MSc (Chemistry) / Department of Chemistry / Surface water is used for domestic and agricultural activities in Musina region and other surrounding areas. This is because of the shortage of potable water. As a result, the people living in the region and its surrounding areas are potentially exposed to hazardous contaminants that may be present in the surface water. It is therefore important to ascertain the quality of the surface water in the region. Surface water samples were collected from Mutale, Nwanedi, Tshipise and Nzhelele rivers. The samples were analysed for anions such as fluoride (F-), chloride (Cl-), nitrate (NO3-), phosphate (PO43-), sulphate (SO42-); cations such as aluminium (Al), calcium (Ca), iron (Fe), potassium (K), magnesium (Mg), sodium (Na) and trace metals such as lithium (Li), vanadium (V), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), molybdenum (Mo), cadmium (Cd), thallium (Tl) and lead (Pb) by using analytical techniques such as IC, ICP-OES and ICP-MS. The same samples were also investigated for other parameters such as pH, temperature, EC, TH, TDS, Na % and SAR. The WHO (2008), SANS 241 (2006) and Canadian guideline (2017) were used as a water quality guideline for drinking purposes. Higher concentrations of Li, V, Cr, Ni, Cu, Zn, Al, Ca, Mg, K and Na in river water were detected in rainy season, whereas higher concentrations of As, Mo, K and Fe were recorded in dry season. The concentration of F-, Cd, Tl and Pb showed low contamination level in river samples. The results demonstrated that Tshipise river water was contaminated with high concentration of parameters: TDS (1864.0.8-3372.8 mg L-1), EC (2960.3-5270 mS cm-1), F- (6.403-8.419 mg L-1), SO42- (289.657-326.598 mg L-1), Na (836.690-922.810 mg L-1) and As (10.017-11.267 μg L-1) and relative to the (WHO) water guidelines. Nwanedi river also showed higher values of EC (298.0-699.0) mS cm-1 and TDS (190.3-447.5) mg L-1. In this study, the results indicated that water from Tshipise and Nwanedi river is not suitable for human consumption based on the guidelines of drinking water. The results also indicated that the soil sample had abundance of Ca, Al, Mn and Fe with concentration ranging from 0.13-10595, 0.0084-4.16, 0.0455-1116.5, 2.4-287404 mg Kg-1 respectively. / NRF

Department of Ecology and Resource Management / PhDENV / Groundwater has traditionally been perceived to be low in chemical species toxicity and microbiologically 'pure'. However, depending on the geological chemistry, formations and anthropogenic activities creating the frequent occurrence of microbiological contamination and excess toxic chemical constituents, the high quality of groundwater as a drinking water source can easily be compromised rendering it unsafe, thus, leading to severe waterborne epidemics. The rapid increase in fluoride and microbial contamination of groundwater have become a global problem to human health. Fluoride in its acceptable concentration in drinking water (< 1.5 mg/L); is known to be beneficial for human growth and development but becomes detrimental at higher concentrations (> 1.5 mg/L) leading to the prevalence of dental and crippling skeletal fluorosis. On the other hand, consumption of microbiologically contaminated water has led to many types of diseases including diarrhea, cholera, typhoid, dysentery and other serious illnesses often leading to millions of deaths annually worldwide. South Africa had experienced water-borne diseases epidemic in the recent past due to failing water treatment facilities in many parts of the country including rural areas. Fluorosis, diarrhea, and cholera are among the chronic health hazards affecting a large population in South Africa. Continuous outbreaks of water-related diseases have been at an unimaginable high level with a reported increase in death rate. The inefficiency of conventional water treatment plants to remove fluoride and disinfect these pathogens from the contaminated domestic and rural community has led to the development of many techniques. These include membrane filtration, ion-exchange, coagulation-precipitation, adsorption among others of which adsorption process proves to be a more significant technology for fluoride removal. Equally, the emergence of nanomaterials has also proved to be the natural answer to solve problems associated with microbes in water since these are absolute barriers to pathogens whose size exceeds most sorbent pore sizes. Also, materials from natural biopolymers or biomass can be utilized at an affordable cost as effective sorbent material for toxic chemical ions and pathogens removal from contaminated water. Consequently, extensive research works have been channeled into the development of more advanced low cost sustainable functionalized sorbent materials and technologies with multifunctional