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

MESMEG / Department of Mining and Environmental Geology / Vhembe District has several clay deposits which are traditionally use for clay products such as burnt bricks without taking into account the chemical and mineralogical characteristics of clay being used. The ever-increasing market demand for these clay products cannot be met with the traditional method of clay utilization due to the paucity of scientific information on properties of the clay in the area. Consequently, there is a need to gain better understanding of the characteristics of the clay in Vhembe District and to establish the suitability of the variety of clay for different purposes. The current study was undertaken to better understand the compositional relationship between the clay deposits and surrounding rocks present in the study area. It further aimed at characterizing the clay deposits on the basis of chemical, mineralogy, physical, mechanical, thermal and micro structural properties with a view of evaluating the clays for possible industrial use. A total of thirty-nine clay and rock samples were collected from thirteen different locations across the Vhembe District. Thirteen representative samples from each location were obtained after thorough mixing until homogenization was attained and then quartered for subsequent analyses. The mineralogical and chemical characteristics of the clay and rock samples were determined using XRD and XRF respectively. Thin-sections of the rock samples were prepared and examined under petrographic microscope to better understand the mineral assemblages present in the rocks. The thermal and micro structural properties of the clays were determined using DTA-TGA and SEM analyses and the physical properties which include colour, cation exchange capacity (CEC) and soil pH were assessed. The particle distribution and Atterberg limits tests of the clay samples were also conducted in order to establish their mechanical properties. The petrographic results showed that the clay deposits exhibited an intense weathering and sedimentation processes which incorporated detrital minerals from the surrounding rock units. The rock units which include basalt, granodiorite, gneiss and quartzofeldspathic gneiss were found to be differentiated from subalkaline and/or tholeiitic magmatic composition. Although the value of SiO2 content in rock samples was higher when compared with clay samples, it indicated an ongoing desilicication and allitization processes. The high values of chemical index of alteration (CIA), low values of K/Cs (<6200), Ce* normalized value and higher values of LILE enrichment in the clay deposits indicated oxidizing environments during period of deposition. v The mineralogical composition of the studied clayey deposits showed that smectite (8.25 - 29.32%), kaolinite (14.91 - 59.26%) and chlorite (5.94 -16.54%) were present as clay minerals although associated with other non-clay minerals such quartz, plagioclase, talc and geothite. The chemical composition results revealed high silica and alumina content in most studied clay samples. Their fluxing oxides which include K2O, Na2O, CaO, and MgO, varied slightly from 0.06% to 1.78% in abundance while the Fe2O3 and TiO2 contents in most samples averages at 9.2% and 1.3% respectively. The plasticity index of the studied deposits ranged from 9.50 to 62.00% while liquid limit ranged from 31.34 to 73.62%. The microanalysis using SEM indicated that the microstructure framework of most studied clay exhibited a porous skeleton structure owing to numerous tiny voids. The composite results of SEM and CEC analyses suggested their possible application in water filter and chemical fertilizer industries since they provided passage for water and soil cations transmission. The particle size distribution demonstrated that the studied soils have clayey silt texture with wide range coverage of the well graded and sorted particle sizes. Compressibility and plasticity properties were found to be high in Mukondeni, Mashamba-1, Mashamba-2 and Mashamba-3 clay samples. The thermal behavior of Mukondeni, Mashamba-1, Mashamba-2 and Mashamba-3 samples showed relatively high shrinkage (>9%). The high shrinkage percentage suggests the preponderance of smectite minerals. Other samples which are rich in kaolinite and chlorite minerals exhibited low shrinkage (<2%). The drying trends of the studied clay suggest their suitability for fast drying processes like soft and hard refractoriness, sanitary wares and ceramics. Empirical assessment of most studied clay showed their suitability for pottery-making and manufacturing of roofing tiles and masonry bricks. / NRF

PhDENV / Department of Ecology and Resource Management / Kaolin dominated soils are common in the tropical and subtropical regions. People depend on kaolin-rich soils for agricultural production of food and fiber. The most popular of all South African soils is the Hutton form which accounts for the marvelous redness of the landscape across the Country. The apedal (structureless) soils in the group are characterised by a relatively low CEC (< 11 cmolc kg-1) reflecting oxidic mineralogy with predominantly kaolinitic assemblage. The geochemical and mineralogical composition of soil kaolin has significant implications on soil fertility, geochemical exploration and engineering properties. Despite the dominance of kaolin in these soils, little is known of their properties in the medium. The nature of kaolin minerals in soils varies with parent material, degree of weathering and pedogenic environment. Most studies conducted in South Africa on kaolins are limited to reference kaolins with little or no publication on soil kaolins, hence, this study. This research involved the evaluation of mineralogical and geochemical characteristics of oxidic soils and soil kaolins developed from four (4) selected parent rocks which were basalt, granite, arkosic sandstone, and gneiss. Soils developed from quartzite were selected as control. Representative soil samples collected from profiles developed from