• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 7
  • 2
  • 2
  • 1
  • 1
  • Tagged with
  • 13
  • 6
  • 6
  • 6
  • 6
  • 6
  • 5
  • 5
  • 5
  • 5
  • 5
  • 5
  • 5
  • 5
  • 5
  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Desenvolvimento e validação de metodologia para a determinação de monocloroacetato de sódio e dicloroacetato de sódio em cocoamido,N-[(3-dimetilamino)propil],betaína via cromatografia a gás: GC/FID, GC/ECD e GC/MS / Development and validation of method for determination of sodium monochloroacetate and sodium dichloroacetate in cocoamide,N-[(3-dimethylamine)propyl],betaine by gas chromatography: GC/FID, GC/ECD e GC/MS

Leão, Cláudio 24 June 2016 (has links)
O monocloroacetato de sódio (MCAS) e o dicloroacetato de sódio (DCAS) são compostos tóxicos e irritantes ao ser humano e nocivos ao meio ambiente, sendo impurezas indesejáveis na cocoamido propil betaína (CAPB), que é um surfactante anfótero utilizado em produtos de consumo dos segmentos cosmético e domiciliar. Diante dos requisitos de concentração em nível de mg/kg exigidos pelos órgãos reguladores de saúde do governo, tornou-se mandatório o emprego de metodologia com limite de quantificação, precisão e exatidão adequados aos rígidos controles de processo pelos fabricantes da CAPB, bem como, dispor de técnicas convencionais com poder de resolução e proficiência pelo controle de qualidade e neste contexto inseriu-se a cromatografia a gás. Neste estudo foram estabelecidos os procedimentos analíticos que definiram as melhores condições para identificar e quantificar as impurezas MCAS e DCAS na matriz CAPB por meio da cromatografia a gás. A preparação das amostras consistiu da derivação das impurezas MCAS e DCAS a ésteres etílicos e a extração líquido-líquido em hexano para separar dos demais constituintes da matriz. Os modos de detecção acoplados à cromatografia a gás foram a ionização pela chama (GC/FID), a captura de elétrons (GC/ECD) e a espectrometria de massas (GC/MS). A validação comprovou que as metodologias são lineares entre 4 e 50 mg/kg com recuperação de 70 a 120%, apresentam limites de quantificação inferiores a 10 mg/kg e produziram médias e incertezas similares na amostra examinada, constituindo-se alternativas para a determinação de cloroacetatos em betaínas. / The sodium monochloroacetate (MCAS) and the sodium dichloroacetate (DCAS) are toxic and irritating compounds to humans and harmful to the environment, being undesirable impurities in cocoamidepropyl betaine (CAPB), which is a amphoteric surfactant used in consumer products of cosmetic and household segments. Considering the content requirements at level mg/kg defined by governmental health agency, became mandatory the use of analytical methods with appropriate precision, accuracy and quantification limit to rigid process controls by CAPB manufacturers, as well as, to have available conventional techniques with good resolution and proficiency for quality control staff and in this context was inserted the gas chromatography. In this study, the analytical procedures were established to define the best conditions to identify and quantify the impurities MCAS and DCAS in CAPB matrix by gas chromatography. The sample preparation consisted of MCAS and DCAS derivation to ethyl esters and liquid-liquid extraction in hexane to separate them from the other constituents of matrix. The detection modes coupled to gas chromatography were the flame ionization (GC/FID), electron capture (GC/ECD) and mass spectrometry (GC/MS). The validation ensured that the methodologies are linear between 4 and 50 mg/kg with recovery 70 to 120%, presents quantification limits less than 10 mg/kg and produced similar averages and uncertainties in the examined sample, constituting an alternative for determination of chloroacetates in betaines.
2

Enhanced Oil Recovery in High Salinity High Temperature Reservoir by Chemical Flooding

