A research report submitted to the Faculty of Science, University of the Witwatersrand, in partial fulfilment of the requirements for the degree of Master of Science in Environmental Sciences Johannesburg, 2017. / PCBs are chemical compounds which were synthesised in the laboratory in the 1920s. They are classified under the category of POPs. They were mainly used in electrical equipments and transformers as the insulating material. PCBs were released to the environment in the form of oil spillages, combustion of PCB-containing equipments and others. Its production was banned in the 1970s after its toxic, persistent, bioaccumulative and carcinogenic behaviour was discovered. This study was conducted to determine and monitor the level of PCB in soil contaminated by oil spillages from pole mounted transformers in Polokwane, Limpopo, South Africa after sites have been remediated. Seventy eight soil samples were collected from five sites. The QuEChERS extraction method and GC-MS was used to extract and analyse PCBs. The PCB congeners targeted in this study are PCB-180, PCB-158 and PCB-101. The concentration of PCB-180 ranges between 10.02 and 78.30 μg kg -1, PCB-158 ranges between 3.89 and 45.36 μg kg -1 and PCB-101 ranges between 2.42 and 39.12 μg kg -1. The PCB congener with the highest concentration at all sites is PCB-180 followed by PCB-158 while PCB-101 has the least concentration; this order is consistent in all sampling sites. PCB concentrations after bioremediation were found to be extremely higher than concentrations before bioremediation which suggest that the bioremediation process was not efficient including actual analytical methods used. In comparison to the range of the PCB levels reported in literature, the PCB concentration determined from this study is found within a higher range. The PCBs concentration at all five sites was found to be below the legal limits. / LG2018

Thesis (M.Sc. (Soil Science)) --University of Limpopo (Turfloop campus), 2007 / The influence of parent material on physical and chemical properties of soil was studied on granite and schist derived soils on the Syferkuil Experimental Farm, situated in the Mankweng area of the Limpopo Province of South Africa. A total of 49 samples of virgin soils were collected, where granite soils constituted 26 samples and schist soils 23. The study design that was used is cross-sectional. The samples were analysed for physical and chemical properties. The physical properties of granite and schist soils were determined as percentages coarse sand, percentages medium sand, percentages fine sand, percentages very fine sand, percentages silt and percentages clay, whilst the chemical properties were determined as concentrations (cmol (+) kg-1) of Na, Mg, Ca, K ,ESP, CEC and P (mg kg-1), as well as pH. Statistical analysis of the results was performed by application of the Unpaired Student’s T Test, with the level of significance at p<0.05. The results showed that soils derived from granite had significantly higher coarse and medium sand fractions than schist soils; whereas schist soils were significantly higher in fine sand, very fine sand, silt and clay. The concentrations of Na, Ca, ESP and P, as well as CEC and pH in schist derived soils were higher than in granite derived soils although the differences were insignificant. However, significant differences occurred in K and Mg concentrations where schist derived soils had higher concentrations than granite derived soils. However, the concentrations of nutrient elements were found to be insufficient for proper production in agriculture. The sodium concentration was found to be low enough to not lead to sodic soil conditions. It was concluded that both granite and schist soils can be used for agriculture but require careful management because both soils indicated poor nutritional status.

Department of Soil Science / PhD (Agric)

MENVSC / Department of Ecology and Resource Management / See the attached abstract below

