètre abdominal, H la hauteur au garrot, BL la longueur du corps, R la résistance, RC le périmètre thoracique , W le poids; and X la réactance. Chez les 10 beagles restants, TBW calculée par les équations TBW1 et TBW2 et celle obtenue par la méthode de dilution sont fortement corrélées (R21 = 0.843 ; R22 = 0.816). La 1ère et la 2ème équations sous-estiment de façon non significative la TBW de respectivement 2.4% and 1.6%. Cependant, l’application de ces formules à des chiens de diverses races ne permet pas l’estimation correcte de la TBW par rapport à la méthode de référence.Conclusion : Cette étude montre qu’il est possible et facile d’utiliser la bioimpédance chez le chien vigile. Deux équations prédictives de la TBW ont été développées et validées chez le beagle mais ne sont pas applicables en l’état à d’autres races de chien. La diversité morphologique des races canines obligent à adapter ces équations en fonction de paramètres de conformation et de format. / Objectives—To develop equations for prediction of total body water (TBW) content in unsedated dogs by combining impedance and morphological variables, and to compare the results of those equations with TBW content determined by deuterium dilution (TBWd). Then to investigate whether these equations were predictive of TBW in various canine breeds.Animals—26 healthy laboratory adult Beagles and 13 healthy adult pet dogs of various breeds.Procedures—TBW content was determined directly by deuterium dilution and indirectly with equations developed from measurements obtained by use of a portable bioelectric impedance device and morphological variables.Results—Impedance and morphological data from 16 of the 26 Beagle dogs were used to determine coefficients for the following 2 equations: TBW1 = –0.019(BL2/R) + –0.199(RC + AC) + 0.996W + 0.081H + 12.31; and TBW2 = 0.048(BL2/R) + –0.144(RC +AC) + 0.777W + 0.066H + 0.031X + 7.47, where AC is abdominal circumference, H is height, BL is body length, R is resistance, RC is rib cage circumference, W is body weight; and X is reactance. Results for TBW1 (R21 = 0.843) and TBW2 (R22 = 0.816) were highly correlated with the TBWd. When the equations were validated with data from the remaining 10 dogs, the respective mean differences between TBWd and TBW1 and TBW2 were 0.17 and 0.11 L, which equated to a nonsignificant underestimation of TBW content by 2.4% and 1.6%, respectively. Applying the two equations to dogs of various breeds showed they are inaccurate to estimate TBW content.Conclusions and Clinical Relevance—Results indicated that impedance and morphological data can be used to accurately estimate TBW content in adult Beagles. This method of estimating TBW content is less expensive and easier to perform than is measurement of TBWd, making it appealing for daily use in veterinary practice. However, the proposed equations need to be modified including morphological parameters such as body size and shape in a first approach. As in humans, morphological-specific equations have to be developed and validated.

