M.Sc. / The increased demand for electricity in South Africa is expected to exceed supply between 2004 and 2007. Electricity supply options in the country would be further complicated by the fact that older power stations would reach the end of their design life beyond the year 2025. In light of this and considering the long lead times required for the commissioning of new plants, new power supply options need to be proactively investigated. The environmental impacts associated with coal-fired generation of electricity have resulted in increased global concern over the past decade. To reduce these impacts, new technologies have been identified to help provide electricity from fossil fuels. The alternatives considered are gas-fired generation technologies and the Integrated Gasification Combined Cycle (IGCC). This study attempts to document and understand the environmental aspects related to gas-fired and IGCC electricity generation and evaluate their advantages in comparison to conventional pulverised coal fired power generation. The options that could be utilised to make fossil fuel electricity generation more environmentally friendly, whilst remaining economically feasible, were also evaluated. Gas-fired electricity generation is extremely successful as electricity generation systems in the world due to inherently low levels of emissions, high efficiencies, fuel flexibility and reduced demand on finite resources. Associated benefits of a Combined Cycle Gas Turbine (CCGT) are lower operating costs due to the reduced water consumption, smaller equipment size and a reduction in the wastewater that has to be treated before being returned to the environment. A CCGT plant requires less cooling water and can be located on a smaller area than a conventional Pulverised Fuel (PF) power station of the same capacity. All these factors reduce the burden on the environment. A CCGT also employs processes that utilises the energy of the fuel more efficiently, with the current efficiencies approaching 60%. Instead of simply being discharged into the atmosphere, the gas turbines’ exhaust gas heat is used to produce additional output in combination with a Heat Recovery Steam Generator (HRSG) and a steam turbine. Furthermore, as finite resources become increasingly scarce and energy has to be used as wisely as possible, generating electricity economically and in an ecologically sound manner is of the utmost importance. The clean, reliable operation of gas-fired generation systems with significantly reduced noise levels and their compact design makes their operation feasible in heavily populated areas, where electricity is needed most. At the same time, energy can be consumed in whatever form needed, i.e. as electricity, heat or steam. The dependence of the South African economy on cheap coal ensures that it will remain a vital component of future electricity generation options in the country. This dominance of coal-fired generation in the country is responsible for South Africa’s title as the largest generator of carbon dioxide (CO2) emissions on the continent and the country could possibly be requested to reduce its CO2 emissions at the next international meeting of signatories to the Kyoto Protocol. Carbon dioxide emissions can be reduced by utilising gas-fired generation technologies. However, the uncertainty and costs associated with natural gas in South Africa hampers the implementation of this technology. There are currently a number of initiatives surrounding the development of natural gas in the country, viz. the Pande and Temane projects in Mozambique and the Kudu project in Namibia, and this is likely to positively influence the choice of fuel utilised for electricity generation in the future. The economic viability of these projects would be further enhanced through the obtaining of Clean Development Mechanism (CDM) credits for greenhouse gases (GHG) emissions reduction. Alternatively, more efficient methods of generating electricity from coal must be developed and implemented. IGCC is capable of achieving this because of the high efficiencies associated with the combined cycle component of the technology. These higher efficiencies result in reduced emissions to the atmosphere for an equivalent unit of electricity generated from a PF station. An IGCC system can be successful in South Africa in that it combines the benefits of utilising gas-fired electricity generation systems whilst utilising economically feasible fuel, i.e. coal. IGCC systems can economically meet strict air pollution emission standards, produce water effluent within environmental limits, produce an environmentally benign slag, with good potential as a saleable by-product, and recover a valuable sulphur commodity by-product. Life-cycle analyses performed on IGCC power plants have identified CO2 release and natural resource depletion as their most significant positive lifecycle impacts, which testifies to the IGCC’s low pollutant releases and benign by-products. Recent studies have also shown that these plants can be built to efficiently accommodate future CO2 capture technology that could further reduce environmental impacts. The outstanding environmental performance of IGCC makes it an excellent technology for the clean production of electricity. IGCC systems also provide flexibility in the production of a wide range of products including electricity, fuels, chemicals, hydrogen, and steam, while utilizing low-cost, widely available feedstocks. Coal-based gasification systems provide an energy production alternative that is more efficient and environmentally friendly than competing coalfuelled technologies. The obstacle to the large-scale implementation of this technology in the country is the high costs associated with the technology. CDM credits and by-products sales could possible enhance the viability of implementing these technologies in South Africa.

Coal-fired power plants constitute a significant source of energy production for the United States, and are projected to do so for decades to come. Most of the scrutiny coal-fired power plants receive is in the form of environmental concerns regarding green house gas emissions of carbon dioxide, sulfur dioxide, and others. It is known that coal fly ash released through the stacks of coal power plants contains concentrated levels of naturally-occurring radiation, such as Radium-226. However, since the source of radiation is natural and the activity levels are low, there are no nuclear regulatory requirements imposed on coal plants. The focus of this study was to use the Nuclear Regulatory Commission’s (NRC) facility release criteria to determine whether the concentration of naturally occurring Radium-226 present in soil surrounding the Centralia Power Plant is elevated relative to soil collected 80 kilometers away. The non-parametric Wilcoxon Rank Sum test was used to compare twenty-eight soil samples collected within 3.4 kilometers of the Centralia Power Plant stacks against an equal number of reference samples collected in Port Orchard, Washington. It was determined that the average concentration of Radium-226 in soil near the power plant was 1.59 pCi/g, while the average concentration in reference soil was 0.59 pCi/g. The study suggests that the area around the power plant would fail to pass the release criteria of a NRC Multi-Agency Radiation Survey and Site Investigation (MARSSIM) Class 3 survey unit. If it is true that coal fired power plants increase background radiation levels measurably, but not at a level sufficient to cause alarm, it may be sensible to revise the strict emissions standards for nuclear facilities or increase requirements for utilities other than nuclear. / Graduation date: 2012

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Strict environmental regulation on flue gas emission has led to the implementation of FGD technologies in power stations. Wet FGD technology is commonly used because it has high SO2 removal efficiency, high sorbent utilization and due to availability of the sorbent (limestone) used. SO2 is removed by passing flue gas through the absorber where it reacts with the slurry containing calcium ions which is obtained by dissolution. This study presents the findings of the dissolution of a calcium-based material (limestone) for wet FGD process. This was done using a pH stat apparatus and adipic acid as acid titrant. Adipic acid was used because of its buffering effect in wet FGD process. The conditions used for this study are similar to what is encountered in a wet FGD process. The extent of dissolution was determined by analyzing the amount of calcium ions in solution at different dissolution periods. The dissolution kinetics were correlated to the shrinking core model and it was found out that chemical reaction at the surface of the particle is the rate controlling step. This study also investigated the dissolution of coal fly ash and bottom ash. Their dissolution kinetics showed that the diffusion through the product layer was the rate controlling step due to an ash layer formed around the particle. The formation of ash layer was attributed to pozzolanic reaction products which is calcium-alumino-silicate (anorthite) compounds were formed after dissolution. The effect of fly ash on the dissolution of rate of limestone was also studied using response surface methodology. Limestone reactivity was found to increase with increase in the amount of fly ash added and the pH was found to be strong function of the rate constant compared to other dissolution variables. The presence of silica and alumina in fly ash led to a significant increase in the specific surface area due to hydration products formed after dissolution. / Eskom

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)