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.

Gegenstand der vorliegenden Arbeit ist die Synthese und Charakterisierung neuer chromophorer Catecholderivate mit ausgeprägten push-pull-pi-Systemen. Die solvatochromen Eigenschaften dieser Verbindungen werden in Abhängigkeit der Wasserstoffbrückenbindungsdonor- und -akzeptorfähigkeit sowie Lösungsmitteldipolarität diskutiert. Mit entsprechenden methoxy- und dimethoxyfunktionalisierten Catecholderivaten ist es möglich, vergleichende Struktur-Eigenschaftsbeziehungen aufzustellen. Durch Untersuchungen zu den Wechselwirkungen der chromophoren Catechole mit Schwermetallionen kann gezeigt werden, dass die synthetisierten Verbindungen als Sensoren eingesetzt werden können. In der vorliegenden Arbeit wird des Weiteren die Adsorption der Catecholderivate an Metalloxide beschrieben. Mit Farbstoffen sensibilisierte Oberflächen stellen derzeit ein interessantes Forschunggebiet dar. Ferner wird über die Umsetzung der Catecholderivate mit Trialkoxysilanen zu zwitterionischen, spirozyklischen, pentakoordinierten lambda5Si-Silicaten sowie mit Tetraalkoxysilanen zu dianionischen, hexakoordinierten lambda6Si-Silicaten berichtet. Besonderes Augenmerk lag dabei auf UV/vis-spektroskopischen Untersuchungen.

In der Dissertation wurden Nanokomposite mit unterschiedlichen Kautschuken (HNBR, EPDM, MAH-g-EPDM) als Basismaterial sowie diversen modifizierten Schichtsilikaten als Füllstoff hergestellt und charakterisiert. Untersucht wurden die sich ausbildenden Strukturen bzw. die Morphologie (Aggregation, mögliche Orientierungen), die mechanischen Eigenschafte (Verstärkungswirkung) sowie die Füllstoff-Füllstoff-Wechselwirkungen und die Polymer-Füllstoff-Wechselwirkungen.

Indiana University-Purdue University Indianapolis (IUPUI) / Brasseler USA (Savannah, GA) developed and introduced a bioceramic putty called EndoSequence Root Repair Material (ERRM) that can be used as a retrofilling material for surgical endodontics. The material is said to have many of the same chemical, physical, and biological properties as mineral trioxide aggregate (MTA), but with superior handling characteristics. The material is composed of calcium silicates, monobasic calcium phosphate, zirconium oxide, tantalum oxide, proprietary fillers, and thickening agents. ERRM is said by the manufacturer to bond to adjacent dentin, have no shrinkage, be highly biocompatible, hydrophilic, radiopaque, and antibacterial due to a high pH during setting. Investigations on the sealing properties of this material have not yet been conducted. The purpose of this study was to compare the microbial leakage of Enterococcus faecalis in teeth with root-end fillings using ProRoot MTA and Brasseler’s ERRM in a dual-chamber bacterial leakage model as described by Torabinejad and colleagues. The aim of this investigation was to compare the bacterial microleakage of these two root-end filling materials exists. Sixty-two human, single-rooted, mandibular premolars in which extraction was indicated were accessed and instrumented in an orthograde fashion with hand and rotary files. Root resection of the apical 3 mm was then completed and root-end retropreparations were created for placement of root-end filling material. Twenty-seven of these premolars had root-end fillings using ProRoot MTA and 27 had root-end fillings using ERRM. Two teeth were used as a positive control group with no root-end filling, and two other teeth were used as a negative control group and were sealed and coated with dentin bonding agent. The teeth were then evaluated for microleakage using a dual-chamber bacterial microleakage model for 40 days as described by Torabinejad and colleagues. Microleakage was determined by the presence of turbidity in the lower chamber of the apparatus and was assessed each day. Fresh samples of E. faecalis were used every three days to inoculate the apparatus and serve as a bacterial challenge for the materials. Results were recorded every day for 30 days. The outcome of interest (bacterial turbidity) and time-to-leakage (in days) were determined for each of the samples. Survival analysis was used to compare the two groups with a Kaplan-Meier plot to visualize the results and a nonparametric log-rank test for the group comparison. The microleakage of ERRM was not statistically different (p > 0.05) than leakage of ProRoot MTA when subjected to E. faecalis over the 40 day observation period. Both groups had a small number of early failures (within 4 days) and no leakage was observed for the remaining 40 days of the study. Therefore, the null hypothesis was rejected. The results of this research support the use of either of these two materials when compared with the controls. The microleakage of Brasseler’s EndoSequence Root Repair Material was at least as good as ProRoot Mineral Trioxide Aggregate when tested with E. faecalis.

Soil aquifer treatment was simulated in 1 m laboratory soil columns containing silica sand under saturated and unsaturated soil conditions to examine the effect of travel length through the unsaturated zone on the removal of wastewater organic matter, the effect of soil type on dissolved organic carbon removal and also the type of microorganisms involved in the removal process. Dissolved organic carbon removal and nitrification did enhance when the wastewater travelled a longer length through the unsaturated zone. A similar consortium of microorganisms was found to exist in both saturated and unsaturated columns. Microbial concentrations however were lowest in the soil column containing silt and clay in addition to silica sand. The presence of silt and clay was detrimental to DOC removal efficiency under saturated soil conditions due to their negative effect on the hydraulic performance of the soil column and microbial growth.

