The aim of this investigation was to extend the knowledge of the bacterial leaching of copper and zinc sulphides into the area of nickel sulphide leaching. By far the major portion of both theoretical and practical expertise which is available in the field of bacterial leaching is based on the treatment of copper and zinc sulphides. As yet there is little information available on the bacterial leaching of nickel sulphides to meet the growing interest in this field both in South Africa and elsewhere. To a large degree, it was necessary to start from basic principles in this novel extension of bacterial leaching technology so that the work covers a fairly wide field in general rather than one particular aspect in detail. A strain of 'nickel adapted' Thiobacillus ferrooxidans was isolated from the tailings dam of a disused nickel mine. The growth characteristics of this strain were studied in some detail on sulphur using both batch and continuous techniques. This was done as it was considered that growth on sulphur would provide useful information which could be correlated with the mineral leaching results. The mineral pentlandite (NiFeS2) was chosen as the one with which to work because of its economic importance. This was prepared in a highly purified form from a concentrate of the Rhodesian Shangani deposit. Bacterial leaching tests in both batch and continuous operation were then carried out in order to define the effects of various physico-chemical parameters on the leaching of nickel from this mineral. As a preliminary to these tests, a detailed chemical kinetic study in the absence of bacteria of the leaching of nickel was carried out using similar physico-chemical conditions. The results of the bacterial and chemical leaching tests were then compared and used to postulate a mechanism and model for the process. It was found that the rate of leaching of nickel from pentlandite in acid ferric sulphate solutions was directly proportional to the concentration of ferric ions and speed of agitation of the stirrer and to the square root of the oxygen concentration. The form of the rate expression was interpreted in terms of a mixed diffusive and chemical rate controlling mechanism. Bacterial growth rates on flowers of sulphur were found to be controlled by the rate of dissolution of oxygen from the gas bubbles into the bulk solution. When this latter condition was made non-rate limiting, it was found that growth rates were still dependent on the rate of agitation, implying mass transport control by another mechanism. The batch bacterial leaching results showed a linear pattern of nickel leaching and bacterial growth, with a marked dependence on oxygen concentration and rate of agitation. A mechanism in accordance with the batch data was postulated, which proposed that the rate of bacterial leaching was proportional to the concentration of bacteria attached at the mineral surface and to the square of the oxygen concentration. The rates of bacterial leaching were computed by taking the difference between the overall measured leach rate and the chemical leach rate based on the chemical kinetic data. The leach rates in continuous bacterial leaching were higher than those predicted from the batch data. This effect was interpreted in terms of higher specific growth rates being achieved in continuous operation. An economic assessment was made of the process based on the optimum leach rates obtained in continuous leaching and found to show some promise. / Thesis (Ph.D.)-University of Natal, Durban, 1974.

One of the main environmental problems associated with the disposal of waste on land is the release of liquid emissions from the site. This wastewater, known as leachate, is a product of the biodecomposition of the waste and filtrates from the landfill once the moisture saturation of the fill has been reached. The chemical composition of leachate is variable over time and between sites. Regardless of these variables, the main pollutants of concern in the leachate are ammonia and organics, both of which can cause environmental degradation in relatively low concentrations. Worldwide and in South Africa, leachate has either been directly released into the environment or into the local domestic sewage system. As more has been learned about the human and environmental health risks associated with these disposal methods, there has been a new focus in waste management toward treating the leachate at the source as part of the broader focus of sustainable landfilling. One of the treatment options being used is constructed wetlands (CW) due to the physical and chemical transformation mechanisms in these biological systems. This treatment process has been demonstrated to be effective as a final polishing treatment for leachate, and it is considered a technology appropriate in the South African context. Therefore the aim of dissertation is to ascertain the use of constructed wetlands as an appropriate treatment option for untreated methanogenic landfill leachate by determining the efficiency of ammonia and organic removal in a pilot-scale vegetated submerged bed (VSB) constructed wetland (CW) planted with Phragmites australis. During the 22-week treatability trial the VSB achieved an ammonia concentration removal efficiency of 91% and mass removal efficiency of 87%. Despite this substantial reduction of ammonia, the VSB was unable to achieve the required discharge standard. There were erratic fluctuations in both the treatment efficiencies for COD and BOO, and the results show no evidence of constant reduction of organics during the treatability trials. This is due to the refractory nature and the low biodegradability of the organics that remain in methanogenic leachate as suggested by the low BOO to COD ratio. Due to the low biodegradability of the organics, a biological treatment system, such as a VSB, will not be able to reliably meet the required discharge standards. Other passive treatment options or a combination of systems need to be explored in order to both satisfy legislative requirements and be appropriate in the South African context. / Thesis (M.Sc.)-University of Natal, Durban, 2003.

