The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

Following the promulgation of new permissible respirable dust standards by MSHA in 2014, new alternative rock dusts were created that combined the advantages of current industry applications while potentially reducing miner exposure to respirable dust. Research was performed to compare the explosion suppressing and ejection characteristics of three new types of rock dust to existing rock dust types. Explosion suppression tests were conducted in a 38-L chamber where pressures were recorded. Angle of ejection tests were conducted using a high explosive shock tube and high speed photography to determine angle of ejection and lift velocity. A comprehensive comparison of the results of these tests shows that these newly developed dusts have improved results for flame suppression and ejection when compared to typical wet dust applications.

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Mark E. Casada / Ronaldo G. Maghirang / The United States grain handling infrastructure is facing major challenges to meet worldwide customer demands for wholesome, quality, and safe grains and oilseeds for food and feed. Several challenges are maintaining grain quality during handling; reducing dust emissions for safety and health issues; growing shift from commodity-based to specialty (trait-specific) markets; proliferation of genetically modified crops for food, feed, fuel, pharmaceutical, and industrial uses; and threats from biological and chemical attacks. This study was conducted to characterize the quality of grain and feed during bucket elevator handling to meet customer demand for high quality and safe products. Specific objectives were to (1) determine the effect of repeated handling on the quality of feed pellets and corn; (2) characterize the dust generated during corn and wheat handling; (3) develop and evaluate particle models for simulating the flow of grain during elevator handling; and (4) accurately simulate grain commingling in elevator boots with discrete element method (DEM). Experiments were conducted at the research elevator of the USDA-ARS Center for Grain and Animal Health Research (CGAHR) to determine the effect of repeated handling on the quality of corn-based feed pellets and corn. Repeated handling did not significantly influence the durability indices of feed pellets and corn. The feed pellets, however, had significantly greater breakage (3.83% per transfer) than the corn (0.382% per transfer). The mass of particulate matter < 125 μm was less for feed pellets than for corn. These corn-based feed pellets can be an alternative to corn in view of their handling characteristics. Another series of experiments was conducted in the same elevator to characterize the dust generated during corn and wheat handling. Dust samples were collected from the lower and upper ducts upstream of the cyclones in the elevator. Handling corn produced more than twice as much total dust than handling wheat (185 g/t vs. 64.6 g/t). Analysis of dust samples with a laser diffraction analyzer showed that the corn samples produced smaller dust particles, and a greater proportion of small particles, than the wheat samples. Published data on material and interaction properties of selected grains and oilseeds that are relevant to DEM modeling were reviewed. Using these material and interaction properties and soybeans as the test material, the DEM fundamentals were validated by modeling the flow of soybean during handling with a commercial software package (EDEM). Soybean kernels were simulated with single- and multi-sphere particle shapes. A single-sphere particle model best simulated soybean kernels in the bulk property tests. The best particle model had a particle coefficient of restitution of 0.6; particle static friction of 0.45 for soybean-soybean contact (0.30 for soybean-steel interaction); particle rolling friction of 0.05; normal particle size distribution with standard deviation factor of 0.4; and particle shear modulus of 1.04 MPa. The single-sphere particle model for soybeans was implemented in EDEM to simulate grain commingling in a pilot-scale bucket elevator boot using 3D and quasi-2D models. Pilot-scale boot experiments of soybean commingling were performed to validate these models. Commingling was initially simulated with a full 3D model. Of the four quasi-2D boot models with reduced control volumes (4d, 5d, 6d, and 7d; i.e., control volume widths from 4 to 7 times the mean particle diameter) considered, the quasi-2D (6d) model predictions best matched those of the initial 3D model. Introduction of realistic vibration motion during the onset of clear soybeans improved the prediction capability of the quasi-2D (6d) model. The physics of the model was refined by accounting for the initial surge of particles and reducing the gap between the bucket cups and the boot wall. Inclusion of the particle surge flow and reduced gap gave the best predictions of commingling of all the tested models. This study showed that grain commingling in a bucket elevator boot system can be simulated in 3D and quasi-2D DEM models and gave results that generally agreed with experimental data. The quasi-2D (6d) models reduced simulation run time by 29% compared to the 3D model. Results of this study will be used to accurately predict impurity levels and improve grain handling, which can help farmers and grain handlers reduce costs during transport and export of grains and make the U.S. grain more competitive in the world market.

