The effects of sulfur dispersing agents (SDAs) in the oxygen pressure leaching of nickel concentrate at medium temperature were investigated. Liquid sulfur-aqueous solution interfacial tensions and liquid sulfur-sulfide mineral contact angles were measured at 140ºC, 690 kPa overpressure by nitrogen, and 1.0 mol/L NiSO₄. The effects of SDAs including lignosulfonate, Quebracho, o-phenylenediamine (OPD), and humic acid were evaluated by the calculation of the work of adhesion in the liquid sulfur-sulfide mineral-aqueous solution systems. It was found that the sulfide mineral surface is sulfophobic at pH from 4.1 to 4.5 due to the hydrolysis of nickel (II) ions to nickel hydroxide and the deposition of nickel hydroxide on the mineral surface. These findings apply to four different sulfide mineral systems, including pentlandite, nickeliferous pyrrhotite, pyrrhotite, and chalcopyrite. Lignosulfonate, Quebracho, and humic acid were found to significantly reduce the work of adhesion indicating they should be effective SDAs. OPD is ineffective in changing the work of adhesion of sulfur on the mineral sulfides indicating that it is not a good candidate for sulfur dispersion. The adsorption behavior of SDAs, including lignosulfonate, Quebracho, OPD, and humic acid on elemental sulfur and on nickel sulfide concentrate was investigated. Lignosulfonate, Quebracho, and humic acid were characterized by their infrared spectra. The charge changes on elemental sulfur surface were characterized by the measurement of the electrokinetic sonic amplitude (ESA) in the absence or presence of SDAs. The adsorption of lignosulfonate on molten sulfur surface was calculated by the Gibbs Equation. The adsorption of lignosulfonate, Quebracho, and humic acid on the nickel concentrate was investigated at ambient temperature. The adsorption of lignosulfonate, Quebracho, and humic acid on the nickel concentrate was found to be monolayer adsorption, which was fitted to the Langmuir adsorption isotherm. Electrostatic interaction and ion-binding are the possible mechanisms for the adsorption of lignosulfonate and humic acid on the nickel concentrate. Quebracho is adsorbed on the nickel concentrate through hydroxyl and sulfonate groups. OPD cannot adsorb on the molten sulfur surface. OPD undergoes chemical change in aqueous solution in the presence of ferric at ambient temperature. Oxygen pressure leaching experiments were performed at 140 or 150ºC under 690 kPa oxygen overpressure. The particle size of the nickel concentrate was found to be an important factor in leaching. During the leaching of nickel concentrate with P₈₀ of 48 µm, the SDAs were believed to be fully degraded before nickel was fully extracted. At most 66% nickel was extracted in the presence of 20 kg/t OPD. Fine grinding (P₈₀ of 10 µm) was sufficient for 99% nickel recovery at low pulp density while at high pulp density, the nickel extraction increased from 95% to 99% with addition of SDAs. Based on the leaching results on a nickel concentrate sample (-44 µm), OPD had the effect of increasing the nickel extraction to about 99%, followed by Quebracho (83%), lignosulfonate (72%), and humic acid (61%). It is suggested that the oxidation product of OPD is effective in solving the sulfur wetting problem in leaching. 97% nickel was recovered in the presence of 5 g/L chloride ion. Chloride ion has an effect to enhance the performance of lignosulfonate under leaching conditions. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

The purpose of this study was to determine if any amount of PAH (Polycyclic aromatic hydrocarbons) was leaching from the paved road surface of road 805 in Jokkmokk municipality. The study was also meant to determine which factors affected the leaching of PAH in the studied area.The surveyed road was divided into eight sections. Groundwater pipes were inserted into drilled holes, three in each section. Samples from soil, water and asphalt were collected from each section and analyzed for its content of PAH. The groundwater level was measured before each sampling. Some soil samples were analyzed for TOC (total organic carbon) and all the water samples for DOC (dissolved organic carbon). The results showed that PAH was leaching in very different amounts. There was a similarity in the amount of coal tar in the road surface and the amount of PAH in most sections. Although in one section the asphalt sample showed low amount of coal tar but high amount of PAH in the soil- and water samples. This anomaly could not be explained - the assumption was that the sampling had been incorrectly handled. The pollution in the surveyed area is assumed to be caused by the road surface and tire wear. Further studies are necessary to determine with certainty how PAH is leaching in different conditions and with different road pavements.

