<p>The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials.</p>

Landfill leachate treatment in South Africa is still in its early stages; research has been conducted but primarily at pilot scale level. Current legislation in South Africa does not prohibit the discharge of landfill leachate into the sewer line, despite the high risk of methane explosions and corrosion of the sewer pipes. Thus, to date, the off site channelling of landfill leachate into the sewer lines for further dilution in municipal wastewater treatment plants is the most common practice. Due to the development of stricter environmental regulations, the design of sustainable landfills is leading to the 'treatment at source' concept. Increasing public pressure is also forcing new landfills to be situated in remote areas where there is no avaliable sewer line to discharge into and 'treatment at source' will be required. Due to these developments, coupled with the lack of full scale leachate treatment experience in South Africa, Durban Solid Waste (The waste service unit of the Durban metropolitan), in an attempt to develop the knowledge and practical experience required for leachate treatment, undertook a research project to investigate the use of nitrification/denitrification pilot scale sequencing batch reactors (SBR) to treat leachate from the Bisasar Road and Mariannhill Landfills. The successful completion of the trials proved that the full removal of nitrogen compounds could be easily achieved, under South African climatic conditions, in a single sludge SBR system. The system was found to be simple to operate and required low maintenance. However, the final effluent required further treatment before it could meet the general discharge standards into natural watercourses. Being South Africa, a 'low gross income' country, it became necessary to consider an appropriate, cost effective and technically feasible 'polishing' treatment system. It was decided that a pilot scale treatment trial, using vegetated submerged bed constructed wetlands, be undertaken to assess the applicability and feasibility of such a passive system for the 'polishing' of the effluent from the pilot scale sequencing batch reactors. The wetland systems were found to be affected by many interrelating climatic factors. The trials concluded that the wetlands could not achieve the required discharge standards, in terms of concentration. However, it also showed that the effluent organics posed no oxygen demand or toxic threat to a receiving environment. The trials showed the ability of the wetlands to behave as mass removal systems, which could achieve the required mass removal efficiency in terms of mass output per day. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2003.

Co-disposal with refuse in a controlled landfill is the cheapest option for the disposal of hazardous waste and, if carefully controlled, can be an effective treatment option. In this present study a high-strength phenolic wastewater and activated sewage sludge were co-disposed with refuse. The effectiveness of phenol catabolism at two organic loading rates (500mgt1 and 1000mgtl) was assessed in the presence of various co-disposal strategies. Leachate recycle at the lower phenol organic loading rate was found to facilitate the greatest rate of phenol catabolism. Despite the effective removal of phenol, however, leachate recycle promoted the production of high concentrations of ammoniacal-N and hydrogen sulphide. At the higher phenol organic loading rate, recirculation was ineffective in reducing the residual phenol concentration due to inhibition of the phenol-catabolisers. Microcosms operated with single elution and batch co-disposal strategies at both phenol organic loading rates resulted in serious detrimental effects on the refuse fermentation and subsequent leachate quality. A high-strength leachate obtained from a closed co-disposal site was characterised to determine its chemical composition and was assessed for its susceptibility to biological treatment. If carefully controlled, co-disposal sites should produce leachates which differ little in quality to those produced by municipal waste sites. The exceptionally high specific conductivity of the leachate used in this present study was, however, uncharacteristic of a leachate from a municipal waste site. The leachate required dilution to 25 % (v/v) before responding to aerobic biological treatment due to the presence of bactericidal/bacteriostatic components. Anaerobic treatment was ineffective even at a final dilution of 10% (v/v) of the original due to the inhibition of methanogenesis caused indirectly by the high concentration of sulphate in the leachate. Following phosphate addition, aerobic biological treatment effected a significant reduction in the chemical oxygen demand (COD) but did not reduce the ammoniacal-N concentration. Scaling and precipitation occurred following addition of the phosphate, and although these did not affect the biological process they can cause operational problems in full-scale leachate treatment plants. Ion exchange, with soil, and lime treatment, were, therefore, considered for their ability to reduce the inorganic content of the leachate prior to biological treatment. However, these particular pretreatments were unsuitable due to their ineffectiveness to reduce calcium, the main inorganic element involved in scaling, to an acceptable concentration. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 1996.

Downed woody debris (DWD) is a carbon-rich form of forest litter and plays a unique role in carbon and nutrient cycling. I present a novel modeling approach describing DWD decomposition and nutrient storage in a managed northern hardwood forest. The predicted half-life of DWD carbon was 7 years, less than previously observed in similar northern hardwood forests. A stage-based nutrient model indicated that harvest slash DWD was a net nitrogen and phosphorus sink for eight years following harvest and accumulated calcium during decay. Field observations of respiration and leaching supported model results with a respired C half-life of 8 years, while leached carbon export constituted 1.37% of the respired flux. DWD leachate carbon and nitrogen concentrations were 11× and 2× greater than from litter, respectively, and DWD leachate contributed disproportionately to soil C stocks. This work represents an expedient means of forecasting DWD abundance and partitioning carbon flux from DWD.

