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Over the last 100 Years, the cyanidation process has been the most popular method for recovering gold from its ores. Despite this, there are still efforts to improve the efficiency of the process, particularly as ores become more difficult to treat. Many investigators have studied the cyanidation process, although a large proportion of these studies have obtained contradictory results. This thesis presents a kinetic and electrochemical study of the leaching of gold in cyanide solutions, and emphasis is placed on rationalising the conflicting results which have been published in the past.The leaching rate of gold was measured using a rotating electrochemical quartz crystal microbalance, an instrument which allows the simultaneous measurement of electrochemical data and mass changes at the solid-solution interface in real time. A proportion of this project was devoted to the on-going design of this instrument, and a number of modifications are discussed in detail. Initially, the leaching of gold in cyanide solutions was investigated under conditions of high purity. Under these conditions, it was found that the gold surface is blocked by a passive film, presumably AuCN. The presence of such a film results in the reaction being chemically controlled, and under typical cyanidation conditions (4 mM cyanide, pH 10.0), the rate of dissolution is very low. These kinetic results were supported by complimentary electrochemical studies, which showed that gold is passive in the potential region where cyanidation occurs.The second part of this thesis presents a study of the effect of system purity on the leaching of gold in cyanide solutions. Solution phase purity was investigated by adding controlled amounts of lead or silver to the leach solutions. It was found that in the presence of low concentrations of lead, the dissolution of gold in 20 mM cyanide solutions was oxygen ++ / diffusion controlled (as compared to chemical control for gold in the absence of lead). However, high concentrations of lead were found to be detrimental to the leaching process. It is believed that the role of lead is to modify the surface by cementation, hence reducing the effect of the passive film. Silver was also found to be effective at reducing passivation, and the role of silver believed to be similar to that of lead. It was found that unlike lead, high concentrations of silver are not detrimental to the dissolution of gold in cyanide solutions.Solid phase purity was also found to be important in the leaching of gold, and it was found that the leaching of a gold sample which contains 1 % silver is diffusion controlled. This finding is important from an industrial viewpoint, as most native gold contains some silver. Consequently, attempts were made to rationalise the leaching of gold/silver with current plant practice. Discussion on the effect of cyanide and oxygen concentrations, temperature and lead addition is presented.

Approximately 70% of the western world's known nickel reserves are contained in laterite ores, but only 30% of the world's nickel production comes from these ores. This is due to the lack of economically viable technology to extract the nickel from these ores. However, recent advances in pressure acid leaching technology have resulted in new commercial attempts to extract nickel and its valuable by-product, cobalt, from laterite ores. The commissioning of three nickel laterite projects in Western Australia in the late 1990s represents the first of these new generation nickel operations, with several other projects; in Australia and overseas, in various stages of development. Unfortunately, several technical issues have hindered full production in these new refineries. Some of these problems are directly attributable to the mixer-settler contactors used in the solvent extraction process. This has highlighted a need to develop alternative contactors for industrial use. Electrostatic Pseudo Liquid Membrane (ESPLIM) is an alternative, novel technique to conduct the solvent extraction process. It combines the basic principles of solvent extraction, liquid membrane and electrostatic dispersion into a simple, compact reactor that utilises many advantages of each technique. The aim of this study w as to develop a method of extracting and separating cobalt from an acidic nickel laterite leach solution using ESPLIM. Bench scale tests using synthetic and actual leach solutions have shown that: the design and construction materials of the baffle plate and electrodes have a significant effect on the performance of the reactor; an AC power supply provided better droplet dispersion than a DC power supply; an increase in the applied electric field strength above a critical value resulted in a decrease in the aqueous droplet size and an increase in residence tune. / These effects increased the extraction efficiency and the concentration of the loaded strip solution. However, further increases in applied electric field strength decreased efficiency due to excessive levels of swelling and leakage; the known extraction isotherms for cobalt and nickel apply in the ESPLIM technique; salts of soluble organic acids influence extraction efficiency by changing the aqueous pH and interfacial tension; the use of ammonia was found to be effective as a replacement for salts of soluble organic acids; the ESPLIM reactor can cope with large changes in the flow rates of both feed and strip solutions. However, an increase in the feed flow rate should be accompanied by a relative increase in the ship flow rate to maintain high extraction efficiencies; the baffle design has a significant impact on the levels of swelling and leakage; provided the electrostatic field strength is maintained and flow rates are increased proportionately to the size of the reactor, no significant scale-up issues were observed, indicating that the data generated in bench scale studies could be applied to plant scale contactors. The optimum conditions, devised as a result of this investigation, to extract cobalt from an acidic nickel laterite leach solution using the ESPLIM technique are as follows: an applied electric field strength of 5.5 kV/cm. a raffinate pH of 5.5, a solvent containing 10% Cyanex 272 with 5% TBP in Solvent HF diluent, a feed to strip flow ratio of approximately 5 and a 1 M H[subscript]2S0[subscript]4 strip solution. At these conditions, almost complete cobalt extraction is achieved after only two extraction stages. A comparable extraction using conventional mixer-settlers could only be achieved after five stages.

