The pollution of South Africa’s water resources puts a strain on an already stressed natural resource. One of the main pollution sources is industrial effluents such as acid mine drainage (AMD) and other mining effluents. These effluents usually contain high levels of acidity, heavy metals and sulphate. A popular method to treat these effluents before they are released into the environment is lime neutralisation. Although this method is very effective to raise the pH of the effluent as well as to precipitate the heavy metals, it can only partially remove the sulphate. Further treatment is required to reduce the sulphate level further to render the water suitable for discharge into the environment. A number of sulphate removal methods are available and used in industry. These methods can be divided into physical (membrane filtration, adsorption/ion exchange), chemical (chemical precipitation) and biological sulphate reduction processes. A literature study was conducted in order to compare these different methods. The ABC (Alkali – Barium – Calcium) Desalination process uses barium carbonate to lower the final sulphate concentration to an acceptable level. Not only can the sulphate removal be controlled due to the low solubility of barium sulphate, but it can also produce potable water and allows valuable by–products such as sulphur to be recovered from the sludge. The toxic barium is recycled within the process and should therefore not cause additional problems. In this study the sulphate removal process, using barium carbonate as reactant, was investigated. Several parameters have been investigated and studied by other authors. These parameters include different barium salts, different barium carbonate types, reaction kinetics, co–precipitation of calcium carbonate, barium–to–sulphate molar ratios, the effect of temperature and pH. The sulphate removal process was tested and verified on three different industrial effluents. The results and conclusions from these publications were used to guide the experimental work. A number of parameters were examined under laboratory conditions in order to find the optimum conditions for the precipitation reaction to take place. This included mixing rotational speed, barium–to–sulphate molar ratio, initial sulphate concentration, the effect of temperature and the influence of different barium carbonate particle structures. It was found that the reaction temperature and the particle structure of barium carbonate influenced the process significantly. The mixing rotational speed, barium–to–sulphate dosing ratios and the initial sulphate concentration influenced the removal process, but not to such a great extent as the two previously mentioned parameters. The results of these experiments were then tested and verified on AMD from a coal mine. The results from the literature analysis were compared to the experiments conducted in the laboratory. It was found that the results reported in the literature and the laboratory results correlated well with each other. Though, in order to optimise this sulphate removal process, one has to understand the sulphate precipitation reaction. Therefore it is recommended that a detailed reaction kinetic study should be conducted to establish the driving force of the kinetics of the precipitation reactions. In order to upgrade this process to pilot–scale and then to a full–scale plant, continuous reactor configurations should also be investigated. The sulphate removal stage in the ABC Desalination Process is the final treatment step. The effluent was measured against the SANS Class II potable water standard and was found that the final water met all the criteria and could be safely discharged into the environment. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

The pollution of South Africa’s water resources puts a strain on an already stressed natural resource. One of the main pollution sources is industrial effluents such as acid mine drainage (AMD) and other mining effluents. These effluents usually contain high levels of acidity, heavy metals and sulphate. A popular method to treat these effluents before they are released into the environment is lime neutralisation. Although this method is very effective to raise the pH of the effluent as well as to precipitate the heavy metals, it can only partially remove the sulphate. Further treatment is required to reduce the sulphate level further to render the water suitable for discharge into the environment. A number of sulphate removal methods are available and used in industry. These methods can be divided into physical (membrane filtration, adsorption/ion exchange), chemical (chemical precipitation) and biological sulphate reduction processes. A literature study was conducted in order to compare these different