Bataweel, Mohammed Abdullah 2011 December 1900 (has links)
Studying chemical enhanced oil recovery (EOR) in a high-temperature/high-salinity (HT/HS) reservoir will help expand the application of chemical EOR to more challenging environments. Until recently, chemical EOR was not recommended at reservoirs that contain high concentrations of divalent cations without the need to recondition the reservoir by flooding it with less saline/ less hardness brines. This strategy was found ineffective in preparing the reservoir for chemical flooding. Surfactants used for chemical flooding operating in high temperatures tend to precipitate when exposed to high concentrations of divalent cations and will partition to the oil phase at high salinities. In this study amphoteric surfactant was used to replace the traditionally used anionic surfactants. Amphoteric surfactants show higher multivalent cations tolerance with better thermal stability. A modified amphoteric surfactant with lower adsorption properties was evaluated for oil recovery. Organic alkali was used to eliminate the water softening process when preparing the chemical solution and reduce potential scale problems caused by precipitation due to incompatibility between chemical slug containing alkali and formation brine. Using organic alkali helped in minimizing softening required when preparing an alkali-surfactant-polymer (ASP) solution using seawater. Solution prepared with organic alkali showed the least injectivity decline when compared to traditional alkalis (NaOH and Na2CO3) and sodium metaborate. Adding organic alkali helped further reduce IFT values when added to surfactant solution. Amphoteric surfactant was found to produce low IFT values at low concentrations and can operate at high salinity / high hardness conditions. When mixed with polymer it improved the viscosity of the surfactant-polymer (SP) solution when prepared in high salinity mixing water (6% NaCl). When prepared in seawater and tested in reservoir temperature (95°C) no reduction in viscosity was found. Unlike the anionic surfactant that causes reduction in viscosity of the SP solution at reservoir temperature. This will not require increasing the polymer concentration in the chemical slug. Unlike the case when anionic surfactant was used and more polymer need to be added to compensate the reduction in viscosity. Berea sandstone cores show lower recovery compared to dolomite cores. It was also found that Berea cores were more sensitive to polymer concentration and type and injectivity decline can be a serious issue during chemical and polymer injection. Dolomite did not show injectivity decline during chemical and polymer flooding and was not sensitive to the polymer concentration when a polymer with low molecular weight was used. CT scan was employed to study the displacement of oil during ASP, SP, polymer and surfactant flooding. The formation and propagation oil bank was observed during these core flood experiments. ASP and SP flooding showed the highest recovery, and formation and propagation of oil bank was clearer in these experiments compared to surfactant flooding. It was found that in Berea sandstone with a permeability range of 50 to 80 md that the recovery and fluid flow was through some dominating and some smaller channels. This explained the deviation from piston-like displacement, where a sharp change in saturation in part of the flood related to the dominated channels and tapered front with late arrival when oil is recovered from the smaller channels. It was concluded that the recovery in the case of sandstone was dominated by the fluid flow and chemical propagation in the porous media not by the effectiveness of the chemical slug to lower the IFT between the displacing fluid and oil.
3

Desenvolvimento e validação de metodologia para a determinação de monocloroacetato de sódio e dicloroacetato de sódio em cocoamido,N-[(3-dimetilamino)propil],betaína via cromatografia a gás: GC/FID, GC/ECD e GC/MS / Development and validation of method for determination of sodium monochloroacetate and sodium dichloroacetate in cocoamide,N-[(3-dimethylamine)propyl],betaine by gas chromatography: GC/FID, GC/ECD e GC/MS

