Dissertation presented in partial compliance with the requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology, 2009. / This study was mainly a response to a challenge faced by ESKOM in its coal-fired power stations. In spite of using high purity water to drive the turbines, the latter were damaged by ‘pitting’, possibly related to acids generated at high temperatures. In the light of this a relatively simple method for determination of short chain organic acids was identified by comparing the efficacies of several methods. It was found that high performance liquid chromatography (HPLC) method preceded by derivatization (with o-nitrophenyl hydrazine) is suitable for analyzing mixtures of simple acids at ppb levels. Calibration was effected by using methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid (propionic acid) and butanoic acid (butyric acid). The HPLC instrument used was from Thermo Separations with P2000 pump, SN 4000 interface and UV1000 with a column heater. A comparative study between the HPLC methods using ion exclusion and partition chromatography was carried out in order to find a suitable method that can be used with aqueous environmental samples. The two essential columns that were used were ion exclusion Phenomenex Rezex OA column and a Nucleodur C8 column. The method of partition chromatography using a C8 column showed the most success using a mobile phase consisted of acidified water using HCl (pH4.5) along with a 60:40 Acetonitrile/Methanol mixture. Both isocratic and gradient programs were utilized. Limits of detection were improved from 800ppb (formic acid), 480ppb (acetic), 350ppb (propionic) and 680ppb (butyric acid) to 25ppb (acetic), 60ppb (propionic) and 90ppb (butyric). Samples used in analysis were collected from the main stream, economiser, condensers, polishing plant and turbines of the Tutuka Power Station in Mpumalanga province and analysed using with final developed method / Eskom Tertiary Support Programme. Durban University of Technology

Weathered sandstone materials have seen increased use in reclamation due to the wide-spread adoption of the Forest Reclamation Approach (FRA) in Appalachia. Runoff from these newly FRA reclaimed sites has the potential to adversely impact aquatic environments without fine sediment retention. To reduce the size and capital investment of settling ponds, flocculant utilization was investigated. Preliminary jar tests were conducted using composite weathered mine spoil samples acquired from a surface coal mine in eastern Kentucky. Four flocculants from the Magnafloc family of products were investigated during the initial screening-level testing. Experiments were conducted at three initial sediment concentrations (500 mg/L, 2,500 mg/L and 5,000 mg/L). A nonionic flocculant, Magnafloc 351, performed best, reducing total suspended sediment to below 50 mg/L. Large scale experiments confirmed that Magnafloc 351 was effective in reducing sediment concentrations. Jar tests were expanded to determine age and environmental effects on a Magnafloc 351 solution. Magnafloc 351 performance was slightly reduced after storage in a controlled building environment for 30 days and significantly decreased after 120 days. Magnafloc 351 solution exposed to UV and high heat (111°F) was ineffective after 30 days, while storage at 4°F and 36°F for 30 days did not adversely influence performance.

The mining industry is a major consumer of rock bolts in the United States. Due to the high humidity in the underground mining environment, the rock bolts corrode and loose their load bearing capacity which in turn reduces the life expectancy of the ground support and, thus, creates operational difficulties and number of safety concerns [1]. Research on rock anchor corrosion has not been adequately extensive in the past and the effects of several factors in the mine atmosphere and waters are not clearly understood. One of the probable reasons for this lack of research may be attributed to the time required for gathering meaningful data that makes the study of corrosion quite challenging. In this particular work underground water samples from different mines in the Illinois coal basin were collected and the major chemical content was analyzed and used for the laboratory testing. The corrosion performance of the different commercial rock anchors was investigated by techniques such as laboratory immersion tests in five different corrosion chambers, and potentiodynamic polarization tests in simulated ground waters based on the Illinois coal basin. The experiments were conducted with simulate underground mining conditions (corrosive). The tensile strengths were measured for the selected rock anchors taken every 3 months from the salt spray corrosion chambers maintained at different pH values and temperatures. The corrosion potential (Ecorr), corrosion current (Icorr) and the corresponding corrosion rates (CR) of the selected commercial rock bolts: #5, #6, #6 epoxy coated and #7 forged head rebar steels, #6 and #7 threaded head rebar steels were measured at the solution pH values of 5 and 8 at room temperature. The open circuit potential (OCP) values of the different rock anchors were recorded in 3 selected underground coal mines (A, B & C) in the Illinois coal basin and the data compared with the laboratory electrochemical tests for analyzing the life of the rock anchors installed in the mines with respect to corrosion potential and corrosion current measured. The results of this research were statistically validated. This research will have direct consequence to the rock related safety. The results of this research indicate that certain corrosive conditions are commonly found in mines but uniform corrosion (around 0.01-0.03mm loss per year across the diameter) is generally not considered a serious issue. From this study, longer term research for long-term excavation support is recommended that could quantify the problem depending on the rock anchor used and specific strata conditions.