Microbial leaching plays a significant role in the natural weathering of silicate containing ores such as diamond-bearing kimberlite. Harnessing microbial leaching processes to pre-treat mined kimberlite ores has been proposed as a means of improving diamond recovery efficiencies. The biomineralization of kimberlite is rarely studied. Therefore, this study investigated the feasibility of exploiting both chemolithotrophic and heterotrophic leaching processes to accelerate the weathering of kimberlite. Preliminary investigations using mixed chemolithotrophic leaching cultures were performed on four finely ground kimberlite samples (<100μm) sourced from different mines in South Africa and Canada. Mixed chemolithotrophic cultures were grown in shake flasks containing kimberlite and inorganic basal media supplemented either with iron (Fe2+, 15g/l) or elemental sulfur (10g/l) as energy sources. Weathering due to dissolution was monitored by Inductive Coupled Plasma (ICP) analyses of Si, Fe, K, Mg and Ca in the leach solutions at known pH. Structural alterations of kimberlite after specified treatment times were analyzed by X-ray Powder Diffraction (XRD). The results of the preliminary investigation showed that weathering can be accelerated in the presence of microbial leaching agents but the degree of susceptibility and mineralogical transformation varied between different kimberlite types with different mineralogical characteristics. In general, the results showed that the kimberlite sample from Victor Mine was most prone to weathering while the sample from Gahcho Kue was the most resistant. It was therefore deduced that kimberlite with swelling clays as their major mineral component weathered relatively more easily when compared to kimberlite that consisted of serpentine and phlogopite as their major minerals. Gypsum precipitates were also distinguished indicating that a partial alteration in the kimberlite mineralogical structure occurred. Both energy sources positively influenced the dissolution process, with sulfur producing superior results. This was attributed to the generation of sulfuric acid which promotes cation dissolution and mineral weathering. Success in the preliminary investigations led to further experimental testing performed to determine the effect of particle size and varying energy source concentrations on the biotransformation of kimberlite. It was observed that although weathering rates of the larger kimberlite particles (>2mm<5mm) were lower than that of the finer particles, slight changes in their mineralogical structures represented by the XRD analyses were seen. Optimisation studies of energy source concentration concluded that although the highest concentration of elemental sulfur (20% w/w) and ferrous iron (35% w/w) produced the most pronounced changes for each energy source tested, the leaching efficiency at these concentrations were not drastically greater than the leaching efficiency of the lower concentrations, as expected. Following the success of batch culture shake flasks weathering tests, the effect of continuous chemolithotrophic cultures on the biotransformation of larger kimberlite particles (>5mm<6.7mm) was investigated. A continuous plug-flow bioleach column was used to model the behaviour of chemolithotrophic consortia in a dump- or heap leaching system. Two sequential columns were setup, in which the first consisted of kimberlite mixed with sulfur and the second purely kimberlite. Inorganic growth medium was pumped to the first column at a fixed dilution rate of 0.25h-1 and the leachate from the first column dripped into the second. After an 8 week investigation period, the ICP and XRD data showed that weathering did occur. However, the pH results showed that the leaching process is governed by the amount of acid produced by the growth-rate independent chemolithotrophic consortia. Data from pH analyses also showed that the leaching bacteria reached ‘steady state’ conditions from day 45 onwards. The pH also remained higher in the second column than in the first column highlighting the alkaline nature of the kimberlite ores and its ability to act as a buffering agent and resist weathering. This important factor, as well as further optimisation studies in process operating conditions and efficiency, needs to be considered when establishing heap-leaching technology for these kimberlite ores. In the preliminary heterotrophic investigation, Aspergillus niger was used to produce organic metabolites to enhance kimberlite mineralization. The results demonstrated that the organic acid metabolites generated caused partial solubilization of the kimberlite minerals. However, it was deduced that for more significant changes to be observed higher amounts of organic acids need to be produced and maintained. The results obtained in this study also showed that the type of kimberlite presents a different susceptibility to the dissolution process and the presence of the fungal cells may improve the leaching efficiency. The results in this study provided an optimistic base for the use of microbial leaching processes in accelerating the weathering of kimberlite. These findings may also serve to supply data to formulate recommendations for further and future column microbial leach tests as well as validation and simulation purposes. / Thesis (M.Sc.) - University of KwaZulu-Natal, Pietermaritzburg, 2008.