The aim of this project was to identify a suitable solution to the problem of landfill leachate at the North Katoomba landfill site. Options were affected by a range of constraints including economics, location and the intrusion of ground water into the landfill. The initial goal was to contain and treat the leachate on site, with the eventual target to discharge into the nearest receiving waters. A constructed wetland option was devised and researched, involving identification of the major pollutants contained within the leachate, developing a concept design and estimating the likely removal efficiencies expected. Investigations identified the primary pollution parameters as microbial and nutrients. Metals were found to be low in concentration although the wetland has the capacity to deal with these pollutants should they become part of the pollution plume. A bench scale constructed wetland system was developed to give an indication of the removal efficiencies. The results suggest that a constructed wetland system would be appropriate for treating landfill leachate at the North Katoomba site. It is recommended that a constructed wetland be established in the field to determine the long term treatment prospects and the potential management problems in a practical application. / Master of Science (Hons)

Acid leaching of different natural chrysocolla samples under ambient conditions demonstrated that the chemical and chrystallographic inhomogenity significantly affects the rate and that it is virtually impossible to use the mineral as a model for the kinetics of hydrometallurgical processing of copper ores.Dissolution experiments, stability diagrams,and X-ray powder diffraction studies are undertaken and studied in this research and results are given.It is found that a complete solid solution series exists in Nature with most tungstenian wulfenites and molybdenum stolzites containing a range of compositions. The first occurrence of a molybdenum stolzite from Broken Hill, Australia, which also contains small amounts of chromium is noted.Raman microprobe spectroscopy has proven to be a very quick and effective non-destructive method for semi-quantitative analysis of the wulfenite-stolzite and powellite-scheelite solid-solution series and in detecting very small amounts of substituted chromate in wulfenite, stolzite and anglesite / Doctor of Philosophy (PhD)

This thesis has developed a suite of compound specific stable isotope tools to monitor landfill leachate and identify the infiltration of leachate to ground water and surface water. These tools have the power to indicate the fractional contribution multiple discrete sources of pollution are making to a single location. This journey began by developing two solid phase extraction (SPE) methods to extract non-polar and polar organic compounds from leachate with minimal fractionation of hydrogen or carbon isotopes. Non-polar compounds were successfully extracted using ENV+ SPE cartridges and polar compounds were successfully extracted using Strata-X SPE cartridges. The isotopic fractionation of non-polar compounds during ENV+ extraction varied significantly (up to 245⁰/₀₀ and 1.8⁰/₀₀ for D and ��C respectively, when eluted with acetonitrile and ethyl acetate, as recommended by manufacturers) but the fractionation of compounds eluted with dichloromethane was negligible (less than instrumental precision). Polar compounds were eluted from Strata-X cartridges with negligible isotopic fractionation using methanol. The direct comparison of SPE and liquid-liquid extraction found SPE to extract slightly more compound from leachate then liquid-liquid extraction (especially for polar compounds) and the isotopic compositions of compounds did not change with extraction methods. These new analytical methods subsequently were used to determine the isotopic compositions of organic compounds dissolved in leachates from three New Zealand landfills. The molecular and isotopic signature of leachate varied significantly between landfills, indicating the isotopic fingerprint of organic compounds in leachate is unsuitable as a universal tracer of leachate. However, compounds such as terpien-4-ol, methylethylbenzene and juvabione maintained their isotopic composition over short geographical distance-indicating their potential as site-specific tracers of leachate. Organic compounds analysed on a transect across the landfill boundary indicated polar compounds were more mobile than semi-volatile compounds and possessed a more conservative isotopic composition. However, hexadecanoic acid extracted from leachate and ground water was highly depleted in ��C (-72 ⁰/₀₀ to -40⁰/₀₀), indicative of methanogenic and sulfate