Cláudio Leão 24 June 2016 (has links)
O monocloroacetato de sódio (MCAS) e o dicloroacetato de sódio (DCAS) são compostos tóxicos e irritantes ao ser humano e nocivos ao meio ambiente, sendo impurezas indesejáveis na cocoamido propil betaína (CAPB), que é um surfactante anfótero utilizado em produtos de consumo dos segmentos cosmético e domiciliar. Diante dos requisitos de concentração em nível de mg/kg exigidos pelos órgãos reguladores de saúde do governo, tornou-se mandatório o emprego de metodologia com limite de quantificação, precisão e exatidão adequados aos rígidos controles de processo pelos fabricantes da CAPB, bem como, dispor de técnicas convencionais com poder de resolução e proficiência pelo controle de qualidade e neste contexto inseriu-se a cromatografia a gás. Neste estudo foram estabelecidos os procedimentos analíticos que definiram as melhores condições para identificar e quantificar as impurezas MCAS e DCAS na matriz CAPB por meio da cromatografia a gás. A preparação das amostras consistiu da derivação das impurezas MCAS e DCAS a ésteres etílicos e a extração líquido-líquido em hexano para separar dos demais constituintes da matriz. Os modos de detecção acoplados à cromatografia a gás foram a ionização pela chama (GC/FID), a captura de elétrons (GC/ECD) e a espectrometria de massas (GC/MS). A validação comprovou que as metodologias são lineares entre 4 e 50 mg/kg com recuperação de 70 a 120%, apresentam limites de quantificação inferiores a 10 mg/kg e produziram médias e incertezas similares na amostra examinada, constituindo-se alternativas para a determinação de cloroacetatos em betaínas. / The sodium monochloroacetate (MCAS) and the sodium dichloroacetate (DCAS) are toxic and irritating compounds to humans and harmful to the environment, being undesirable impurities in cocoamidepropyl betaine (CAPB), which is a amphoteric surfactant used in consumer products of cosmetic and household segments. Considering the content requirements at level mg/kg defined by governmental health agency, became mandatory the use of analytical methods with appropriate precision, accuracy and quantification limit to rigid process controls by CAPB manufacturers, as well as, to have available conventional techniques with good resolution and proficiency for quality control staff and in this context was inserted the gas chromatography. In this study, the analytical procedures were established to define the best conditions to identify and quantify the impurities MCAS and DCAS in CAPB matrix by gas chromatography. The sample preparation consisted of MCAS and DCAS derivation to ethyl esters and liquid-liquid extraction in hexane to separate them from the other constituents of matrix. The detection modes coupled to gas chromatography were the flame ionization (GC/FID), electron capture (GC/ECD) and mass spectrometry (GC/MS). The validation ensured that the methodologies are linear between 4 and 50 mg/kg with recovery 70 to 120%, presents quantification limits less than 10 mg/kg and produced similar averages and uncertainties in the examined sample, constituting an alternative for determination of chloroacetates in betaines.
4

Unprotected Amino Aldehydes in Organic Synthesis

Hili, Ryan Matthew 07 March 2011 (has links)
In 1908, H. Emil Fisher attempted to prepare glycinal, an unprotected amino aldehyde, which he found to be inherently unstable and prone to polymerization. This instability arises from the propensity of amines to condense with aldehydes. Accordingly, amino aldehydes require protection of the amine functional group. On the contrary, aziridines do not condense with aldehydes; the aziridine ring-strain precludes the formation of an iminium ion. Predicated upon this orthogonal reactivity, a stable class of unprotected amino aldehydes has been prepared, and an in-depth investigation into their chemical reactivity has been undertaken. Reactions designed to utilize both their nucleophilic (amine) and electrophilic (aldehyde) centres have demonstrated their capacity to forge multiple bonds in a single transformation, and have been implemented in the synthesis of complex heterocycles and cyclic peptides.
5

Unprotected Amino Aldehydes in Organic Synthesis

Hili, Ryan Matthew 07 March 2011 (has links)
In 1908, H. Emil Fisher attempted to prepare glycinal, an unprotected amino aldehyde, which he found to be inherently unstable and prone to polymerization. This instability arises from the propensity of amines to condense with aldehydes. Accordingly, amino aldehydes require protection of the amine functional group. On the contrary, aziridines do not condense with aldehydes; the aziridine ring-strain precludes the formation of an iminium ion. Predicated upon this orthogonal reactivity, a stable class of unprotected amino aldehydes has been prepared, and an in-depth investigation into their chemical reactivity has been undertaken. Reactions designed to utilize both their nucleophilic (amine) and electrophilic (aldehyde) centres have demonstrated their capacity to forge multiple bonds in a single transformation, and have been implemented in the synthesis of complex heterocycles and cyclic peptides.
6

Capillary Electrochromatography-Mass Spectrometry (CEC-MS) of Surfactants

Norton, Dean Stephen 06 August 2007 (has links)
This research presents advancements in the coupling of capillary electrochromatography (CEC) to mass spectrometry (MS) for the analysis of different chemical classes of surfactants. Chapter 1 provides a brief introduction that summarizes the mechanics and fundamentals of CEC, including instrumentation and applications for CEC-MS. Chapter 2 describes the on-line hyphenation of a packed CEC column with an internally tapered tip coupled to electrospray ionization-mass spectrometry (ESI-MS) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) for the analysis of betaine-type amphoteric or zwitterionic surfactants (Zwittergent®). The interesting aspects include CEC-MS column manufacture and charaterization, as well as a comparison between the CEC-ACPI-MS and CEC-ESI-MS ionization pattern of zwittergents. In Chapter 3, the CEC-MS of alkyltrimethyl-ammonium ions (ATMA+) with chain length ranging from C1-C18 is optimized using an internally tapered CEC-MS column packed with mixed mode C6/strong cation exchange stationary phase and coupled to an ESI source. In addition, the optimized CEC-ESI-MS protocol is applied for the challenging analysis of commercial sample Arquad S-50 ATMA+ containing cis-trans unsaturated and saturated soyabean fatty acid derivatives. In Chapter 4, a novel CEC-UV method for separation of the various Triton X-100 oligomers is presented. A systematic mobile phase tuning and comparison of monomeric vs. polymeric stationary phases was conducted. In Chapter 5, we present the first application of CEC coupled to MS for analysis of Triton X (TX-) series surfactants. A characterization from the viewpoint of the ion and adduct formation for TX-series nonionic surfactants with a variable number of ethoxy units (n=1.5-16) in the scan mode are first discussed. Next, utilizing the TX-series as model alkylphenolpolyethoxylates (APEOs), a detailed investigation of the chromatographic separation and MS detection are performed followed by analysis of very long chain TX series with n=30-70. In Chapter 6, CEC-MS utilizing full scan positive ion mode of ESI was employed to study the effect of fragmentor voltage on the in-source collision induced dissociation (IS-CID) of several APEO nonionic surfactants. Finally, in Chapter 7, the preparation and characterization of a novel liquid crystalline stationary phase suitable for separation of neutral and charged compounds in packed column CEC is evaluated.
7

Experimental exploration of the amphoteric defect model by cryogenic ion irradiation of a range of wide band gap oxide materials

Borgersen, J., Vines, L., Frodason, Y.K., Kuznetsov, A., von Wenckstern, Holger, Grundmann, Marius, Allen, M., Zuniga-Perez, J., Johansen, K.M. 27 April 2023 (has links)
The evolution of electrical resistance as function of defect concentration is examined for the unipolar n-conducting oxides CdO, β-Ga 2 O 3 , In 2 O 3 , SnO 2 and ZnO in order to explore the predictions of the amphoteric defect model. Intrinsic defects are introduced by ion irradiation at cryogenic temperatures, and the resistance is measured in-situ by current–voltage sweeps as a function of irradiation dose. Temperature dependent Hall effect measurements are performed to determine the carrier concentration and mobility of the samples before and after irradiation. After the ultimate irradiation step, the Ga 2 O 3 and SnO2 samples have both turned highly resistive. In contrast, the In 2 O 3 and ZnO samples are ultimately found to be less resistive than prior to irradiation, however, they both show an increased resistance at intermediate doses. Based on thermodynamic defect charge state transitions computed by hybrid density functional theory, a model expanding on the current amphoteric defect model is proposed.
8