methods. The ABC (Alkali – Barium – Calcium) Desalination process uses barium carbonate to lower the final sulphate concentration to an acceptable level. Not only can the sulphate removal be controlled due to the low solubility of barium sulphate, but it can also produce potable water and allows valuable by–products such as sulphur to be recovered from the sludge. The toxic barium is recycled within the process and should therefore not cause additional problems. In this study the sulphate removal process, using barium carbonate as reactant, was investigated. Several parameters have been investigated and studied by other authors. These parameters include different barium salts, different barium carbonate types, reaction kinetics, co–precipitation of calcium carbonate, barium–to–sulphate molar ratios, the effect of temperature and pH. The sulphate removal process was tested and verified on three different industrial effluents. The results and conclusions from these publications were used to guide the experimental work. A number of parameters were examined under laboratory conditions in order to find the optimum conditions for the precipitation reaction to take place. This included mixing rotational speed, barium–to–sulphate molar ratio, initial sulphate concentration, the effect of temperature and the influence of different barium carbonate particle structures. It was found that the reaction temperature and the particle structure of barium carbonate influenced the process significantly. The mixing rotational speed, barium–to–sulphate dosing ratios and the initial sulphate concentration influenced the removal process, but not to such a great extent as the two previously mentioned parameters. The results of these experiments were then tested and verified on AMD from a coal mine. The results from the literature analysis were compared to the experiments conducted in the laboratory. It was found that the results reported in the literature and the laboratory results correlated well with each other. Though, in order to optimise this sulphate removal process, one has to understand the sulphate precipitation reaction. Therefore it is recommended that a detailed reaction kinetic study should be conducted to establish the driving force of the kinetics of the precipitation reactions. In order to upgrade this process to pilot–scale and then to a full–scale plant, continuous reactor configurations should also be investigated. The sulphate removal stage in the ABC Desalination Process is the final treatment step. The effluent was measured against the SANS Class II potable water standard and was found that the final water met all the criteria and could be safely discharged into the environment. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

The Coalfields of the Republic of South Africa (RSA) discharge approximately 360 Ml d-1 of mine impacted water, referred to as Acid Mine Drainage (AMD), requiring neutralization to reduce risk to the environment. High Density Sludge Process (HDSP) is commonly used to treat AMD, and neutralization is typically with either limestone (CaCO3) alone to save costs, or with limestone plus hydrated lime (Ca(OH)2) to effectively reduce acidity and improve metal removal. This water either needs to be further treated to reduce metal content and salinity, or a potential option is to use it for irrigation. Since, it would be possible to lime a soil and irrigate directly with AMD as this would be potentially easy to manage than an HDS plant and save costs on the plant. The treatment process produces a circum-neutral mine water that requires further treatment with reverse osmosis to potable water. Suitability of these waters for irrigation can be evaluated with the Irrigation Water Quality Decision Support System (IWQDSS) for RSA. This study therefore evaluated the two specific mine impacted waters for irrigation. The treatment process also generates gypseous products, referred to as High Density Sludges (HDS), which may be classified as hazardous, based on metal (Mn, Ni, Pb) content, in which case expensive waste storage is required. However, these sludges may have some value for use in agriculture since they are gypseous. Four out of six sludges considered in this study were investigated for potential use in agriculture since their chemical characteristics depend on the quality of AMD and the treatment process. If hazardous, a potential approach was to add phosphate to them since this has been shown before to immobilize metals. The influence of phosphate on the availability of elements in sludges was therefore investigated. Hence, the objectives were to investigate; 1) the fitness for use of AMD and circum-neutral mine impacted waters for irrigation with IWQDSS, 2) chemical and physical properties of sludges, 3) hazardous