MESHWR / Department of Hydrology and Water Resources / Communities in South Africa have been noted to consume earthy materials such a soil among others. Geophagy is largely practised in the rural areas as opposed to urban places, and in these places the level of sanitation is low and people usual practice open defecation. The practice of Geophagia has been associated with cultural, medicinal, psychological, religious and nutritional deficiency among others. The aim of the study was to investigate the effects of open defecation on geophagic soils and water resources in Siloam village. The study also aimed to understand the reasons why people practice geophagia in Siloam village and the health effect associated with consumption of geophagic soils. To carry out the aim of the study, a questionnaire survey was conducted among women who practice geophagia between the ages of 18 and above in Siloam village. Two hundred and eighty-three (283) women were selected using snowball sampling method to take part in the study. From the (283) women, (200) women represent the geophagic group and (83) women represent the control group. The existing standard questionnaire adopted to generate data on human geophagia included aspects on demography, socio-economic, cultural, ecological, physicochemical aspects, indigenous knowledge and health effects of geophagic consumers. Participants were asked basic questions on why they practice geophagy, their geophagic material preferences, where they collect the geophagic material and other related questions. A total of twelve soil samples were collected from Siloam village, from the twelve soil samples collected eight were collected from sites known for geophagic practice and another four soil samples were collected from sites where geophagia is not practiced and the samples were used as control soil samples. All the twelve soil samples were analysed for the presence of geohelminths ova using Ammonium Bicarbonate Protocol (AMBIC protocol). The AMBIC protocol consists of four analytical procedures, namely, sample preparation, sample washing with AMBIC solution, geohelminths ova recovery through a modified zinc flotation method and microscopic analysis. vi Furthermore, a total of twelve water samples were collected from Nzhelele River and ponds water in Siloam village. From the twelve water samples, eight samples were collected close to where geophagic materials were collected and where open defecation is reported to be taking place and the remaining four water samples were collected randomly from Nzhelele river and water ponds in Siloam village and was recorded as a control group. A total of 12 water samples were analysed for total coliform and faecal coliform Escherichia Coli (E.coli) indicator using the membrane filter technique. The results from the administration of the questionnaire revealed there was prevalence in the practice of geophagia in the area. The study found that most of the villagers in Siloam consumed soil nearly on daily basis. According to the results, only women were involved in the geophagic practices in the area. Additionally, the study revealed that geophagic consumers were mainly in the age of child bearing age group and reddish and yellowish soils were the most preferred. Furthermore, the results showed that geophagic consumers in the area generally consumed soil commonly because of cravings and pregnancy, however, those who were not pregnant also consumed soil. The respondents reported that they mostly consumed clay and this material was consumed in its dry state and mostly unprocessed, if processed, it would be baked. This geophagic material was mainly found in the wild (riverbed, valley etc.); it was also found that most of the soil consumers did not know that the substances they consumed could be harmful to them. Among those who knew the consequences of consuming the material stated that soil consumption causes constipation, tooth decay, body poisoning, and abdominal pains. The results from the control group, 83 women who do not practice geophagia, aged between 18 and above, analysed using chi-square revealed a significant association of age with consuming soils (p<0.05), while there was no association of income source (p>0.05) and educational level (p>0.05) with consuming soils. Chi-square (χ2) analyses further revealed that there was no association of knowledge on the harmful nature of the substance (p>0.05), frequency of getting infections (p>0.05) and experiencing chronic illnesses (p>0.05) with frequency of consuming soils. vii The results of geophagic soils revealed the absence of geohelminths ova in the entire geophagic sample. Meaning geophagic consumers in Siloam village are not at risk of acquiring geohelminths infection which may be of potential risk to human health. However, geophagic consumers may be exposed to various other potentially hazardous biological and non-biological soil contents. The results of the water samples revealed that most of the water samples in the areas where open defection is reported to be practised had higher composition of faecal and total coliform bacteria. The composition was above the South African recommended standard for negligible risk of microbial infection. This has caused a great threat to those who consume soil collected near water resources, especially from riverbed and those who also use these water sources on their daily basis. The study recommends that geophagic consumers should continue to bake their materials before consumption as it might reduce the bacteria and toxic substances found in soils. The study also recommends that the residents of Siloam be made aware of the potential health hazards that might be posed to soil consumers and the effects of practicing open defecation near community water resources as high level of faecal coliform (E. coli) were found in the water. / NRF

