A Research Report submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science, 2018 / The aim of this research was to assess the status of water quality in a selected area of the Waterberg over a twenty-year period and to gain insight into the perceptions of stakeholders about water management. The objectives were met through the comparison of historical water quality variable records for various water uses, by measuring the level of stakeholder commitment in water quality measurement and verifying a relationship between the two approaches. This study focuses on measuring the extent of different stakeholders’ involvement in the management and decision-making processes of water quality in the Waterberg region of Limpopo province, which is encouraged by the formulation of South African policies. The specific area of interest is in the north-western part of the Waterberg. There are three distinct settlements, Lephalale, Marapong and Steenbokpan, located in the Lephalale Local Municipality. Close by are major industrial and mining activities from Eskom’s Matimba and Medupi power stations, and Exxaro’s Grootegeluk Coal Mine. To address the specific research questions and objectives for this study, two approaches were necessary: A quantitative approach that required surface water and groundwater data from 1995 to 2015, to determine the quality of water, and a qualitative approach that comprised of the distribution of 20 questionnaires in the residential areas, and 15/20 successful pre-selected individual interviews, to assess the different levels of stakeholder participation. Each approach presented its own challenges. For example, the water quality data provided were incomplete, which created limitations in the interpretation and during the questionnaire distribution, time constraints and language preferences, though anticipated amongst different social groups, there was difficulty communicating the concept of the study. Also, during the planning phase of selecting interviewees, there was a lack of interest in the study from environmental consultants, who are vital role players in the environmental status of the area. The water quality data indicated that pH levels in the surface water sites have remained steady and are not significantly different from one another. The results from the one groundwater site, reveals that there is a significant difference between the pH levels of surface water and groundwater which is to be expected. The results also suggest that the high concentration of ammonium, phosphate and nitrate midstream in the Mokolo River are related to the waste water being discharged mid-stream into the river via a pipeline. The high concentrations of sodium and potassium in the groundwater site are linked to the interaction time with the surrounding geology and the overall EC levels correspond with the fluxes in sodium in the groundwater site resulting in the significant difference in EC between the surface water and the groundwater sites. No data were available for the midstream site. The questionnaire results indicate that there’s limited stakeholder involvement in water quality management from participants in Steenbokpan and Marapong, which are socio-economically disadvantaged areas, when compared with Lephalale, a more affluent area. In contrast to Lephalale, Marapong and Steenbokpan residents are less educated, have higher unemployment numbers, and have restricted access to water related information, and electricity, water and sanitation services. In the overall area, there is also a 30% unawareness amongst general water users about the topic of water pollution, but again it is mostly from participants in Steenbokpan and Marapong. The interview results signified a higher level of stakeholder involvement in water quality management from individuals in influential positions. This, however, does not mean that water related issues in the area are adequately addressed. Interviewees revealed that there is a lack of funding, skills, infrastructure, manpower and competence. There is also an apparent inequality with regards to water access to informal settlements, farmers and rural villages. Additionally, there is a high level of dependency on Eskom and Exxaro, rather than the local municipality, to provide its water users with proper water services. The dependency on Eskom and Exxaro is largely due to their high level of influential development. Improvements and maintenance on basic service from these structures to the surrounding communities form part of their offset programmes to continue major development in the area. Due to the large difference of the qualitative and quantitative approaches, it was difficult to prove how one supports the other, even though, on its own, both are crucial components in water quality management practices. Even though the water quality data provide more reliable support on the condition of surface- and groundwater in the Waterberg, the social aspect (partially revealed through the subjective view of the general users who completed the questionnaire) is required to determine the community’s relationship with water use and to identify management practices through stakeholders responsible for them. / XL2018

Thesis (M. Tech. - Dept. of Chemistry, Faculty of Applied and Computer Sciences) -- Vaal University of Technology, 2010 / The increased production and application of pesticides for agricultural and non-agricultural purposes has caused the pollution of air, soil, ground and surface water. This has a negative impact on the environment as well as human health due to direct exposure or through residues in food and drinking water. The continuous monitoring of pesticides residues in environmental samples has great importance and demands high efficiency, unique selectivity and high sensitivity techniques. Gas chromatography and high performance liquid chromatography have been established for years as the techniques for the analysis of pesticides residues. The dissertation deals with the qualitative and quantitative determination of selected pesticides in the Southern Gauteng region using Liquid- liquid extraction solid-phase extraction, high performance liquid chromatography, gas chromatography equipped with electron capture detector and gas chromatography mass spectrometry. Liquid-liquid extraction and solid-phase extraction using dichloromethane, hexane and ethyl acetate as the extracting solvent were optimized and evaluated for the determination of pesticides in surface water in the Southern Gauteng region. From the developed method the techniques were applied to water samples taken from different rivers selected namely: Zuikerbosch, Rand Water barrage and Kliprivier for sampling. Dichloromethane was used as a solvent in this study since a recovery test was done between dichloromethane, Ethyl acetate and n-hexane. The percentage recovery test for 4,4-DDT, 4,4-DDE, 2,4-DDD and Endosulfan 1 & 2 ranged from 89.9% -97.3% for dichloromethane, 87.3%-96.8% for hexane 88.4%-97.1% for ethyl acetate. The extracts obtained were subjected to column chromatography for clean up. Thereafter 1µl of the cleaned extracts were injected into the Gas chromatography equipped with an electron capture detector. Organochlorines 4,4-DDT and its metabolites, Organophosphate Chlorypyriphos and carbamates were detected using Gas chromatography electron capture, Gas chromatography mass spectrometry and high performance liquid chromatography.