the different parent rocks were analysed for physico-chemical, mineralogical, and geochemical data. The mineralogical and geochemical data obtained by x-ray diffractometry (XRD), x-ray fluorescence (XRF), and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) were used in unraveling the influence of the provenance and degree of weathering on the soil characteristics. The mineralogical and geochemical data for soil kaolins were determined through XRD, scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis and differential scanning calorimetry, XRF, and LA-ICPMS to establish their mineralogical and geochemical properties with respect to their parent rocks. Comparison between the soil kaolins and selected reference kaolins were also conducted. The phosphorus (P) sorption data acquired photometrically were employed to evaluate the relationship between the P sorption capacities of the soils and soil kaolins. The influence of soil properties on the fertility of the soils were assessed based on the physico-chemical (pH, particle size distribution, and electrical conductivity (EC)) and chemical (organic matter (OM) content, cation exchange capacity (CEC), available P, exchangeable cations (Ca, K, Mg, Na, and Al), and P sorption) data. The mineralogical and geochemical data for the parent rocks were obtained by XRD, optical microscopy, XRF, and LA-ICPMS. Multivariate statistical analyses were also conducted. Results showed that the dominant colour in the studied bulk soils was dusky red (31 %) followed by brown (23 %), reddish brown, yellowish red, and yellowish brown (23 %) as well as strong brown, dark brown, reddish grey, very dark greyish brown, and dark red. Soil textures were clayey to sandy loamy with OM contents between 0.41 and 4.76 %. The pH, EC, CEC, exchangeable cations, and available P values generally ranged from 5.22 to 8.38, 10.25 to 114.40 μS/cm, 2.93 to 18.30 cmol/kg, 0.03 to 13.92 cmol/kg, and <0.01 to 54.99 mg/kg, respectively. Kaolinite and quartz were the dominant phases for soils developed from basalt whereas, quartz and plagioclase were the dominant mineral phases in soils developed from granite, arkosic sandstone, and gneiss, respectively. Other minerals present in the soils were microcline, muscovite, hematite, goethite, montmorrillonite, anatase, gibbsite, chlorite, and actinolite. Geochemical compositions of the bulk soils show relative enrichment of Fe2O3, TiO2, CaO, K2O, MgO, MnO, and Na2O (except for CaO, K2O, MgO, MnO, and Na2O in soils developed from basalt). Chemical index of alteration (CIA), chemical index of weathering (CIW), and plagioclase index of alteration (PIA) values varied between 54.92 and 99.81 % which suggest low to high degree of chemical weathering. The ACN-K and A-CNK-FM diagrams for the different soils also support these observations. Trace elements were generally enriched in soils developed from basalt and gneiss (except for Rb, Sr, and Ba in soils developed from basalt), but were depleted in soils developed from granite and arkosic sandstone (except for Cr and Ta). The principal factors responsible for the mineralogical and geochemical characteristics of the soils were the parent rocks and degree of weathering. In the soil kaolins, the dominant clay mineral was kaolinite accounting for 23 to 85 wt % followed by montmorrillonite, chlorite, and gibbsite. The non-clay minerals like quartz, plagioclase, muscovite, microcline, anatase, goethite, hematite, and actinolite accounted for the remaining percentages. The soil kaolins were characterised by thin platy kaolinite particles with partially to poorly-ordered structural order. The platy kaolinite crystals have their longest dimension sizes between 0.06 and 0.25 μm. The dehydroxylation temperatures for the studied soil kaolins ranged from 425 to 475 ˚C. The SiO2/Al2O3 ratio was lowest in soil kaolins developed from basalt and higher in soils developed from granite, arkosic sandstone, and gneiss which is consistent with their mineralogy since the former have more kaolinite. Higher Fe2O3 and CEC values were obtained relative to reference kaolins which could be attributed to the presence of more structural iron in the soil kaolins as well as their smaller crystal sizes. The presence of weatherable and accessory minerals accounted for the enrichment of Co, Ni, Cu, Zn, and Pb in the soil kaolins. The kaolinite in the soils were formed by leaching and desilication of the primary minerals in the parent rocks under suboxic conditions. H-type P adsorption isotherms obtained for both the soils and soil kaolins indicated their high affinity for phosphorus by chemisorption. The average maximum P adsorption values were in decreasing order of soils developed from basalt > granite > arkosic sandstone > quartzite (control) > gneiss, respectively whereas, for soil kaolins is basalt > granite > quartzite (control) > arkosic sandstone > gneiss, respectively. Relative to other soils developed from different parent rocks, soils developed from basalt (with more clay content) had higher capacity and buffer power for P adsorption. The standard P requirements for the soils ranged from 7.78 to 92.91 mgP/kg and were classified as low based on the Langmuir model. Significant correlation between the P adsorption parameters for the soils and soil kaolins indicated that the later could be taken as a good predictor for P sorption dynamics in the soils. Electrical conductivity of the soils were taken to be negligible in interfering with plant growth. The available P values were generally below the critical level of 12 – 15 mg/kg for soils developed from basalt, gneiss, and quartzite (control) but higher in soils developed from granite and arkosic sandstone. All the soil evaluation factor (SEF) average values estimated were greater than five indicating that they are not of poor soil fertility. The correlation results between the soil properties and P sorption parameters suggest that several variables can influence the P sorption dynamics of the soil. Regression analyses further indicated that CEC, pH, OM, and clay content in the soils account for 99 % bounding P energy variation whereas, Fe2O3 accounts for 76 % P sorption maximum variation in the soils. In addition, variations in Fe2O3 and sand contents in the soils account for 96 % and 95 % maximum buffering capacity and external P requirement (EPR) variations, respectively. Models to advance the interplay between the various soil properties and P sorption parameters in the soils were developed. Mineralogical and geochemical characteristics of the soils were principally controlled by the parent rocks and degree of weathering. The soil kaolins displayed significant differences relative to reference kaolins. Langmuir model is most suited for describing P sorption in soils and soil kaolins developed from different parent rocks within the studied area. P sorption parameters for the soils can readily be obtained from the P sorption parameters of the kaolins present in them. EPR obtained and models for predicting P sorption parameters from selected soil properties developed for the various soils will improve the efficiency of routine P fertilizer applications. Iron oxide (Fe2O3) played the most crucial role in explaining the P sorption dynamics of the soils. The major contributions from this study have been: better understanding of the influence of parent rock characteristics and degree of weathering on the soil characteristics, the nature of soil kaolins and its influence on soil properties as well as P sorption dynamics in soils have been better established, and improvement of the understanding on the relationship between soil properties and P sorption dynamics in the soils. / NRF

MESMEG / Department of Mining and Environmental Geology / Although clay brick manufacturing has been going on for many years in South Africa, informal small-scale clay brick manufacturing enterprises are not officially regulated. Consequently, informal brick makers in the study area do not adhere to the demanding requirements of the South African National Standards for burnt clay masonry. Therefore, their clay bricks lack uniformity in terms of quality. Preliminary work revealed that over time, buildings constructed with these bricks develop cracks, thereby compromising safety. The importance of product quality management is not well understood in the informal brick manufacturing enterprises. As a result, they do not have any product quality management guidelines. The main purpose of this research was to develop the product quality management guidelines for ensuring quality in small-scale brick making enterprises in Dididi area. The specific objectives were to characterize the raw materials for clay brick manufacturing, identify and assess the technical problems of clay brick production, analyse the process of clay brick production and determine areas where product quality improvement is warranted. The research involved fieldwork which included soil sampling, analysis of clay brick production through the use of questionnaires and onsite observation of the production process, collection of samples of burnt bricks which were examined for compressive strength, water absorption as well as dimension measurements. These were then compared with the prescribed quality standards. Laboratory analyses of samples of raw materials were conducted and these included sieve analysis which was conducted in order to establish the particle size distribution of the raw materials; Atterberg limit tests were conducted in order to establish the physical characteristics of the soil. Chemical and mineralogical analyses were carried out to determine the chemical and mineralogical composition of the soil using XRF and XRD respectively. The textural characterisation of the material revealed abundance of sand sized particles and significantly low amounts of clay and silt. The plasticity of the soil used for bricks manufacturing in the study area was found to be ranging from slight to medium plasticity. Chemical analysis showed elevated silica contents with minor amounts of alumina and iron oxide. XRD analysis revealed the dominance of non-clay minerals with the highest concentration of quartz. The average compressive strengths of the tested brick samples for site A was 3.8, and 2.9 and 3.8 MPa for sites B and C respectively. The water absorption of the bricks was 13.5, 15.0 and 16.1% for samples from Site A, B and C respectively. The bricks dimensions met the recommended standards although their sizes were not uniform. v The survey conducted on brick manufacturing process revealed that the technical inefficiencies were mostly influenced by human and mechanical factors as well as the material inappropriateness. The production process was found to be too manual and labour intensive. Selection of the raw materials for brick manufacturing was based on indigenous knowledge and experience and most of the brick manufacturers lacked the prerequisite experience for making quality bricks. On the basis of the results of this research, it can be concluded that the materials used for manufacturing of clay bricks in Dididi are not well suited for making good quality bricks due to the reduced plasticity of the soil and the high concentration of quartz. These render the bricks brittle. It was also concluded that the production process also contributes to the poor quality of the bricks as the nature of the process was too manual. Selection of materials based merely on knowledge and experience and no scientific tests resulted in selection of inadequate materials which in turn affect the quality of the final bricks. It is therefore recommended that plastic clays be added to the raw clay materials to enhance its moulding property. In addition, materials such as internal fuels and anti-shrinkage materials should be incorporated into the process cycle to prevent cracking during drying and firing. Based on the findings of the analysis of the production process, it is recommended that mechanized techniques be employed in the operation and awareness training conducted to improve the understanding and skills of the brick manufacturers and to ensure production of good quality bricks. / NRF