A quartz diorite intrusion of probable early Tertiary age that crops out over at least 6 square miles in the Palo Verde Ranch area in Pinal County, Arizona was mapped as a distinct intrusion. The quartz diorite intrudes an area comprising Pinal Schist, Oracle granite, andesitic flows, granoaplite, and dike rocks including both pegmatite and diabase. Two major physical features, the Owl Head Buttes and Chief Buttes volcanic areas, both remnants of an extensive early Tertiary series of flows of intermediate composition that covered the area, now remain as lava-capped buttes above the pediment. Weak but persistent fracture-controlled copper mineralization is found in the quartz diorite and the Pinal Schist at or near their mutual contacts in the form of chrysocolla, malachite, black copper oxides, chalcocite, chalcopyrite, and bornite, in decreasing order. Pyrite is rare. Alteration related to northeast and northwest-trending fractures increases in intensity from the common propylitic to argillic to the northeast toward the San Juan claims area. A barely discernible increase in copper sulfides mirrors the alteration zoning, although geochemical sampling showed background copper in the quartz diorite to be more uniform away from fractures.

Numerous organisms produce ornately detailed inorganic structures (often known as shells) with features on length scales from 50 nm to several centimeters. One class of such organisms are the diatoms; microscopic algae that form silica frustules. Another group of algae, the coccolithophorids, produce similar calcium carbonate structures. Over 100,000 species comprise these two classes of algae, every one of which is endowed with a unique cytoskeleton structure. Using various types of displacement reactions, the chemistry of the original structure can be modified to produce a new material. Magnesium vapor has been found to displace the silicon in diatom frustules to yield an MgO structure. The conversion has been reported at temperatures from 650°C to 900°C. In the current work, the conversion and processing of silica frustules to MgO was examined in depth. The effect of reaction temperature on grain size and extent of conversion was evaluated. With the goal of obtaining high purity MgO structures, various methods for removing the silicon products of reaction were investigated. Wet chemistry and high temperature vapor etches were evaluated. The MgO reaction served as an intermediate step in the production of magnesium tungstate diatoms, which were imbued with photoluminescent properties. Reactions were identified to allow the conversion of calcium carbonate (calcite) structures to alternative chemistries. Calcite sand-dollars were converted to calcium tungstate or calcium molybdate by aqueous solution chemistry. In this process, sand dollar tests (shells) and coccolithophore frustules were reacted with ammonium para-molybdate or ammonium para-tungstate. The reactions were evaluated for shape preservation, phase purity, and photoluminescence of the structures.

The aim of the project was to study the mineral, chemical and morphological characteristics of the fallout dust samples. The dust fallout samples were collected at five different sites following the internationally accepted standard procedure for collection and analysis, South African National Standard and American Standard for Testing Methods (ASTM) D1739-98 (2010). Passive single buckets containing ¾ of distilled water and 10.0 ml of sodium hypochlorite (NaOCl) solution, hoisted at a height of about 2.5 m were exposed from March – June 2013 and were collected every month, taken to the laboratory for characterization. First, the samples were filtered and mass concentrations per month were gravimetrically measured. The samples were then prepared for further characterization by the MicroScan Particle Analyser (MSPA)(Microscope UOP UB 100j) which measured the mineral content and the Scanning Electron Microscope - Energy Dispersive X- ray (SEM - EDX) measured the images of different particles (size, shape) and their elemental content. The results from the MicroScan analysis showed the prevalence of sandy rounded-shaped quartz (SiO2) particles across all sites. Minerals detected within the crustal material at all sites were quartz (SiO2), haematite (Fe; Fe2O3; Al2O3), feldspar (Na, K, Mg, Ca: AI2Si2O8), garnet (SiO4), aluminium silicates (AI2Si2O8) and calcium hydroxide [Ca (OH)2]. Evidently, sites A, B and C dominated the abundance of these minerals. On the other hand, sites D and E showed fine and rounded quartz and quartzite with various trace metal oxides. Measured elements in decreasing concentrations were Si, Ca, P, Al, K, S, Fe, Cu, Ti and Mg. Both coarse particle (2.5 - 10.0 μm) and fine particle sizes ranges (< 1.0 to 2.5 μm) were detected. Large irregular shaped particles sizes were common and were linked to crustal material. The results provide good baseline information which requires further characterization of samples by different analytical techniques and validation of possible sources. The ICP-MS was used to determine the elemental composition of dust fallout and the mean concentration of the elements of concern ranged from 1.1 - 2.6 for As, 0.2 - 0.6 for Cd, 17.0 - 21.9 for Ni, 449.8 - 751.1 for Pb, 9.9 - 22.3 for V and 101.7 - 293.0 μg/m3 for Zn. The elements such as Cd exceeded the set limit 0.005 μg/m3 by OSHA (2015) and NIOSH (2007); Pb exceeded the set standard of 0.5 μg/m3 set by OSHA (2015), NIOSH (2007), WHO (2000), USEPA (2012) and DEA (2013). The rest of the elements fell within the set guidelines by various regulatory national and international bodies. The study concludes that, although, all the sampling sites recorded the dust fallout rates within the SANS 1929 (2011) and DEA (2013) average RESIDENTIAL limit of 600 mg/m2/day, the future accumulation and exceedances cannot be ruled out owing to the increasing developments in urban areas / Environmental Sciences / M. Sc. (Environmental Science)

ABSTRACT This thesis deals with the development of silicate based reverse grouts for the purpose of rehabilitation of sewers. The work also examines the possibility of substitution of basic input raw materials with secondary raw materials, meaning replacements of both filler components and binder components. As secondary raw materials, we refer to wastes from the production process which, after the necessary treatment, are used in another production. The development and experimental verification of the functionality of the developed grout was focused mainly on the use of secondary raw materials as much as possible, while maintaining or even improving its physical and mechanical properties. Based on the results of the work, it can be stated that with a 100% replacement rate of filler components in combination with 20% replacement rate of binder components, it is possible to largely maintain the properties of the material, or even optimize them. The results of the thesis also point to the possibility of reducing the economic and environmental demands of production of building materials.

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.