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.)

Plant-based remediation techniques that can address mixtures of heavy metals and organic contaminants in soil warrant investigation due to their cost effectiveness and public acceptability. The potential of phytoremediation to remediate mixtures of heavy metals and hydrocarbons in soil is presented in two papers. A hydropic screening of twenty-seven forage grasses, grown in a solution containing 100 muM Zn, 5 muM Cu and 1 muM Cd, provided six species that were exceptionally metal tolerant. These six species were examined for their growth response and root phenolic secretion at five levels of hydroponic heavy metal contamination. Phenolic secretion, an indicator of a plant's capacity to promote polycyclic aromatic hydrocarbon (PAH) degradation, increased with heavy metal contamination, however, the values were low (<30 mug/g root). Two high biomass producing, metal-tolerant grasses, Bromus riparius and Arrhenatherum elatius, were combined with M2Rhizo4, a strain of plant growth-promoting rhizobacteria. The plant-bacterial combinations were established in artificial and genuine soils contaminated with heavy metals and PAHs at a range of concentrations. In contaminant-free artificial soil, inoculation promoted B. riparius growth by 25% compared to non-inoculated plants. In artificial soil, contaminated with 495 mg/kg Zn, 263 mg/kg Cu and 23 mg/kg Cd, M2Rhizo4 promoted B. riparius growth by 22%. In chromated-copper-arsenate (CCA) and creosote contaminated soil, M2Rhizo4 inoculated A. elatius had 15% more biomass and greater survival rates than non-inoculated A. elatius. A phytoremediation system composed of metal-tolerant plants inoculated with hydrocarbon-degrading or plant growth promoting bacteria may be suitable for sites contaminated with a mixtures of hydrocarbons and heavy metals.

Heavy metals in the environment are a source of some concern because of their potential reactivity, toxicity, and mobility in the soil. Soil contamination by metals is placing human and environmental health at risk through possible contamination of food chain. / Soil washing can be used to remove metals from the soil. Chemical treatment involves the addition of extraction agents that react with the contaminant and leach it from the soil. The liquid, containing the contaminants, is separated from the soil resulting in a clean solid phase. Six chelating reagents, EDTA, Citric acid, ADA, DTPA, SCMC, and DPTA, were employed to determine the relative extraction efficiencies of the six chelating reagents for the target metals. Recycling of chelating reagent was the main interest of this study. The experiments were divided into four parts: (1) preliminary studies on the preparation and characterization of soil that included grinding, sieving, soil texture measurements, total metals content post digestion and the distribution of metals in different soil fractions as well as (2) a comparison of the extraction efficiencies of six chelating reagents toward Cu, Pb, Zn, Fe, and Mn. Additionally, the chelating reagent was liberated and recycled by treatment of the metal-complexes with disodium diethyl dithiocarbomate (DEDTC). Additionally, supercritical CO2 was used to extract metal-DEDTC complexes using various surfactants to maintain the metal-DEDTC complexes in suspension. Finally, (4) magnesium metal was evaluated as an alternative method for liberating the water-soluble chelating reagent from the complex so as to be able to recycle this reagent as well. / The different approaches were promising in terms of recycling the chelating reagents that suggests a means of optimizing the experimental conditions in future applications.

The state of soil is of great significance because it is a common medium for plant growth, which provides important nutrients to plants. Water pollution is the build-up of harmful substances in water bodies to the level that results in health problems for people and animals. Heavy metal pollution (of soil, water, and plants) and their health effects on people is a persistent social issue, and several types of research have recognized health risks of residents living close to open dumpsites. Dump sites are sources of heavy metal impurity and toxicity to the surrounding environment. Analyses were done on water and soil samples for temperature, pH, Electrical conductivity (EC), Total dissolved solids (TDS), alkalinity, organic matter, organic carbon and total hardness. The pH results range from slightly acidic (6.79) to neutral soil pH (7.09), and have been recorded within the normal range from WHO. All the determined physicochemical properties in soil and water have been recorded within the normal range, except for EC in water which was found to be above the permissible limits by WHO. The heavy metals concentration was determined using the AAS technique. The results obtained shows that the dumpsite‘s soil consists of high metal concentration when compared to control site. The concentration in dumpsites ranges between 1.2783 ± 0.83 mg/kg to 26.3213 ± 6.37 mg/kg. The descending order for selected metal concentrations were in this following order Mn> Cu>Hg>Pb. The Pb and Hg mean concentration was recorded above permissible limits, while the Mn and Cu were within the normal range suggested by WHO. In both water and Acacia karroo samples the Cu was not detected. The trend of metal concentration in water sample was found to be in this order Hg> Mn > Pb> Cu, while in Acacia karroo metal concentration is Hg> Mn> Pb> Cu. The one-way ANOVA test was used to compare the mean concentration of selected metals in each sampling site. The results show that there is a statistically significant difference between the mean concentrations of selected metals; this is supported by the value of F-static and p-value (p <0.05)

M.Sc. (Zoology) / Please refer to full text to view abstract

M.Sc. (Zoology) / Tilapia sparrmanii (Smith) was exposed to sub-lethal doses of chromium, manganese, zinc and iron for 96 hours at an acidic pH (5), a physiological pH (7,4) and an alkaline pH (9), as well as a prolonged exposure (2 - 4 weeks) at an uncontrolled pH. In the laboratory fish were kept in aquaria which were supplied with continuously flowing borehole water. Controlled laboratory conditions existed during experimentation. Blood and liver samples of the experimental fish were sampled after exposure. The bioconcentration and the effect of the selected metals at the mentioned conditions, were thereby determined on bloodcoagulation, total and differential leucocyte counts, and liver enzYmes to investigate the possible damage to the liver. As metals have the ability to enter and concentrate in the body, the bioconcentration of each metal was determined by atomic absorption sPectrophotometry in the blood and liver. Chromium showed an increase in concentration in both the blood and liver, with an increase in pH after short term (96h) exposure. The statistical significant increases of manganese concentration in the blood over a short term were not reflected in the liver. It may be indicative of homeostatic control. A similar phenomenon was found with .zd.nc , The concentration of zinc in the liver did not reflect the progressive decrease in the blood wi th a increase in pH. Iron revealed a statistical significant increase in bioconcentration in the liver with, an increase in pH, which is indicative of the activity of the liver. The long term exposure of fish to chromium and manganese caused a significant increase in the concentration of the metals in the blood and liver. The only significant increase in concentration after exposure to iron, occured . in the Iiver. Exposure to zinc however caused a statistical significant decrease in concentration in both the blood and liver. Differential leucocyte counts reflected lymphocytosis, eosinophilia, monocytopenia and neutropenia, after short term exposure. These conditions nearly always resulted in leucopenia. Long term exposure to manganese and zinc reflected both eosinophilia and neutropenia. Chromium reflected eosinophilia, and iron, neutropenia. The only statistically significant change in the number of leucocytes after long term exposure, was caused by zinc and resulted in leucopenia. According to the photokymographic observation of blood coagulation by the thrombelastograph, exposure to the selected heavy metals lead to a prolonged clotting time and thrombocytopenia. Long term exposure (4 weeks) to manganese caused another bleeding disease, called hemophilia. It was thus evident that the exposure to heavy metals led to clotting defects, which caused bleeding.

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