In this thesis, it was aimed to select and propose a feasible method, or series of methods, for the recovery of zinc (Zn) and lead (Pb) that are present in disposed &Ccedil / iNKUR leach residues having 12.43 % Zn, 15.51 % Pb and 6.27 % Fe. Initially, physical, chemical and mineralogical characterizations of the leach residues were done. Results of these analyses showed that lead was present as lead sulfate (PbSO4), and zinc was present as zinc sulfate heptahydrate (ZnSO4.7H2O), zinc ferrite (ZnFe2O4) and zinc silicate (2ZnO.SiO2) in the leach residues. Initially, water leaching experiments were carried out to determine water soluble amount of blended leach residue, and the maximum zinc recovery was obtained as 18 %. After these trials, sulphuric acid and brine leaching were used to recover zinc and lead, respectively. Firstly, due to the insufficient recovery in water leaching trials acid leaching experiments were done for zinc recovery and the parameters studied were acid concentration, reaction duration, leaching temperature and solid-liquid ratio (pulp density). About 72 % Zn was recovered after hot acid leaching by using 150 g/l H2SO4 at 95 oC in 2 hours with a pulp density of 200 g/l. For lead recovery brine leaching experiments were done with the secondary leach residue obtained after H2SO4 leaching. In brine leaching experiments, NaCl concentration, pulp density (solid/liquid ratio), reaction duration and leaching temperature were chosen as variables. Effect of HCl addition was also investigated. In brine leaching while lead recoveries up to 98 % could be attained at a low pulp density in laboratory scale, the maximum recovery obtained was 84.9 % at a high pulp density (200 g/l) with 300 g/l NaCl concentration in 10 minutes at 95 oC.

>Magister Scientiae - MSc / Most of the world's energy production is still mainly achieved by the combustion of coal in power stations. Coal fly ash is the inevitable waste product that accumulates to metric ton volumes each year. These vast volumes pose a problem in the disposal of the coal fly ash which conventionally is loaded onto ash dumps located near the coal power stations. Alternatives need to be investigated for the use of the coal fly ash in applications that would make the coal fly ash useful and thereby help to mitigate the environmental strain imposed by conventional ash dump disposal. This study focussed on investigating the extraction of Si and Al from CFA. The investigation into the removal of the magnetic iron oxide content and calcium content from coal fly ash was also carried out to enhance the extraction of the Si and Al from CFA e.g. the removal of calcium was attempted to promote the leaching of aluminium from the ash. The rationale for this process was that by removing and recovering these major constituent elements from the ash, it would be easier to concentrate and isolate the trace elements especially the rare earth elements that are present in the CFA. Coal fly ash sourced from Matla coal power station was characterised using x-ray diffraction to determine the mineral phases present in the raw coal fly ash and elemental composition determined by x-ray fluorescence and laser ablation ICP-MS. The main mineral phases in coal fly ash were determined to be quartz, mullite, magnetite and lime (CaO). Magnetic extraction was initially carried out on the coal fly ash to remove the iron rich magnetic material. Extraction tests were then performed on the coal fly ash using alkaline and acidic media namely; NaOH, HCl and H₂SO₄. The extraction tests were assessed and a sequential extraction experimental procedure developed to achieve the highest extraction yield for Si, Al, Fe, Ca, and Mg from the coal fly ash. Lastly the rare earth element content in coal fly ash was tracked from the beginning till the end of the sequential extraction procedure to ascertain whether the rare earth elements partitioned to the leachates or the solid residues. The total element recoveries for Al, Si, Ca Fe, Mg were 53.36 %, 39.96 %, 93.8 %, 25.6 % and 67.3 % respectively using the sequential extraction procedure developed in this study. The rare earth elements contents were not affected by the sequential extraction procedure and on the whole remained in the solid residues at the completion of the sequential extraction, resulting in a residue with enriched levels of recoverable or extractable REE content after the removal of the major oxides from the CFA. The lowest enrichment being approximately 5 % for Thulium and the highest being approximately 76 % for Erbium.