reducing bacteria. These bacteria only live in highly reducing environments such as leachate; therefore their presence in the pristine environment can potentially indicate the release of leachate from the landfill. The final experiments traced the uptake and utilisation of leachate by periphyton. The isotopic composition of bulk periphyton, fatty acids and phytol indicated that microbial assimilation and utilisation of nutrients is a complex process. Fatty acid biomarkers for green algae and diatoms showed signs of leachate derived nutrients, however the availability of nutrients (carbon, nitrogen, water and light) caused significant changes in metabolic processes and isotopic compositions. Under slow growing conditions, the [delta]��C composition of periphyton became enriched in ��C as solar irradiation levels decreased (including shading by detritus and periphyton), while the [delta]D composition of fatty acid was controlled by the internal recycling of hydrogen. This study indicated the power of compound specific isotope analysis as a tool to detect the release of landfill leachate from a landfill, especially at locations with multiple potential sources of contaminants, and provides a sound platform for future research.

Dryland salinity is increasing in the upper catchments of central and northern New South Wales, Australia. Consequently, salts may be exported downstream, which could adversely affect cotton irrigated-farming systems. In order to assess the potential threat of salinity a simple salt balance model based on progressively saline water (i.e., ECiw 0.4, 1.5, 4.0 and 9.0 dS/m) was used to simulate the potential impact of salinisation due to the farming systems. The study was carried out in the lower Namoi valley of northern New South Wales, Australia. A comparison has been made of the various non-linear techniques (indicator kriging, multiple indicator kriging and disjunctive kriging) to determine an optimal simulation method for the risk assessment. The simulation results indicate that potential salinisation due to application of the water currently used for irrigation (ECiw) is minimal and may not pose any problems to sustainability of irrigated agriculture. The same results were obtained by simulation based on irrigation using slightly more saline water (ECiw 1.4 dS/m). However, simulations based on irrigation using water of even lower quality (ECiw of 4 and 9.0 dS/m), shows potential high salinisation, which will require management inputs for sustainable cropping systems, especially legumes and wheat, which are used extensively in rotation with cotton. Disjunctive kriging was the best simulation method, as it produced fewer misclassifications in comparison with multiple-indicator kriging and indicator kriging. This study thus demonstrates that we can predict the salinity risk due to application of irrigation water of lower quality than that of the current water used. In addition, the results suggest here problems of excessive deep drainage and inefficient use of water might be a problem. The second part of this thesis deals with soil information required at the field scale for management practices particularly in areas where deep drainage is large. Unfortunately, traditional methods of soil inventory at the field level involve the design and adoption of sampling regimes and laboratory analysis that are time-consuming and costly. Because of this more often than not only limited data are collected. In areas where soil salinity is prevalent, detailed quantitative information for determining its cause is required to prescribe management solutions. This part deals with the description of a Mobile Electromagnetic Sensing System (MESS) and its application in an irrigated-cotton field suspected of exhibiting soil salinity. The field is within the study area of part one of this thesis-located about 2 km south west of Wee Waa. The EM38 and EM31 (ECa) data provide information, which was used in deciding where soil sample sites could be located in the field. The ECa data measured by the EM38 instrument was highly correlated with the effective cation exchange capacity. This relationship can be explained by soil mineralogy. Using different soil chemical properties (i.e. ESP and Ca/Mg ratio) a detailed transect study was undertaken to measure soil salinity adjoining the water storage. It is concluded that the most appropriate management option to remediation of the problem would be to excavate the soil directly beneath the storage floor where leakage is suspected. It is recommended that the dam not be enlarged from its current size owing to the unfavourable soil mineralogy (i.e. kaolin/illite) located in the area where it is located.