Rock dust has been historically applied to mitigate the coal dust explosion in either dry or wet form. Dry rock dust performs best in inerting the potential coal dust explosion due to the greatest dispersive properties. However, it undesirably exposes underground coal miners to respirable dust particles which imposes a severe health danger. Wet dust application is able to significantly reduce the floatable dust particles but another problem associated with caking is predominant. Caking phenomenon is usually used to describe the change of free-flowing bulk solids into agglomerated chunks. Unfortunately, the environmental conditions of an underground mine have the potential to cause caking of the rock dust, especially for wet dust application, which reduces the dispersive characteristics needed for effective explosion mitigation and is also the focus of the present study. Surface modification of rock dust to generate a hydrophobic surface is believed to alleviate the caking problem by allowing instant water drainage and eliminating the formation of water and solid bridges. Surface modification of rock dust was evaluated in the present study with a series of potential modifying reagents including oleic acid, sodium oleate and stearic acid. The modification efficiency in terms of measured contact angle, zeta potential and dispersibility values was investigated with sodium oleate generating the best modification effect. Dispersants were investigated as well in the present work aiming to further increase the particles dispersibility in addition to the excellent hydrophobization effect generated by sodium oleate. However, dispersibility test results indicated that the adsorption of dispersant and sodium oleate was competitive. The preferential adsorption of dispersants over oleate deteriorated the surface hydrophobicity of particles and the dispersibility was decreased as a result. As anticipated, dry rock dust always provided the best dispersibility with almost 95% of the dust remaining in suspension at a dispersion time of 30 seconds. The percentage dust dispersion values of sodium oleate treated rock dust was increased to as high as 71% in contrast to 47% of untreated wet rock dust and the explosion potential was correspondingly reduced by almost 83%. The effect of sodium oleate was further studied as a function of reagent concentration to determine the optimum application condition. The dispersibility of rock dust particles was initially increased until the application of 0.1 wt% sodium oleate, after which it slightly decreased up to 0.5 wt% oleate. When the concentration was above 0.5 wt%, the dispersibility of dust particles substantially decreased to a value lower than the value obtained for regular wet dust. The optimum sodium oleate concentration was thus determined at approximately 0.1 by weight of rock dust particles with a corresponding contact angle of around 110 degrees. The pivotal of rock dust modification efficiency is its long-term stability which can be corroborated by irreversible chemical adsorption rather than the short-term physical adsorption. Therefore, the fundamental adsorption mechanism of sodium oleate on rock dust surface was continuously investigated by means of using surface tension measurements, FTIR, Thermogravimetric, SEM analyses and constructing the species distribution diagram. Based on the surface tension measurements and calculated apparent surface area occupied by per oleate molecule, the monolayer adsorption of oleate on dust surface was proposed with oleate concentration falling between 0.1-0.15 wt% which guarantees the long-term surface modification efficiency. Calcium oleate started precipitating out of bulk solution and depositing on the dust surface when the oleate concentration was above 0.15 wt% which became more predominant under high oleate concentration. Super hydrophobic particles together with nucleated calcium oleate nanoparticles tend to increase particles aggregation significantly through attractive hydrophobic particle-particle interactive force, which renders the particles more agglomerated instead of dispersed. Systematic and economic evaluation of the wet form rock dusting process in underground coal mine applications was conducted at the end to determine the safety effects, potential benefits and improvement for future implementation. Suggestions for future work were given as well to shed light on the dusting process together with rock dust surface chemistry modification.

Farmworkers and their families may experience increased levels of agricultural pesticides in their homes due to both (1) take-home/soil track-in on shoes, clothes and skin, and (2) air infiltration from nearby agriculture fields via agricultural pesticide drift in the vapor phase or adhered to resuspended soil particles. This dissertation estimates the relative contributions o the take-home/soil track-in and air infiltration pathways of agricultural pesticides into homes, as well as identifies the risk factors for increased in-home agricultural pesticide levels for farmworkers and their families living near agriculture fields. Samples of outdoor air, yard soil, and house dust from 21 farmworkers' homes in Yuma County, Arizona were collected and analyzed for a suite of agricultural pesticides. To capture household information, such as behaviors, demographics, and housing structure, a participant questionnaire was administered at the time of the sampling. A pesticide transport model was developed, evaluated, and applied to quantify relative contributions of the air infiltration and the take-home/soil track-in pathways of agricultural pesticides into the house dust of the farmworkers' homes. To explore a wide-range of potential risk factors for increased agricultural pesticide levels in the homes, traditional statistical methods and Classification and Regression Tree (CART) analyses were used. The results of this study, found that the air infiltration pathway contributes to over 90% of some agricultural pesticides in the house dust found in the farmworkers' homes. In addition, among the influential risk factors for increased in-home agricultural pesticide levels was the home being a closer distance to an agricultural field, as well as the home having carpeted floors, more farmworkers per square footage of the home, and less months of heating and cooling the home. It is suggested that future intervention efforts to reduce in-home agricultural pesticide levels put more emphasis on targeting the air infiltration pathway, and take into consideration relevant risk factors for increased pesticide levels in the home.