status of sludges using the RSA waste classification system including those of the United States Environmental Protection Agency (USEPA), Australia, China and Canada, 4) phosphate potential in reducing the solubility of metals in sludges, 5) crop and soil response to sludges applied on their own as soil amendments and when co-applied with phosphate, 6) the influence of phosphate co-applied with sludges to the phyto-availability and uptake of Ni and Pb, including food safety. Assessment with IWQDSS showed that both waters were not fit for irrigation because of some quality issues. However, AMD can only be used if the soil can be limed and used as a reactor and further showed that there would be no leaf scorching. The circum-neutral mine water was found to be not effectively saline. Micro irrigation should not be considered for these waters due to suspended solids they contain. Four of the six sludges assessed for agricultural use included; a Ferriferrous Gypseous sludge (GypFeMnNi) with Fe, Mn and Ni from a limestone process, and three others generated from three stages of a limestone plus hydrated lime process; Ferriferrous Gypseous sludge with Mn (GypFeMn), Gypseous sludge with Brucite (GypB) and Gypseous sludge (Gyp) with Fe removed. Chemically, the sludges, GypFeMn, GypB and Gyp showed pH values of 8.2, 9.4 and 9.5, exhibiting CaCO3 equivalents (CCE) of 510, 601, 617 mg kg-1. The sludge, GypFeMnNi, had a pH of 5.5 and a CCE of 250 mg kg-1. All four sludges showed to be largely gypsum (72 – 95 %) composed. Physically, all sludges had particle sizes falling between 0.4 to 906 µm. These four sludges were further considered for hazardous assessment, including two sludges; GypFeNi and GypFe from a different limestone process. USEPA rated all six sludges non-hazardous, while Canada and China found GypFeNi as hazardous based on Ni solubility, Australia found GypFeMn as hazardous. RSA considered GypFeMnNi and GypFeNi hazardous, based on Ni and Mn solubility. Limestone was therefore less effective in reducing the solubility of Ni and Mn in the sludges than limestone plus hydrated lime. The sludges found hazardous (GypFeMnNi and GypFeMn) were then phosphated to reduce Mn and Ni solubility. Their solubility was reduced in both sludges. GypFeMnNi and Gyp, were further considered for use as soil amendments and selection was based on differences in the treatments that generates them. A pot trial was conducted where both were applied at 10 and 20 t ha-1 each to a soil with pH 3.75 and co-applied with phosphate at application rates of 40 and 100 kg ha-1. Maize (Zea mays) was planted and harvested at physiological maturity. Effect on soil showed that both sludges marginally increased pH, with Gyp at 20 t ha-1 and 100 kg ha-1 P increasing it the most by 0.46 units. This pH was still not suitable for plant growth. The sludge, Gyp increased soil salinity the most from 7.8 mS m-1 to 728 mS m-1, suitable only for salt tolerant crops. The effect on the maize showed that both sludges on their own marginally increased plant height and biomass, but co-application with phosphate increased these parameters. Grain was present only in treatments where phosphate was co-applied with either sludge. The highest grain yield was obtained when Gyp was applied at 20 t ha-1 with 100 kg ha-1 P. With food safety, Ni and Pb concentrations in the grain were below thresholds regarded as toxic. It is suggested that irrigation with AMD may be possible on condition that the soil is limed and used as treatment reactor to prevent the reduction of soil pH. Also, micro irrigation systems are to be avoided when irrigating with AMD and circum-neutral mine impacted waters because they contain suspended solids that can clog them. Irrigation should be with an appropriate leaching fraction to reduce accumulation of salts in the soil profile. It can also be concluded that two of the sludges from a limestone only HDSP were found to be hazardous by the RSA waste classification system due to Mn and Ni solubility., whereas international systems felt these materials were non-hazardous. The RSA waste classification system was found to be overly cautious compared to international systems and should be revisited. Sludges from HDSP can rather be used as soil amendments instead of being classified hazardous and destined to expensive waste management sites. If certain trace elements are excessively available, the study demonstrated that phosphating reduces mobility and toxicity, ensuring the safety of produce from soils treated with HDS. Keywords: AMD, HDS, Circum-neutral mine water, waste classification, amendment / Thesis (PhD (Soil Science)--University of Pretoria, 2020. / WRC / Plant Production and Soil Science / PhD (Soil Science) / Unrestricted

