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Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-04-14T11:38:02Z No. of bitstreams: 0 / Made available in DSpace on 2015-04-14T11:38:02Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-04-14T11:38:02Z No. of bitstreams: 0 / Made available in DSpace on 2015-04-14T11:38:02Z (GMT). No. of bitstreams: 0 / Neste trabalho foi investigada uma mudança na linha base observada em curvas de calorimetria exploratória diferencial em um trabalho onde microesferas de vidros aluminossilicatos contendo Ho foram estudados para a aplicação em radioterapia interna seletiva para o tratamento de carcinoma hepatocelular. Os vidros com composição nominal 53,7 SiO2 .10,5 Al2O3 . 35,8 MgO em %mol foram produzidos pelo método de fusão tradicional. As fritas obtidas foram moídas e peneiradas na faixa de 45 a 63 μm. O material foi utilizado para produzir microesferas pelo método de esferolização por queda gravitacional. O pó de vidro e as microesferas foram caracterizados por espectrometria de fluorescência de raios X, difração de laser, difração de raios X, calorimetria exploratória diferencial, análise térmica diferencial, termogravimetria, espectrometria de massa e microscopia eletrônica de varredura. Após as análises térmicas foram formadas pastilhas nos cadinhos que foram analisadas por microscopia eletrônica de varredura, difração de raios X e picnometria a gás He. A mudança na linha base foi associada ao processo de sinterização por fluxo viscoso e ocorre devido a diminuição do fluxo de calor detectado devido à retração da amostra. Outros processos como cristalização concomitante com a sinterização também foram estudados. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

PhDENV (Geology) / Department of Mining and Environmental Geology / The Cretaceous period marked the breaking up of Gondwana, giving rise to the separation of the African and South American continents with the subsequent emergence of the South Atlantic Ocean. Most correlation studies between the two continents with respect to paleoenvironmental conditions and tectonic settings during the Cretaceous- Tertiary periods have been concentrated more on the use of flora and fauna as indicators with less application of kaolinite as paleoenviromental proxies, hence, this study. The research involved the evaluation of paleoenvironmental conditions and tectonic settings of four (4) selected Cretaceous-Tertiary kaolin deposits with two (2) each from the Eastern Dahomey (Eruku and Lakiri) and Niger Delta (Awo-Omama and Ubulu-Uku) Basins in Nigeria. Representative kaolin samples collected from the selected deposits were analysed for physico-chemical, mineralogical, geochemical, isotopic, and geochronological data. The geochemical data obtained by x-ray fluorescence (XRF) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LAICPMS) were used in unraveling the provenance and tectonic settings of the kaolins. The kaolinite stable isotopic data for oxygen and hydrogen determined using a Finnigan Delta XP Mass Spectrometer were used to assess the paleoenvironmental and paleoclimatic conditions under which the kaolins were formed. The detrital zircon geochronological data acquired by laser ablation – single collector – magnetic sectorfield – inductively coupled plasma – mass spectrometry (LA-SFICP-MS) as well as kaolinite stable isotopic data were employed in constraining the probable timing of kaolinisation. The industrial applications of the kaolins were assessed based on the physico-chemical (Colour, particle size distribution (PSD), pH, electrical conductivity, and Atterberg limits), mineralogical, and geochemical data. The mineralogical data were obtained through x-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, Thermogravimetric analysis and differential scanning calorimetry, and scanning electron microscopy (SEM). Correlative studies between selected Cretaceous African and South American kaolins were conducted. The results showed that the dominant colour in the studied kaolins was pale red (39 %) followed by pinkish and light grey (35 %) as well as reddish yellow, light pink, light brown, vii reddish brown, and pinkish white. The pH and EC values generally ranged from 4.27 to 5.29 and 0.2 to 13.1 μS/cm, respectively. The kaolins predominantly have clay to sandy clay textures with plasticity indices between 10 and 22 wt %. Bulk mineralogical quantitative results indicated that the Cretaceous kaolins have kaolinite, quartz, and muscovite present in that decreasing order with anatase, goethite, and hematite in traces whereas Tertiary kaolins have kaolinite and quartz present in that decreasing