D.Tech. (Extraction Metallurgy) / Please refer to full text to view abstract

M.Tech (Metallurgy) / Nickel in South Africa is scarce. Other than as a by-product from platinum mining, its only source is the Uitkomst Complex, a satelite of the Bushveld Igneous Complex, located between Machadodorp and Barberton and mined by Nkomati Nickel. Pentlandite occurs as the main nickel-bearing mineral, disseminated within a sulfide matrix of pyrrhotite, pyrite and chalcopyrite. Accessories are of chromite and platinum in solid solution with the sulfides. The sulfides are hosted in mainly ultramafic rocks. The presence of talc is of particular nuisance. Head grade is in the decline, from earlier 0.7 to more recently 0.3% or even lower. Standard froth flotation yields a concentrate of 7 – 9% nickel at a recovery of up to 70%. A higher nickel recovery from such low – grade feed stock would be desirable. To achieve these two methods were investigated and reported in the following:  Non-oxidative leaching as an alternative to flotation, using strong hydrochloric and sulfuric acid and also aqueous ammonia solutions at various liquid-to-solid ratios. Only the degree of nickel dissolution over time at room temperature was studied and no attempt was made to recover the dissolved metal from solution.  Froth flotation after pre-treatment with microwaves at various power levels and over various periods of time of irradiation. It was surmised that a certain amount of inter-granular cracking could thus be achieved that would improve the flotation behavior in respect of grade and recovery. An extensive literature study, in particular, of the nature of microwaves, their interaction with matter and possible metallurgical benefits derived as a consequence of such interaction, forms part of the investigation and is reported in detail. A lot of theoretical and experimental work has been done in this respect, although the obtained results were not conclusive.

M.Tech. (Chemical Engineering) / Please refer to full text to view abstract

M.Tech. / The study presented, investigated the acid leaching behavior of calcines emanating from conventional roasting and microwave assisted roasting of sulphide ores. The aim was to investigate a possible change in the mineral composition of the calcine produced and to investigate the leaching behavior of the calcine produced by conventional and microwave assisted roasting. Two sulphide concentrates were received, pyrite concentrate from OTJIHASE concentrator and sphalerite concentrate from ZINCOR. The mineralogical study was done using the XRD (PANalytical X-PertPro X-Ray diffractometer) to determine the mineral composition of the concentrate and the head grade of each concentrate was determined with an Atomic Absorption Spectrometry (AAS) machine for copper, iron and zinc. The concentrates were wet screened at 500, 355, 212, 150, 106 and 75 μm screens for size distribution and for the purpose of the study it was required that 80% of concentrate should pass the 75 μm screen since after roasting, the calcine obtained were to be acid leached. Conventional roasting was carried out at temperatures of 500oC, 700oC, 850oC and 1000oC at durations of 5min, 10min, 20min, 30min, 1hour and 2hours, while microwave assisted roasting carried out at powers of 200W, 400W, 600W, 800W and time intervals of 3s, 10s, 30s, 30min and 1hour