properties for effective water purification. The present study focused on the development of a functionalized chitosan-cellulose hybrid nanocomposite decorated with metal-metal oxides nanoparticles for simultaneous fluoride and microbial removal from groundwater. This was to increase the selectivity and disruption of such pollutants for effective groundwater purification technology. The thesis is presented in nine chapters: (1) General introduction, problem statement, and motivation, research objectives, hypothesis and delimitations of the research are briefly discussed, (2) This chapter gives the literature review of occurrence and sources of fluoride, various fluoride removal techniques; sources, control measures and prevention of microbial pollution in groundwater; the importance of biosynthesis of nanomaterials as emerging novel water treatment adsorbents, the strength of Point-Of-Use as a means of water treatment, water treatment adsorbents synthesis and types of adsorbents with emphasis on hydroxyapatites and biopolymeric based sorbent materials, (3) Optimization of microwave-assisted synthesis of silver nanoparticle by Citrus paradisi peel extracts and its application against pathogenic water strain, (4) Biosynthesis of ultrasonically modified Ag-MgO nanocomposite and Its potential for antimicrobial activity, (5) Green synthesis of Ag/MgO nanoparticle modified nanohydroxyapatite and its potential for defluoridation and pathogen removal in groundwater (6) Green Synthesis of AgMgOnHaP nanoparticles supported on Chitosan matrix: defluoridation and antibacterial effects in groundwater, (7) Biosynthesis of nanofibrous cellulose decorated Ag-MgO-nanohydoxyapatite composite for fluoride and bacterial removal in groundwater, (8) Defluoridation and removal of pathogens from groundwater by hybrid vi cross-linked biopolymeric matrix impregnated Ag-MgOnHaP nanocomposite (9) Conclusions and Recommendations. It is important to point out that Chapters 3 to 8 contains a collection of the research deliverables produced in forms of paper publications and manuscripts and are summarized in a systemic order of experimental protocol. This first output (Chapter 3) of this study evaluated the optimization of a time-dependent microwave-assisted biosynthesis of silver nanoparticles using aqueous peel extracts of Citrus paradisi (Grapefruit red) as a reducing, stabilizing and capping agent with emphasis on its antibacterial property. Optical, structural and morphological properties of the synthesized Citrus paradisi peel extract silver nanoparticle (CPAgNp) were characterized using UV-visible spectrophotometer, transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Brunauer–Emmett–Teller (BET) and X-ray diffractometer (XRD). The antimicrobial activity was evaluated using the well- and disc-diffusion as well as microdilution methods. Characteristic surface plasmon resonance (SPR) wavelength in the range of 420-440 nm at an optimized intensity growth rate typical of silver nanoparticles was obtained. Microwave irradiation accelerates the reaction medium within seconds of nucleation compared to conventional heating methods of synthesis. The influence of the reaction mixtures affected the SPR patterns on the different nucleation, stability and nanoparticle growth. The mixing ratio of 2:3 (C. paradisi peel extracts: 1 mM AgNO3) was chosen as the optimum reaction mixing ratio relative to the bio-reduction intensity of SPR process contributing to the particle size growth of CPAgNps. The presence, interaction and shifting of the functional groups in the FT-IR spectra of biosynthesized CPAgNps indicated that bioactive compounds present in C. paradisi peel extract were responsible for the bio-reduction of the silver ion to silver nanoparticles. The electron micrographs of the synthesized CPAgNps showed a face-centered cubic (FCC) unit phase structure, spherically-shaped nanoparticles size of 14.84 ± 5 nm with a BET pore diameter of 14.31 nm. The use of biological material allowed the control of the size and stability of the nanoparticle but was obtained in low quantity. The Citrus paradisi peel extract mediated AgNp were found to possess a broad-spectrum antimicrobial activity against water-borne pathogenic microbes in the order: Escherichia coli > Staphylococcus aureus > Klebsiella pneumonia. In Chapter 4, a synergistic bi-layered Ag-MgO nanocomposite from Ag and MgO precursor salts using a natural source from the waste product (citrus fruits outer cover) as a reducing and capping agent was successfully synthesized by a simple rapid, integrated bio-mediated microwave and ultrasonic methods. This was carried out to investigate the interfacial interaction and the encapsulated growth rate behind their combination in obtaining an enhanced antibacterial activity against common water fecal pathogen (Escherichia coli). The growth sequence, structural and morphology interface as well as the composition of the nanocomposite were examined and evaluated by the different characterization techniques. The respective potential application as an antimicrobial agent was evaluated and compared against Escherichia coli. The bio-mediated core-shell Ag-MgO nanocomposite showed characteristic synergetic UV-visible absorption bands at 290 nm for MgO nanoparticle and at around 440 nm for Ag nanoparticle, which moved to a lower wavelength of 380 nm in the composite. The shifting to a lower wavelength confirmed the reduction in the particle size as influenced by the growth rate optical property of biomolecular capped Ag-MgO nanocomposite from the phytochemical constituents in the peel extract of the Citrus paradisi. FTIR analysis further elaborated the role of the organic moieties in the Citrus paradisi extracts acting as the capping and stabilizing agent in the formation of the core-shell Ag-MgO nanocomposite. SEM analysis revealed an agglomeration of layered clustered particles, which was poly-dispersed while XRD showed the cubical crystal lattice network phase structure of the Ag-MgO nanocomposite. The TEM micrograph vii showed a structurally uniform and spherical biosynthesized Ag-MgO nanocomposite with a diameter of about 20–100 nm with an average particle size of 11.92 nm. The bi-layered Ag-MgO nanocomposite exhibited a higher level broad-spectrum of antibacterial potential on E. coli with 22 mm zone of inhibition and MIC of 20 (μg/mL) in comparison with the Ag (9 mm; 40 μg/mL) and MgO (9 mm; 80 μg/mL) nanoparticles. The leaching and toxicity level of the time-dependent releases of metal ions indicates that the effluents contain a lower concentration of Ag and Mg ions as compared to World Health Organization permissible limit of < 100 ppb (Ag). The biosynthesized Ag-MgO nanocomposite exhibited an enhanced antibacterial activity synergistic effect against E. coli than Ag and MgO nanoparticles, thus, proving to be a potential disinfect material against common pathogens in water treatment. Chapter 5 presented the biosynthesis, characterization, and assessment of simultaneous fluoride and pathogen removal potential in aqueous solutions of a multi-layered Ag-MgO/nanohydroxyapatite (Ag-MgOnHaP) composite. The successful incorporation of Ag-MgO into nanohydroxyapatite (Ag-MgOnHaP) sorbent via an in-situ solution-gelation (sol-gel) method was ascertained from UV-visible absorption spectrum bands at 290 and 440-378 nm typical of MgO and Ag nanoparticles combination in Ag-MgOnHaP composite. FTIR analysis showed the main surface functional groups involved to be –OH, C=N, carbonate and phosphate species on the backbone of Mg-O-Mg vibrational mode. The hydroxyl and amine groups indicated the interaction of a variety of metabolites components present in citrus peel extract as bio-reductive compounds associated with the Ag-MgO and also in fluoride ion exchange. SEM, TEM images and XRD analysis showed a well-dispersed discretely embedded layered-spherical Ag-MgOnHaP nanocomposite without any form of agglomeration after ultrasound exposure ranging in size from 20 to 100 nm with an average mean particle size diameter of 16.44 nm. The high purity of the synthesized Ag-MgOnHaP nanocomposite was confirmed by the presence Ag, Mg and O impregnated on the nanohydroxyapatite template from EDS spectrum analysis. Batch sorption studies using the nanocomposite under different experimental parameters were conducted and optimized. Equilibrium fluoride adsorption capacity of 2.146 mg/g at 298 K was recorded with more than 90% fluoride removal at optimized conditions of 60 min, 10 mg/L initial F- concentration, 0.3 g/L dosage, and pH 6 at 250 rpm. pHpzc of Ag-MgOnHaP nanocomposite was established to be 8. The equilibrium data were best fitted to the Freundlich isotherm model and followed the pseudo-second-order kinetics model at room temperature. The presence of competing anions such as Cl−, NO3−, does not have an impact on percentage fluoride uptake efficiency, but SO42− and CO32− reduce the F- removal efficiency. Moreover, as the concentration of the co-anions increased, fluoride adsorption uptake decreases. The biosynthesized nanohydroxyapatite incorporated Ag/MgO nanoparticle adsorbent (Ag-MgOnHaP) showed strong antibacterial activity against Escherichia coli and Klebsiella pneumonia when compared to hydroxyapatite alone. The presence and interaction between the Ag, MgO nanoparticles with the respective bacterial genomes was suggested to have accounted for this bioactivity. The synthesized Ag-MgOnHaP sorbent was found to portray a better sorption capacity compared to other adsorbents of similar composition in the literature and could be successfully regenerated with 0.01 M NaOH with fluoride