order with anatase and goethite in traces. In the silt fractions, kaolinite and quartz were the dominant mineral constituents, whereas in the clay fractions, the dominant clay mineral was kaolinite accounting for 69 to 99 wt % with the non-clay minerals like quartz, anatase, hematite and goethite accounting for percentages between 1 to 28 wt % in the Cretaceous – Tertiary kaolins. Morphologically, the studied kaolins were characterised by pseudohexagonal stacks to books and thin platy kaolinite particles with moderate structural order. The chemical compositions of the Cretaceous-Tertiary kaolin deposits were identical to hydrated alumino-silicates based on the dominance of SiO2, Al2O3 and LOI. The chemical index of alteration (CIA) and chemical index of weathering (CIW) values varied between 96.98 to 99.39 % and 98.95 to 99.89 %, respectively. The clay fractions were enriched in Cr, Nb, Sc, Th, U, V, Zr, and LREE and depleted in Ba, Co, Rb, Sr, and HREE, respectively, relative to the average Upper Continental Crust (UCC). The Th/Sc, La/Sc, Th/Cr, and Eu/Eu* ratios were within the range of sediments derived from felsic rocks. The TiO2 versus Al2O3 and La-Th-Sc plots indicated source rocks with granitic – granodioritic - gabbroic compositions. Geochemical discrimination plots showed that the Cretaceous and Tertiary kaolins were deposited in passive margin tectonic settings. The stable isotopic results indicated that the values of the Cretaceous kaolins ranged from – 47 to – 57 ‰ and 19.1 to 19.8 ‰, respectively, with paleotemperatures between 29.0 and 32.2 ˚C, whereas the δD and δ18O corresponding values for the Tertiary kaolins ranged from – 54 to – 66 ‰ and 20 to 21.5 ‰, respectively, with paleotemperatures between 17.0 and 23.9 ˚C. viii The U-Pb dating of the detrital zircons showed that the Cretaceous - Tertiary kaolins have inputs from rocks of Eburnean (2500 – 2000 Ma) and Pan African (750 – 450 Ma) ages. The age of maximum deposition determined from the least to statistically robust approach corresponds to the Ediacaran Period (645 – 541 Ma) of the Neoproterozoic Era (1000 – 541 Ma). The Cretaceous – Tertiary kaolins were formed under intense anoxic chemical paleoweathering conditions of predominantly felsic rocks in addition to contributions from intermediate and mafic rocks in passive margin tectonic settings. The Cretaceous kaolins were formed under warmer conditions relative to the Tertiary kaolins. The West African Massif rocks were the main sediment sources for the Cretaceous kaolins, whereas both the West African and Northern Nigerian Massif rocks were the major sediment sources for the Tertiary kaolins. The most probable timing of kaolinisation for the Cretaceous – Tertiary kaolins occurred between the Ediacaran (645 – 541 Ma) and Early Cretaceous Periods for the Cretaceous kaolins and between the Ediacaran Period (645 – 541 Ma) and Oligo – Miocene age for the Tertiary kaolins. The Nigerian and Brazilian Cretaceous kaolins formed under similar warm tropical paleoclimate. The study corroborated the occurrence of the Eburnean (Transamazonian) and Pan African (Brasiliano) orogenic events across the African and South American continents. Beneficiation of the Cretaceous – Tertiary kaolins will allow large scale industrial applications in paper coating, ceramics, pharmaceutical, and cosmetics industries. The major contributions from this study have been: the better understanding of the past environmental conditions and tectonic settings, the dating of the possible timing of kaolinisation, and improvement on the potential industrial applications of the Cretaceous – Tertiary kaolins. / NRF

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T14:16:56Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T14:16:56Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T14:16:56Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T14:16:56Z (GMT). No. of bitstreams: 0 / A demanda crescente por água tem feito de seu reúso planejado um tema atual e de grande importância, já citada na Agenda 21, que recomendou implementação de políticas de gestão dirigidas para o uso e reciclagem de efluentes, integrando proteção de saúde pública de grupos de risco com práticas ambientais adequadas. De acordo com as Resoluções CONAMA nº 357 e 420 os efluentes somente podem ser descartados em corpos d´água se os seus parâmetros característicos se situarem de acordo com o balizamento dado para cada classe de corpo de água. Íons metálicos podem ser removidos de soluções aquosas por diferentes processos sendo a adsorção em argilas um método que pode ser considerado efetivo e barato quando comparado aos demais. Neste estudo