The threshold friction velocities of potential dust sources in the US Southwest were measured in the field using a Portable Wind Tunnel, which is based on the Desert Research Institute's Portable In-Situ Wind Erosion Laboratory (PI-SWERL). A mix of both disturbed and undisturbed surfaces were included in this study. It was found that disturbed surfaces, such as those at the Iron King Mine tailings site, which is part of the EPA's Superfund program and contains surface concentrations of arsenic and lead reaching as high as 0.5% (w/w), had lower threshold friction velocities (0.32 m s⁻¹ to 0.40 m s⁻¹) in comparison to those of undisturbed surfaces (0.48 to 0.61 m s⁻¹). Surface characteristics, such as particle size distribution, had effects on the threshold friction velocity (smaller grain sized distributions resulted in lower threshold friction velocities). Overall, the threshold friction velocities of disturbed surfaces were within the range of natural wind conditions, indicating that surfaces disturbed by human activity are more prone to causing windblown dust.

The research presented in this thesis investigates several aspects of the evolutionary processes of T Tauri stars and their accompanying circumstellar disks. The versatile Monte Carlo radiation transfer technique, with several modifications and extensions, is used throughout to study the structure and constitution of both the circumstellar disk at large and the changeable and dynamic inner disk regions. The photopolarimetric variability of AA Tau in the Taurus star forming region is modelled in a fully 3D manner. I find that a magnetospherically induced warp in the accretion disk at roughly the stellar co-rotation radius occults the star and reproduces both the observed period and duration and the required brightness and polarisation variations. The model SEDs allow estimates of the disk mass, radial extent and large- scale density structure. Using a modified SPH code we find the interaction of a 5.2kG stellar magnetic field inclined at 30° to the rotation axis with the disk, is capable of generating a warp of the size and shape needed to reproduce the observed variations. Modified Monte Carlo models capable of incorporating any number of dust particle grain sizes distributed throughout the disk in vertical and radial distributions, in a fully 3D manner are presented. This versatile tool allows the investigation of evolutionary processes such as dust settling and grain growth predicted to occur in T Tauri sources as they age. A Mie Scattering code was also adapted and incorporated into the models allowing us to determine optical properties for dust grains and distributions of any size. I present model SEDs fitting the latest publicly available IR data for a number of T Tauri sources and reproduce the observational effects of dust grain growth and settling with a high degree of success. The fits are by no means unique and the structural parameters required to produce them are quite uncertain but it is possible to determine useful information on the larger scale structure and bulk constituents of these disks. A fully 3D non-LTE radiative transfer code using CO line emissions as a tracer of the disk dynamics and able to simulate any disk structure or geometry, either analytical or imported from a hydrodynamic simulation, is presented. Signatures attributed to the disk dynamics and spiral density structure derived from hydrodynamic simulations of massive disks are investigated and resolved. Line profiles and contour maps of the velocity of the emitting material are generated and compared with observations.