O uso de protocolos de diluição bitérmica está aumentando em centros de inseminação artificial e é necessário garantir que as doses de inseminação tenham a mesma qualidade quando comparado com protocolos de diluição isotérmica. Quatro ejaculados de cada 19 reprodutores PIC® foram coletados e distribuídos em split sample em três tratamentos: diluição bitérmica em duas etapas (T1), diluição isotérmica em duas etapas (T2) e diluição isotérmica em uma etapa (T3). A curva de temperatura para os três tratamentos foi feita utilizando um data logger com sensor de temperatura. As doses inseminantes foram preparadas utilizando o diluente BTS e armazenadas a 16ºC e usadas para avaliação dos parâmetros espermáticos através do Sistema CASA e avaliação de morfologia espermática, durante 120 horas. A temperatura das amostras de sêmen submetidas à diluição bitérmica em duas etapas alcançou 24,1ºC durante 120 minutos , enquanto que as amostras submetidas à diluição isotérmica em uma ou duas etapas alcançou 26,8ºC e 27,0ºC, respectivamente. A motilidade total, a progressiva e BCF foram influenciadas (P<0,05) pelo tempo de diluição, mas não pelo protocolo de diluição. A motilidade total e progressiva diminuiu com o tempo de armazenamento (91.0 ± 0.91 para 81.5 ± 1.08 % e 74.0 ± 2.48 para 60.4 ± 2.59% de 24h para 120h, para MOT e PROG, respectivamente) enquanto BCF diferiu entre 24 e 120h (28.6 ± 0.76 e 27.3 ± 0.79 Hz). As seguintes características de motilidade não foram afetadas pelo protocolo de diluição e pelo tempo de armazenamento: DAP, DCL, DSL, VAP, VCL, VSL, STR, LIN, WOB e ALH. Às 72 h de armazenamento, a morfologia espermática não diferiu entre os tratamentos (P>0.05), apresentando uma média geral de 9.2 ± 0.36 defeitos totais. Concluindo, a diluição bitérmica torna o processo de produção de doses inseminantes mais rápido, pois demoraram menos tempo para alcançar a temperatura próxima de armazenamento, sem comprometer a qualidade das doses inseminantes produzidas. / The use of bithermic dilution protocols is increasing in artificial insemination centers, being necessary to guarantee that the quality of insemination doses remain the same when compared to isothermic dilution protocols. Four ejaculates from each one of 19 crossbreed PIC® boars were collected and assigned, in a split sample design, in to three treatments: two step bithermic dilution (T1), two step isothermic dilution (T2) and one step isothermic dilution (T3). Temperature curve for the three treatments was recorded using a temperature sensor data logger. Semen doses prepared with BTS extender were stored at 16°C and were used to evaluate sperm parameters through CASA system and sperm morphology, during 120 h. The temperature in semen samples submitted to a two-step bithermic dilution reached 24.1ºC during 120 min, whereas one or two-step isothermic dilution samples reached 26.8ºC and 27.0ºC, respectively. Total motility, progressive motility and BCF were influenced (P<0.05) by the storage time but not by the dilution procedure. Total and progressive motility reduced throughout the storage time (91.0 ± 0.91 to 81.5 ± 1.08 % and 74.0 ± 2.48 to 60.4 ± 2.59% from 24h to 120h, for MOT and PROG respectively) whereas BCF differed between 24 and 120h (28.6 ± 0.76 and 27.3 ± 0.79 Hz). The following motility traits were neither affected by the dilution procedure nor by the time of storage: DAP, DCL, DSL, VAP, VCL, VSL, STR, LIN, WOB, and ALH. At 72 h of storage, sperm morphology was not different among treatments (P>0.05), showing an overall mean of 9.2 ± 0.36 total defects. In conclusion, the bithermic dilution makes the process of artificial insemination doses production faster by taking less time to reach a temperature close to that of storage, without impairing semen quality.