removal of 74.24% at the 4th cycle of re-use. The impregnation of metal-metal oxide nanoparticles on sustainable natural biopolymers from waste products was presented in Chapters 6, 7 and 8. The use of these sustainable natural biopolymers (chitosan and cellulose) was targeted with more emphasis on surface functionalization, improved structural diversity and improved specific surface area with the sole aim of increasing the adsorptive capacity of fluoride ions as well as antimicrobial properties. The selected polymers were chosen because of their biodegradability, viii non-toxicity, renewability, selectivity and abundance in nature, which makes them promising starting materials for the purpose of sustainable water treatment. Chapter 6 presents the successful sol-gel biosynthesis, characterization, potential application for fluoride and pathogens removal from aqueous solution using Ag-MgOnHaP embedded on a chitosan polymer backbone (AgMgOnHaP@CSn) sorbent material. The overall formation of the AgMgOnHaP@CSn nanocomposite from different surface functionalization precursors and phases were supported by the various characterization methods such as UV–vis spectroscopy, SEM-EDS, FTIR, TEM, and Brunauer–Emmett–Teller (BET) techniques. Batch fluoride sorption experiments were conducted to assess fluoride uptake efficiency through optimization of several operational parameters such as contact time, adsorbent dosage, initial pH and co-competing anions. The antimicrobial activity of the synthesized AgMgOnHaP@CSn nanocomposites was also determined. The presence and bio-reduction processes of both Ag and MgO chemical species due to the interaction and coordination of bonds within the bioactive functional species of the polymer matrix was confirmed by the emergence of a sharp peak appearing at around 290 nm to a broad plateau plasmon absorbance above 440 nm on the AgMgOnHaP@CSn nanocomposite. FTIR analysis further supported the presence of the main bioactive functional species to be –OH, –NH2 CO32−, PO43-, Mg–O-Mg amongst other groups on the material surface. SEM and TEM displayed homogeneously dispersed particles within the aggregated biopolymeric composite with a diameter ranging between 5-30 μm. Pore sizes were observed to be in the micro-mesoporous range with an average size of about 35.36 nm and a pore diameter of 33.67 nm. The optimized conditions were as follows: 30 mins contact time, a dose of 0.25 g/50 mL, adsorbate concentration of 10 mg/L F-, initial pH 7 while adsorption capacity decreases with increase in temperature. AgMgOnHaP@CSn composite has a pHpzc value of ≈ 10.6 and the maximum sorption capacity was established to be 6.86 mg/g for 100 mg/L F- concentration at 303 K. The effect of co-existing anions was observed to be of the following order: Cl- < NO3- < SO42- << CO32-. The fluoride sorption experimental data was well described by Langmuir adsorption isotherm while the sorption reaction mechanisms were diffusion-controlled and followed the pseudo-second-order sorption model. F- sorption process could best be described as a combination of ligand exchange, electrostatic attraction, and improved structural surface modification. The antimicrobial susceptibility analysis through the zone of inhibition (mean and standard deviation) showed the potency to pathogens of the following order: Staphylococcus aureus > Escherichia coli. Chapter 7 gives an insight into the development of cellulose nanofibrous matrix (isolated from saw-dust) decorated with Ag-MgO-nanohydroxyapatite (CNF-AgMgOnHaP) and its application in fluoride and pathogen removal from contaminated water. The synthesized CNF-AgMgOnHaP, unlike the cellulose nanofiber, showed characteristic absorption bands in UV–vis spectroscopy between 270-290 nm typical of MgO together with a broad band around 420 nm associated with the characteristic of silver nanoparticles. FTIR spectrometry suggested the presence of nanohydroxyapatite (nHaP) and MgO species impregnation within the CNF matrix. SEM, TEM, XRD, and EDS analysis showed a well-established structural and morphological modifications between cellulose nanofiber alone, biosynthesized CNF-AgMgOnHaP and fluoride sorbed CNF-AgMgOnHaP nanocomposite. A granulated aggregation of micro-mesoporous particles with an improved BET surface area of 160.17 m²/g was developed. Optimum fluoride sorption capacity was 8.71 mg/g for 100 mg/L F- solution at 303 K. F- sorption capacities decreased as the operating temperatures increases. Optimum F- removal of 93 % was achieved at optimum conditions established: pH 5, solid/liquid ratio of 0.25 g/ 50 mL, 10 mg/L F-, contact time 10 min, temperature 25 ± 3 °C and shaking speed of 250 rpm. Percent F- removal decreased with increasing initial adsorbate concentration. The pHpzc value of the CNF-AgMgOnHaP occurred at ≈ 4.7. Co-existing ions were observed to have an effect on the adsorption of F- in the following order: NO3- < Cl- < SO42- <<CO32-. Equilibrium fluoride sorption onto the CNF-AgMgOnHaP was best described by non-linear Freundlich isotherm model across all the operating temperatures. The linear Dubinin-Radushkevvich (D-R) model for F- sorption energies were in the 3.54 – 4.08 kJ/mol across all operating temperature. This suggested the physical adsorption mechanism processes were involved in the F- uptake by the CNF-AgMgOnHaP sorbent. The overall kinetic results indicated that the mechanisms not only depend on the pseudo-second-order process but were also governed by mass transfer of the adsorbate molecules across the CNF-AgMgOnHaP surface. The thermodynamic parameters revealed that the sorption process of F- onto CNF-AgMgOnHaP was endothermic and spontaneous at the sorbent/solution interface. The regeneration-reuse study showed that the synthesized adsorbent can be reused for a maximum of 5 adsorption-desorption cycles using Na2CO3 and NaOH as regenerants. Overall surface chemistry by XPS, FTIR, EDS as well as sorption isotherm and kinetic models analysis suggested that both physical and chemical adsorption processes were involved in the fluoride uptake by CNF-AgMgOnHaP nanocomposite. The observed zone of inhibition demonstrated that CNF-AgMgOnHaP adsorbent possesses antibacterial activity against all the bacterial strains in the following order: E. Coli > S. aureus > K. pneumonia. The antibacterial potency increased with increasing sorbent concentration. In chapter 8, Defluoridation and antimicrobial activity of synthesized cross-linked cellulose-chitosan impregnated with the developed nanomaterial (AgMgOnHap) are presented. The before and after fluoride sorption by the synthesized CECS@nHapAgMgO nanocomposites were characterized using several physical and chemical techniques which include, BET, SEM-EDS, TEM, XPS, XRD, and FTIR. The overall batch fluoride sorption processes and adsorption capacity through optimization of different experimental sorption parameters, sorption isotherms, and kinetic mechanisms as well as antibacterial potency were studied and reported. SEM and TEM analysis showed densely irregular multiple-layered structures, homogeneous deposition of the AgMgOnHaP on the polymeric matrices. Equilibrium fluoride sorption capacity on CECS@nHapAgMgO sorbents showed an increased affinity of 26.11 mg/g for 150 mg/L F- solution at 313 K.at optimized conditions of 40 min contact time, dosage of 0.3 g and pH of 5. The pH point of zero charge was found to be 7.27. The reaction pathway model sequence of fitness follows the order Pseudo first order < Elovich < Pseudo-second order kinetic model while intra-particle diffusion model and mass transfer of fluoride molecules from the external surface onto the improved pores of the adsorbent were found to be involved in the rate-controlling step. Although both non-linear Langmuir and Freundlich isotherms showed appropriate trends in the F- sorption process, the adsorption isotherm data were better fitted to the non-linear Freundlich isotherms models, suggesting stronger heterogeneous adsorption onto the active binding sites of the CECS@nHapAgMgO surface. The fluoride sorption was observed to be a favorable process across the operating temperatures. Temkin heat of sorption (BT) and the mean free adsorption energy (E) of the D-R isotherm model was within the range of 0.68-3.39 J/mol and 1.58 -7.45 kJ/mol respectively. The fluoride sorption process was observed to be temperature-dependent; while adsorption capacities (Qm) and Temkin heat of sorption (BT) increased with increasing temperature, D-R Mean free sorption energy (E) decreased at higher temperatures. The thermodynamic analysis demonstrated that fluoride sorption on the CECS@nHapAgMgO surface was exothermic, feasible and spontaneously inclined with a decrease in the degree of randomness at the sorbate-sorbent interface. The influence of co-existing anions on fluoride removal exhibited the following trend Cl−< NO3− <SO42- << CO32- <<HCO3−. The practical and economic viability, potential for regeneration showed its reusability up to 3 cycles with water and Na2CO3 as regenerants. The potential ability of CECS@nHapAgMgO to disinfect both gram- positive and gram-negative water bacterial was confirmed by the zone of inhibition and Minimum Inhibitory Concentration (MIC) measurements. The observed values showed the inhibitory efficiency in the following order: S. aureus > E. Coli > K. pneumonia where the MIC values of 20 μg/mL were recorded for S. aureus and E. Coli respectively and 10 μg/mL for K. pneumonia. Lastly, the applicability of the sorbents was tested with a field water sample collected from a high fluoride borehole water from a local village (Lephalale Municipality of Limpopo