Swine slurry is a source of nutrients to grasslands. However, accumulation of N or P can lead to their movement to groundwater. This thesis’ research was conducted using a tame pasture fertilized over six years with swine slurry at N-requirement rates, on a gravelly soil in south-eastern Manitoba. Objectives were to determine N and P soil surplus and accumulation over time, soil profile P fractions and soil surface P saturation, and nitrate and dissolved-P in shallow groundwater for treatment combinations of forage utilization (Hay and Grazed), slurry application in spring (Single), split in fall and spring (Split) and no slurry (Control), and Grassed areas of grazed paddocks and Bare areas where cattle congregated around water troughs. There were less surplus and accumulation of extractable-P in the soil surface for the Split compared to the Single treatment because of less P in fall- than in spring-applied manure. With Grazing, there were greater surpluses of N and P than with Haying, and surface accumulation of extractable-P over time was linear being 16.5 and 11.9 mg P kg-1 year-1at 0-5 cm for Grazed and Hay treatments, respectively. Labile inorganic-P fractions (water- and bicarbonate-extractable) increased in the Bare and in the Single Grassed treatments. In the Bare treatment, P-sorption capacity at 0-5 cm decreased compared to the Grassed treatment. The surface soil of the Bare areas had large concentrations of water-soluble-P up to 165 mg P kg-1 associated with an increase in P-saturation to 88 % of the sorption capacity, and nitrate was elevated in the soil profile. Concentrations of nitrate-N and dissolved-P in groundwater were below the environmental thresholds of 10 mg nitrate-N L-1 and 0.025 mg P L-1, respectively, in both the Hay and the Grazed Grassed treatments. In contrast, the Control and Single Bare treatments had nitrate concentrations always above the threshold, and the Bare areas in the Single paddocks had P concentrations of environmental concern in 2009, averaging 0.7 mg total dissolved P L-1. Nitrogen-based slurry applications did not cause leaching of N or P, but Bare areas in grazed pastures are at risk of N and P leaching.

Despite improved liner design, there are still reported incidences of landfill leachate, rich in heavy metals, percolating through to groundwater and threatening ecosystems. This thesis introduces the concept of segregating municipal solid wastes (MSW) according to their major heavy metals and their metal's adsorption compatibility. Each segregated portion can be disposed in a different landfill compartment to minimize leaching of these heavy metals with the greatest bioactive impact. The validity of the concept was evaluated by batch and column retention mobility studies using copper (Cu) alone or with either lead (Pb) or cadmium (Cd) in solutions bearing various pHs. This was supported by selective sequential extraction (SSE) to determine the affinity to specific liner fractions. The following summarizes the procedure used. / Beforehand, a soil column test using sand with 5 and 10% bentonite was conducted to develop an equation predicting liner permeability, k , under simulated field conditions. The column permeability test revealed that a liner with 5% bentonite resulted in a k value which respected the North American criteria of 10-5 m/s. / In the batch experiments, solutions with Cu alone or with Cd or Pb, adjusted to pH of 3.7, 5.5 or 7.5, were applied to sand liners with 0%, 5% or 10% bentonite, having CEC's of 2.0, 6.4, and 10.8 (cmol(+) kg-1 ), respectively. Bentonite, pH and Pb significantly affected Cu adsorption. Cu was adsorbed by the liners at pH <6.5 whereas Cu precipitated at pH >6.5. Cu retention was higher in the presence of Cd than in that of Pb, at all combinations of CEC and pH. Competition between metals was greater in liners with lower CEC and therefore fewer adsorption sites. Limiting Pb in a landfill compartment can improve Cu adsorption at pH's below the precipitating threshold. / In the SSE procedure, the liner samples were centrifuged, decanted from their solutions and each adsorption fraction analyzed for Cu content. Results indicated that the carbonate fraction adsorbed more Cu, and that Pb significantly increased the mobility of Cu due to competition for exchangeable sites. / In the final soil column test using a sand liner with 5% bentonite, the leachate had an initial pH of 3.7. The leaching test confirmed the compatibility of Cu with Cd. The leaching of Cu was greater in the presence of Pb. Total metals in leachate was greater for the Cu-Cd solutions than for the Cu-Pb, because of Cd's relatively high mobility. The sequential extraction results showed again that the carbonate fraction dominated metal adsorption. Total heavy metal leaching followed the order of Cu/Cd > Cu/Pb > Cu alone. / Thus, disposing MSW in landfill compartments based on their heavy metal compatibility can minimize migration of heavy metals.