Unintentional nitrogen (N) loss from agroecosystems produces greenhouse gases, induces eutrophication, and is costly for farmers; therefore, adoption of conservation agricultural management practices, such as no-till and cover cropping, has increased. This study assessed N loss via leaching, NH3 volatilization, N2O emissions, and N retention in plant and soil pools of corn conservation agroecosystems across a year. Three systems were evaluated: 1) an unfertilized organic system with cover crops Vicia villosa, Triticum aestivum, or a mix of the two; 2) an organic system with a Vicia cover crop employing three fertilization schemes (0 N, organic N, or a cover crop N-credit approach); 3) a conventional system with a Triticum cover crop and three fertilization techniques (0 N, urea N, or organic N). During cover crop growth, species affected N leaching but gaseous emissions were low across all treatments. During corn growth, cover crop and fertilizer approach affected N loss. Fertilized treatments had greater N loss than unfertilized treatments, and fertilizer type affected gaseous fluxes temporally and in magnitude. Overall, increased N availability did not always indicate greater N loss or yield, suggesting that N conserving management techniques can be employed in conservation agriculture systems without sacrificing yield.

Selective oxidation and sulfation roasting of nickel concentrate followed by leaching was investigated as a novel route for nickel production. In the oxidation roasting stage, the iron species in the nickel concentrate was preferentially oxidized to form iron oxides, leaving non-ferrous metals (Ni, Cu, Co) as sulfides. The roasted product was then sulfation roasted to convert the sulfides of the latter metals into water-soluble sulfates. The sulfates were then leached into solution for further recovery and separation from iron oxides. The oxidation of nickel concentrate was firstly studied by means of thermogravimetric and differential thermal analysis over a wide temperature range. A reaction scheme was deduced, in which preferential oxidation of iron sulfide species occurred over a wide temperature range up to about 700 ºC, forming a Ni1-xS core with iron oxide shell. A batch fluidized bed roaster was then constructed to study the oxidation and sulfation roasting of nickel sulfide concentrate. Oxidation roasting tests were carried out at temperatures between 650 °C and 775 °C. It was found that low temperatures (e.g. 650 °C) are favorable for the preferential oxidation of iron sulfide species while minimizing the formation of nickeliferous oxides, i.e. trevorite and NiO. Several parameters were varied in the sulfation roasting experiments, including the sulfation gas flowrate, sulfation roasting temperature, the addition of Na2SO4, sulfation roasting time, and the oxidation roasting temperature. Under optimized conditions of sulfation gas composition (95% air, 5% SO2), temperature (700 °C), Na2SO4 addition (10 wt%) and time (150 min), the conversions to sulfates were 79% Ni, 91% Cu, and 91% Co. Only 5% Fe forms water-soluble sulfate. The residue from the leaching of calcine in water contained 49% Fe and 10% Ni, which is a suitable feedstock for the production of ferronickel alloys. Therefore, further studies were also conducted to evaluate the reduction behavior of the residue with CO, H2 and graphite.

Agricultural management practices geared towards reducing nutrient leaching are in focus for the research presented in this thesis. Critical measures for reducing diffuse pollution from the agricultural sector depend on decisions of individual farmers. It is useful to take stock of what different stakeholders are actually doing to reduce nutrient leaching and analyze their reasoning before defining a new administrative process. Stakeholder perceptions about potentials and problems concerning management of agricultural practices are analyzed with a systems approach using various analytical methods, and put in relation to the implementation of EC Water Framework Directive in Sweden. The methods used include surveys, focus group interviews, model comparison, sensitivity analyses and analyses of climate change implications. The results indicate a general positive attitude among stakeholders towards the main characteristics of the newly introduced directive. They also reveal that a move towards a pro-active process was perceived as an additional positive factor for the improvement of water quality, where specific activities and measures are carried out according to planning based on local assessments. The respondents pointed out that a national approach would put necessary pressure on local politicians to define environmental objectives and provide resources to fulfil them. The current findings indicate that decision making for farmers is a complex procedure and that the different factors need to be addressed in order to obtain a change in agricultural practices. Consistent legislation that is clear about power and rights is fundamental for cooperation to function when volunteerism and enthusiasm are absent. Environmental and socio-economic conditions change constantly, and administration has to be flexible to be able to adapt. Having access to and being able to use relevant data is only one important factor for stakeholder involvement. To give farmers the opportunity to further develop production towards reduced nutrient losses, appropriate information provided in all the right arenas is crucial.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.