Liquid wastes discharged from industrial outfalls have been researched for many years in the past. Majority of past studies, initiated in 1960s, were experimental studies mainly focused on basics of discharges such as key geometrical properties. Eventually, more robust experimental studies were performed to measure the mixing properties of effluent discharges with various jet configurations and ambient water conditions. Discharges could be as a means of submerged diffusers or surface channels and receiving water could vary from a homogenous calm ambient to a very complex stratified turbulent cross flow ambient. Depending on the bathymetric and economic situation around an outfall project, submerged discharges are preferred designs for most of ocean outfalls. It is the reason that majority of past studies have evaluated the mixing characteristics of submerged jets. Since early 1990s, the numerical modelling has emerged to support complex fluid mechanic problems. Later in 1990s and early in 2000s, the use of computational fluid dynamic (CFD) tools emerged in predicting the jet properties for the effluent discharges. Since then different numerical models have been developed for different applications. Similar to experimental studies, most of numerical studies have been focused on the submerged dense jet discharges. The current study intends to stay focused on the numerical modelling of such jets too; however, to cover the gaps in the literature. To achieve this, a thorough literature review was performed on the past CFD studies of over past 20 years to better understand what was done and what the gaps are. The results of this thorough review revealed that although there has been a great progress in the CFD studies in the field of effluent discharges, there are some applications that have not been investigated before, yet. It was found that there are some discharge inclinations that were not studied numerically before. Four discharge angles of 60°,75°, 80° and 85° were selected in this study, as previous studies mostly focused on 30° and 45°. The higher inclinations are more suitable for deep water outfalls where terminal rise height of the jet does not attach to the ambient water surface. The numerical model OpenFOAM was used in this study which is based on the Finite Volume Method (FVM) applying LRR turbulence model closure. LRR turbulence models was proved to be a capable choice for effluent discharge modelling. The second gap identified in the comprehensive literature review completed was the submerged dense effluent discharge into shallow water with surface attachment (for both inclined and vertical discharges). There was no previous numerical study of such jets identified. Three different regimes were identified: full submergence, plume contact and centerline impingement regimes (i.e. FSR, PCR and CIR). Key geometrical and dilution properties of these jets at surface contact (Xs, Ss) and return point (Xr, Sr) were extracted numerically and compared to those available from experiments. Two discharge angles (30° and 45°) were investigated based on the available experimental data. Five Reynolds-averaged Navier-Stokes (RANS) turbulence models were examined in this study: realizable k-ε and k-ω SST models (known as two-equation turbulence models), v2f (four equations to model anisotropic behavior) and LRR and SSG turbulence models (known as Reynolds stress models - six equations to model anisotropic behavior). Vertical dense effluent discharges are popular in the design of outfall systems. Vertical jets provide the opportunity to be efficient for a range of ambient currents, where the jet will be pushed away not to fall on itself. This research work investigates worst case scenario in terms of mixing and dilution of such jets: vertical dense effluent discharges with no ambient current and in shallow water where jet impacts the surface. This scenario provides a conservative design criteria for such outfall systems. The numerical modelling of such jets has not been studied before and this research work provides novel, though preliminary, insights in simulations of vertical dense effluent discharges in shallow waters. Turbulent vertical discharges with Froude numbers ranging from 9 to 24 were simulated using a Reynolds stress model (RSM), based on the results from inclined dense discharges to characterize the geometrical (i.e., maximum discharge rise Zm and lateral spread Rsp) and dilution μmin properties of such jets. Three flow regimes were reproduced numerically, based on the experimental data: deep, intermediate and impinging flow regimes.

Given the high salinity, prevailing annual high temperatures, and ultra-oligotrophic conditions in the Red Sea isolation and characterization of important microbial groups thriving in this environment is important in understanding the ecological significance and metabolic capabilities of these communities. By using a high-­throughput cultivation technique in natural seawater amended with minute amounts of nutrients, members of the rare biosphere (PS1), methylotrophic Betaproteobacteria (OM43), and the ubiquitous and abundant SAR11 group (Pelagibacterales), were isolated in pure culture. Phylogenetic analyses of Red Sea isolates along with comparative genomics with close representatives from disparate provinces revealed ecotypes and genomic differentiation among the groups. Firstly, the PS1 alphaproteobacterial clade was found to be present in very low abundance in several metagenomic datasets form divergent environments. While strain RS24 (Red Sea) harbored genomic islands involved in polymer degradation, IMCC14465 (East (Japan) Sea) contained unique genes for degradation of aromatic compounds. Secondly, methylotrophic OM43 bacteria from the Red Sea (F5, G12 and H7) showed higher similarities with KB13 isolate from Hawaii, forming a ‘H-­RS’ (Hawaii-­Red Sea) cluster separate from HTCC2181 (Oregon isolate). HTCC2181 members were shown to prevail in cold, productive coastal environments and had an nqrA-­F system for energy generation by sodium motive force. On the contrary, H-­RS cluster members may be better adapted to warm and oligotrophic environments, and seem to generate energy by using a proton-­translocating NADH:Quinone oxidoreductase (complex I; nuoA-­N subunits). Moreover, F5, G12, and H7 had unique proteins related to resistance to UV, temperature and salinity, in addition to a heavy metal ‘resistance island’ as adaptive traits to cope with the environmental conditions in the Red Sea. Finally, description of the Red Sea Pelagibacterales isolates from the Ia (RS39) and Ib (RS40) subgroups, principally revealed unique putative systems for iron uptake and myo-inositol utilization in RS39, and a potential phosphonates biosynthetic pathway present in RS40. The findings presented here reflect how environments influence the genomic repertoire of microbial communities and shows novel metabolisms and putative pathways as unique adaptive qualities in diverse microbes encompassing from rare to predominant bacterioplankton groups from the Red Sea.