Hemp, eucalyptus, coal, hemp and coal blended fuel, and eucalyptus and coal blended fuel were ashed and then heat treated for 1 hour at temperatures from 600-1100°C. X-ray diffraction analysis indicated reactions between the phases present after initial ashing of the fuel showed biomass-biomass, biomass-coal and coal-coal interactions. Two phase systems were identified as dominant in the biomass and coal ash blends, these were CaO-MgO-SiO2 and CaO-Al2O3-SiO2. The phases identified in these systems have also been identified in ceramics produced at high temperatures which have similar compositions to the ash matrix of the laboratory synthesised ash; this indicates that phase diagrams can be powerful tools in phase formation prediction. Structures identified as trichomes (phosphate-silicate structures with melting points above 1100°C) from the hemp fuel which had not decomposed were present in both the hemp ash and the hemp and coal ash. The composition determined by Energy-dispersive X-ray spectroscopy analysis of laboratory synthesised ashes was also in agreement with the phases identified through X-ray diffraction. Hemp and coal, eucalyptus and coal, and eucalyptus ash samples (deposited, quenched, cyclone, and bottom ash) removed from a full scale 1MWth combustion rig were analysed. Phase composition of the fly ash samples are similar to those identified in the analagous samples produced in the laboratory with several of the same phases present; confirming that laboratory testing is useful for the predictions of phases present on the industrial scale combustion rig. Particle morphology is one of the largest differences between the laboratory scale tests and combustion rig samples. The dominant particle shape of fly ash particles removed from the combustion rig is spherical. These particles of characteristic shape are often referred to as plerospheres and cenospheres and were first identified in coal fly ash. The presence of the spheres in the combustion rig when only biomass (eucalyptus) is present indicates the formation mechanism of the particles is similar to that of coal. There are similarities between the chemical composition of the spheres which are solely of biomass origin and co-fired; it is likely that phase composition of the sphere and not the fuel origin contributes to the formation of the spheres. Phases identified in the bottom ash are similar to those identified in the fly ash. High temperature phases such as (e.g. Ca9MgK(PO4)7) ocur in the bottom ash suggesting that higher temperatures are reached in the bottom of the rig than in the flue gas. Analysis of 15Mo3 alloy corrosion coupons with fly ash deposited onto the surface, alongside the interactions between gas phases and coupons, deposits and coupons, and gas phases and deposits, showed that some oxidation/reduction of the metal had occurred. The presence vi of metal oxide flakes indicated corrosion. Oxidation of 15Mo3 alloy was observed in hemp and coal, and eucalyptus and coal combustion trials, likely due to the observed deposition of potassium chloride which has caused detachment of several scales. Between the metal-deposit interface, hematite whiskers were observed; magnetite octahedra were also present on the surface of scales. The phases present in the coupon deposit ash differ from those observed in the laboratory and fly ash due to the length of time spent in the high temperature environment. This indicates that some phases will not form until the deposits have built up and are in the furnace for an extended period of time. When the coupon samples were coated, fewer metal scales were observed meaning that the coatings are an affective method of corrosion reduction leading to an increased lifetime of boiler components. The dominant particle morphology present in the combustion rig is the cenospheres and plerospheres. The phases formed can be broadly catergorised into CaO-MgO-SiO2, CaO-Al2O3-SiO2, and K2O-Al2O3-SiO2 phases. Potassium chloride is observed in the laboratory ash and combustion rig ash indicating, alongside the presence of metal oxide scales, that the fuel blends are likely to lead to corrosion during combustion.

In May 1981, at the South Wales Area NUM annual conference, Area president Emlyn Williams addressed the delegates and told them that the south Wales miners 'are associated in people's minds with resistance and struggles ... There is no doubt in my mind that miners have an historical mission to lead in class struggles'.1 This statement expressed the conscious self-image of the South Wales Area and was also a reaffirmation of an important historical trend. During the twentieth century the miners were generally considered to be amongst the most militant sections of the British labour movement, with South Wales very much in the forefront of this. This thesis examines both how and why the south Wales miners held this prominent 'vanguard' role. My research explores the history of the south Wales miners between 1964 and 1985, examining the interrelationship of coal, community and politics through the prism of their Union. The period covers the concerted run-down of the coal industry under the Wilson government, the growth of miners' resistance and the brief prospect of a secure future for them, through to eventual NUM defeat in 1985. In this socio- political history, the emphasis is on the dynamics of the relations between colliery lodges, the South Wales Area and the national NUM, the response of the Area to industrial and political developments, and also the impact of this upon its relationship with the wider labour movement. In many respects however, labour history is not currently 'fashionable'. The decline of the densely-unionised heavy industries, together with the global hegemony of neo-liberalism, has led many to believe that this subject is no longer relevant - even though the working class has not disappeared just because more people in Britain now work in call centres and supermarkets than in collieries or steelworks. Nevertheless, as Mcllroy and Campbell point out, '[t]he [current] debility of labour studies ... have to be related to the defeats and the consequent sense of demoralisation the labour movement has suffered from, as well as state policies and academic responses to them'.