Coal fly ash is a by-product of coal combustion that has drawn renewed public scrutiny due to the negative environmental impacts from accidental release of this waste material from storage facilities. Historically, the leaching of toxic elements from coal fly ash into the environment has always been a major environmental concern. Despite extensive efforts into the characterization of coal fly ash, effective models for the fate and transport of toxic fly ash constituents have remained lacking, making it difficult to perform accurate environmental impact assessment for coal fly ash. To close this critical knowledge gap, the overall objective of this study was to develop a predictive model for the leaching of toxic elements from fly ash particles. First, physical properties of coal fly ash were characterized to evaluate their contribution to elemental transport. Unburned carbon was shown to contribute to the sorption of arsenic to fly ash, which slowed the release of arsenic from fly ash. In parallel, leaching properties of various elements were determined to differentiate species of varying leaching capacities, demonstrating that the majority of toxic elements were not mobile under environmentally relevant conditions. Subsequently, a mechanistic model for the dissolution of fly ash elements was developed and validated with batch kinetics studies. Furthermore, elemental dissolution was integrated with hydrodynamic modeling to describe the leaching of toxic elements from fly ash in dry disposal facilities, which was validated by column studies. The mechanistic model developed and validated in this research represents the first such model that successfully characterized the complex processes underlying the release and transport of toxic elements in coal fly ash, providing a valuable tool to predict the environment impact of coal fly ash and develop more effective management practices for both the industry and regulators.

Nitrogen deposition leads to environmental damage in areas where the nitrogen deposition is high. Southwest Sweden receives an annual nitrogen deposition of up to 20 kg N/ha. Nitrogen that is not assimilated by the vegetation is accumulated in the soil, which may lead to nitrogen saturation and an elevated risk of nitrogen leaching. Nitrogen leaching from forest areas in southern Sweden has proven to be higher than from agricultural areas, which have been thought to be the main contributors to elevated nitrogen levels in rivers and lakes. The amount of nitrogen that leaches depends on the fraction of the total nitrogen in the soil that consists of nitrate, since nitrate is easily transported through the soil. Nitrogen leaching increases after clear-cutting since the uptake by vegetation is greatly reduced. In this study the soil chemistry of two clear-cut spruce stands in Halland, in southwest Sweden, has been analyzed. A previous study in these areas has indicated higher nitrate concentrations in the groundwater in one of the areas and thus a greater nitrogen leaching. Nitrogen deposition in the two areas is estimated to be the same and therefore the soil chemistry has been analyzed to evaluate if differences in the soil can have resulted in differences in the nitrate concentration in the groundwater. The hypothesis is that the area with higher nitrate concentrations in the groundwater has properties more favorable for nitrification, which would be especially apparent in a lower carbon to nitrogen ratio. The pH and storage of nitrate, ammonium, total carbon, total nitrogen and exchangeable cations was analyzed in soil samples from both areas. In addition, a study of stand properties and previous use of the areas was made. The analyses performed in this study indicate that the soil properties could not explain the differences in nitrate concentration in the groundwater. The differences found between the areas were that the area with lower nitrate concentrations in the groundwater had higher nitrate and ammonium concentrations and higher pH in the soil. The reason for this might be that the soil in this area has larger capacity to bind