In der Reaktorsicherheitsforschung sind auftriebsgetriebene Strömungen von Relevanz für Störfall-szenarien mit Verdünnung der Borkonzentration und für thermische Schockbelastungen des Reak-tordruckbehälters. In der numerischen Simulation der Strömungen werden neben der Berücksichtigung der Auftriebskräfte Quell- und Korrekturterme in die Bilanzgleichungen für die turbulente Energie und die turbulente Dissipation eingeführt. Es wurden erweiterte Modelle entwickelt, in die zusätzliche Gleichungen für die Turbulenzgrößen turbulenter Massenstrom und Dichtevarianz eingehen. Die Modelle wurden in den CFD-Code ANSYS-CFX implementiert. Die Validierung der Modelle erfolgte an einem speziellen Versuchsaufbau (VeMix-Versuchsanlage), mit Einspeisung von Fluid höherer Dichte in eine Vorlage. Als Kriterien für die Validierung wurde der Umschlag zwischen impulsdominiertem Strömungsregime mit vertikalem Jet oder ein vertikales Absinken bei Dominanz von Dichteeffekten herangezogen sowie lokale Konzentrationsmessungen mit Hilfe eines speziell entwickelten Leitfähigkeits-Gittersensors. Eine Verbesserung der Simulation dichtedominierter Vermischungsprozesse mit den erweiterten Turbulenzmodellen konnte allerdings nicht nachgewiesen werden, da die Unterschiede zwischen den Rechnungen mit verschiedenen Turbulenzmodellen zu gering sind. Andererseits konnte jedoch die Simulation der Stratifikation von Fluiden unterschiedlicher Dichte im kalten Strang einer Reaktoranlage deutlich verbessert werden. Anhand der Nachrechnung von Ver-suchen am geometrisch ähnlichen Reaktor-Strömungsmodell ROCOM wurde gezeigt, dass diese Stratifikation von bedeutendem Einfluss auf die Vermischung und somit letztendlich auch auf die Temperatur- bzw. Borkonzentrationsverteilung innerhalb des Reaktordruckbehälters ist. Sie lässt sich nur korrekt simulieren, wenn ausreichend große Abschnitte des kalten Stranges mit modelliert werden. Somit konnte doch eine bessere Vorhersagegenauigkeit der Simulation der Vermischung erreicht werden. In reactor safety research, buoyancy driven flows are of relevance for boron dilution accidents or pressurised thermal shock scenarios. Concerning the numerical simulation of these flows, besides of the consideration of buoyancy forces, source and correction terms are introduced into the balance equations for the turbulent energy and its dissipation rate. Within the project, extended turbulence models have been developed by introducing additional balance equations for the turbulent quantities turbulent mass flow and density variance. The models have been implemented into the computati-onal fluid dynamics code ANSYS-CFX. The validation of the models was performed against tests at a special experimental set-up, the VeMix facility, were fluid of higher density was injected into a vertical test section filled with lighter fluid. As validation criteria the switching-over between a momentum controlled mixing pattern with a horizontal jet and buoyancy driven mixing with vertical sinking down of the heavier fluid was used. Additionally, measurement data gained from an especially developed conductivity wire mesh sensor were used. However, an improvement of the modelling of buoyancy driven mixing by use of the extended models could not be shown, because the differences between calculations with the different models were not relevant. On the other hand, the modelling of the stratification of fluids with different density in the cold leg of a reactor primary circuit could be significantly improved. It has been shown on calculations of experi-ments at the ROCOM mixing test facility, a scaled model of a real reactor plant, that this stratification is relevant as a boundary condition for the mixing process inside the reactor pressure vessel. It can be correctly simulated only if sufficient large parts of the cold legs are included in the modelling. On this way, an improvement of the accuracy of the prediction of mixing processes was achieved.