Once current nuclear reactor operation ceases in the U.K. there will be an estimated 99,000 tonnes of irradiated nuclear graphite waste which may account for up to 30% of any future UK geological ILW disposal facility [1]. In order to make informed decisions of how best to dispose of such large volumes of irradiated graphite (I-graphite) within the UK nuclear programme, it is necessary to understand the nature and migration of isotopes present within the graphite structure. I-graphite has a combination of short and long term isotopes such as 14C, 3H and 36Cl, how these behave prior to and during disposal is of great concern to scientific and regulatory bodies when evaluating present decommissioning options. Various proposed decontamination and immobilisation treatments within the EU Euroatom FP7 CARBOWASTE program have been explored [2, 3]. Experiments have been carried out on UK irradiated British Experimental Pile Zero and Magnox Wylfa graphite in order to remove isotopic content prior to long term storage and to assess the long term leachability of isotopes. Several leaching conditions have been developed to remove 3H and 14C from the irradiated graphite using oxidising and various acidic environments and show mobility of 3H and 14C. Leaching analysis obtained from this research and differences observed under varying leaching conditions will be discussed. Thermal analysis of the samples pre and post leaching has been performed to quantify and validate the 14C and 3H inventory. Finally the research objectives address differences in leachability in the graphite to that of structural and operational variation of the material. Techniques including X-ray Tomography, Scanning Electron Microscopy, Autoradiography and Raman spectroscopy have been examined and show a significant differences in microstructure, isotope distribution and location depending of irradiation history, temperature and graphite source. Ultimately the suitability of the developed chemical treatments will be discussed as whether chemical treatment is a viable option prior to irradiated graphite long term disposal.

The recovery of mineral from ore in the heap leaching process requires the mineral to come into contact with the leaching solution. However, heap hydrology is prone to non-uniform behaviour due to the inhomogeneity of the ore particles and the heap structure. The primary aim of this thesis was therefore to develop a magnetic resonance imaging (MRI) technique which would allow for the novel non-invasive imaging of the liquid hold-up in representative laboratory-scale heap leaching systems. The ferro- and paramagnetic species in the ore were found to cause significant distortions in frequency encoded MRI acquisitions. These distortions were mitigated through the application of single point imaging techniques. Comparison with equivalent X-ray CT acquisitions, which are immune to magnetic susceptibility distortions, confirmed the accuracy of the single point acquisitions. Spin echo single point imaging (SESPI) was demonstrated to be more robust than the simple single point imaging (SPI) technique because the effect of $\textit{T}$$_{2}$ weighting on the MRI signal was less significant than that of $\textit{T}$$_{2}$*. Mapping of the gas, liquid and solid distributions in unsaturated leaching columns using SESPI allowed for the quantification of the hold-up and voidage values. These compared favourably to gravimetric measurements and literature values, thereby confirming their validity. Novel measurement of the liquid film thickness and the interfacial areas between the three phases was achieved and insight into the liquid behaviour was obtained through different flow rate experiments as well as MRI tracer experiments. Drip irrigation of the ore was considered for beds of large, fine and agglomerated ore. Liquid distribution in the fine ore closely resembled that of irrigation of clay soils whereas flow through the large ore was gravity dominated. Slumping of the agglomerated ore caused permanent limitation of the liquid distribution and the effect of flow rate changes was observed to be limited to the region below the irrigation point. In both the column and drip irrigation experiments, increases in the liquid flow rate caused small increases in the liquid hold-up in the form of new, relatively thicker rivulets, thereby improving the liquid-solid interfacial area. However it did not affect capillary held liquid volume so the effect of flow rate changes decreased as the lateral distance from the irrigation point increased. Finally, X-ray CT images of a long term ferric leach were analysed to assess the factors affecting the mineral leaching. Proximity of the mineral to the ore surface was found to be the critical factor, as only mineral located within 2 mm of the surface was recovered, though liquid distribution effects were also observed.