Yield and chemical changes of second-cutting alfalfa hay treated with artificial rain were determined in a 2 x 3 x 2 factorial experiment. Factors were 2 stages of maturity (1 late vegetative; 2 early bloom), 3 levels of artificial rain applied (1 =no rain; 2 =low or approximately 5 mm; 3 =high or approximately 20 mm), and 2 times of applying artificial rain (1 = when drying forage was 40-60% dry matter; 2 =when drying forage was 60-75% dry matter). Thirty samples of alfalfa were collected at the 2 stages of maturity when the alfalfa was fresh cut, pre-sprinkled, pre-baled and prefeeding. Alfalfa samples were analyzed for dry matter, nitrogen, ash, plant cell walls, cellulose, hemicellulose, lignin, total lipids and acid insoluble ash. Available carbohydrates and soluble ash were calculated. Yield of dry matter increased with advancing maturity. Plant cell content fraction was lowered but plant cell wall constituents were increased with advancing stage of growth. Artificial rain significantly affected chemical composition of alfalfa hay. Available carbohydrates, soluble ash and ash decreased due to the effect of leaching. Total lipids was slightly reduced by leaching, while protein content was not changed. Cellulose, lignin and cell wall fractions of alfalfa hay increased consistently under the effect of artificial rain. Sprinkling and processing time did significantly change the chemical composition of alfalfa hay. DM and AlA content increased in relation to process. Interactions among treatment factors were generally nonsignificant. The only significant interactions were maturity-by-artificial rain level effect on available carbohydrate, lipids, cellulose and cell wall. In general, alfalfa hay treated with artificial rain had a lower nutritive and economic value than when it is not affected by any rain.

Corn (Zea mays L.) and soybean (Glycine max (L.) Merr.) production in Illinois has a significant impact on the economy and environmental footprint in the state and the Midwest region. Nutrient leaching from Midwestern agricultural fields is one of the major reasons for the hypoxic zone developed in the Gulf of Mexico. Winter-fallow and early spring (after fertilizer application) are the two most critical periods for nutrient leaching due to increased precipitation and availability of nutrients. Cover crops (CCs) in these seasons are a promising best management practice (BMP) to reduce nutrient leaching in the winter-fallow season. No-till (NT) and reduced tillage (RT) are some other BMPs that farmers in Illinois adopt to reduce erosion. The adoption of CCs is limited due to the lack of knowledge and data on the yield and environmental benefits of CCs in different climatic and soil regimes. Thereby, this doctoral dissertation addresses several critical questions about CC and tillage impacts in claypan soils of southern Illinois with four principal projects with multiple objectives. Research study 1 was a field experiment conducted from 2013-to 2021 to understand the effect of CCs (CCs vs. noCC) and two tillage (NT and RT) practices on soil nitrate-N leaching. The experimental design was a complete randomized design with CC treatments that had two levels (two crop rotations) corn-cereal rye (Secale cereale L.)-soybean-hairy vetch (Vicia villosa R.) [CcrShv] and corn-noCC-soybean-noCC [CncSnc] and tillage treatments with two levels (NT and RT) replicated three times in the field. Each plot had a pan lysimeter installed below the A horizon (22-30 cm depth) to collect water samples weekly or biweekly depending on the rainfall. The corn yield was significantly greater in RT rotations compared to NT rotations with a 36% increase in the yield in 2019 and 2021 corn rotations. The yield was significantly greater in CcrShv rotations compared to the CncSnc rotations. The greatest yield was observed in the interaction of CcrShv-RT in all years. This increase in yield is inversely correlated to the remaining soil N values when the N credit from CCs was not accounted for. Soil nitrate-N leaching was significantly greater in CcrShv rotations compared to the CncSnc rotation in 2021 indicating vetch CC biomass decomposition can lead to increased leaching losses if the window between CC termination and corn planting is not minimized. Precipitation during the early spring can play a vital role in flushing the newly applied fertilizer as well as the N released from decomposing CC residue. The excessively wet year of 2019 showed that N losses are dominated by both nitrate-N leaching and nitrous oxide emissions, but in a typical growing season N losses are dominated by leaching compared to emissions. Research study 2 was designed to better understand the N cycling and fate of applied N in a complete corn-soybean rotation in southern Illinois with CCs and tillage practices. The research was overlayed in the same field with the same crop rotation and tillage practices. In this study, 15N labeled urea fertilizer (9.2% atom) was applied before the corn and soybean seasons. Soil, water, and biomass samples were collected to understand N distribution in each pool. In the corn season in 2017 a significantly greater 15N recovery was observed in CC (CcrShv) plots compared to the noCC plots in the sample collected seven days after planting (DAP). In the CC and depth interaction, a significantly greater 15N recovery was observed in 15-30 cm depth showing that the increased macropores due to CCs can lead to subsurface movement of N through the topsoil. The 15N recovery in water samples was high in CncSnc rotations in the cereal rye season but was significantly greater in CcrShv rotations (8.95 kg ha-1) in hairy vetch seasons. In the two years of complete rotation, the cumulative 15N recovery (quantity derived from fertilizer in water) was significantly greater in CC rotation. In the corn plants, the 15N recovered from the soil was greater than the 15N recovered from fertilizer. This shows the importance of the residual N from prior fertilizer and organic matter input. In the cereal rye season, CCs recovered significantly greater 15N from fertilizer compared to noCC rotations, assuring that cereal rye is an effective nutrient scavenger. A similar pattern was observed in the hairy vetch season as well. However, the soybean 15N recovery was greater in noCC rotations compared to CC rotations. The third study was a field trial on CCs and tillage to understand their individual and combined impact on soil physical parameters. Soil physical parameters were first measured in 2014 and were repeated in 2021. Bulk density at the 0-5 cm depth was 5% lower in 2021 compared to 2014 with the lowest BD in CC rotations with RT practices. For the depth of 0-15 cm, the lowest BD was observed in CC rotation with RT but, the largest reduction was observed in the CC rotation with NT. The wet aggregate stability was improved from 15-28 % over the years in all rotations. The lowest percentage improvement was observed in noCC rotation with RT practice. Penetration resistance was significantly lower in CC plots for the depth of 0-2.5 cm. CCs further improved the time to runoff in plots even though the infiltration rates were not affected. Chemical soil health indices were not significant overtime for CCs or tillage practices. However, a large number of earthworm counts were observed in NT systems compared to RT systems. The final project was a field trial to identify the soil P response to the CC and tillage practices. For this study, three different CC rotations, [corn-cereal rye-soybean-hairy vetch / corn-cereal rye-soybean-oats+radish / corn-noCC-soybean-noCC] and two tillage practices (NT and RT) were used. Soil samples were collected after the corn harvest in 2015 and 2021 and were analyzed for soil Phosphorus (P), inorganic P fractions by Chan and Jackson method, and dissolved reactive phosphorus (DRP) in leachate. The soil Mehlich-3 and Bray-1 P values indicate a great concentration of P in 0-15 cm depth for both years. More refined sampling in 2021 showed that the majority of P in 0-15 cm depth concentrates at the near-surface soil, in 0-5 cm depth irrespective of the CC and tillage treatment. Inorganic soil P fractions were not significantly different between CCs or tillage practices over time. Yet, irrespective of the treatment the non- labile P forms increased in 2021in the soil compared to 2015. The average and cumulative DRP values were highly dependent on the precipitation amounts and timing. However, in general, NT systems had greater average and cumulative DRP leaching compared to RT in both years. In general, CCs in the winter-fallow season is a good recommendation for farms that seek to maximize their production with a minimal environmental footprint. In the long run, CCs can improve soil physical and chemical properties which ultimately can increase the yield potential for corn and soybean. The added benefit of N credit due to leguminous CCs can reduce the fertilizer inputs. The CC benefits including the reduction in nutrient leaching depend on the type of CCs used in the field. More importantly, the CC termination time will be critical to obtain the maximum benefit of CCs. Even though the NT practices improve soil physical properties, long-term NT can increase the risk of soil P stratification in near-surface soils and can ultimately lead to more P loss via erosion, runoff, and soil water leaching. However, the combined use of CC and NT practices can help minimize the potential for erosion and runoff.