<p>    </p> <p>Space has become ever more crowded since the launch of Sputnik. The need for predictions of possible collisions between space objects has only ever grown. The development of space, particularly around Earth, increases the density of space objects and skyrockets the number of close approaches between these objects, called conjunctions. This investigation is conducted in the context of probability dilution, a phenomenon leading to a false negative collision prediction where increasing positional uncertainty decreases the predicted likelihood of a collision. Dilution is investigated along two avenues: how to generate accurate collision predictions in an efficient manner and how to obtain better input data with which to make these predictions. Along the first avenue, this research presents a novel analytical rectan- gular probability of collision expression as well as a variety of new covariance scale factor formulations for maximum collision probability that indicate the maximum possible collision risk for any conjunction. Along the second avenue, this research tests new sensor tasking regimes to mitigate dilution, ultimately showing that while dilution can be reduced, shrink- ing the positional covariance through optimal measurement updates may not be enough to avoid false negatives in orbital conjunctions. </p>

Adolescents in the United States are currently experiencing a mental health crisis. While evidence shows that parents play an important role in shaping the mental health of youth, little has been done to understand how siblings may contribute to the psychological well-being of adolescents. I examine this association through the lenses of social capital and resource dilution perspectives. Social capital theory suggests that siblings may act as an additional source of resources, such as social support, which promote positive mental health. In contrast, resource dilution theory posits that the presence of siblings decreases the availability of parental resource in a way that negatively impacts adolescent psychological well-being. Utilizing a sample of 6,454 American youth from the National Longitudinal Study of Adolescent to Adult Health, I estimate a series of Generalized Linear Models predicting adolescent CES-D depression scores. Results, which are largely consistent with a resource dilution perspective, indicate that having three or more siblings is detrimental to the mental health of adolescents. These results indicate that interventions aimed at improving or protecting adolescent mental health should be targeted at creating networks that provide additional sources of adult social support for children from large families.

Following stringent mandates from environmental regulatory authorities worldwide, various steps are being implemented to ensure clean combustion with minimum emissions, including fuel dilution, mild combustion and additives. Due to the need to understand combustion characteristics in primary applications (engines and turbines) with minimum emissions, the laminar burning velocity of natural gas has been measured with CO2 dilution and a wide range of blends with higher hydrocarbons. And because it has improved anti-knock quality to reduce greenhouse gas emissions (GHGE), the demand for oxygenated gasoline is now worldwide, making a compelling case for determining combustion behavior of oxygenated gasoline doped with hydrogen, ozone and carbon monoxide. The first section of this dissertation discusses dilution of methane with CO2 at elevated pressures, providing insight into comparative laminar burning characteristics in a wide range of equivalence ratios, particularly significant at elevated initial pressure. Utilizing CHEMKIN, a detailed kinetic study has been performed that explains the varying dependence on dilution ratio controlled by initial pressure. The second phase of this work reports the laminar burning velocity measurement of commercial gasoline. A TPRFE surrogate was used here to investigate burning characteristics and to provide detailed kinetic analysis of gasoline doped with additives (hydrogen, carbon monoxide and ozone). A study was also made of the behavior of gasoline with these additives in practical applications like engine and turbines. For this purpose, laminar burning velocity was measured at elevated pressures and temperatures, by varying the concentrations of synthetic EGR, and followed by measuring turbulent burning velocity at two turbulent intensities.