<p>The production of ferrochromium alloys at Vargön Alloys AB contributes to formation of unwanted ferrochromium dust, which contains toxic Cr(VI). The dust is since summer 2005 treated with an iron-sulphate solution to reduce Cr(VI) to the non-toxic Cr(III). A year later the treatment technique was improved and disposal occurs in cells on the landfill. The cells can be up to 300 m3 and the edges can be made out of fro example concrete. Tests are conducted on the treated dust when it is disposed. The analyses show low contents of Cr(VI), which indicates that the reduction is successful. Analyses of leakage water from a small scale cell however showed an increasing content of Cr(VI) and pH under the first two months.</p><p>This thesis has evaluated the new treatment method. An investigation was conducted to determine if the same changes have occurred in the full scale cells. Half of the 18 collected samples from the disposed dust showed high or very high contents of Cr(VI). The other half had a almost no detectable content. pH was over 12. No correlation between Cr(VI)-content and pH, conductivity, age or water content in the disposed dust could be shown.</p><p>An experiment was also performed in small scale to reduce the number of influencing parameters. The results showed that if the dust has access to oxygen the Cr(VI) content increases during the first days from a few mg/kg dry substance to over 20 mg/kg dry substance, a level which was maintained during the rest of the experiment period. The content of Cr(VI) was almost constant at 4 mg/kg dry substance when oxygen was eliminated during the whole experiment period. When the water content was below 5 %, the content of chromium did not increase more.</p><p>Since almost all newly created Cr(VI) is reduced to Cr(III) by the addition of ferrous sulphate, recreation of Cr(VI) occurs. Today there is now possibility to follow the changes in the dust from untreated to after disposed. The addition of iron-sulphate is based upon an average Cr(VI) content in the dust and the variation of disposal occasions can be significant. To determine if the increase in Cr(VI) is caused of an incorrect addition of solution a smaller disposal cell can be constructed. The initial content of Cr(VI) can be controlled and the dust can be examined during the time it ages. If the dosage could be improved the addition can be optimized. It is also important to minimize the infiltration and accelerate the drying of the slurry since the Cr(VI) content can increase the as long as the water content is high the Cr(VI) content can increase.</p> / <p>Vid produktionen av ferrolegeringar på Vargön Alloys AB bildas ferrokromstoft som en oönskad biprodukt, vilken innehåller hälsofarligt sexvärt krom. Sedan sommaren 2005 behandlas stoftet med järnsulfatlösning för att reducera Cr(VI) till mindre hälsofarliga Cr(III). Ett år senare förbättrades tekniken och deponering sker sedan dess i iordningställda celler på deponin. Cellerna rymmer cirka 300 m3 och har kanter av bland annat betongstöd. Provtagning sker på det behandlade stoftet i samband med deponeringen. Analyserna visar mycket låga halter av Cr(VI), vilket tyder på att reduktionen lyckas. Analyser av lakvatten från en småskalig provcell visade däremot att Cr(VI)-halter och pH ökade under de två första månaderna.</p><p>Detta arbete har utvärderat den nya behandlingsmetoden. Undersökning huruvida samma förändring har skett i fullskaliga celler har utförts. Utav de 18 prov som inhämtades från det deponerade stoftet visade hälften på höga eller mycket höga Cr(VI)-halter och resterande hade nästan omätbara halter. I det deponerade stoftet var pH genomgående drygt 12. Inget samband mellan Cr(VI)-halt och pH, konduktivitet, ålder eller vatteninnehåll i deponerat stoft erhölls.</p><p>Försök utfördes även i liten skala i för att minska antalet påverkande parametrar. Utan tillgång till syre var Cr(VI)-halten cirka 4 mg/kg torrsubstans under hela försöksperioden. Försöken visade att om stoftet har tillgång till syre ökar Cr(VI) från några mg/kg torrsubstans till dryga 20 mg/kg torrsubstans efter bara några dagar. Halten förblev konstant under resten av försökstiden. Ett samband som sågs var att när Cr(VI)- halten har stagnerat är vatteninnehållet i provet under 5 %.</p><p>Eftersom nästan allt krom reduceras till Cr(III) vid tillsatsen av järnsulfatlösning har det nyreducerade Cr(VI) återbildats. I nuläget går det inte att följa hur stoftet förändras från obehandlat och vad som händer när det åldras efter att det har behandlats och deponerats. Tillsatsen av järnsulfat doseras efter en medelhalt Cr(VI)-innehåll i stoftet och variationen i Cr(VI)-halt mellan deponeringstillfällen kan vara stor. För att avgöra om ökningen av Cr(VI) beror på felaktig tillsatts av järnsulfatlösning kan en mindre deponeringscell anläggas. Ingående Cr(VI)-halter kan kontrolleras och stoftet kan undersökas medan det åldras på deponin. Visar det sig att dosering behöver förbättras kan tillsatsen optimeras. Det är även viktigt att minska infiltrationen samt påskynda torkningen av slurryn eftersom så länge vattenhalten är hög kan Cr(VI)-halterna öka.</p>

The IceCube Neutrino Telescope is designed to detect high energy neutrinos with a large array of photomultiplier tubes placed deep within the Antarctic ice. The way that light propagates through the ice needs to be modelled accurately to enable the paths of charged particles to be reconstructed from the distribution of their Cerenkov radiation. Light travelling through even the purest of ice will undergo scattering and absorption processes, however the ice in which IceCube is embedded has optical properties that vary significantly with depth which need to be accurately modelled. Currently, simulation of the muon background using the current ice model is unable to fully replicate experimental data. In this thesis we investigate a potential method of improving on the current generation of ice models. We introduce thin, highly absorbing layers into the current description of the detection medium and investigate the effect on the simulation of muon tracks in IceCube. We find that better agreement between simulation and data can be seen in the occupancy of optical modules, through the introduction of such absorptive layers into the existing ice layers.