foi avaliada a capacidade de adsorção dos íons metálicos Cr3+, Zn2+, Cd2+, Pb2+, Cu2+ e Ni2+ em solução utilizando-se caulinita comercial com a finalidade de reúso e/ou descarte. A caracterização mineralógica e química das amostras comerciais obtidas indicou que aquela denominada caulinita C foi a que mais se adequou ao estudo visto que apresenta elevado teor de pureza mineralógica, baixos teores de elementos traço, e maior capacidade de troca catiônica. O estudo da remoção dos íons em solução indicou que o aumento razão adsorvente:adsorvato aumenta a eficiência de adsorção. O estudo da influência do pH indicou que a maior adsorção ocorre em pH levemente alcalino, pH 8. E o estudo do tempo de contato indicou que o equilíbrio de adsorção é atingido em menos de trinta minutos para todos os íons, exceto para o Ni. A análise das isotermas de adsorção indicou que a caulinita empregada neste estudo é adequada principalmente à remoção dos íons Zn (II), Cu (II) e PB (II). / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

PhD (Geology) / Department of Mining and Environmental Geology / Cretaceous-Tertiary Periods marked the break-up of Gondwana, a large landmass composed of most of the present-day southern continents. In understanding the events of the supercontinental break-up, paleoenvironmental studies need to be carried out. In such studies, kaolinites could be used as paleoenvironmental proxies due to their small particle sizes and large surface area. It is in this context that this research sought to reconstruct the paleoenvironments in which selected Cretaceous-Tertiary kaolin deposits in the Douala Sub-Basin in Cameroon formed. To achieve this objective, mineralogical and geochemical characterisations were carried out using x-ray diffractometry, scanning electron microscopy, Fourier transform infrared spectrometry, thermal analyses and x-ray fluorescence spectroscopy. Trace elements and stable isotopes were analysed using mass spectrometries. Ages of zircons in the kaolins were determined using laser ablation magnetic sector-field inductively coupled plasma mass spectrometry (LA-SF-ICP-MS) U-Pb geochronology. Diagnostic evaluation for industrial applications of the kaolins were carried out using particle size distribution, texture, moisture content, pH, and electric conductivity. Six kaolin deposits from Cretaceous-tertiary Formations of the Douala Sub-Basin were studied; namely, Bomkoul (Tertiary), Dibamba (Tertiary), Ediki (Cretaceous), Logbaba (Cretaceous), Missole (Tertiary) and Yatchika (Cretaceous). The nature and occurrences of these kaolin deposits in Cameroon were determined through thorough mineralogical and geochemical characterisations of bulk (< 2 mm size fraction), silt (2-63 μm size fraction) and clay samples (< 2 μm size fraction). By quantifying the mineral phases present, the morphology and the functional groups in the kaolins are presented as the mineralogical characteristics of kaolins of each study site; whereas, the major oxides geochemistry and the micro-elemental composition constitute the geochemical characteristics of these kaolins. The minerals’ geneses were also determined and the prevailing paleoenvironmental and paleoclimatic conditions in which they were formed were reconstructed using trace elements and stable isotopes of oxygen and hydrogen in kaolinite. The maximum age of the kaolins were determined using U-Pb LA-SFICP-MS dating of zircons in the kaolin deposits. Diagnostic evaluation of the kaolins was carried out, and involved the determination of physical characteristics (particle size, texture, colour and moisture content) and physico-chemical characteristics (pH and electrical conductivity). Results showed that kaolinite and quartz (as major phases), smectite and/or illite (as minor phases), anatase and rutile (as minor or trace phases), goethite and hematite (as trace viii phases) were the mineral phases present in bulk and silt samples. Whereas, in the < 2 μm fractions, the mineral phases are made up of kaolinite and smectite (as major phases), smectite and/or illite (as minor phases), anatase and rutile (as minor or trace phases), goethite and hematite (as trace phases). The kaolins are mostly made up of thin platy or pseudo-hexagonal particles or flakes, books or stacks of kaolinite. The Dibamba, Logbaba and Missole II kaolins have well-ordered structures. Exothermic peak temperatures were generally between 943-988oC. The most abundant major oxides are silica and alumina, followed by iron oxide and titania; though Logbaba and Missole II had higher titania than iron oxide. 