MSc (Chemistry / Department of Chemistry / In this study, three sampling sites (Tshipise thermal spring, Mphephu thermal spring and Siloam borehole) in Limpopo Province South Africa were considered for an investigation into the mineral composition of their water and soil samples. Tshipise and Mphephu thermal springs are well developed and located within tourist resorts. On the other hand, Siloam is a borehole on the grounds of a private household. The water is used for various domestic purposes such as laundry, general cleaning of the household and bathing. Water and soil samples from the three sites were collected once per week every week in February 2018. The sampling bottles were spiked with 1M HNO3 before sampling to keep any metal ions present in the water samples in solution. The soil and water samples were analysed for their chemical composition using X-ray fluorescence (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) respectively. XRF analysis of the soil samples found many major oxides of which SiO2 made up 63.67%, 85.37% and 46.28% by mass of Tshipise, Mphephu and Siloam soil samples respectively. XRF analysis also showed the presence of dangerous levels of heavy metals such as As, Tl, Pb and V. The analysis of the water samples by ICP-MS found that Tshipise, Mphephu and Siloam mineral water were soft, soft-moderately hard and soft-hard respectively with regards to the water hardness scale according to the United States Geological Survey (USGS) and the Water Quality Association (WQA). Analysis of water samples also found the presence of As, Cd, Cr and V. Arsenic was found to occur at concentrations above the Maximum Allowable Concentration (MAC) set by the World Health Organisation (WHO) (10 μg L-1) for Tshipise, Mphephu and Siloam mineral water (13.63 μg L-1, 15.83 μg L-1 and 20.97 μg L-1 respectively). Water temperatures for the three sites ranged from 38°C (Siloam borehole) to 64°C (Tshipise thermal spring). The pH values were 7.25 (Siloam borehole), 7.40 (Mphephu thermal spring) and 8.67 (Tshipise thermal spring). Due to the presence of As, Tl, Pb, V, Cd and Cr, the mineral water from all three thermal springs is unsafe to consume as it would lead to serious negative health effects some of which are outlined in this study. / NRF

PhDENV / Department of Hydrology and Water Resources / Geothermal springs are natural geological phenomena that occur throughout the world. South Africa is endowed with several springs of this nature. Thirty-one percent of all geothermal springs in the country are found in Limpopo province. The springs are classified according to the residing mountain: Soutpansberg, Waterberg and Drakensberg. This study focused on the geothermal springs within the Soutpansberg region; that is, Mphephu, Siloam, Sagole and Tshipise. The study was aimed at elucidating on the isotopic signatures and trace metals concentrations from the geothermal springs to their environmental media in Soutpansberg region. This study also assessed the interconnectivity of the isotopic signatures within the ecosystem and evaluated the potential human health risks associated with trace metals from geothermal springs and surrounding soils in the study areas. Geothermal springs and boreholes were sampled for a period of twelve months (May 2016 – May, 2017) to accommodate two major seasons in the study areas. The surrounding soils were sampled vertically from a depth of 10 cm to 50 cm for trace metals and isotopic compositions. Three different plants were sampled at each of the study sites, namely, Amarula tree, Guava tree and Mango tree at Siloam; Acacia tree, Fig tree and Amarula tree at Mphephu; Amarula tree, Lowveld mangosteen and Leadwood tree at Sagole; Sausage tree, Amarula tree and Acacia tree at Tshipise. To achieve the objectives, the physicochemical, geochemical and isotopic compositions of the geothermal springs, boreholes, soils and vegetation were analysed using ion chromatography (IC) (Dionex Model DX 500), inductively coupled plasma-mass spectrometer (ICP-MS), HTP-Elemental analyzer, Liquid water isotope analyzer (LWIA-45-EP) and Liquid scintillation analyzer. The temperature, electrical conductivity (EC), pH and total dissolved solid (TDS) of the geothermal springs and boreholes samples were measeured in situ and in the laboratory. Trace metals analysed in geothermal springs, boreholes, soil and vegetation include Beryllium (Be), Chromium (Cr), Manganese (Mn), Cobalt (Co), Nickel (Ni), Copper (Cu), Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb), Barium (Ba), Vanadium (V), Zinc (Zn), and Mercury (Hg). vii | Isotopic signatures and trace metals in geothermal springs and their environmental media within Soutpansberg Results obtained from this study in the studied geothermal springs and boreholes were classified according to their temperature as hot and scalding; except for tepid boreholes. This study has provided comprehensive physicochemical, geochemical and isotopic compositions of the geothermal springs within the Soutpansberg region (Siloam, Mphephu, Sagole and Tshipise). The local meteoric line (δD = 7.56δ18O + 10.64) was generated from rainwater in Vhembe district. This is a crucial component for depicting the source and flow path of the geothermal springs/boreholes; and could be used for future isotopic hydrological studies within the locality. Rain formation processes within Soutpansberg occurred