The discharge of a landfill leachate to a receiving water body can cause a serious pollution problem. One component of leachate that can have a severe impact on a receiving water body is ammonia and its oxidized form, nitrate. This study investigated the biological treatibility of a high ammonia leachate, with specific regard to nitriification and denitrification. A continuous-feed, single sludge denitrification system with recycle was used. Leachate ammonia concentrations of up to 288 mg/L-N were reduced to less than 1 mg/L. The ammonia was removed by nitrification and bacterial uptake. About 25% of the incoming ammonia was taken up by the bacteria in the anoxic reactor; the rest was subsequently nitrified in the aerobic reactor. The nitrates produced in the aerobic reactor were recycled back to the anoxic reactor to undergo denitrification. Glucose was added directly to the anoxic reactor to aid denitrification. The degree of denitrification was dependent on the glucose loading to the anoxic reactor; however, 100% denitrification was achieved on several occasions. The influent leachate COD removal was 20%; however after the addition of glucose to the system, a mean COD removal of 74% was obtained. Of the COD removed across the system, 85% was used in the anoxic reactor for denitrification, and the remaining 15% was used by the heterotrophs in the aerobic reactor. The four metals monitored regularly, zinc, manganese, nickel and iron were removed by the biomass, but not to the same extent During the latter part of the study, the system was first spiked with manganese, and then - zinc, to try and induce an inhibitory effect on the nitrification process. The manganese had no detectable effect on the system. However, total zinc (>95% soluble) levels of between 14.9 and 17.6 mg/L caused substantial inhibition of the nitrification process, resulting in approximately 70 mg/L ammonia in the effluent (feed = 216 mg/L). This inhibition was also evident from the lower percent nitrification values and the unit nitrification rates. This high influent zinc concentration also caused deflocculation, resulting in the loss of significant quantities of biomass with the effluent. The high zinc concentrations also inhibited the denitrifiers, resulting in a decrease in the ammonia uptake, as well as an increase in the COD (used)/Nitrate+Nitrite (NOT) (reduced) ratios in the anoxic reactor. The zinc levels were then lowered to allow the system to return to normal; after this state had been reached, the influent total zinc (>95% soluble) levels were again increased up to 19.5 mg/L. This concentration of zinc did not result in any ammonia appearing in the effluent; thus, it is possible that the bacteria had acclimatized to these high influent zinc concentrations. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate

Water table control by subsurface drainage has been shown to affect leaching losses of nitrate-nitrogen: a concern both for economic use of fertilizer, and for maintenance of water quality. The effect of water table height on leaching of NO₃⁻-N was investigated in this study in nineteen 15cm x 100cm undisturbed cores of silty clay loam. The experiment simulated fertilization followed by rainfall, then rapid water table rise and fall, under conditions similiar to those experienced in the early spring in the Lower Fraser Valley. In the first part of the experiment, a concentrated solution of KNO₃ and KG (equivalent to 35 kg/ha of N and 22 kg/ha of Cl) was applied to the columns, followed by intermittent leaching with distilled water. Leachate from two depths in each column was collected before and after a period of static water table, and analyzed for NO₃⁻, No₂⁻, NH₄⁺, and Cl⁻. This procedure was repeated without nutrient addition in the second part of the experiment. Chloride was used an inert tracer to follow anion movement and retention within the columns. There was no significant difference in the leachate NO₃⁻ concentration or leachate N/CI ratio from any of the four water table heights tested (15, 35, 55, and 75 cm above drain depth). The NO₃⁻ concentrations and N/CI ratios decreased with depth in the soil columns, indicating removal of N from the percolating soil solution, either by denitrification or immobilization. The variability in leachate concentrations among all columns was very high (eg. for a typical sample time, NO₃⁻-N ranged from 0.01 to 15.72 mg/L, and Cl⁻ ranged from 4.8 to 14.5 mg/L), as was the variability in constant head satiated hydraulic conductivities (range: 1 to 1468 cm/day; CV = 181%), and drainable porosity (range: 2.7 to 10.4%; CV = 39%). Cross sections of columns leached with 1% methylene blue solution did not reveal differences in patterns of water transmission between low and high conductivity columns. Indications were that penetration of dye was greater in columns with higher conductivities, and that preferential flow occurred in all columns examined. Leachate concentrations and N/CI ratios correlated significantly with hydraulic conductivity: Spearman's correlation coefficients were always > 0.8 for samples obtained from the bottom of the columns. However, even when the conductivity was included as a covariate in an analysis of covariance, there was no significant effect of water table height on nitrate leaching. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate