Made available in DSpace on 2017-07-24T19:38:02Z (GMT). No. of bitstreams: 1 Elisandra Martins.pdf: 1709825 bytes, checksum: 2b439c92219786f120cb58b442ce0499 (MD5) Previous issue date: 2010-03-08 / In order to better benefit from agriculture development it is necessary to know the soil physical and chemical properties which enable the reposition of nutrients through mineral and organic fertilization in the correct way. These soil properties might vary according to the content and composition of minerals in the clay fraction. In such a context the objective of this work was to characterize minerals from the clay fraction, of the Bi diagnostic horizon, of seven cambisols from the Irati region in the State of Paraná. For the characterization, clay fraction and air dried fine earth from Bi horizon of these soils were studied. Firstly, the particles density was determined using the pycnometer method in order to be used later for the sedimentation calculation through the Stokes Law and to obtain the clay fraction through physical fractioning, which also determined soil texture. Mineralogical analysis was carried out employing X-ray diffraction supported by the knowledge of local geology, with this data and the Rietveld method, the quantification of crystalline phases in the clay fraction was carried out. X-ray fluorescence technique was employed as elemental analysis, in order to compare to the results obtained by the Rietveld method. The average particle density obtained was 2,54 gcm-3. Textural class according to the American classification was very clayey for one of the samples and clayey for the others. The Rietveld method refinement presented good adjustment, with χ2 varying from 1,54 to 6,23. Elemental comparison between the fluorescence and the Rietveld method presented some divergences, which were granted to crystal imperfections, chemical composition variation and the presence of amorphous substances, which hampered the adjustment through the Rietveld Method and might lead to mistakes in the elemental quantification. From eight to nine mineral phases were identified in each sample of the clay fraction. The majority mineral phases for this fraction were kaolinite, muscovite and quartz, illite in some samples and in lower amounts hematite, goethite, gibbsite, lepidocrocite and calcite. These minerals are in accordance with the geology and are usually associated among themselves, mainly in young soils, in which weathering was not enough to transform the minerals entirely. / Para fazer uso dos benefícios decorrentes do desenvolvimento da agricultura é necessário conhecer propriedades físicas e químicas do solo que possibilitem a reposição de nutrientes por adubação mineral e orgânica de forma correta. Estas propriedades do solo variam em grande parte de acordo com o teor e composição dos minerais da fração argila. Neste contexto o objetivo desse trabalho foi caracterizar os minerais da fração argila, do horizonte diagnóstico, Bi, de sete Cambissolos da região de Irati, Paraná. Para a caracterização foram estudadas a fração argila e a Terra Fina Seca ao Ar do horizonte Bi desses solos, primeiramente determinou-se a densidade de partículas pelo método do picnômetro para posterior utilização no cálculo de sedimentação pela Lei de Stokes e obtenção da fração argila pelo fracionamento físico, que também possibilitou determinar a textura do solo. A análise mineralógica foi feita pela técnica de Difração de Raios X com auxílio de conhecimentos da geologia local, com esses dados e o Método de Rietveld foi feita a quantificação das fases cristalinas apenas na fração argila. A técnica de Fluorescência de Raios X foi utilizada como análise elementar, para comparar com os resultados obtidos com o Método de Rietveld. A densidade de partículas média obtida foi de 2,54 g.cm-3. A classe textural, de acordo com a classificação americana, foi muito argilosa para uma amostra e argilosa para as demais. O refinamento pelo método de Rietveld apresentou bom ajuste, com χ2 variando de 1,54 a 6,23. A comparação da quantificação química elementar pela Fluorescência e método de Rietveld apresentou algumas divergências, as quais foram atribuídas a imperfeições dos cristais, variação na composição química e presença de substâncias amorfas, que dificultam o ajuste pelo Método de Rietveld e podem levar a erros na quantificação elementar. Foram identificadas de sete a oito fases minerais em cada amostra da fração argila. As fases minerais majoritárias da fração argila foram a caulinita, muscovita e quartzo, e em algumas amostras também a ilita e em menor quantidade hematita, goethita, gibbsita, lepidocrocita, calcita. Esses minerais estão de acordo com a geologia e normalmente aparecem associados entre si, principalmente em solos jovens, em que o intemperismo não foi suficiente para transformar totalmente os minerais.

O fósforo (P) é um elemento essencial para o desenvolvimento das plantas e precisa ser suprido em quantidades adequadas para obtenção de altas produtividades das culturas agrícolas. O conteúdo de P no solo e consequente perda deste para as águas superficiais são importantes fatores relacionados a eutrofização de ambientes aquáticos. Nesse trabalho foi obtido o Grau de saturação de P (GSP) em 29 solos tropicais altamente intemperizados e seus valores foram correlacionados com atributos químicos, físicos e mineralógicos dos solos. Antes de calcular o GSP, foram determinados parâmetros como Índice de sorção de P (ISP), Capacidade de sorção de P (CSP) e fator de escala ?. Os solos foram divididos em grupos, e os solos de cada grupo receberam doses diferenciadas de P para obtenção do ISP devido a variação na capacidade de adsorção,. As doses utilizadas foram 200, 500, 1000, 1500 e 3000 mg L-1 de P. Os períodos de reação avaliados foram 1, 3, 7, 21, 42, e 84 d. A porcentagem média de P adsorvida no final do período de contato (84 d) variou de 23% a 49% do P adicionado inicialmente. Os Latossolos, os Gleissolos e os Nitossolos apresentaram os maiores valores de ISP, enquanto os Argissolos e os Neossolos tiveram os menores valores. Os maiores valores foram encontrados nos solos com elevados teores de argila, matéria orgânica (MO) e óxidos cristalinos e mal cristalizados de Fe e de Al. O ISP foi maior no final do período de contato (84 d), o que realça a influência do tempo na adsorção do P. O fator de escala ? e o GSP foram calculados em todos os períodos de contato. Os valores de ? aumentaram e os de GSP diminuíram em função do tempo devido à maior interação do P com o solo. Os menores valores de GSP foram obtidos nos solos com alta capacidade de adsorção de P, ao passo que os maiores valores de GSP foram dos solos com menor capacidade de adsorção. O maior GSP (31%) foi obtido no Neossolo Litólico. O valor limite de GSP considerado nesse trabalho foi 23%. As relações entre GSP, CSP, ISP e alguns atributos dos solos foram abordadas por meio da análise de componentes principais. Com o agrupamento de todos os solos, os teores de óxido mal cristalizado de alumínio (Alox), argila, MO e de óxido cristalino de alumínio (AlDCB) foram os que melhor se correlacionaram com o ISP e a CSP. Avaliando somente os Latossolos, os teores de argila e de óxidos cristalinos e mal cristalizados de ferro e de alumínio (Feox, FeDCB, AlDCB e Alox) representaram os componentes principais ligados à adsorção de P. Com a adição dos demais solos, os teores de fósforo extraídos por solução ácida de oxalato de amônio (Pox), Alox, argila e MO formaram os componentes principais para ISP e CSP. O GSP não correlacionou significativamente com nenhum dos atributos. A partir do dendograma, os solos foram separados em dois grupos. O grupo I foi composto por solos pouco suscetíveis a perdas de P em função dos valores de CSP e de GSP. Já o grupo II reuniu os solos mais suscetíveis. Equações de regressão linear múltipla foram utilizadas na predição do ISP e CSP e duas delas obtiveram um alto coeficiente de determinação (R2 = 0,94 para ambas), podendo ser utilizadas para estimar a CSP e o ISP nos solos. / Phosphorus (P) is an essential element for plant growth and must be supplied in adequate quantities to the growers obtain high yields of agricultural crops. The content of P in the soil and its loss to surface water are important factors related to eutrophication of aquatic environments. In this study, we obtained the degree of P saturation (DPS) in 29 highly weathered tropical soils, and their values were correlated with chemical, physical and mineralogical soil attributes. Before calculating the DPS, parameters such as P sorption index (PSI), P sorption capacity (PSC) and the scaling factor ? were obtained. Because of the variation in the soils` ability to adsorb P, they were divided into groups, and the soils from each group received different P rates for obtaining the PSI. The rates were 200, 500, 1000, 1500 and 3000 mg L-1 of P. The periods of reaction evaluated were 1, 3, 7, 21, 42, and 84 d. The average percentage of P adsorbed at the end of the contact period (84 d) ranged from 23% to 49% of P added initially. The Oxisols, the Gleysols and the Alfisols showed the highest values of PSI, while the Ultisols and Entisols had the lowest values. The highest values were found in soils with high clay contents of organic matter (OM) and crystalline and poorly crystalline Fe and Al oxides. ISP was higher at the end of the contact period (84 d), which highlights the influence of weathering on P adsorption by soils. The scale factor ? and the DPS were calculated for all periods of contact. The values of ? increased while DPS decreased as a function of time because of the greater interaction of P with the soil. The lowest values of GSP were obtained in soils with high P adsorption capacity, whereas the highest values of DPS were obtained in soils with lower adsorption capacity. The largest DPS (31%) was obtained in the Typic Udorthent. The limit value of DPS considered in this study was 23%. Correlations between DPS, PSC, PSI and some soil attributes were addressed by principal component analysis. By grouping all soils, the levels of poorly crystalline aluminum (Alox), clay, OM and crystalline aluminum oxide (AlDCB) were the atributes best correlated with both PSI and PSC. When evaluating only the Oxisols, it was observed that the contents of clay and crystalline and poorly crystalline iron and aluminum oxides (Feox, FeDCB, AlDCB and Alox) represented the main components related to the adsorption of P. When the other soils were added, the contents of P extracted by an acid ammonium oxalate solution (Pox), Alox, MO and clay composed the main components for PSC and PSI. DPS did not correlate significantly with any of the attributes. From the dendrogram, the soils were separated into two groups: group I, consisted of soils with little susceptiblity to P loss based on the PSC and DPS, and group II, that met the more susceptible soils for P losses. Multiple linear regression equations were used to predict PSI and PSC, and two of them had a high determination coefficient (R2 = 0.94 for both). So, they can be used to estimate the PSC and PSI at the soils.

No description available.

Les différentes lithologies sédimentaires du Groupe Belqa présentent un enrichissement en P et en toute une série d'éléments sensibles aux conditions redox. Il est montré que l'enrichissement en U, Cu, Co, Mo, V résulte d'un dépôt syn-sédimentaire sous conditions suboxiques. Par contre, les éléments Cr, Ni, Cd, Zn sont beaucoup plus enrichis et requierent un flux exogénique de métal probablement relié à l'altération de roches ultrabasiques obductées à la même période au nord de cette région, lors de la collision de la plaque arabo-africaine avec la plaque eurasienne. Les phosphates représentent le principal hôte de l'uranium et des terres rares. L'analyse des apatites par ablation laser ICP-MS a permis de montrer leur évolution, depuis le stade sédimentaire-diagénétique, puis pyrométamorphique, jusqu'à l'altération supergène. La libération de l'uranium de la structure de l'apatite lors du pyrométamorphisme et de l'altération supergène permet sa mise à disposition pour la formation de minéralisations. Le pyrométamorphisme, dû à une combustion des niveaux riches en matière organique, est responsable de la déstabilisation des apatites, et de la formation de roches de compositions semblables à des ciments clinker/Portland. L'uranium a également été libéré de la structure de l'apatite par altération supergène. L'altération météorique et les fluides évaporitiques ont permis le lessivage et le transport des éléments (U, V) des roches carbonatées métamorphiques, et des carbonates puis a conduit au dépôt des vanadates d'uranyles dans les carbonates pulvérulents ayant subi une dissolution importante / The different lithologies of the Belqa Group present an enrichment in P and various redox sensitive elements. The U, Cu, Co, Mo, V enrichment results from synsedimentary deposition in suboxic conditions. However, the higher Cr, Ni, Cd, Zn enrichment requires an exogenic metal flux probably related to the terrestrial leaching of ultrabasic rocks obducted during the collision between African-Arabian and Eurasian plates to the north of the study region, at the same time. Phosphates are the main host lithology for uranium and rare earth elements. The analysis of the apatites by laser ablation ICP-MS shows their evolution along the sedimentary-diagenetic and pyrometamorphic stages, up to the supergene weathering. The uranium liberation from the apatite structure during the pyrometamorphism and surficial weathering led to its availability as supergene ore mineralization. Pyrometamorphism resulted from the combustion of organic-rich layers and caused the destabilization of the apatites, and the formation of rocks which have compositions similar to clinker/Portland cements. Uranium has been also released from the structure of the apatite by supergene alteration. Meteoric weathering and the evaporitic groundwater resulted in the leaching and the transport of the elements (U, V) from the metamorphic carbonated hills, and from the surrounding permeable limestone which has undergone dissolution in the near surface zone

The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped, weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station.

<p>The management and disposal of huge volumes of coal combustion by products such as fly ash has constituted a major challenge to the environment. In most cases due to the inadequate alternative use of coal fly ash, the discarded waste is stored in holding ponds, slag heaps, or stock piled in ash dumps. This practice has raised concerns on the prospect of inorganic metals release to the surface and groundwater in the vicinity of the ash dump. Acceptable scientific studies are lacking to determine the best ash disposal practices. Moreover, knowledge about the mobility patterns of inorganic species as a function of mineralogical association or pH susceptibility of the dry disposed ash dump under natural weathering conditions are scarce in the literature. Fundamental understanding of chemical interactions of dry disposed ash with ingressed CO2 from atmosphere, percolating rain water and brine irrigation within ash disposal sites were seen as key areas requiring investigation. The mineralogical association of inorganic species in the dry disposed ash cores can be identified and quantified. This would provide a basis for understanding of chemical weathering, mineralogical transformations or mobility patterns of these inorganic species in the dry ash disposal scenario. The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped,&nbsp / weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station. The core samples were characterized using standard analytical procedures viz: X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transforms infrared (FTIR) techniques, Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) and Acid neutralisation capacity (ANC) test. A modified sequential extraction (SE) method was used in this study. The chemical partitioning, mobility and weathering patterns in 1 year, 8 year and 20-year-old sections of the ash dump were respectively investigated using this modified sequential extraction scheme. The sequence of the extractions was as follows: (1) water soluble, (2) exchangeable, (3) carbonate, (4) iron and manganese and (5) residual. The results obtained from the 5 steps sequential extraction scheme were validated with the total metal content of the original sample using mass balance method. The distribution of major and trace elements in the different liquid fractions obtained after each step of sequential extraction of the 59 drilled core samples was determined by inductively coupled plasma mass spectrometry (ICPMS). The data generated for various ash core samples were explored for the systematic analysis of mineralogical transformation and change in ash chemistry with ageing of the ash. Furthermore, the data was analyzed to reveal the impact of ingressed CO2 from atmosphere, infiltrating rain water and brine irrigation on the chemistry of ash core samples. Major mineral phases in original ash core samples prior to extraction are quartz (SiO2) and mullite (3Al2O3&middot / 2SiO2). Other minor mineral phases identified were hematite (Fe2O3), calcite (CaCO3), lime (CaO), anorthite (CaAl2Si2O8), mica (Ca (Mg, Al)3 (Al3Si) O10 (OH)2), and enstatite (Mg2Si2O6). X-ray diffraction results show significant loss of crystallinity in the older ash cores. The presence of minor phases of calcite and mica in dry disposed ash cores are attributed to reduction in the pore water pH due to hydration, carbonation and pozzolanic reactions. The X-ray diffraction technique was unable to detect Fe-oxyhydroxide phase and morealuminosilicate phases in ash core samples due to their low abundance and amorphous character. X-ray fluorescence results of the original ash core samples showed the presence of major oxides, such as SiO2, Al2O3, Fe2O3, while CaO, K2O, TiO2, Na2O, MnO, MgO, P2O5, and SO3 occur in minor concentrations. The ratio of SiO2/Al2O3 classified the original core samples prior to extraction as a silico-aluminate class F fly ash. The ternary plot of major elements in 1-year-old ash core samples was both sialic and ferrocalsialic but 8 year and 20-year-old ash core samples were sialic in chemical composition. It is noteworthy that the mass % of SiO2 varies through the depth of the core with an increase of nearly 3 %, to 58 mass % of SiO2 at a depth of 6 m in the 1-year-old core whereas in the case of the 8-year-old core a 2 % increase of SiO2 to a level of 57.5 mass % can be observed at levels between 4-8 m, showing dissolution of major components in the matrix of older ash cores.. The Na2O content of the Tutuka ash cores was low and varied between 0.6-1.1 mass % for 1-year-old ash cores to around 0.6-0.8 mass % for 8-year-old ash cores. Sodium levels were higher in 1-year-old ash cores compared to 8 year and 20-year-old ashcores. Observed trends indicate that quick weathering of the ash (within a year) leached out Na+ from the ash dump. No evidence of Na+ encapsulation even though the ash dump was brine irrigated. Thus the dry disposal ash placement method does not result in a sustainable salt sink for Na-containing species over time. The total content of each of the elements in 1 year and 20-year-old ash cores was normalised with their total content in fresh ash from same power station to show enrichment and depletion factor. Major elements such as K+, Mn showed enrichment in 1-year-old ash cores whereas Al, Si, Na+, Ti, Ca, Mg, S and Fe showed depletion due to over time erosion. Trace elements such as Cr, Sr, P, Ba, Pb, V and Zn showed enrichment but Ni, Y, Zr showed depletion attributed to over time erosion. In 20-year-old ash cores, major elements such as Al, Na+ and Mn showed enrichment while Si, K+, Fe, Mg and Ca showed depletion highlighting their mobility. Trends indicated intensive flushing of major soluble components such as buffering constituents (CaO) by percolating rain water. The 1-year-old and 20-year-old coal ash cores showed a lower pH and greater loss/depletion of the soluble buffering constituents than the 2-week-old placed ash, indicating significant chemical weathering within a year. Based&nbsp / on ANC results the leaching behaviours of Ca, Mg, Na+, K+, Se, Cr, and Sr were found to be controlled by the pH of the leachant indicating high mobility of major soluble species in the ash cores when in contact with slightly acid rain water. Other investigated toxic metals such as As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. Chemical alterations and formation of transient minor secondary mineral phases was found to have a significant effect on the acid susceptibility and depletion pattern of chemical species in the core ash samples when compared to fresh ash. These ANC results correlated well with the data generated from the sequential extraction scheme. Based on sequential extraction results elements, showed noticeable mobility in the water soluble, exchangeable and carbonate fractions due to adsorption and desorption caused by variations in the pore water pH. In contrast, slight mobility of elements in the Fe and Mn, and residual fractions of dry disposed fly ashes are attributed to the co-precipitation and dissolution of minor amount of less soluble secondary phase overtime. The 1-year-old dry disposed ash cores were the least weathered among the 3 drilled ash cores. Therefore low concentration of toxic metals in older ash cores were ascribed to extensive weathering with slower release from residual mineral phases over time. Elements were found to associate with different mineral phases depending on the age or depth of the core samples showing greater heterogeneity in dispersion. For instance the average amount of total calcium in different mineral associations of 1-year-old ash cores is as follows / water soluble (10.2 %), exchangeable (37.04 %), carbonate (37.9 %), Fe and Mn (7.1 %) and residual (2.97 %). The amount of total Na+ in different mineral phases of 1-year-old ash cores followed this trend: water soluble (21 %), exchangeable (11.26 %), carbonate (2.6 %), Fe and Mn (4.7 %) and residual (53.9 %). The non-leachable portion of the total Na+ content (namely that contained in the residual fraction) in the 1-year-old ash core samples under conditions found in nature ranged between 5-91 %. This non-leachable portion of the Na+ showed the metastability of the mineral phases with which residual Na+ associates. Results showed older ash cores are enriched in toxic elements. Toxic elements such as As, B, Cr, Mo and Pb are enriched in the residual fraction of older ash cores. For instance As concentration in the residual fraction varied between 0.0003- 0.00043 mg kg-1 for 1-year-old ash cores to around 0.0003-0.0015 mg kg-1 for 20-year-old ash cores. This suggests that the older ash is enriched in toxic elements hence dust from the ash dump would be toxic to human health. The knowledge of mobility and ecotoxicological significance of coal fly ash is needed when considering its disposal or reuse in the environment. The mobility and ecotoxicology of inorganic metals in coal fly ash are determined by (i) mineralogical associations of inorganic species (ii) in-homogeneity in the ash dumps (iii) long and short term exposure to ingress CO2 and percolating rain water. Management issues such as inconsistent placement of ash in the dumps, poor choice of ash dump site, in-homogeneity in brine irrigation, no record of salt load put on the ash dumps and lack of proper monitoring requires improvement. The thesis provides justification for the use of the modified sequential extraction scheme as a predictive tool and could be employed in a similar research work. This thesis also proved that the dry ash disposal method was not environmental friendly in terms of overall leaching potential after significant chemical weathering. Moreover the study proved that the practice of brine co-disposal or irrigation on ash dumps is not sustainable as the ash dump did not act as a salt sink.</p>

<p>The management and disposal of huge volumes of coal combustion by products such as fly ash has constituted a major challenge to the environment. In most cases due to the inadequate alternative use of coal fly ash, the discarded waste is stored in holding ponds, slag heaps, or stock piled in ash dumps. This practice has raised concerns on the prospect of inorganic metals release to the surface and groundwater in the vicinity of the ash dump. Acceptable scientific studies are lacking to determine the best ash disposal practices. Moreover, knowledge about the mobility patterns of inorganic species as a function of mineralogical association or pH susceptibility of the dry disposed ash dump under natural weathering conditions are scarce in the literature. Fundamental understanding of chemical interactions of dry disposed ash with ingressed CO2 from atmosphere, percolating rain water and brine irrigation within ash disposal sites were seen as key areas requiring investigation. The mineralogical association of inorganic species in the dry disposed ash cores can be identified and quantified. This would provide a basis for understanding of chemical weathering, mineralogical transformations or mobility patterns of these inorganic species in the dry ash disposal scenario. The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped,&nbsp / weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station. The core samples were characterized using standard analytical procedures viz: X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transforms infrared (FTIR) techniques, Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) and Acid neutralisation capacity (ANC) test. A modified sequential extraction (SE) method was used in this study. The chemical partitioning, mobility and weathering patterns in 1 year, 8 year and 20-year-old sections of the ash dump were respectively investigated using this modified sequential extraction scheme. The sequence of the extractions was as follows: (1) water soluble, (2) exchangeable, (3) carbonate, (4) iron and manganese and (5) residual. The results obtained from the 5 steps sequential extraction scheme were validated with the total metal content of the original sample using mass balance method. The distribution of major and trace elements in the different liquid fractions obtained after each step of sequential extraction of the 59 drilled core samples was determined by inductively coupled plasma mass spectrometry (ICPMS). The data generated for various ash core samples were explored for the systematic analysis of mineralogical transformation and change in ash chemistry with ageing of the ash. Furthermore, the data was analyzed to reveal the impact of ingressed CO2 from atmosphere, infiltrating rain water and brine irrigation on the chemistry of ash core samples. Major mineral phases in original ash core samples prior to extraction are quartz (SiO2) and mullite (3Al2O3&middot / 2SiO2). Other minor mineral phases identified were hematite (Fe2O3), calcite (CaCO3), lime (CaO), anorthite (CaAl2Si2O8), mica (Ca (Mg, Al)3 (Al3Si) O10 (OH)2), and enstatite (Mg2Si2O6). X-ray diffraction results show significant loss of crystallinity in the older ash cores. The presence of minor phases of calcite and mica in dry disposed ash cores are attributed to reduction in the pore water pH due to hydration, carbonation and pozzolanic reactions. The X-ray diffraction technique was unable to detect Fe-oxyhydroxide phase and morealuminosilicate phases in ash core samples due to their low abundance and amorphous character. X-ray fluorescence results of the original ash core samples showed the presence of major oxides, such as SiO2, Al2O3, Fe2O3, while CaO, K2O, TiO2, Na2O, MnO, MgO, P2O5, and SO3 occur in minor concentrations. The ratio of SiO2/Al2O3 classified the original core samples prior to extraction as a silico-aluminate class F fly ash. The ternary plot of major elements in 1-year-old ash core samples was both sialic and ferrocalsialic but 8 year and 20-year-old ash core samples were sialic in chemical composition. It is noteworthy that the mass % of SiO2 varies through the depth of the core with an increase of nearly 3 %, to 58 mass % of SiO2 at a depth of 6 m in the 1-year-old core whereas in the case of the 8-year-old core a 2 % increase of SiO2 to a level of 57.5 mass % can be observed at levels between 4-8 m, showing dissolution of major components in the matrix of older ash cores.. The Na2O content of the Tutuka ash cores was low and varied between 0.6-1.1 mass % for 1-year-old ash cores to around 0.6-0.8 mass % for 8-year-old ash cores. Sodium levels were higher in 1-year-old ash cores compared to 8 year and 20-year-old ashcores. Observed trends indicate that quick weathering of the ash (within a year) leached out Na+ from the ash dump. No evidence of Na+ encapsulation even though the ash dump was brine irrigated. Thus the dry disposal ash placement method does not result in a sustainable salt sink for Na-containing species over time. The total content of each of the elements in 1 year and 20-year-old ash cores was normalised with their total content in fresh ash from same power station to show enrichment and depletion factor. Major elements such as K+, Mn showed enrichment in 1-year-old ash cores whereas Al, Si, Na+, Ti, Ca, Mg, S and Fe showed depletion due to over time erosion. Trace elements such as Cr, Sr, P, Ba, Pb, V and Zn showed enrichment but Ni, Y, Zr showed depletion attributed to over time erosion. In 20-year-old ash cores, major elements such as Al, Na+ and Mn showed enrichment while Si, K+, Fe, Mg and Ca showed depletion highlighting their mobility. Trends indicated intensive flushing of major soluble components such as buffering constituents (CaO) by percolating rain water. The 1-year-old and 20-year-old coal ash cores showed a lower pH and greater loss/depletion of the soluble buffering constituents than the 2-week-old placed ash, indicating significant chemical weathering within a year. Based&nbsp / on ANC results the leaching behaviours of Ca, Mg, Na+, K+, Se, Cr, and Sr were found to be controlled by the pH of the leachant indicating high mobility of major soluble species in the ash cores when in contact with slightly acid rain water. Other investigated toxic metals such as As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. Chemical alterations and formation of transient minor secondary mineral phases was found to have a significant effect on the acid susceptibility and depletion pattern of chemical species in the core ash samples when compared to fresh ash. These ANC results correlated well with the data generated from the sequential extraction scheme. Based on sequential extraction results elements, showed noticeable mobility in the water soluble, exchangeable and carbonate fractions due to adsorption and desorption caused by variations in the pore water pH. In contrast, slight mobility of elements in the Fe and Mn, and residual fractions of dry disposed fly ashes are attributed to the co-precipitation and dissolution of minor amount of less soluble secondary phase overtime. The 1-year-old dry disposed ash cores were the least weathered among the 3 drilled ash cores. Therefore low concentration of toxic metals in older ash cores were ascribed to extensive weathering with slower release from residual mineral phases over time. Elements were found to associate with different mineral phases depending on the age or depth of the core samples showing greater heterogeneity in dispersion. For instance the average amount of total calcium in different mineral associations of 1-year-old ash cores is as follows / water soluble (10.2 %), exchangeable (37.04 %), carbonate (37.9 %), Fe and Mn (7.1 %) and residual (2.97 %). The amount of total Na+ in different mineral phases of 1-year-old ash cores followed this trend: water soluble (21 %), exchangeable (11.26 %), carbonate (2.6 %), Fe and Mn (4.7 %) and residual (53.9 %). The non-leachable portion of the total Na+ content (namely that contained in the residual fraction) in the 1-year-old ash core samples under conditions found in nature ranged between 5-91 %. This non-leachable portion of the Na+ showed the metastability of the mineral phases with which residual Na+ associates. Results showed older ash cores are enriched in toxic elements. Toxic elements such as As, B, Cr, Mo and Pb are enriched in the residual fraction of older ash cores. For instance As concentration in the residual fraction varied between 0.0003- 0.00043 mg kg-1 for 1-year-old ash cores to around 0.0003-0.0015 mg kg-1 for 20-year-old ash cores. This suggests that the older ash is enriched in toxic elements hence dust from the ash dump would be toxic to human health. The knowledge of mobility and ecotoxicological significance of coal fly ash is needed when considering its disposal or reuse in the environment. The mobility and ecotoxicology of inorganic metals in coal fly ash are determined by (i) mineralogical associations of inorganic species (ii) in-homogeneity in the ash dumps (iii) long and short term exposure to ingress CO2 and percolating rain water. Management issues such as inconsistent placement of ash in the dumps, poor choice of ash dump site, in-homogeneity in brine irrigation, no record of salt load put on the ash dumps and lack of proper monitoring requires improvement. The thesis provides justification for the use of the modified sequential extraction scheme as a predictive tool and could be employed in a similar research work. This thesis also proved that the dry ash disposal method was not environmental friendly in terms of overall leaching potential after significant chemical weathering. Moreover the study proved that the practice of brine co-disposal or irrigation on ash dumps is not sustainable as the ash dump did not act as a salt sink.</p>

The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped, weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station.

Granular materials are characterized by its discrete nature which makes their behaviour very complex to understand when subjected to various loading situations. Comparing other materials, the understanding of granular materials is poor. This is because experimental analysis provides the macroscopic responses of the considered assembly whereas the discrete nature of the particles point to the fact of understanding the micro scale details and correlating it with the overall behaviour. Among the various modeling tools viz. analytical, physical or numerical, Discrete Element Method (DEM) a numerical technique, originally developed by Cundall (1971, 1974) and modified by Cundall and Strack (1979a, 1979b) is widely used for granular materials. Later a thorough description of DEM was given by Cundall (1988) and Hart et al (1988). Moreover Cundall & Hart (1992) reported discrete element code as one which allows finite displacements and rotations of discrete bodies along with recognition of new contacts as the calculation progresses which is followed in particle flow code and is used for this study. Generally the discrete particles are modeled as discs or spheres in 2-D and 3-D simulations respectively. The discs or spheres were considered as it is very easy to characterize the grain interactions and the contact detection. Even though the significance of particle shape has been reported in literature, a comprehensive 3-D study of the effect of particle shape on the various aspects of soil behaviour is lacking and is not reported. Particle shape is generally defined in terms of elongation, roundness and texture. Elongation is an indication of the particle aspect ratio whereas roundness measures the sharpness or angularity of particle’s edges and corners. Texture is related to the roughness of the surface. Particle gradation also plays a role in the mechanical behaviour. The influence of each of these factors on the mechanical behaviour of the assembly is important. Hence the major factors like elongation, texture etc which are used to define the particle shape are incorporated in this study. Evaluating the particle shape is another hurdle. In this study, the particle shape is analyzed using a 3D laser scanner which helps to identify the major and minor axis lengths of the particle. Additionally, the effective use of 3D DEM on large scale real life applications incorporating the particle shape effect is also not dealt with very extensively. Hence in this research, a comprehensive study on the calibration of DEM using glass beads, effect of particle shape on drained and undrained monotonic behaviour, liquefaction, post liquefaction and dynamic properties and the application of DEM to a grain polishing machine and an underground tunnel assembly is presented. In the present study, a set of drained triaxial tests were done on glass bead assembly using a laboratory triaxial set up. The glass beads used for the test were spherical and ellipsoidal in shape. The shape of glass beads was characterized through a sophisticated method of 3D laser scanning. In this scanning, the shape of the image of the glass bead is captured through an array of digitized points. These images obtained as unstructured 3D triangular meshes on processing will render the long and short axes of the particle which can be used for proper modeling of the particle shape. After obtaining the long and short axes for the particles, the same is used for the numerical modeling of the glass beads. The numerical simulation results have shown that the assembly modeled with clumped particles gives results qualitatively and quantitatively similar to the observed experimental macro responses. Hence this is used to demonstrate the power of DEM to realistically model the granular behaviour by incorporating the particle shape effect. In addition, undrained simulation of granular material has been numerically predicted from drained triaxial tests which are similar to the approach proposed by Norris et al (1997). An excellent correlation between undrained results predicted from drained triaxial test and undrained test (performed under constant volume conditions) has been observed. This further underlines the fact that the constant volume simulations are equivalent to undrained tests. Having validated the DEM results to the values obtained from the experiments on glass beads, a series of monotonic drained and undrained triaxial tests were performed on cylindrical assemblies of height to diameter ratio 2:1. Four different sets of assemblies were prepared which consists of particles of different aspect ratio to study the influence of particle shape. The behaviour of these assemblies under drained shearing indicates that the strength of the clumped assemblies is higher than that of the spherical assembly at all confining pressures. This has been explained from the magnitude of the anisotropic vi coefficients associated with the fabric and normal contact force tensors. It is also noted that eventhough both assemblies reach the peak strength at the same axial strain, the strain softening associated with the clumped assembly is very rapid which is due to the fact that clumps try to push each other apart as it offers more resistance to rotation resulting in dilation. Another significant observation is that a general increase in aspect ratio will not keep on increasing the strength. As the aspect ratio increases, the particles have a tendency to orient along their larger dimensions. This helps them to attain the lowest potential energy leading to a stable equilibrium and resulting in inherent fabric anisotropy. But when the particles try to align along the larger dimension, the formation of strong contact forces along the direction of loading is hindered. In addition, the lower strength associated with the higher aspect ratio particle assembly can also be attributed to the formation of unexpected void spaces when these longer particles bridge gaps over the underlying grains. The critical state studies indicate that the clumped assembly is having a higher residual strength compared to that of the spherical assembly. In the case of clumped assemblies also, irrespective of the initial loose or dense state of the assembly and the confining pressure applied, the samples reached the same critical state which underlines that the critical state is unique for a granular material. Moreover, the critical state line is non-linear for both the spherical and clumped assemblies. The studies conducted on the liquefaction behaviour indicates that at lower confining pressures the assemblies with particles consisting of lower aspect ratios loses its strength at less number of cycles which can be attributed to the interlocking of non-spherical particles resulting in higher number of contacts per particle. Moreover, during the initial cycles of loading, it is seen that the strong contacts are predominantly in the vertical direction or more precisely along the direction of maximum axial strain. But the plots extracted at higher cycles indicated that the strong contacts along the vertical direction have diminished considerably. This reduction in contact force magnitude and force chain indicates a drop in the number of contacts and is clearly visible in the gradual decrease of average coordination number. Another significant observation is that as the confining stresses increases, the rate of pore pressure generation of the assembly vii consisting of only spherical particles is less compared to the other two samples. Furthermore, at higher confining pressures, when the load direction reverses, the fabric of the clumped assemblies fails to change to a new orientation immediately. But to retain equilibrium the force anisotropy will quickly adjust itself. This mismatch results in losing the contacts and resulting in lower strength and less resistance to liquefaction at higher stresses for assemblies consisting of clumped particles. The post liquefaction study of the numerically liquefied samples shows that the assembly consisting of clumped shaped particles gained strength at a much faster rate compared to the assembly consisting of only spheres. This may be attributed to the ability of the clumps to rearrange themselves on a faster rate compared to that of the spherical particles. The rate of development of average coordination number is very significant as it explains the ability of the assembly to build up the deviatoric stress from a complete collapsed structure. As the contacts develop, the average coordination number as well as the deviatoric stress starts increasing with both the values higher for the assembly consisting of clumped particles. The evaluation of the dynamic properties viz. shear modulus and damping ratio showed a trend similar to the experimental observations on real granular materials. It is observed that the normalized shear modulus reduces with an increase in shear strain and the rate of reduction is very high at low strains for all the samples. It can be seen that as the confining pressure increases, the normalized shear modulus value also increases and the rate of increment is higher for the assemblies consisting of non-spherical particles. Furthermore, for all the samples the threshold shear strain is about 0.001 up to which the behaviour is elastic. Beyond the threshold shear strain, the variation of the normalized shear modulus ratio is non-linear. At small shear strains, the energy dissipation is low resulting in smaller values of damping. As the strains increase, the non-linearity in the constitutive behaviour results in higher material damping leading to high damping value. The simulations of the food polishing machine helps to understand the pattern of hitting of clumped grains on the wall with due importance to the velocity of hit, angle of hit, force of hit, and the number of grains hitting the wall. The modeling and subsequent extraction of the data helped to identify that the wear and tear of the machine was not uniform and was clustered to specific regions due to the non-uniform distribution of the considered parameters. This helped to design a more sophisticated system such that the parts which are subjected to more deterioration are provided with additional support. To bring out the effect of the particle shape, simulations are performed using spherical particles and the results show that the pattern of variation is same, but the magnitudes are different owing to the less surface area associated with the spherical particles. The 3-D simulations of an underground tunnel assembly in a weak weathered rock helped to understand the variation in the stability of the system with and without lining. It was observed that the introduction of lining resulted in a more stable configuration and the circumferential stresses were found to be distributed uniformly around the tunnel. FEM simulations also show a similar trend of stress and strain variations but were unable to capture the ground loosening around the tunnel and the formation of the ground arch whereas DEM could realistically capture all these phenomena. It was observed that as the shape changes from sphere to non-spherical particles, circumferential stresses around the tunnels increased. In addition, as the distance from the tunnel face increases, the strains are reduced. The maximum vertical strain near the crown of the tunnel is observed for the assembly consisting of spherical particles. In short, this research is focused on a comprehensive understanding of the particle shape effect on the mechanical behaviour of granular mass. Numerical simulations incorporating the shape effect has been done on drained and undrained monotonic shear tests, critical state, liquefaction, post liquefaction and dynamic properties. Besides, the granular dynamics simulation of the movement of long food grains in a food polishing machine and the behaviour of an underground tunnel in a granular assembly is also reported.

Philosophiae Doctor - PhD / The management and disposal of huge volumes of coal combustion by products such as fly ash has constituted a major challenge to the environment. In most cases due to the inadequate alternative use of coal fly ash, the discarded waste is stored in holding ponds, slag heaps, or stock piled in ash dumps. This practice has raised concerns on the prospect of inorganic metals release to the surface and groundwater in the vicinity of the ash dump. Acceptable scientific studies are lacking to determine the best ash disposal practices. Moreover, knowledge about the mobility patterns of inorganic species as a function of mineralogical association or pH susceptibility of the dry disposed ash dump under natural weathering conditions are scarce in the literature. Fundamental understanding of chemical interactions of dry disposed ash with ingressed CO2 from atmosphere, percolating rain water and brine irrigation within ash disposal sites were seen as key areas requiring investigation. The mineralogical association of inorganic species in the dry disposed ash cores can be identified and quantified. This would provide a basis for understanding of chemical weathering, mineralogical transformations or mobility patterns of these inorganic species in the dry ash disposal scenario. The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped, weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station. The core samples were characterized using standard analytical procedures viz: X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transforms infrared (FTIR) techniques, Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) and Acid neutralisation capacity (ANC) test. A modified sequential extraction (SE) method was used in this study. The chemical partitioning, mobility and weathering patterns in 1 year, 8 year and 20-year-old sections of the ash dump were respectively investigated using this modified sequential extraction scheme. The sequence of the extractions was as follows: (1) water soluble, (2) exchangeable, (3) carbonate, (4) iron and manganese and (5) residual. The results obtained from the 5 steps sequential extraction scheme were validated with the total metal content of the original sample using mass balance method. The distribution of major and trace elements in the different liquid fractions obtained after each step of sequential extraction of the 59 drilled core samples was determined by inductively coupled plasma mass spectrometry (ICPMS). The data generated for various ash core samples were explored for the systematic analysis of mineralogical transformation and change in ash chemistry with ageing of the ash. Furthermore, the data was analyzed to reveal the impact of ingressed CO2 from atmosphere, infiltrating rain water and brine irrigation on the chemistry of ash core samples. Major mineral phases in original ash core samples prior to extraction are quartz (SiO2) and mullite (Al2O3·2SiO2). Other minor mineral phases identified were hematite (Fe2O3), calcite (CaCO3), lime (CaO), anorthite (CaAl2Si2O8), mica (Ca (Mg, Al)3 (Al3Si) O10 (OH)2), and enstatite (Mg2Si2O6). X-ray diffraction results show significant loss of crystallinity in the older ash cores. The presence of minor phases of calcite and mica in dry disposed ash cores are attributed to reduction in the pore water pH due to hydration, carbonation and pozzolanic reactions. The X-ray diffraction technique was unable to detect Fe-oxyhydroxide phase and morealuminosilicate phases in ash core samples due to their low abundance and amorphous character. X-ray fluorescence results of the original ash core samples showed the presence of major oxides, such as SiO2, Al2O3, Fe2O3, while CaO, K2O, TiO2, Na2O, MnO, MgO, P2O5, and SO3 occur in minor concentrations. The ratio of SiO2/Al2O3 classified the original core samples prior to extraction as a silico-aluminate class F fly ash. The ternary plot of major elements in 1-year-old ash core samples was both sialic and ferrocalsialic but 8 year and 20-year-old ash core samples were sialic in chemical composition. It is noteworthy that the mass % of SiO2 varies through the depth of the core with an increase of nearly 3 %, to 58 mass % of SiO2 at a depth of 6 m in the 1-year-old core whereas in the case of the 8-year-old core a 2 % increase of SiO2 to a level of 57.5 mass % can be observed at levels between 4-8 m, showing dissolution of major components in the matrix of older ash cores.. The Na2O content of the Tutuka ash cores was low and varied between 0.6-1.1 mass % for 1-year-old ash cores to around 0.6-0.8 mass % for 8-year-old ash cores. Sodium levels were higher in 1-year-old ash cores compared to 8 year and 20-year-old ashcores. Observed trends indicate that quick weathering of the ash (within a year) leached out Na+ from the ash dump. No evidence of Na+ encapsulation even though the ash dump was brine irrigated. Thus the dry disposal ash placement method does not result in a sustainable salt sink for Na-containing species over time. The total content of each of the elements in 1 year and 20-year-old ash cores was normalised with their total content in fresh ash from same power station to show enrichment and depletion factor. Major elements such as K+, Mn showed enrichment in 1-year-old ash cores whereas Al, Si, Na+, Ti, Ca, Mg, S and Fe showed depletion due to over time erosion. Trace elements such as Cr, Sr, P, Ba, Pb, V and Zn showed enrichment but Ni, Y, Zr showed depletion attributed to over time erosion. In 20-year-old ash cores, major elements such as Al, Na+ and Mn showed enrichment while Si, K+, Fe, Mg and Ca showed depletion highlighting their mobility. Trends indicated intensive flushing of major soluble components such as buffering constituents (CaO) by percolating rain water. The 1-year-old and 20-year-old coal ash cores showed a lower pH and greater loss/depletion of the soluble buffering constituents than the 2-week-old placed ash, indicating significant chemical weathering within a year. Based on ANC results the leaching behaviours of Ca, Mg, Na+, K+, Se, Cr, and Sr were found to be controlled by the pH of the leachant indicating high mobility of major soluble species in the ash cores when in contact with slightly acid rain water. Other investigated toxic metals such as As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. Chemical alterations and formation of transient minor secondary mineral phases was found to have a significant effect on the acid susceptibility and depletion pattern of chemical species in the core ash samples when compared to fresh ash. These ANC results correlated well with the data generated from the sequential extraction scheme. Based on sequential extraction results elements, showed noticeable mobility in the water soluble, exchangeable and carbonate fractions due to adsorption and desorption caused by variations in the pore water pH. In contrast, slight mobility of elements in the Fe and Mn, and residual fractions of dry disposed fly ashes are attributed to the co-precipitation and dissolution of minor amount of less soluble secondary phase overtime. The 1-year-old dry disposed ash cores were the least weathered among the 3 drilled ash cores. Therefore low concentration of toxic metals in older ash cores were ascribed to extensive weathering with slower release from residual mineral phases over time. Elements were found to associate with different mineral phases depending on the age or depth of the core samples showing greater heterogeneity in dispersion. For instance the average amount of total calcium in different mineral associations of 1-year-old ash cores is as follows; water soluble (10.2 %), exchangeable (37.04 %), carbonate (37.9 %), Fe and Mn (7.1 %) and residual (2.97 %). The amount of total Na+ in different mineral phases of 1-year-old ash cores followed this trend: water soluble (21 %), exchangeable (11.26 %), carbonate (2.6 %), Fe and Mn (4.7 %) and residual (53.9 %). The non-leachable portion of the total Na+ content (namely that contained in the residual fraction) in the 1-year-old ash core samples under conditions found in nature ranged between 5-91 %. This non-leachable portion of the Na+ showed the metastability of the mineral phases with which residual Na+ associates. Results showed older ash cores are enriched in toxic elements. Toxic elements such as As, B, Cr, Mo and Pb are enriched in the residual fraction of older ash cores. For instance As concentration in the residual fraction varied between 0.0003- 0.00043 mg kg-1 for 1-year-old ash cores to around 0.0003-0.0015 mg kg-1 for 20-year-old ash cores. This suggests that the older ash is enriched in toxic elements hence dust from the ash dump would be toxic to human health. The knowledge of mobility and ecotoxicological significance of coal fly ash is needed when considering its disposal or reuse in the environment. The mobility and ecotoxicology of inorganic metals in coal fly ash are determined by (i) mineralogical associations of inorganic species (ii) in-homogeneity in the ash dumps (iii) long and short term exposure to ingress CO2 and percolating rain water. Management issues such as inconsistent placement of ash in the dumps, poor choice of ash dump site, in-homogeneity in brine irrigation, no record of salt load put on the ash dumps and lack of proper monitoring requires improvement. The thesis provides justification for the use of the modified sequential extraction scheme as a predictive tool and could be employed in a similar research work. This thesis also proved that the dry ash disposal method was not environmental friendly in terms of overall leaching potential after significant chemical weathering. Moreover the study proved that the practice of brine co-disposal or irrigation on ash dumps is not sustainable as the ash dump did not act as a salt sink. / South Africa