Chemical treatment of contaminated soils (in-situ or ex-situ) is the current most practical option for remediation. The degree of metal complexation by organic acids depends on the type, concentration, metal type, pH and temperature. The influence of pH, temperature on the extraction efficiency of lead, zinc and copper was evaluated using Sodium citrate and sodium acetate buffers. Sodium citrate buffer was selected for the soil treatment. The soil was characterized for its pH, total metal content and the distribution of target heavy metals in soil fractions. Optimal conditions for Pb extraction with 0.5M citrate buffer was used to treat soil in batches and in columns, to evaluate their extraction efficiency and possible use for in-situ remediation. / Chitosan, a derivative of chitin is a versatile biopolymer with metal uptake capabilities. Due to the large amounts of chitosan required to treat heavily contaminated leachates, magnesium (Mg) and iron (Fe) metals granules were evaluated for stripping the heavy metals from solution before the use of chitosan at optimized conditions to effectively polish the soil washing. (Abstract shortened by UMI.)

The study of biogeochemical cycles and their role in ecosystem function has helped to highlight the impacts of human activities on natural processes. However, our understanding of the effects of nitrogen (N) deposition on forested ecosystems remains limited due to the variable controls on N cycling. Soils, microclimate, and vegetation can influence rates and processes of N cycling, singly or in concert at multiple scales. Understanding how these factors influence N cycling across the landscape will help to elucidate the impacts of N deposition. The objectives of this study were to characterize variation in soils, microclimate and vegetation characteristics, and N cycling and decomposition dynamics across the landscape in a region impacted by N deposition. Relationships among these factors were explored to determine the main factors influencing N cycling and decomposition. Strong differences in net N mineralization and nitrification were found between forest stands with contrasting species composition and moisture availability. Nitrate production and leaching were related to sugar maple abundance, and base cation leaching was correlated with nitrate concentrations in soil solutions. Decomposition experiments were installed to examine the effects of substrate quality, microclimate and N availability on decay rates. Nitrogen amendments for the most part did not affect decomposition rates of wood and cellulose, and mass loss rates were correlated with microclimate and forest floor characteristics. In contrast, microclimate did not seem to affect leaf litter decay rates, and the results suggest that the presence of invertebrates may influence mass loss to a greater degree than moisture or litter quality. This work highlights the large degree of variability in N processing across the landscape and suggests that differences in microclimate and species composition may help to predict the impacts of chronic N deposition on N cycling and retention.

The transfer of N from legume green manures (GMr) can satisfy the needs of a successive cash crop, but rotations that have over-wintering legumes also carry an increased risk of off-season (Sep.–June) N losses, especially during spring thaw. Spring-wheat yield among four GMr systems were evaluated with respect to off-season (GMr; Sep.–June) and in-season (wheat; June–Sep.) N2O emissions, as well as full-year NO3– leaching and dissolved N2O losses during spring-thaw from a tile-drained sandy loam soil in Atlantic Canada over 2 rotations (2011–2013). Four GMr systems (treatments) differed in the timing and season of GMr incorporation and the use of additional N as fertilizer or manure. The majority (66%) of cumulative N2O emissions were measured during the off-season because of high N2O emissions events during spring thaw. There was no clear effect of GMr system on these emissions, which may have been a result of the pattern and duration of soil freezing and thawing. Spring thaw also coincided with the highest dissolved N2O concentrations (100–300 µg N2O-N L–1) in tile-drained water, which represented potential N2O emissions of 21 to 116 g N2O-N ha–1. Belowground N2O concentrations and soil water content measurements during winter provided further evidence of the relationship of N2O dissolved in drainage water and N2O emissions at the soil surface. Wheat yield among treatments in either year of study were not different, but was 1.5 times greater in Year 2 (2.62 ± 0.27 Mg ha–1), than Year 1 (1.05 ± 0.12 Mg ha–1). The highest NO3– concentrations in drainage water (Oct.; 13.8 mg NO3–-N L–1) were measured from the GMr system with the earliest fall incorporation (i.e., Sep.) and the addition of spring fertilizer when compared to the mean of all other treatments (9.8 mg NO3–-N L–1). The use of supplemental N did not translate into additional gains in yield, yet increased in-season N2O emissions and greater NO3– leaching. Off-season N losses proved to be a substantial part of the annual N loss budget and dissolved N2O in drainage water was identified as an additional pathway for N loss at spring thaw.