elements. The fact that the soil samples were sampled during different seasons probably had a major effect on these results. The history and stand properties of the two areas were similar. According to site index one area was more fertile, which benefits nitrification. This fact was not confirmed by the analyses, but it probably caused the nitrification rate to be higher in this area. / Det stora nedfallet av föroreningar i form av kväve i framförallt sydvästra Sverige leder till försurning och övergödning av både skogsmarker och vattendrag. Kvävedepositionen i södra Sverige kan uppgå till 20 kg N/ha och år. Det kväve som inte tas upp av vegetationen ackumuleras i marken som efterhand riskerar att bli kvävemättad vilket ökar risken för kväveutlakning. Kväveutlakningen från svenska skogsmarker har visat sig kunna vara i samma storleksordning som från jordbruksmarker som anses vara en av de största orsakerna till ökande kvävehalter i sjöar och vattendrag. Kväveutlakningens storlek beror till stor del på hur stor del av markens kväveförråd som finns i den oorganiska formen nitrat eftersom den är en lättrörlig jon. Efter skogsavverkning ökar nitratutlakningen betydligt på grund av att det finns väldigt lite vegetation kvar som tar upp kväveföreningarna. I den här studien har markkemin i två avverkade granskogsområden i Halland undersökts. Tidigare studier i dessa två områden har visat att halterna av nitrat var högre i grundvattnet i det ena området än i det andra, och således var även nitratutlakningen större i detta område. Eftersom kvävedepositionen anses vara densamma i de två områdena har markemin undersökts för att finna skillnader där som kan förklara de olika nitratnivåerna i grundvattnet. Hypotesen var att det ena området skulle ha mer gynnsamma förhållanden för nitrifikation, framförallt en lägre C/N-kvot. Markens förråd av nitrat- och ammoniumkväve, totalkol, totalkväve, utbytbara katjoner samt pH undersöktes i båda områdena. En studie av områdenas historia gjordes även för att kunna utesluta skillnader där som kunde ge upphov till skillnaden i nitrat i grundvattnet. Slutsatsen som kan dras från studien är att de analyserade egenskaperna inte visade på mer gynnsamma förhållanden för nitrifikation i det ena området än i det andra. Ingen skillnad i C/N-kvot uppmättes. Skillnaderna som hittades var att området med lägst halter av nitrat i grundvattnet hade högst halter av oorganiskt kväve i marken och högre pH. Att nitrathalterna var högre i grundvattnet men inte i marken kan ha sin förklaring i att marken i det ena området har större förmåga att binda till sig kväve vilket gör att det inte lika lätt kommer ut i grundvattnet. Antagligen spelade det stor roll för dessa resultat att jordproven tagits vid olika årstider. Undersökningen av tidigare användningsområde i skogarna visade att de hade en tämligen liknade historia. Det ena området har enligt ståndortsindex högre bördighet vilket gynnar nitrifikation. Detta framgick dock inte av analyserna men är antagligen orsaken till de högre nitrathalterna i grundvattnet i detta område.

Leaching is the most widely used process for extraction of nickel metal from lateritic ores. In this study, nickel extraction from Manisa-G&ouml / rdes region laterites by hydrochloric acid leaching is aimed. The mineralogical analysis of sample showed that hematite, goethite, dolomite, quartz and smectite are the main minerals in the ore. Attrition scrubbing, cycloning and magnetic separation with permroll were used as preconcentration processes but results were unsatisfactory. HCl leaching experiments were conducted both at room temperature and at elevated temperatures. The effects of various parameters such as leaching duration, particle size, concentration of HCl, pulp density, Cl- concentration and temperature on nickel recovery were examined. The results showed that under the optimised leaching conditions (particle size: 100 % -1 mm, HCl concentration: 3 N, leaching duration: 3 hours, leaching temperature: 100 oC, pulp density: 1/30 solid to liquid ratio by volume) it was possible to extract 87.26 % of nickel in the ore.