Ion - conducting polymeric membranes for electrochemical energy devices / Membranes conductrices ioniques pour les systèmes électrochimiques de l'énergie / Membrane polimeriche conduttrici di ioni per sistemi elettrochimici dell' energia

Pasquini, Luca 05 November 2015 (has links)
La recherche vise à proposer des membranes pour des dispositifs électrochimiques capables d'atteindre le bon compromis en terme de conduction ionique, de stabilité et de longue durée de vie pour une haute efficacité.Nous avons réalisé des membranes échangeuses des protons, d'anions ou amphotères à base de polymères aromatiques stables fonctionnalisés. Des groupes sulfonique on été introduit sur la squelette du PEEK, des groupes d'ammonium sur le PEEK et le PSU ou le deux au même temps pour échanger ensemble des protons et des anions.L'optimisation continue des paramètres de synthèse, le choix des différents polymères et/ou des groupes de fonctionnalisation et l'amélioration des procédures et des traitements des membranes coulée, a conduit à de bons résultats en termes de conductivité ionique, sélectivité et stabilité.L'étude des principaux paramètres des membranes démontre une stabilité thermique entre 140 et 200 ° C selon la membrane sélectionnée, un comportement mécanique caractérisé par une résistance à la traction et un module d'élasticité élevée et un relativement faible ductilité, influencé par le niveau d’ hydratation de la membrane ou l éventuelle présence de cross-link. En optimisant le degré de fonctionnalisation et les types de groupes de fonctionnalisation, nous avons obtenu une accordable absorption d'eau, une conductivité ionique élevé pour différent ions (jusqu'à ≃ 3 mS / cm pour le polymère conducteurs des anions) et une perméabilité aux ions vanadium très faible (applications dans RFB) jusqu'à ≃ 10-10 cm2/min, ce qui est bien au-dessous des données typiques de la littérature et un paramètre très important pour applications technologiques. / The research aims to propose membranes for electrochemical devices alternative to the commercial ones able to reach the right compromise in term of good ionic conduction, stability and long life time for an high efficiency. We realized proton exchange, anion exchange and amphoteric membranes based on stable functionalized aromatic polymers (PEEK, PSU). We thus introduced sulfonic groups on a PEEK backbone to exchange protons or ammonium groups on PEEK and PSU to exchange anions. We also realized amphoteric membranes able to exchange at the same time both kinds of ions. The continuous optimization of synthesis parameters, the choice of different polymers and/or functionalization groups and the improvement of casting procedures and treatments of membranes, led to good results in terms of ionic conductivity, selectivity and stability.The study of the main parameters of the synthesized membranes demonstrates a thermal stability between 140 and 200°C depending on the selected membrane, a mechanical behavior characterized by a high elastic modulus and tensile strength and a relatively low ductility strongly influenced on the degree of hydration of the membrane as well as the eventual presence of cross-linking. Working on the degree of functionalization and the type of functionalizing groups, we obtained a tunable water uptake, an elevated ionic conductivity for different ions (up to ≃ 3 mS/cm for anionic conducting polymers) and a very low ion permeability (vanadium ions for RFB applications) down to ≃ 10-10 cm2/min, which is much below typical literature data for cation- and anion separation membranes and a challenge parameters for technological applications.
9

Geochemical and mineralogical evaluation of toxic contaminants mobility in weathered coal fly ash : as a case study, Tutuka dumpsite, South Africa

Akinyemi, Segun Ajayi. January 2011 (has links)
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.
10

Geochemical and mineralogical evaluation of toxic contaminants mobility in weathered coal fly ash: as a case study, Tutuka dump site, South Africa

Akinyemi, Segun Ajayi January 2011 (has links)
<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>

Page generated in 0.4595 seconds