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Made available in DSpace on 2015-05-14T13:21:21Z (GMT). No. of bitstreams: 1 ArquivoTotal.pdf: 2474612 bytes, checksum: c81546edfad45aee18046ef7339ed083 (MD5) Previous issue date: 2013-06-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Clay minerals have been used for adsorption of pollutant substances. In this work, sodium palygorskite (pali) was applied for adsorption of the RN blue, RB red and yellow reactive dyes from aqueous solutions and the modified forms with silanes 3-aminepropyltrimethoxysilane (N) and 3-propylethylenediaminetrimethoxissilane (NN) were obtained. The sample pali-N were utilized for removing Cu2+, Co2+ and Ni2+ cations and the same dyes. The experimental factors as time of contact, pH and initial concentration of the adsorbates were investigated. The solids were characterized using composition chemical analysis, X-ray diffraction, 27Al and 29Si nuclear magnetic resonance, infrared spectroscopy, nitrogen adsorption-desorption measurements, thermogravimetry, scanning electronic microscopy and C, H, N elemental analysis. The results showed that the precursor pali was pure clay mineral containing traces of quartzo. The sample was a dioctaedrical type with surface area of 118 m2 g-1 constituted of aggregates of fibers. The modified solids showed an immobilization degree of 0.92 and 0.67 mmol g-1 for pali-N and pali-NN, respectively. The results of dye adsorption on pure sample showed the maximum retention of 55 mg g-1 for reactive blue RN and red RB and 45 mg g-1 for reactive yellow GR. For sample pali-N, the maximum adsorption capacities were 120, 110 and 100 mg g-1 for red RB, blue RN and yellow GR, respectively, which all processes were described by pseudo- second-order kinetic and the equilibrium data were fitted to Langmuir model. In the adsorption of metal cation on pali-N, the maximum adsorbed quantities were 0.73, 0.62 and 0.58 mmol g-1 for Cu2+, Co2+ and Ni2+, respectively. The data were fitted to pseudo-second-order kinetic and the equilibrium data were fitted to Langmuir model. / Os argilominerais têm sido largamente utilizados na retenção de diversos poluentes. Neste trabalho, a paligorsquita sódica (pali) foi aplicada na remoção dos corantes reativos azul RN, vermelho RB e amarelo GR em soluções aquosas e as formas modificadas com o agente sililante 3-aminopropiltrimetoxissilano (Pali-N) e 3-propiletilenodiaminotrimetoxissilano (Pali-NN) foram obtidas. A amostra pali-N foi utilizada na remoção dos íons metálicos Cu2+, Co2+ e Ni2+ e dos mesmos corantes. Os fatores como tempo de contato, pH e concentração inicial dos adsorvatos foram investigados. Os diversos sólidos foram caracterizados por análise de composição, difratometria de raios X, ressonância magnética nuclear de 27Al e 29Si, espectroscopia de absorção na região do infravermelho, medidas de sorção-dessorção de nitrogênio, análise termogravimétrica, microscopia eletrônica de varredura e análise elementar de carbono, hidrogênio e nitrogênio. Os resultados mostraram que a pali apresentou-se como um argilomineral de elevada pureza, sendo do tipo dioctaédrica com área superficial de 118 m2 g-1 e constituída por feixes de fibras formando agregados. As amostras modificadas obtiveram graus de imobilização de 0,92 e 0,67 mmol g-1 para a pali-N e pali-NN, respectivamente. Os resultados da sorção na amostra pura para os corantes reativos azul RN e vermelho RB mostraram retenções máximas de 55 mg g-1 e de 45 mg g-1 para o corante reativo amarelo GR. Na amostra pali-N, as capacidades máximas de sorção foram de 120, 110 e 100 mg g-1, para o vermelho reativo RB, azul reativo RN e amarelo reativo GR, respectivamente, sendo que todos esses processos seguiram uma cinética de pseudo 2ª ordem e foram descritos pelo modelo de Langmuir. Nos ensaios de retirada dos íons metálicos Cu2+, Co2+ e Ni2+ em pali-N, as quantidades máximas adsorvidas foram de 0,73, 0,62 e 0,58 mmol g-1, respectivamente. Os dados seguiram o modelo cinético de pseudo 2ª ordem e para os estudos de equilíbrio houve ajuste ao modelo de Langmuir.