It is an ordinary practice to cover the areas after brown-coal mining with natural topsoil cover (topsoiling). Topsoiling is removal one topsoil from agricultural land, forest or area with vegetation and excavating to another place with poor organic matter content or in our case the brown-coal mining dumpsite. Advantages of topsoiling include higher organic matter and greater available water-holding capacity and nutrient content. Content of potentially toxic elements is very low. Ammonia nitrate (NH4NO3) extraction, BCR sequential analysis and aqua regia determination were applied in this study to prove that the proportion of bioavailable forms of PTE in reclaimed soils is also low. Amounts of potentially toxic elements were compared between different types of reclamation: an agricultural shown higher value for Pb and Cd, forestry has only one contaminant -- Cd. The research shows that toxicity of soil is low and has no dangerous influence for agricultural application.

Burning of fossil fuels by coal-fired power plants (CFPPs) is one of the largest sources of environmental mercury in the United States and there have been conflicting reports of local impacts due to CFPPs in the US. Illinois has 23 coal-fired electrical generating plants that may be contributing to elevated environmental mercury concentrations that have contributed to mercury advisories for 13 bodies of water located throughout the state. The objective of the current study is to determine if there is a pattern of total mercury concentrations in sediment and tadpoles collected from ponds located upwind and downwind of 4 coal-fired electrical generating plants in Illinois. Baldwin, Joppa, Newton, and Southern Illinois Power Cooperative (SIPC) coal-fired power plants were chosen for study. Three sediment samples were collected from ponds located 3-5, 8-10, and 13-15 km downwind and from ponds located 3-5 km upwind of each power plant and analyzed for total mercury concentration. Temperature of overlying water (C), pH, oxidation-reduction potential (mV), and texture were determined for each sediment sample. Bullfrog (Lithobates catesbeiana) or Green frog (Lithobates clamitans) tadpoles were collected opportunistically from 29 of the 44 ponds chosen for study. Each tadpole was identified to species and Gosner stage, and then weighed and measured for total length prior to total mercury analysis. For Baldwin, Joppa, and SIPC power plants, no significant pattern of total mercury could be determined from either sediment or tadpole data. For Newton power plant, total mercury concentrations were significantly greater 3-5 km downwind for sediment, and 8-15 km downwind for tadpoles compared to concentrations at upwind locations. Sediment total mercury concentrations were not significantly correlated with any of the characteristic variables (e.g. pH). Tadpole total mercury was significantly negatively correlated with length and weight, but not significantly correlated with any of the sediment variables. Sediment and tadpole concentrations were not significantly correlated.

Coal is a combustible sedimentary rock composed of a complex heterogeneous mixture of mostly organic constituents and minor inorganic phases. Coal is a vital energy resource providing more than half of the electric power generated in the United States. However, coal combustion is responsible for a significant portion of anthropogenic release of different toxic elements including sulfur into the environment. Therefore, deciphering the residence of the different fractions of sulfur in coal is essential. In this study, eight different sulfur fractions from Pennsylvanian-age coal samples collected from the Murphysboro, Mount Rorah, Springfield (No. 5), and Herrin (No. 6) coal seams from the Illinois Basin were separated using a wet sequential chemical extraction procedure in order to evaluate the coal quality and to test the efficiency of this technique. The average weight percent of sulfur in each seam was 1.98%, 2.1%, 2.26%, and 2.4%, respectively, showing that the coal samples were of medium-sulfur-type. Among the eight different sulfur fractions extracted, kerogen sulfur was found to be the most abundant, followed by sulfate sulfur, fulvic acid sulfur, pyritic sulfur, and elemental sulfur. However, XRD and coal petrography revealed the significant amounts of pyrite still present in the coal sample even after pyritic sulfur extraction, indicating that the finely disseminated pyrite in the coal was not completely removed during the sequential extraction. The sulfur isotopic study showed the average δ34S values of pyritic sulfur and sulfate sulfur in the Murphysboro coals as 7.82 / and 2.44 / and that of Mount Rorah coals were 10.68 / and 7.87 /, respectively. The heavier δ34S values of pyritic sulfur compared to the sulfate sulfur can be explained by a bacterial sulfate reduction (BSR) model in a closed system where most of the sulfate reservoir was consumed at the top of the seam. Similarly, the average δ34S values of elemental sulfur for the same coals (8.05 / and 14.54 /, respectively) were also heavier than the sulfate sulfur which suggests the pyrite oxidation followed by disproportionation of intermediate sulfur species. The δ34S values of handpicked pyrite samples and the mercury concentration for the Herrin (No.6) and Springfield (No. 5) coals indicated at least two stages of hydrothermal inputs into these coal seams. SEM/EDS and petrographic microscopy of the Illinois coal samples revealed the presence of different syngenetic and epigenetic sulfur-containing minerals such as framboidal pyrite, euhedral pyrite, galena, anhydrite, anglesite, and also non-sulfur containing minerals such as calcite and clay. Based on these results, it can be said that sulfur in Illinois coals is present in different phases extractable by wet sequential chemical extraction however; care should be taken during each individual extraction step to obtain better results.