No description available.

The process of natural gas extraction through hydraulic fracturing produces large quantities of fluid containing naturally-occurring salt, radionuclides, and heavy metals which form residual solids during storage and treatment. The purpose of this research was to characterize the residual solids from hydraulic fracturing operations in the Marcellus Shale to predict the leaching behavior of select elements in disposal environments. Samples collected for this research were: (1) drilling mud, (2) treated sludge from the chemical treatment of process waters, (3) solids from the gravity settling of produced water, and (4) sludge solidified prior to disposal in a municipal landfill. These samples were subjected to various digestion techniques to determine the composition and leaching potential for elements of concern. Strong acid digestions were performed to determine the total environmentally available composition, whereas weak acid digestions were used to predict the leaching potential of these solids under various environmental conditions. The extraction fluids for the leaching experiments included weak acetic acid, acid rain, reagent water, and synthetic landfill leachate. Solids were agitated in a standard tumbling apparatus to simulate worst-case conditions based on ASTM and EPA recommendations. Results from EPA's Toxicity Characteristic Leaching Procedure (TCLP) were used to determine if solids were considered hazardous based on the metal leaching potential. The results from strong and weak acid digestions were compared to better understand the types and quantity of materials that have the potential to leach from the samples. This research may be used to develop best management practices for hydraulic fracturing residual solids. / Master of Science

