Anthropogenic activities generate waste products that pollute the environment with bacteria and heavy metals. This research assessed pollution of the Kahwa River, Bukavu Town, DRC with cadmium and lead (HMs) and bacterial enteropathogens. A survey of businesses, households and healthcare facilities showed general use of the river to remove effluent and waste. Indicator organisms were cultured at over 200 cfu/100 ml showing faecal contamination of the river water. Antibiotic resistance was shown by enteropathogenic Vibrio cholerae and Salmonella typhi to ampicillin and cotrimoxazole with some sensitivity shown to ciprofloxacin. River water contained HMs at around 40 times the World Health Organisation limit for drinking water. The bacteria, particularly from river sediment, tolerated HMs up to a concentration of 1.5 mg/ml. The presence in the Kahwa River of antibiotic-resistant pathogens showing tolerance to HMs has serious public health implications / Environmental Management / M.Sc. (Environmental management)

The spatio-temporal patterns in concentrations of selected metals within the sediment (Cd, Co, Cu, Fe, Pb, Ni and Zn) and water (Cd and Pb) of three permanently open estuaries (Kariega, Kowie, Great Fish) and six temporary open-closed estuaries (Mpekweni, East Kleinemonde, West Kleinemonde, Riet, Kasouga, Boknes) were investigated. The concentrations of metals were influenced by size composition and total organic content of the sediments. Enrichment factors (EFs), using Fe as a reference element, and baseline linear regression models for metals vs. Fe were calculated to assess the extent of metal enrichment in the sediments. The mean concentrations of metals in the sediments(mg·kg⁻¹) showed ranges of 0.28 – 2.31 for Cd, 1.26 – 6.24 Co, 0.69 – 6.93 for Cu, 2119 – 14912 for Fe, 2.29 –14.01 for Ni, 4.81 – 22.20 for Pb and 5.77 – 21.75 for Zn. Mean normalized enrichment factors ranged between 0.75 – 6.19 for Cd, 0.53 – 2.71 for Co, 0.22 – 0.84 for Cu, 0.30 – 1.87 for Ni, 0.99 – 3.17 for Pb and 0.14 – 0.98 for Zn. All nine estuaries had average enrichment factors of greater than 1 for Cd. In general there was no enrichment of Cu and Zn in the sediments of any of the estuaries included in this study (EFs < 1). The Kariega, East Kleinemonde, West Kleinemonde, Riet and Great Fish Estuaries showed some degree of enrichment for Co (1 < EF < 4), Ni (1 < EF < 2) and Pb (1 < EF < 4), while the Mpekweni, Kasouga, Boknes and Kowie Estuaries were unenriched with these metals (EF < 1). Enrichment factors for Cd, Co and Pb typically followed the development gradient along the estuaries, suggesting anthropogenic enrichment. The concentrations of Cd and Pb in the water of the nine estuaries were also determined. The average concentrations of Cd and Pb in the water (μg·ℓ⁻¹) ranged between 0.05 – 3.32 and 0.75 – 34.13 respectively. On average the concentrations of Cd and Pb in the water of all the estuaries were below the South African recommended water quality guidelines for coastal marine waters. Variations in metal concentrations associated with changes in hydrology (wet vs. dry season) were determined in the water and sediment of the Kariega, East Kleinemonde and Riet Estuaries. Cobalt, Pb and Ni enrichment in the Kariega Estuary sediment was significantly higher during the dry season, and the mean concentrations of Pb and Cd in the water column were 19-fold and 66-fold higher in the dry season. The elevated concentration of metals during the dry season could be related to accumulation of diffuse pollution from human activities within the catchment area. Conversely, inflow of fresh water into the estuary had the net effect of reducing the concentration and enrichment of these metals within the Kariega Estuary due to scouring and outflow of estuarine water and sediment into the marine environment. The temporal variations in metal concentrations and enrichment factors were less pronounced in the temporary open-closed estuaries than the permanently open Kariega Estuary. The observed trend can probably be related to the low anthropogenic impact within the catchment areas of these systems, and the relatively smaller size of the catchments. Significant spatial variations existed in metal enrichment in the sediment of both the East Kleinemonde and Riet estuaries, with the highest degrees of enrichment occurring in the sediments from the marine environment and lower reaches.