Swine slurry is a source of nutrients to grasslands. However, accumulation of N or P can lead to their movement to groundwater. This thesis’ research was conducted using a tame pasture fertilized over six years with swine slurry at N-requirement rates, on a gravelly soil in south-eastern Manitoba. Objectives were to determine N and P soil surplus and accumulation over time, soil profile P fractions and soil surface P saturation, and nitrate and dissolved-P in shallow groundwater for treatment combinations of forage utilization (Hay and Grazed), slurry application in spring (Single), split in fall and spring (Split) and no slurry (Control), and Grassed areas of grazed paddocks and Bare areas where cattle congregated around water troughs. There were less surplus and accumulation of extractable-P in the soil surface for the Split compared to the Single treatment because of less P in fall- than in spring-applied manure. With Grazing, there were greater surpluses of N and P than with Haying, and surface accumulation of extractable-P over time was linear being 16.5 and 11.9 mg P kg-1 year-1at 0-5 cm for Grazed and Hay treatments, respectively. Labile inorganic-P fractions (water- and bicarbonate-extractable) increased in the Bare and in the Single Grassed treatments. In the Bare treatment, P-sorption capacity at 0-5 cm decreased compared to the Grassed treatment. The surface soil of the Bare areas had large concentrations of water-soluble-P up to 165 mg P kg-1 associated with an increase in P-saturation to 88 % of the sorption capacity, and nitrate was elevated in the soil profile. Concentrations of nitrate-N and dissolved-P in groundwater were below the environmental thresholds of 10 mg nitrate-N L-1 and 0.025 mg P L-1, respectively, in both the Hay and the Grazed Grassed treatments. In contrast, the Control and Single Bare treatments had nitrate concentrations always above the threshold, and the Bare areas in the Single paddocks had P concentrations of environmental concern in 2009, averaging 0.7 mg total dissolved P L-1. Nitrogen-based slurry applications did not cause leaching of N or P, but Bare areas in grazed pastures are at risk of N and P leaching.

The use of high N fertilizer in sweet corn (Zea mays L.) and wheat (Triticum aestivium L.) production often results in leaching losses and contamination of ground water. Cover crops planted after harvest of sweet corn and wheat may reduce residual soil NO$ sp- sb3$-N levels by crop N uptake and subsequently minimize NO$ sp- sb3$-N content in gravitational water. Field experiments were conducted on a Ste. Rosalie heavy clay (Humic Gleysol) and a St. Bernard sandy clay loam (Melanic Brunisol) to determine the contribution of the six cover crops to nutrient uptake, subsequent N release, leaching losses, denitrification rates and soil properties such as aggregate stability, organic matter. The cover crops were red clover (Trifolium pratense L.), crimson clover (Trifolium incarnatum L.), forage radish (Raphanus sativus L.), canola (Brassica rapa L.), barley (Hordeum vulgare L.), annual rye grass (Lolium multiflorum L.). Three replicates were used in a split plot arrangement of a randomized complete block experiment. Sweet corn and wheat were grown at three fertilizer N rates, 0-75-150 kg N ha$ sp{-1}$ for sweet corn and 0-45-90 kg N ha$ sp{-1}$ for wheat. Cover crop of forage radish, canola and barley were more effective at absorption or soil N than rye grass and clover species at all sample times. Levels of soluble N in the soil were reduced with cover crop in the off-season. Cover crop plots had higher NO$ sp- sb3$-N levels than control plots in the spring, indicating net mineralization and nitrification. Gravitational water NO$ sp- sb3$-N contents were higher in the control plots relative to cover crop plots at both sites. Therefore growing cover crops after harvest of sweet corn and wheat can reduce residual NO$ sb3$-N level in the soil and thus restrict ground water contamination with fertilizer N.