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

MSCAGR (Soil Science) / Department of Soil Science / The effects of tillage on soil structure and associated soil properties such as soil respiration may differ in different soils. The study determined the effects of tillage, soil texture and mineralogy in selected soil properties on different soil types. Soil samples were collected from four different sites in the Limpopo province, South Africa. The soils were classified as Glenrosa with sandy loam texture, Dundee with loamy sand, Hutton with clay, and Shortlands with clay. Glenrosa and Dundee were dominated by quartz, while Hutton and Shortlands with kaolinite. Soil samples were taken from the surface 0 – 20 cm under conventional tillage and no-till land. Soil organic matter, texture, and mineralogy were determined. The soils were wetted to activate the microorganisms and incubated for 70 days at 30℃ and soil respiration was determined using alkali trap method on a weekly basis. The study was conducted in triplicates and arranged in a completely randomized design. Data was subjected to analysis of variance using general linear model procedure of Minitab version 19. Means were compared using paired t-test at (p ≤ 0.05). The Pearson correlation coefficient (r) was used to measure the strength of linear dependence between variables. There was a significant difference in soil organic matter (p≤0.000) among all studied soils. The mean values of soil organic matter were 2.19% in Hutton, 2.0% in Shortlands, 0.54% in Glenrosa, and 0.43% in Dundee. Quartz had a strong negative linear relationship (r = -0.66) with soil organic matter while kaolinite had a strong positive linear relationship (r = 0.96). Soil respiration increased in soils dominated with quartz and decreased in soils dominated with kaolinite. The soil respiration increased by 18.95 g CO2 m-2 d-1 in conventional tillage and decreased by 13.88 g CO2 m-2 d-1 in no-tillage due to increased exposure of soil organic matter under conventional. It was concluded that less intensive tillage such as no-tillage reduces soil respiration. / NRF