province, South Africa). The before and after analysis showed the excellent potential of CECS@nHapAgMgO sorbent in removing fluoride. In conclusion, the successful surface functionalization synthesis of these improved surface area hybrid nano-sorbents supported by the different morphological techniques was found to be effective in creating more surface-active binding sites for fluoride adsorption and disinfection of waterborne pathogens from aqueous solution. The originality of this developed sorbent lies firstly, in the ability to simultaneously remove both chemical and biological water pollutants; secondly, the use of biodegradable, eco-friendly and non-toxic abundance wastes raw materials to develop a water purification material and in solving waste management issues was a key factor towards environmental sustainability. Above all the developed materials were established to possess superior fluoride adsorption capacity when compared to other reported sorbent materials. Lastly, the project findings /innovation will contribute to Sustainable Development Goals (SDG) 3 and 6, aimed at improving clean water supply and health of the communities and the world at large. However, the following recommendations were made following the findings from this study: 1) In order to increase the surface area to volume ratio, greater selectivity, porosity, and mechanical stability of the polymers as well as size-exclusion mechanism without a large energy penalty of the microbes and fluoride ion for effective water treatment, a more effective and an enhanced multifunctional, multi-layer nanofibrous hybrid sorbent through electrospinning techniques should be considered for future work, 2) More studies on the mode of actions and morphological changes in the pathogens leading to the cell death through the influence of the nanocomposites should be further explored, 3) Application of this advanced technology vis-à-vis other biomaterials to generate filter membrane towards efficient microbial removal and deflouridation is a great challenge worth looking at, 4) Lastly, materials developed in the present study should be modeled, tested and fabricated at the point of use for fluoride and pathogen removal at household level. / NRF

PhDENV (Hydrology) / Department of Hydrology and Water Resources / This study developed operating rules for groundwater supply from a probabilistic (risk-based) approach. Groundwater supply systems are often operated without relating groundwater yield/availability to demand which makes groundwater resource planning and management challenging and unpredictable. Risk-based approaches for developing groundwater operating rules comprehensively incorporate assurance of supply and also account for uncertainty due to model inputs, model structure and climate variability. A groundwater resource unit (GRU) was delineated and its hydrogeological conceptual model developed. Automatic curve matching was used to identify appropriate aquifer models and test solutions for estimating hydraulic characteristics (storativity, transmissivity and hydraulic conductivity) based on Aquifer Test Solver (AQTESOLV) Pro version 4.5. Limited groundwater levels and rainfall data were infilled and/or extended using Output Error-Nonlinear Hammerstein Weiner (OE-NLHW) and non-parametric regression (NPR), respectively. Performances of these models were based on relative error (RE), correlation coefficient (COR), root mean square error (RMSE), coefficient of determination (R2) and Nash Sutcliffe coefficient of efficiency (NSE). A program for generation of monthly groundwater levels for the GRU was coded in FORTRAN based on the revised version of the Pitman model (referred to as GW-PITMAN model). The model was calibrated using groundwater levels from a neighbouring borehole due to lack of observed representative data for the GRU. Validation was done by establishing the realistic nature of simulated runoff, recharge and groundwater levels. A Variable Length Block (VLB) bootstrapping model was used for simultaneous generation of stochastic inputs (rainfall, evaporation and groundwater levels) of the groundwater operating rules model. Operating rules were developed from statistical analysis of 100 base yields for the GRU simulated from 5-year long stochastically generated sequences (with length of 34 years) of rainfall, evaporation and groundwater levels. The hydrogeological conceptual model indicated presence of faults and diabase dykes which influence preferential flow paths and storage of water in the aquifer. Identified aquifer test solutions were found to be suitable for estimation of hydraulic characteristics, since they had generally good model fits and low mean residual errors. Heterogeneous aquifer types were identified though leaky aquifer dominated. Storativity, transmissivity and hydraulic