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 FranciscoCBS_DISSERT.pdf: 2327685 bytes, checksum: 7ea91ee570c997cb17e15b80242eeaa3 (MD5) Previous issue date: 2013-07-30 / The present work was to carry out a study on the adsorption of hydrogen sulfide (H2S) in arrays synthesized from a commercial clay mineral formed by a mixture of dolomite and quartz. To produce the ion exchange matrix were made using aqueous solutions of salts of cobalt II chloride hexahydrate (CoCl2.6H2O) II cadmium nitrate tetrahydrate (Cd (NO3)2.4H2O) I mercuric chloride (HgCl) nitrate and chromium III pentahydrate (Cr (NO3)3.5H2O). The arrays were subjected to hydrogen sulphide gas passage for one hour. To check the amount of gas adsorbed was used gravimetric process. The best result was in the adsorption matrix doped with cadmium and the solution retained for a longer time than the largest amount of H2S was the cobalt matrix. The matrix unmodified exhibited poor adsorption capacity. The characterization of the matrices were used XRD, XRF and IV. Mother with cadmium showed a high capacity in ion exchange, because the percentage of cadmium increased from 0% to 81.38% by replacing atoms of calcium and silicon which increased from 96.54% to 17.56% and 15, 72% to 0.32%, respectively, but also the best performance in adsorption of H2S adsorbing 11.89507 mg per gram of matrix / O presente trabalho teve como finalidade realizar um estudo sobre a capacidade de adsor??o de g?s sulf?drico(H2S) em matrizes sintetizadas a partir de um argilomineral comercial formado por uma mistura de dolomita e quartzo. Para produzir as matrizes foram feitas trocas i?nicas utilizando as solu??es aquosas dos sais: cloreto de cobalto II hexaidratado(CoCl2.6H2O), nitrato de c?dmio II tetraidratado (Cd(NO3)2.4H2O), cloreto de merc?rio I (HgCl) e nitrato de cromo III pentaidratado(Cr(NO3)3.5H2O). As matrizes foram submetidas a passagem de g?s sulf?drico durante uma hora. Para verificar a quantidade de g?s adsorvido foi utilizado o processo de gravimetria. O melhor resultado na adsor??o foi com a matriz dopada com a solu??o de c?dmio e a que reteve por mais tempo a maior quantidade de H2S, foi a matriz com cobalto. A matriz n?o modificada apresentou uma fraca capacidade de adsor??o. Na caracteriza??o das matrizes foram utilizadas an?lises de DRX, FRX e IV. A matriz com c?dmio apresentou uma alta capacidade na troca i?nica, pois a porcentagem de c?dmio passou de 0% para 81,38%, substituindo ?tomos de c?lcio e de sil?cio que passaram de 96,54% para 17,56% e de 15,72% para 0,32%, respectivamente, como tamb?m, o melhor desempenho na adsor??o, adsorvendo 11,89507mg de H2S por grama de matriz

Made available in DSpace on 2016-12-08T17:19:32Z (GMT). No. of bitstreams: 1 Rubia Raquel Luvizao.pdf: 2856384 bytes, checksum: 11aac33ded8309a4b3c237cbdecbfdb7 (MD5) Previous issue date: 2008-07-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Scrap weathered green foundry sand (WGFS), generated in a southern Brazilian steel casting industry, was studied in this work. According to Brazilian standards, the Green foundry sand waste is classified as a non-inert residue due to the potential leaching of toxic metal ions. Its disposal in controlled landfills is the main form of final destination. The aim of this research study presented here was the characterization of weathered green foundry sand waste and to evaluate its applications on asphalt concrete. The material was characterized by X-ray fluorescence spectroscopy (XFA), powder X-ray diffraction (XRD), thermogravimetric analysis (TG), granulometric analysis, scanning electron microscopy (SEM). Environmental behavior tests were performed: solubilisation, neutral and alkaline leaching. The aggregates were characterized by granulometric analysis and sand content equivalent. The characteristics of asphalt binder were obtained as melting point and viscosity at the specified standard temperature. The determination of the optimum mix ratio used for the weathered green foundry sand waste on asphalt concrete was obtained using the Marshall method. The mechanical properties available were resilience modulus, static strength and reduction of the strength by induced humidity. The environmental behavior analyses results of solubilisation and leaching coupled with X-ray fluorescence spectroscopy shown that the scrap WGFS presents a lower content of Clay mineral linked to the sand particles surface and reduced contents of aluminum, iron, sodium and sulphate. The chemical, mineralogical and physical characterizations shown that the WGFS presents pH of 8,44, reduced Fe2O3 and Al2O3 contents and lower quantities of clay mineral montmorilonite, and quartz. The resilience modulus (circa of 5400 MPa) and static strength (circa of 1.20 MPa) results obtained using 15 wt.% of WGFS were higher that the found with freshly green foundry sand or natural sand. However, the reduction of 43 % on strength for the induced humidity test was higher to the specified for the standard (30 %). / O resíduo de areia verde de fundição, objeto de estudo deste trabalho, foi fornecido por uma fundição localizada no município de Joinville-SC, região sul do Brasil. De acordo com as normas brasileiras, o resíduo de areia verde de fundição e classificado como não inerte devido a presença de alguns elementos considerados tóxicos e, por este motivo, sua disposição final tem sido feita em aterros controlados. Este trabalho teve por objetivo a caracterização do resíduo de areia verde de fundição intemperizado e sua incorporação no concreto asfáltico usinado a quente. O resíduo foi caracterizado através da microscopia eletrônica de varredura, difração de raios X, fluorescência de raios X, analise térmica e p11 Alem disso, foram realizados os ensaios ambientais de solubilização, lixiviação e lixiviação neutra Os agregados foram caracterizados quanto ao tamanho das partículas através da analise granulométrica e com o resíduo de areia verde de fundição foi realizado o ensaio de equivalente de areia O ligante asfáltico foi caracterizado através dos ensaios de penetração, ponto de amolecimento, viscosidade e índice de suscetibilidade térmica A determinação do teor ótimo de ligante foi obtido através do Método Marshall Foram avaliadas as propriedades mecânicas de modulo de resiliência, tração estática e dano por umidade induzida Os resultados obtidos com os ensaios ambientais de solubilização e lixiviação, microscopia eletrônica de varredura, fluorescência de raios X e pH apresentaram redução nos teores de alumínio, ferro, sódio e sulfato, devido a redução no teor de material argiloso aderido a superfície dos grãos de areia O resultado do ensaio de modulo de resislência (cerca de 5400 MPa) e tração estática (cerca de 1 ,2OMPa) mostram que a incorporação do resíduo não afetou significativamente as propriedades mecânicas do concreto asfáltico. Entretanto, a redução de 43% de resistência no ensaio de dano por umidade induzida ficou acima do que especifica a norma brasileira, que determina a perda de resistência máxima de 30%.

Water quality and space constraints have become major concerns regarding the No. 7 waste water dam at Petra Diamonds’ Cullinan mine. The unique location of the dam constrains further development, while unsustainable accumulation of waste water inside the dam increases the risk of potential environmental contamination from seepages and spillages. The dam retains a significant amount of very poor quality water. Its excessively high pH, dissolved salt content, density and extreme turbidity result from the concentration of natural weathering products of the diamond bearing kimberlite ore. The turbidity results from the dispersion of colloidal chlorite, saponite and nontronite clay. Along with the chemistry of the solution, their colloidal shape contributes equally significantly to the non-settlement of these suspended clays. Flocculation of the dispersed clay particles will provide (a) for easy and effective separation of the clay material from the waste water and (b) more convenient options for water treatment (and subsequent redistribution) This study was aimed at contributing to a better understanding of the dynamic interactions in the No 7 Dam system to contribute towards identifying a suitable means/method for chemical flocculation of the clay particles. The individual components of the system (clays, water quality) and influx contributors (kimberlite and its leachate) were systematically characterized by means of X-Ray Diffraction, X-Ray Fluorescence, petrographic microscopy, electron microscopy, electrophoretic mobility and standard water- and soil quality analyses. The baseline quality of the Cullinan kimberlite leachate was obtained based on ASTM D5744 principles. It was found that adjusting the pH-level and ionic strength of the waste water to the critical coagulation point (cK) (as determined by electrophoretic mobility and batch jar experiments) automatically induced coagulation. Higher valence cations were displaced from pH dependent surface charge sites by proton adsorption. The resultant increased ionic strength, in combination with decreased thickness of the ionic double layer, was sufficient for the automatic initiation of high strength disordered face-face and edge-face bonds. During batch Jar tests, flocculation initiated within 4 minutes after the addition of HCl (0.5 M) and total sedimentation completed within 3 hours. The use of commercial flocculants might decrease the sedimentation time. As expected a significant increase in dissolved salt content of the clear supernatant was observed. No re-dispersion of the dried clay occurred. Throughout the study geochemical modeling was performed with PHREEQC software to identify/determine possible effective experimental conditions, minimizing experimental time and expenses. The program was also used to model outcomes of the possible water treatment options, indicated in literature as viable options for similar situations. These options can be tested to extend upon the current research. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

Water quality and space constraints have become major concerns regarding the No. 7 waste water dam at Petra Diamonds’ Cullinan mine. The unique location of the dam constrains further development, while unsustainable accumulation of waste water inside the dam increases the risk of potential environmental contamination from seepages and spillages. The dam retains a significant amount of very poor quality water. Its excessively high pH, dissolved salt content, density and extreme turbidity result from the concentration of natural weathering products of the diamond bearing kimberlite ore. The turbidity results from the dispersion of colloidal chlorite, saponite and nontronite clay. Along with the chemistry of the solution, their colloidal shape contributes equally significantly to the non-settlement of these suspended clays. Flocculation of the dispersed clay particles will provide (a) for easy and effective separation of the clay material from the waste water and (b) more convenient options for water treatment (and subsequent redistribution) This study was aimed at contributing to a better understanding of the dynamic interactions in the No 7 Dam system to contribute towards identifying a suitable means/method for chemical flocculation of the clay particles. The individual components of the system (clays, water quality) and influx contributors (kimberlite and its leachate) were systematically characterized by means of X-Ray Diffraction, X-Ray Fluorescence, petrographic microscopy, electron microscopy, electrophoretic mobility and standard water- and soil quality analyses. The baseline quality of the Cullinan kimberlite leachate was obtained based on ASTM D5744 principles. It was found that adjusting the pH-level and ionic strength of the waste water to the critical coagulation point (cK) (as determined by electrophoretic mobility and batch jar experiments) automatically induced coagulation. Higher valence cations were displaced from pH dependent surface charge sites by proton adsorption. The resultant increased ionic strength, in combination with decreased thickness of the ionic double layer, was sufficient for the automatic initiation of high strength disordered face-face and edge-face bonds. During batch Jar tests, flocculation initiated within 4 minutes after the addition of HCl (0.5 M) and total sedimentation completed within 3 hours. The use of commercial flocculants might decrease the sedimentation time. As expected a significant increase in dissolved salt content of the clear supernatant was observed. No re-dispersion of the dried clay occurred. Throughout the study geochemical modeling was performed with PHREEQC software to identify/determine possible effective experimental conditions, minimizing experimental time and expenses. The program was also used to model outcomes of the possible water treatment options, indicated in literature as viable options for similar situations. These options can be tested to extend upon the current research. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

Clays and clay mineral distribution studies are important for understanding the geological history of the Gulf of Mexico Basin, but few studies document any subsurface clay mineral distribution in the Gulf of Mexico. Shale samples from nine wells (30 samples) in the South Timbalier protraction were selected near known paleontological markers identifying the Miocene, Pliocene, and Pleistocene boundaries. Bulk mineralogy of each sample, determined by XRD, is primarily mixed-layer smectite and illite with a minor amount of kaolinite. The mixed-layer mineralogies are end-member smectite, mixed-layer smectite, mixed-layer illite, and end-member illite. These clay mineral fractions do not correlate with age. The illite mixed layer percentage correlates with depth, but the correlation decreases when depth is converted to temperature. However, the illite mixed layer fraction does not exhibit a strong correlation in this multiwell study when compared to a single well study in Ship Shoal using identical methods (Totten et al., 2002).

Les pesticides sont des molécules utilisées en grandes quantités en France et dans le monde entier pour la protection des cultures. Lorsque ces substances sont répandues une grande quantit é rejoint les sols. Dans cette thèse, le devenir de pesticides dans le sol est étudié. Pour cela, trois pesticides ont été sélectionnés : l'atrazine, la métamitrone et le fenhexamide ; et une argile de type montmorillonite a été choisie. Les simulations menées lors de cette thèse emploient le formalisme de la Théorie de la Fonctionnelle de la Densité (DFT). La première partie de cette thèse porte sur l'étude statique de l'interaction de l'atrazine avec la pyrophyllite et la montmorillonite. Dans les chapitres suivants, la Dynamique Moléculaire Car-Parrinello en DFT est utilisée. L'étude débute par les pesticides seuls, métamitrone et fenhexamide, puis leurs complexes avec un ou deux cations Na+ et Ca2+. Ensuite, l'adsorption de ces entités, en présence ou non d'eau, sur une surface de montmorillonite, est envisagée à l'aide de calculs périodiques. Dans le second chapitre de ce travail, des résultats issus d'optimisations de géométries en phase gazeuse sont présentés. La troisième partie développe les résultats obtenus pour l'adsorption de la métamitrone et du fenhexamide sur le modèle d'argile choisi. Dans le dernier chapitre, certaines des structures les plus stables de chaque pesticide adsorbé sur la surface ont été solvatées et une étude de la désorption du fenhexamide de la surface de montmorillonite a été réalisée à l'aide de la méthode Umbrella Sampling. Ce travail a permis de quantifier théoriquement la barrière d'énergie libre à franchir pour désorber le fenhexamide de la montmorillonite hydratée. / Pesticides are widely employed molecules for crop protection in France and all over the world. When these substances are spread an important quantity reaches soils. In the present thesis, pesticide fate is under study. For this purpose, three pesticides have been selected: atrazine, metamitron and fenhexamid ; and the most abundant smectite clay type, montmorillonite, has been chosen. The computational simulations conducted in this thesis use the Density Functional Theory (DFT) formalism. The first part of this thesis treats a static study of atrazine interaction with pyrophyllite and montmorillonite. In the following chapters, Car-Parrinello Molecular Dynamics through DFT is used. This study begins with isolated pesticides, metamitron and fenhexamid, then their complexes with one or two Na+ and Ca2+. Finally, the adsorption of these entities, in the presence of water or not, onto a montmorillonite surface, is considered using periodic calculations. Within the second chapter of the present work, results from geometry optimisations in gas phase are presented. The third part develops the obtained results on the adsorption of metamitron and fenhexamid over the chosen clay model. In the last chapter of this thesis, some of the most stable structures of each adsorbed pesticide onto the surface have been solvated and a study of fenhexamid desorption from the montmorillonite surface using Umbrella Sampling has been done. This work allowed to quantify theoretically the free energy barrier to overcome to desorb fenhexamid from the hydrated montmorillonite.

Expansive clay mineral contamination of road aggregate materials in Texas is a persistent problem. Hydrous layer silicate minerals - particularly smectites - in concretes are associated with decreased strength and durability in Portland cement and asphalt concretes. The Texas Department of Transportation (TXDOT) and Texas A&M Transportation Institute (TTI) evaluated the methylene blue adsorption test for its potential to identify and estimate quantities of expansive clays in aggregate stockpiles. Clay mineral quantification was completed for 27 geologically-diverse aggregate materials from Texas, Oklahoma, and Arkansas. X-ray diffraction analysis (XRD) of separated clays on glass was conducted, and NEWMOD was utilized to model the resulting diffraction patterns. Methylene blue adsorption (MBA) and cation exchange capacity (CEC) of clay fractions (< 2µm) and -40 mesh screenings (< 400 µm) were determined for most aggregates. Many of the aggregates exhibited significant quantities of expansive clay minerals such as smectite, which are linked to deleterious performance properties in concretes. While the majority of aggregates were derived from crushed limestone or calcareous river gravel parent materials, severalexhibited uncommon origins and unusual clay mineralogy. Due to the relatively low number of aggregates tested and diverse geological origins of the different aggregates,it proved difficult to formalize any conclusions abouttrendsbetweenthedifferent aggregate performance properties.

MENVSC / Department of Mining and Environmental Gelogy / In the present study, the physico-chemical, applications, mineralogy, geochemistry and stable isotope of Lwamondo and Zebediela kaolin is documented, in order to understand the genesis, paleoenvironmental conditions and possible utilization. Mineral identification studies were conducted using X-ray diffractometer (XRD), Fourier transform infrared spectrophotometer (FTIR) and scanning electron microscope with energy dispersive X-ray micro analysis (SEM-EDX). Major oxides were identified by X-ray Florescence (XRF) whereas trace elements were identified by Laser Ablation Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). Hydrogen and oxygen isotopic composition were determined by δ18O and δD isotopic measurements. Kaolinite was dominant mineral in all the kaolin samples whereas muscovite, quartz, goethite, hematite, smectite, anatase occurred in minor to trace quantities. The chemical data show that the kaolins are composed mainly of SiO2 and Al2O3 due to the presence of quartz and kaolinite, with minor to trace amounts of other elements such as Ca, Na, Cr, K, Fe, Mn, Mg, P and Ti which affected the kaolin application negatively. Lower concentration of Ca, Na, K, Fe, Mn, Mg, and Ti show the extent of the kaolinitisation. The samples were enriched in Ni and depleted in some other trace elements. The chondrite-normalised rare earth elements patterns show enrichmnent in Heavy Rare Earth Elements (HREE) than Light Rare Earth Elements (LREE) with slight positive Eu anomaly. The Rare Earth Elements (REE) pattern and the content of other trace elements show evidence of weathering processes related to kaolinitisatioon. Kaolin genesis is explained using kaolin mineralogy, particle morphology, structural order (functional group), major and trace elements geochemical data. The data suggest that kaolin is derived from the intensive chemical weathering of intermediate to mafic rocks deposited in non-marine environment. The stable isotopes were used to determine the paleoenvironmental conditions which influenced kaolinitisation of Lwamondo and Zebediela kaolins. Stable isotopes mean values for kaolinite from both Lwamondo and Zebediela were as follows: δ18O for Lwamondo= +18.57‰ and for Zebediela = +16.67 ‰ vii and δD for Lwamondo = -65‰ and for Zebediela = -64‰. The calculated mean temperatures were 26.94 ⁰C for Lwamondo kaolin and 36 ⁰C for Zebediela kaolin. Low temperatures were inferred from stable isotope values to have been involved in the kaolinitisation wherein hydrothermal processes were eliminated. The data suggests that kaolin was formed in a weathering environment. The kaolin is found to be suitable for brick making and based on the physico-chemical, mineralogical and chemical data it was suggested that the kaolin could also be used in producing low temperature ceramics, refractory materials, pottery and stoneware