MENVSC / Department of Environmental Sciences

Department of Ecology and Resource Management / MENVSC

PhD (Environmental Sciences) / Department of Ecology and Resource Management / The presence of arsenic in groundwater has drawn worldwide attention from researchers and public health officials due to its effects on human health such as, cancer, skin thickening, neurological disorders, muscular weakness, loss of appetite and nausea. World Health Organisation (WHO) has set the limit of 10 μg/L for arsenic in drinking water in trying to reduce the effects of arsenic. This was further adopted by South African National Standard (SANS). The present study aims at evaluating arsenic concentration in selected groundwater sources around Greater Giyani Municipality in Limpopo Province and further synthesize clay based adsorbents for arsenic removal using Fe3+ and Mn2+ oxides and hexadecylammonium bromide (HDTMA-Br) cationic surfactant as modifying agents. The first section of the work presented the hydrogeochemical characteristics of groundwater in the Greater Giyani Municipality. The results showed that the pH of the samples ranges from neutral to weakly alkaline. The dominance of major anionic and cationic species was found to be in the order: HCO3 ->Cl->SO4 2->NO3 - and Na+>Mg2+>Ca2+>K+>Si4+, respectively. Hydrogeochemical facies identified in the study area include CaHCO3 (90%) and mixed CaNaHCO3 (10%) which shows the dominance of water-rock interaction. About 60% of the tested samples contains arsenic concentration above 10 μg/L as recommended by SANS and WHO. Concentration of arsenic was found to be ranging between 0.1 to 172.53 μg/L with the average of 32.21 μg/L. In the second part of this work, arsenic removal efficiency of locally available smectite rich and kaolin clay was evaluated. Results showed that the percentage As(V) removal by kaolin clay was optimum at pH 2 while the percentage As(III) removal was greater than 60% at pH 2 to 12. For smectite rich clay soils, the percentage of As(III) and As(V) removal was found to be optimum at pH between 6 and 8. The adsorption isotherm data for As(III) and As(V) removal by both clays fitted better to Freundlich isotherm. Adsorption of both species of arsenic onto the clay mineral occurred via electrostatic attraction and ion exchange mechanisms. Both clay soils could be regenerated twice using Na2CO3 as a regenerant. Kaolin clay showed a better performance and was selected for further modification. In the third section of this work, Fe-Mn bimetal oxide modified kaolin clay was successfully synthesized by precipitating Fe3+ and Mn2+ metal oxides to the interlayer surface of kaolin clay. Modification of kaolin clay increased the surface area from 19.2 m2/g to 29.8 m2/g and further v decreased the pore diameter from 9.54 to 8.5 nm. The adsorption data fitted to the pseudo second order of reaction kinetics indicating that adsorption of As(III) and As(V) occurred via chemisorption. The adsorption isotherm data was described by Langmuir isotherm models showing a maximum As(III) and As(V) adsorption capacities of 2.16 and 1.56 mg/g, respectively at a temperature of 289 K. Synthesized adsorbent was successfully reused for 6 adsorptiondesorption cycles using K2SO4 as a regenerant. Column experiments showed that maximum breakthrough volume of ≈2 L could be treated after 6 hours using 5 g adsorbent dosage. Furthermore, the concentration of Fe and Mn were within the WHO permissible limit. In the fourth part of the work kaolin clay was functionalized with hexadecyltrimethylamonium bromide (HDTMA-Br) cationic surfactant and its application in arsenic removal from groundwater was investigated. The results revealed that adsorption of As(III) and As(V) is optimum at pH range 4-8. The maximum As(III) and As(V) adsorption capacities were found 2.33 and 2.88 mg/g, respectively after 60 min contact time. Pseudo first order model of reaction kinetics described the adsorption data for As(V) better while pseudo second order model described As(III) adsorption data. The adsorption isotherm data for As(III) and As(V) fitted well to Langmuir model indicating that adsorption of both species occurred on a mono-layered surface. Adsorption thermodynamics model revealed that adsorption of As(III) and As(V) was spontaneous and exothermic. The As(III)/As(V) adsorption mechanism was ascribed to electrostatic attraction and ion exchange. The regeneration study showed that synthesized adsorbent can be used for up to 5 times. In the firth part of the work inorgano-organo modified kaolin clay was successfully synthesized through intercalation of Fe3+ and Mn2+ metal oxides and HDTMA-Br surfactant onto the interlayers of the clay mineral. The batch experiments showed that As(III) removal was optimum at pH range of 4-6, while the As(V) removal was optimum at pH range 4-8. The adsorption data for both species of arsenic showed a better fit to pseudo second order of reaction kinetics which suggest that the dominant mechanism of adsorption was chemisorption. The isotherm studies showed better fit to Langmuir isotherm model as compared to Freundlich model. The maximum adsorption capacity As(III) and As(V) at room temperature as determined by Langmuir model were found to be 7.99 mg/g and 7.32 mg/g, respectively. The thermodynamic studies for sorption of As(III) and As(V) showed negative value of ΔGᴼ and ΔHᴼ indicating that adsorption process occurred spontaneously and is exothermic in nature. The regeneration study showed that the vi inorgano-organo modified kaolin clay can be reused for up 7 adsorption-regeneration cycles using 0.01 M HCl as a regenerant. Thomas kinetic model and Yoon-Nelson model showed that the rate of adsorption increases with increasing flow rate and initial concentration and decreases with increasing of the bed mass. In conclusions, adsorbents synthesized from this work showed a better performance as compared to other adsorbents available in the literature. Among the synthesized adsorbents, inorgano-organo modified clay showed highest adsorption capacity as compared to surfactant functionalized and Fe-Mn bimetal oxides modified kaolin clay. However, all adsorbents were recommended for use in arsenic remediation from groundwater. The following recommendations were made following the findings from this study: 1) routine monitoring of arsenic in groundwater of Greater Giyani Municipality, 2) evaluating the possible link between arsenic exposure and arsenic related diseases within Giyani in order to find the extent of the problem in order to establish the population at risk, 3) The toxicity assessment for HDTMA-Br modified kaolin clay should be carried out, 4) Materials developed in the present study should be modeled and tested at the point of use for arsenic removal, and lastly, 5) this study further encourage the development of other arsenic removal materials that can be used at household level. / NRF