85% of the kaolins, portrayed extreme silicate weathering (chemical index of alteration > 80%) and are compositionally mature (index of compositional variability > 0.78). The geochemical composition of the kaolins showed that source rocks of these kaolins vary between rhyolite/granite and rhyolite/granite + basalt. The geochemistry also suggested that the kaolins formed in a marine environment (except Logbaba samples). Trace elements results revealed that Cretaceous-Tertiary kaolins in the Douala Sub-Basin are mainly enriched in rare earth elements compared to the upper continental crust, and have negative Eu anomaly. Large ion lithophiles (mainly Rb and U) were highly enriched in samples, high field strength elements (Y and Nb) were enriched in studied samples of all fractions; and transition trace elements generally had concentrations quite similar to upper continental crust values. Stable isotopes showed that the kaolins were formed in a supergene environment; and temperatures of kaolinitisation (assuming equilibrium with the global meteoric water line) were 26.58oC ± 9.65oC for Cretaceous kaolins and 29.40oC ± 7.22oC for Tertiary kaolins. Assuming equilibrium with the local (Douala) meteoric water line, the temperatures of kaolinitisation were 24.64oC ± 9.48oC for Cretaceous and 27.42oC ± 7.08oC for Tertiary kaolins. Four main zircon populations were identified from radiogenic dating: the 1st between 550 and 650 Ma, the 2nd between 950 and 1050 Ma, the 3rd around 1600 Ma and the 4th between 2800-3200 Ma. These four zircon populations belong to the Proterozoic (Neo-, Meso- and Paleoproterozoic) and the Archean. The maximum depositional ages of the kaolins, reflected by the youngest weighted averages of zircon populations varied between 588 ± 2 Ma and 612 ± 2 Ma, all belonging to the Ediacaran Period (Neoproterozoic). The diagnostic evaluation of the kaolins revealed that the kaolins are very sandy, with 50% of the samples having a sandy loamy clay or sandy loam texture. The colour of the samples varied considerably from white to darker colours (dark grey); with 15% of the kaolins being light reddish brown. The moisture content was generally very low (< 2 wt %) in all size fractions, except in Yatchika samples (moisture content > 2 wt %). The kaolins are generally acidic, with ix a pH(KCl) varying between 3.06 and 3.81, except in Missole I samples, which had a pH (KCl) < 2. The electrical conductivity (EC) generally varied between 20 to ~ 50 μS/cm, except Dibamba and MSL II 01 samples which had EC values in the interval 50 μS/cm < EC < 80 μS/cm; and Missole I samples having an EC > 7500 μS/cm. In conclusion, no great distinction was found between Cretaceous and Tertiary kaolins of the Douala Sub-Basin based on their mineralogy and geochemistry. The best kaolins in terms of these characteristics, and in comparison with the Georgia Kaolins (known for their high kaolinite quality), were the Dibamba (Tertiary), Logbaba (Cretaceous) and Missole II (Tertiary) kaolins. Based on their compositional maturity and mineralogical characteristics, these three kaolins are considered to be second cycle sediments; unlike Bomkoul, Yatchika and Ediki kaolins, which are believed to be first cycle sediments. Based on the trace elements and stable isotopes composition, Cretaceous and Tertiary kaolins of the Douala Sub-Basin were derived from felsic rocks. However, Cretaceous kaolins were formed in a cooler anoxic reducing environment; whereas the Tertiary kaolins were formed in a warmer oxidising environment, with higher precipitation. Ages of zircons in Cretaceous-Tertiary kaolins suggested that the zircon formed during two main tectonic events: the Eburnean orogeny, during which older zircons crystallised and the Pan-African orogeny, during which younger zircons crystallised. The maximum depositional ages of the kaolins varied between 588 ± 2 Ma and 612 ± 2 Ma. The main identified sources of these zircons are the Archean Ntem Complex, the Paleoproterozoic Nyong Group and the Neoproterozoic Yaounde Group. The diagnostic evaluation indicated that the particle size greatly influences the mineralogy and geochemistry of the kaolins because the finer particles (< 2 μm) have higher amounts of kaolinite and Al2O3. The moisture content of the kaolins makes them suitable as paint fillers and in soap production. Paper coating, paper filler, ceramics, pharmaceutics and cosmetics are potential applications for the kaolins, though particle size reduction and beneficiation will give them a higher quality. However, because these kaolin deposits are not big and extensive, they cannot be recommended for large scale industrial applications; but they can be used for bricks, pottery and stoneware manufacturing.