under isotopic equilibrium conditions with minor evaporation effect during rainfall. The δD and δ18O values of the geothermal spring water/boreholes confirm that the waters are of meteoric origin, which implies that rainfall is the fundamental component of these groundwaters because they were derived from the infiltration of rainwater, with significant contribution of another type of water in the deeper part of the aquifer. Na-Cl and Na-HCO3 were established as the water types, which are typical of marine and deep groundwaters which are influenced by the ion - exchange process. The reservoir/aquifer temperature of these springs ranges between 95 – 185°C (Na-K geothermometer), which implies most of the waters are mature water (not native). Hence, geothermal springs water is a mixture of the rainwater and salt water. Radiocarbon values of the geothermal springs ranged from 2700 to 7350 BP, this implies that they are submodern and a mixture of submodern and modern waters. Tritium relative age also corroborates with radiocarbon age, that is the groundwaters were recharged before and after 1952. This gives an indication that the rainfall contributes to the geothermal springs recharge. Various radiocarbon correction models were employed and constrained by tritium relative age. Ingerson and Pearson, Eichinger and Fontes and Garnier correction models have been shown to be the most appropriate models for radiocarbon correction of groundwater in this semi-arid region. Although, geothermal springs water and boreholes are not fit for drinking due to high fluoride content, they could be used for the following: domestic uses (drinking exclusive) due to its softness, direct heating in refrigeration, green-housing, spa, therapeutic uses, aquaculture, sericulture, concrete curing, coal washing and power generation. In contrast with mentioned uses, viii | Isotopic signatures and trace metals in geothermal springs and their environmental media within Soutpansberg the studied geothermal springs are currently used for domestic purposes (drinking inclusive), limited irrigation and spa (swimming and relaxation). This is an eco-hydrological study that shows the interconnectivity of isotopic signatures among water (rainwater, geothermal springs and boreholes), soils and vegetation. The soil-water reflects the rainwater/geothermal springs water in isotopic composition, which is more depleted as a result of isotopic fractionation in soil. δD values of soil-water increase, whereas δ13C values in soil-water decrease with the soil depth at all sites. Two equations connecting δD and δ13C in soil-water were deduced per season for soil-water; δ13C = 0.0812δD - 10.657 in winter; δ13C = -0.0278δD - 21.945 for summer. δ13C in soil-water is induced by Crassulacean Acid Metabolism (CAM) (mixture of C3 and C4 photosynthetic cycles) with a stronger C4 trend, which corroborates with δ13C of the geothermal springs. From literature, Amarula and Acacia trees have been documented for isotopic compositions, while this study has given additional information on other plants including Lowveld, Leadwood, Sausage, Fig, Guava and Mango trees. These plants are categorised as C3, C4 and CAM plants. C3 plants include Amarula, Lowveld and Leadwood trees; C4 plants include Acacia and Sausage trees; and CAM plants include Fig, Guava and Mango trees. This study shows that with CAM soils, there is a possibility of having either C3, C4 or CAM vegetation. This finding has shown that the δD and δ13C isotopes in water, soil and vegetation are interrelated, which has been statistically justified. This study has shown the potential human health risks associated with trace metals concentrations from geothermal springs and their surrounding soils. From the geothermal spring’s water, it was found that As, Cr and Cd were the highest contributors to the cancer risk with children having a higher risk than adults. Whereas in soils, it was found that Cr, As and Co were the highest contributors to the cancer risk in the studied communities. Therefore, the cancer risk is high in the general population; that is 1 in 72-162 individuals in children and 1 in 7-107 individuals for adults. The ingestion route seems to be the major contributor to excess lifetime cancer risk followed by the dermal pathway. Therefore, proper monitoring and control measures to protect human health, particularly in children, should be implemented for safety. The study also explored the use of surrounding trees ix | Isotopic signatures and trace metals in geothermal springs and their environmental media within Soutpansberg for phytoremediation and found their uptake capacity to be high, thus, they could be used as bio-indicators to assess the level of contamination of trace metals in the soil. In conclusion, this study has eludicated on the isotopic signatures and trace metals concentrations from the geothermal springs and their surrounding soils and vegetation within Soutpansberg. This study has contributed towards the advancement and enhancement of the existing knowledge of the geothermal systems, such that water resource management could be applied successfully in the respective areas with similar characteristics for the benefit of the local communities and society at large. Hence, this study recommends that proper monitoring and control measures need to be put in place to protect human health, especially in children. / NRF