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

Landfills have served as the major sites for waste disposal in both developed and developing countries. Upon closure of a landfill site, the surface could be converted to a golf course, recreation park, playground, animal refuge, tennis court and industrial site. Even when closed, landfills still have the potential to contaminate the surrounding environment as a result of the migration of leachate from decomposing waste contained in the site. This study focused on assessing the impacts of a closed landfill on soils and plants at Lumberstewart closed landfill site in Bulawayo, Zimbabwe. Soil samples were collected at three different depths (0-30 cm, 30 - 60 cm and 60-90 cm) at the landfill and a control site. The soil samples were analysed for their texture, pH, electrical conductivity, organic matter content, cation exchange capacity and concentrations of Cd, Cu, Cr, Fe, Ni and Zn. Samples of jimson weed and pigweed growing at the closed landfill and the control site were collected from the same sites where soil samples were collected, and the concentrations of the same set of heavy metals in these weeds determined. Soil samples were digested using EPA method 3050B: Acid Digestion of Sediments, Sludge and soils whereas nitric acid and hydrogen peroxide was used for digestion of plant samples. Both plant and soil digests were analyzed for heavy metals concentrations using Flame Atomic Absorption Spectrometry (AAS). Soils from the landfill as well as the control site had a high content of sand with soil pH values which were alkaline. The electrical conductivity values of the soil samples were relatively low ranging from 0.39 to 1.67 dS/m, indicating low levels of salts in soils at the landfill. The concentrations of heavy metals at the closed landfill site were higher than the control site. Heavy metals concentrations in soils at the closed landfill followed the order Fe>Zn>Cu>Cr>Ni>Cd. Results indicated that Fe was exceptionally higher than the other metals with concentration values averaging 45690±17255 mg/kg. Cadmium on the other hand had the least concentration with values of 0.01±0.00 mg/kg. Values of Enrichment Factors of heavy metals around the soil at different depths indicated that the enrichment of heavy metals increased with depth at the landfill up to 30-60 cm after which a decrease was observed. Values for heavy metal Contamination Factor of soils around the landfill ranged from low concentration (CF<1) to very high concentration (CF>6). The Pollution Load Index (PLI) values for the soil at the Lumberstewart landfill indicated that all sites were polluted (PLI>1). Site 6 had significantly higher mean concentration of heavy metals in soils at the landfill whereas site 11 had the least. The concentrations of Cd and Ni in soils at the landfill were below permissible limits of South African National Norms and Standards (NNS) as prescribed by NEMA (2008) in South Africa whereas Cr, Cu and Zn in soils were above the NNS permissible limits. Heavy metal concentrations in soils at the landfill were above World Health (WHO) permissible limits except for Cd which was equal (0.01 mg/kg) to the permissible values of Cd in the soils at sites 5, 8, 9, 10, 11 and 12. Mean concentrations of heavy metals in jimson weed and pigweed were in the order Fe>Zn>Cu>Cr>Ni>Cd. The concentrations of Cd, Cr, Cu, Fe and Zn in both plants from all sites at the landfill were significantly higher than the control site. Heavy metal transfer coefficient for both plants indicated that heavy metal uptake was more species dependent than soil heavy metal concentration dependent. The results from this research indicate that though the Lumberstewart Landfill has been closed, it is still affecting the soils in the vicinity of the landfill. Plants and water around the Lumberstewart closed landfill could be at risk from heavy metal contamination. High concentrations of heavy metals observed in the soil could present a health risk to communities should they decide to use the landfill site for arable purposes. / Environmental Sciences / M. Sc. (Environmental Science)