MENVSC / Department of Ecology and Resource Management / Some boreholes in South Africa which serve as a source of drinking water for rural communities are reported to have high fluoride concentration, much above the WHO guideline of 1.5 mg/L. This study aimed at activating aluminosilicate clay soil mechanochemically, modifying aluminosilicate clay soil with Al-oxide and fabricating porous ceramic granules using Al-oxide modified mechanochemically activated aluminosilicate clay soil/ mechanochemically activated clay soil/ corn starch and evaluating their performances in defluoridation of groundwater. The raw clay materials were mechanochemically activated for 5, 10, 15 and 30 minutes for physicochemical transformation of the solid aggregate. The morphology of the samples showed the honeycomb structure. The surface area analyses of samples using Brunauer–Emmett–Teller (BET) gave the highest surface area of 50.5228 m2/g at 30 min activation time. Hence, the optimum activation time was 30 min. The Fourier Transform Infrared (FT-IR) analysis showed increase in the absorbance of FT-IR by Si-O-H groups at 510 cm-1 with increasing milling time. This is evidence that more surface Si-O-H groups were available at higher particle surface area that would be necessary to interact with fluoride. X-ray diffraction (XRD) analyses revealed that, at 30 minutes milling time, the peak broadening is intensified whereas the reflection peak intensities decreased. The X-ray fluorescence spectrometry (XRF) results for 30 minutes milling time showed that silica and alumina were the highest components in the clay soil. Using the activated clay in batch defluoridation of fluoride-spiked water, a maximum fluoride removal of 41% was achieved at a pHe of 2.41. The initial fluoride concentration was 9 mg/L while the sorbent dosage was 0.6 g/100 mL and the contact time being 30 minutes. The adsorption data fitted to both Langmuir and Freundlich isotherms. The adsorption data fitted only the pseudo-second-order kinetic, showing chemisorption. Optimization of Al3+ concentration for modification was carried out by modifying the mechanochemical activated aluminosilicate clay soil with different concentrations of Al3+ from which the optimum modification was achieved with 1.5 M. Characterisation studies on the Al-oxide modified mechanochemically activated aluminosilicate clay soil by SEM, BET, FT-IR, XRD and XRF, analyses were carried out to determine the resultant changes in physicochemical properties of the adsorbent owing to modification. The SEM image of Al-oxide modified mechanochemically activated clay soil showed many small pores and honey-comb structure on the surface of different images. The BET surface area and the BDH adsorption cumulative area of the Al-oxide modified mechanochemically activated v aluminosilicate clay soil were more than double those for the raw clay soil. There was also an increase in pore volume of the Al-oxide modified mechanochemically activated aluminosilicate clay soil. The FT-IR spectra showed that there was increase in the absorbance by the Si-OH, H-O-H, Al-O-H and Si-O-Al. The equilibrium pH of solution was higher than the point-of-zero charge (pHpzc) implying that fluoride removal occurred at solution pH > pHpzc where the net surface charge of the mechanochemically activated clay aluminosilicate soil was negative.The efficiency of 1.5 M Al-oxide modified aluminosilicate clay soil to remove fluoride from water was studied and found to be 96.5 % at pHe 6.86, contact time of 30 minutes and dosage of 0.3 g/100 mL for 10 mg/L fluoride solution at 200 rpm shaking speed. The result shows that Al-oxide modified mechanochemically activated aluminosilicate clay soil is effective for defluoridation. The adsorption data fitted to both Langmuir and Freundlich isotherms. The adsorption data fitted only the pseudo-second-order kinetic, showing chemisorption. Al-oxide modified mechanochemically activated aluminosilicate clay soil was tested for fluoride removal on field water and the percentage fluoride removal was 96.5 % at the dosage of 0.6 g/100 mL with the pHe of 6.48. The optimum Al-oxide modified mechanochemically activated aluminosilicate clay soil/ mechanochemically activated clay soil/ corn starch mixing ratio for fabrication of porous ceramic granules was determined by varying ratios and temperature. The optimum ratio found was 20:5:1.The porous ceramic granules were characterised using SEM, BET, FT-IR, XRD and XRF. SEM analysis showed that the porous ceramic granules have the porous structure of the organic foam template. The porous ceramic granule showed an increase in pore surface area and volume as compared to mechanochemically activated aluminosilicate clay soil. The FT-IR showed the presence of a strong broad bending and stretching vibrations band at about 993 cm-1 which shows the presence of Si–O–Si bonds. Mineralogical characterisation showed the presence of quartz, albite, horneblende and microcline as the main minerals of the calcined porous ceramic granules. The major oxides of the porous ceramic granules as shown by XRF analysis were SiO2, Al2O3, MnO and Na2O. The porous ceramic granules reduced the concentrations of fluoride in the water from 10 to 3.31 mg/L. The optimum adsorption capacity was 0.6648 mg/g at a pHe of 6.32 and the percentage fluoride removal was 66.9 % at an adsorbent dosage of 1.0063 g/100 mL and a temperature of 600 ⁰C. The porous ceramic granules were tested for fluoride removal on field water and the percentage fluoride removal was 45.4 % at the dosage of 1.0009 g/100 mL with the pHe of 7.87. Mechanochemically activated aluminosilicate clay soil showed higher adsorption capacity at acidic pH, therefore it is recommended that future work should focus on improving their adsorption capacity at wider range of pH. The porous ceramic granules can also be evaluated in column dynamic flow experiments.