Fanny Creek drains from Island Block opencast coal mine, near Reefton on the West Coast of the South Island of New Zealand, and is impacted by acid mine drainage (AMD). The objectives of this study were to characterise drainage chemistry in Fanny Creek catchment, and to determine optimal passive treatment strategies for Fanny Creek AMD for future pilot or full-scale application. This was undertaken by monthly monitoring in Fanny Creek catchment between February 2008 and January 2009 to collect drainage chemistry and flow data. Laboratory trials of suitable passive AMD treatment systems were conducted and their treatment performance assessed to select and design optimal passive treatment strategies for Fanny Creek AMD. Oxidation of pyrite in Brunner Coal Measure sediments at Island Block mine generates AMD. Fanny Creek originates from a number of AMD seeps on the eastern waste rock slope of Island Block mine. Seeps have low pH (<3.23) and a single detailed metal analysis indicates drainage is enriched with aluminium and iron, and contains elevated concentrations of manganese, copper, nickel, zinc and cadmium relative to applicable water quality criteria such as ANZECC guidelines. Acidity and metal loadings of drainage in the catchment indicates AMD from the northern waste rock slope contributes most of the acidity (~70%) and metal (60%) in Fanny Creek, and acts to re-dissolve additional metals upon mixing with drainage from other slopes. The most suitable location for a passive AMD treatment system in Fanny Creek catchment is on the Waitahu Valley floor, near monitoring site R12, because this allows for sediment removal prior to a treatment system. Fanny Creek AMD at site R12 was characterized in detail because this data assists with selection and design of passive AMD treatment systems. Fanny Creek at site R12 contains on average 6.0 mg/L aluminium, 1.3 mg/L iron, 3.1 mg/L manganese, 0.49 mg/L zinc, 0.14 mg/L nickel, 0.0071 mg/L copper and 0.00048 mg/L cadmium. Average pH at site R12 was 3.95, calculated acidity averaged 42.7 mg CaCO₃/L, and flow rate ranged from 1.5 L/s to about 30 L/s. Acidity and metal generation from Island Block mine increases linearly with flow in the catchment, and therefore Fanny Creek drainage chemistry is not significantly affected by rainfall dilution. Natural attenuation of AMD occurs by addition of un-impacted alkaline drainage from Greenland Group basement rocks, wetland ecosystem processes, and geochemical reactions along Fanny Creek that decrease acidity and metal concentrations before AMD discharges into the Waitahu River. During low flow conditions (summer months), surface flow of AMD into the Waitahu River does not occur because of subsurface flow loss. Three suitable passive AMD treatment options for Fanny Creek AMD were selected and trialed at ‘bench top’ scale in a laboratory. These included a sulfate reducing bioreactor (SRBR), a limestone leaching bed (LLB), and an open limestone channel (OLC). The potential to mix Waitahu River water with Fanny Creek to neutralize AMD was also investigated. Fanny Creek AMD was employed for laboratory trials, and influent flow rates into SRBR, LLB and OLC systems were regulated to assess performance at different hydraulic retention times (HRT). Optimal HRTs for future treatment system designs were determined from effective AMD treatment thresholds, and include 51 hours, 5 hours and 15 hours for SRBR, LLB and OLC systems, respectively. To determine optimal treatment options for Fanny Creek AMD the effectiveness of each trial option was compared to applicable water quality criteria, and scale up implications of treatment options was assessed. The SRBR system had most effective AMD treatment, with water quality criteria achieved for metals, greatest alkalinity generation, and highest pH increase. However, a full scale SRBR system has significant size requirements, and long term treatment performance may be limited. The LLB system decreased metals to below, or just slightly above criteria for all metals, and has significantly smaller size requirements compared to a SRBR system. The OLC system was least effective, with effluent above water quality criteria for all metals except iron, and with lowest alkalinity generation. The Waitahu River is capable of neutralizing AMD because it is slightly alkaline. The flow volume of river water required for neutralization is between 65 L/s and 140L/s, which can be gravity fed to mix with Fanny Creek. These results indicate that either a LLB treatment system or the Waitahu River Mixing option are the optimal passive treatment strategies for Fanny Creek AMD. On site pilot scale testing of SRBR and LLB systems, and the Waitahu River Mixing option is recommended because of AMD treatment uncertainty, and to more accurately select and design full scale passive treatment strategies.