The variation in the cleat permeability of coalbed methane (CBM) reservoirs is attributed primarily to two cardinal processes, with opposing effects. Increase in effective stresses with reduction in pore pressure tends to decrease the cleat permeability, whereas the sorption-induced coal matrix shrinkage actuates reduction in the effective stresses which increases the reservoir permeability. The net effect of the two processes determines the pressure-dependent-permeability and, hence, the overall trend of CBM production with depletion. Several analytical models have been developed and used to predict the dynamic behavior of CBM reservoir permeability during production through pressure depletion, all based on combining the two effects. The purpose of this study was to introduce modifications to two most commonly used permeability models, namely the Palmer and Mansoori, and Shi and Durucan, for permeability variation and evaluate their performance when projecting gas production. The basis for the modification is the linear relationship between the volume of sorbed gas and the associated matrix shrinkage. Hence, the impact of matrix shrinkage is incorporated as a function of the amount of gas produced, or that remaining in coal, at any time during production. Since the exact production from a reservoir is known throughout its life, this significantly simplifies the process of permeability modeling. Furthermore, the modification is also expected to streamline the process of modeling by classifying the shrinkage parameters for coals of different regions, but with similar characteristics. A good analogy is the San Juan basin, where sorption characteristics of coal are so well understood and defined that operators no longer carry out laboratory sorption work. The goal is to achieve the same for incorporation of the matrix shrinkage behavior. Another modification is to incorporate the matrix, or grain, compressibility effect of coal as a correction factor in the Shi and Durucan model so as to assess the permeability variation based on the true shrinkage of coal matrix with reservoir drawdown. Finally, application of the modified models may be carried out for scenarios where the gas content of coal varies with time, either due to injection of a second gas to enhance the recovery of methane, or gas enhancing techniques, such as, bio-stimulation of coal. The original models are currently unable to handle this, particularly when the gas content of the reservoir increases. The research is aimed at simplifying and, in fact, improving the performance of the theoretical models in predicting the variation of coal reservoir permeability.

This dissertation uses mixed methods to examine the role of the coal industry in the reproduction of Central Appalachia as an internal periphery within the United States and the economic, ecological, and human inequalities this entails. It also analyzes the related political economy and power structure of coal in a national context. Particularly important for analysis of the region's underdevelopment are the class relations involved in unequal ecological exchange and the establishment of successive "modes of extraction." I employ a historical comparative analysis of Appalachia to evaluate Bunker's thesis that resource dependent peripheries often become locked into a "mode of extraction" (with aspects parallel to Marxist concepts of mode of production) triggering economic and ecological path dependencies leading to underdevelopment. This historical comparative analysis establishes the background for a closer examination of the political economy of the modern US coal industry. After sketching the changes in the structure of monopoly and competition in the coal industry I employ network analysis of the directorate interlocks of the top twenty coal firms in the US within the larger energy policy-planning network to examine their connections with key institutions of the policy formation network of think tanks and business groups. My findings show the importance of the capacities of fossil fuel fractions of the capitalist class in formulating energy policy around issues such as the 2009 climate legislation. As a contribution to the growing literature applying the concept of metabolism as link between contemporary and classical theory, I examine the conflict at Coal River Mountain from the vantage points of ecology, political economy, and human development in dialectical rotation. Utilizing Marx's method of successive abstractions, the mountain is presented as a nexus of metabolic rifts in the human relationship to the earth's natural systems and an impediment to genuine human development. Finally, I conclude with some implications of this analysis for building a critical environmental sociology of extractive economies. This dissertation includes previously published materials. / 2016-09-29