Master of Science / Department of Horticulture, Forestry, and Recreation Resources / Dale J. Bremer / Jack D. Fry / Irrigation management may influence nitrate leaching under tall fescue (Festuca arundinacea) and also affect its mowing requirements. Two experiments were conducted on tall fescue growing on a Chase silt loam soil near Manhattan, Kansas. Each experiment was arranged in a split-plot design, with irrigation treatments applied to whole plots: 1) frequency-based irrigation, water was applied three times weekly to deliver a total of 19 mm water wk⁻¹ regardless of weather conditions; and 2) soil moisture sensor (SMS)--based irrigation, 34 mm of water was applied when soil dried to a predetermined threshold. In the first experiment, sub-plots consisted of unfertilized turf, and N applied as urea or polymer-coated urea at 122 and 244 kg ha⁻¹ yr⁻¹. Suction lysimeters at a 0.76 m depth were used to extract nitrate leachate bi-monthly. Turf quality was rated weekly. In the second experiment, subplots were mown at 5.1 cm or 8.9 cm, based upon the 1/3 rule, with or without monthly applications of the growth regulator trinexapac-ethyl (TE). Data were collected on total mowings and visual turf quality. Soil moisture sensor-based irrigation resulted in water savings of 32 to 70% compared to frequency-based irrigation. Leaching levels did not exceed 0.6 mg L⁻¹ and no differences in leaching were observed between irrigation treatments or among N sources. All fertilized turf had acceptable quality throughout the study. In the second experiment, irrigation strategy did not influence total number of mowings. In the first year, TE application reduced total mowings by 3 in tall fescue mowed at 5.1 cm, but only by 1.5 when mowed at 8.9 cm. In the second year, mowing at 8.9 vs. 5.1 cm or using TE vs. not resulted in a 9% reduction in total mowings each. The SMS-based irrigation saved significant amounts of water applied compared to frequency-based irrigation, while maintaining acceptable quality, but irrigation treatments did not affect nitrate leaching or mowing frequency in tall fescue on fine silt-loam soil. Nitrate leaching, regardless of amount, was well below the standards set for human health (10 mg L⁻¹). Applications of TE are more beneficial for turfgrass mowed at lower cutting heights.

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Thesis (PhD (Process Engineeering))--University of Stellenbosch, 1995. / The hydrometallurgical leaching of sulphide concentrates was introduced in the 1950's. Generally the leaching mechanisms of these processes are not understood fundamentally. The reasons for this are the inherently complex nature of sulphide chemistry and that the sulphide concentrates usually consist of highly intergrown sulphide minerals. The leaching kinetics of sulphide concentrates where only one metal-sulphide mineral occurs have been investigated intensively, but not for sulphide concentrates with more than one metal-sulphide mineral. The behaviour of these mixed metal-sulphide minerals has mostly been investigated on plant scale to qualitatively determine the leaching trends of the process. The consequence of the relatively unKnown leaching mechanism and kinetics is that these processes are not controlled efficiently. This study was conducted on the acid-oxygen pressure leaching of Ni-Cu matte (the first stage leach process at the Ni-Cu refinery of Impala Platinum Ltd.). As a first step to improve the control efficiency of the process, the process must be stabilised. Therefore, an off line computer simulation program is proposed to control the repulping section of the plant that has previously been controlled solely by an operator. Controlling the repulping section is very important, because conditions exist in the repulping tanks for leaching to occur. This causes perturbations in the pulp entering the pressure leach autoclave. Due to the fast reaction kinetics of the matte in the pressure leach autoclave the perturbations entering the autoclave will influence the performance of the acid-oxygen pressure leach process. The simulation program was tested on the plant and indicated that considerable improvement in the stability of the operation could be achieved. In obtaining a better understanding of the behaviour of this process, it is essential that key variables and trends are identified. A methodology is proposed to analyse and model this ill-defined and poorly understood process from historical data by v artificial neural networks (ANN), inductive learning by decision trees and statistical techniques. The back propagation neural network, learning vector quantization neural network and the decision trees yielded comparable classification rates between 73% and 84%, and could serve as a basis for the adjustment of operating conditions to improve the efficiency of the process. The relative importance of the process variables is determined by a method of sensitivity analysis and together with the statistical mean, the effect of an increase or decrease in the variable on the process is quantified. These results are substantiated by experimental findings. A leaching mechanism for the acid-oxygen pressure leach of Ni-Cu matte is postulated. The leaching sequence of the nickel and copper sulphides is Ni3Sr Ni7S" NiS-Ni3S4, and CU2S-CU31SWCU1.BS-CUS, respectively. Ni7Sa and CU31 S1a are intermediate nickel and copper sulphide phases that form during the leaching process. Ni alloy has a galvanic effect on the sulphide minerals which inhibits the overall leaching rate and results in the formation of H2S and the intermediate nickel and copper sulphides (Ni7Sa and CU31 S1a). A semi-empirical kinetic model was developed based on the chemical reaction rate expressions of the leaching mechanism. This model can accurately simulate the batch leaching process for variations in the oxygen partial pressure, oxygen flowrate, temperature, particle size, initial acid concentration and pulp density. A sensitivity analysis on the model indicated that for a matte with a lower initial Ni alloy content the leaching rate of nickel is much faster.