conductivity values ranged from 0.0003-0.060, 0.78-12.3 m2/day and 0.074-0.460 m/day, respectively, indicating limited storage with potential for local groundwater supply for private consumption. Graphical fits for observed and estimated rainfall and groundwater levels were mostly comparable, though scatter plots indicated cases of underestimation and overestimation of observed values. R2, COR, NSE, RMSE and RE values were 0.76 and 0.7, 0.87 and 0.84, 0.75 and 0.68, 3.67 and 3.03 mm and 30 and 29% for both calibration and validation runs, respectively, for NPR model. R2, COR, NSE, RMSE and RE were 0.99 and 0.86, 0.97 and 0.93, 0.99 and 0.84, 0.03 and 0.01 m and 0.08 and 0.11% for both calibration and validation runs, respectively, for OE-NLHW model. The models were therefore found to have efficient calibration and validation, and were thus, suitable for data extension. Estimated groundwater levels, streamflow and groundwater recharge for both calibration and validation runs of the GW-PITMAN model, generally fluctuated with changes in rainfall, indicating that they are realistic. Majority (9 out of 10) of the historical statistics were mostly well preserved by VLB, except for skewness. Historic highest groundwater levels were also not well preserved. Superimposing the cumulative demands on the base yield curves and analysis of percentages of water demands that can be supplied indicated that the groundwater system could not meet the water demands at all times. To promote sustainable multipurpose use of water that can enhance rural livelihoods, allocating water using priority classification was found to be essential. Operating rule curves for groundwater supply were derived using a risk-based approach. The operating rule curves indicated that if priority classification is used all water demands are met up to maximum groundwater level of 25 m. The developed operating rule curves are therefore expected to improve water supply to both domestic and productive water uses, if they are adequately implemented and hence improve livelihoods. The procedures followed in developing risk-based groundwater operating rules for Siloam Village were summarised to assist in their application in any delineated groundwater resource unit. Though minimal infrastructure is available to support implementation of the operating rules, additional monitoring boreholes are required to aid in estimation of average groundwater levels for further calibration and validation of the GW-PITMAN model. Detailed geological and geophysical investigation are required to improve on characterisation of the GRU and its hydrogeological conceptual model. Undertaking a study of this nature in other areas including those which are data-scarce could promote wide implementation of risk-based groundwater operating rules. / NRF

Thesis (MSc)--Stellenbosch University, 2005. / ENGLISH ABSTRACT: Water resources in South Africa are limited and groundwater plays an important role in supporting basic human needs, sustaining ecosystems and enabling industrial and agricultural development. Sound management practices are necessary to ensure sustainable development of water resources. All groundwater usage must be licensed in compliance with the National Water Act of 1998. A Spatial Decision Support System (SDSS) can be used to assist in the groundwater usage licensing process of the Department of Water Affairs and Forestry (DWAF). The main aim of this study was to develop a SDSS, named Groundwater Abstraction & Licence Evaluation Tool (GALET), that could assist in the process of allocating water use licences and determining the local impact of abstraction, based on existing theory and data. The development was done within ArcView 3.2 using the scripting language Avenue. The Sandveld, an arid stretch of land along the west coast of South Africa that is heavily impacted by groundwater abstraction, was the chosen study area. The data collected for this study included existing borehole, recharge, rainfall and geological information. GALET proved to be capable of calculating essential information needed to evaluate groundwater abstraction, which included drawdown in the water table, zone of influence and the possible effects on features such as rivers and wetlands. Targeted potential users regarded GALET as a useful tool in the process of licensing and groundwater abstraction impact assessment and plans are under way to implement GALET or a derivative thereof at the DWAF regional offices. / AFRIKAANSE OPSOMMING: Waterhulpbronne in Suid-Afrika is beperk en grondwater speel 'n belangrike rol in die ondersteuning van basiese menslike behoeftes, volhouding van ekosisteme asook industriële en landbou-ontwikkeling. Betroubare bestuurspraktyke is noodsaaklik om die volhoubare ontwikkeling van waterhulpbronne te verseker. Alle grondwatergebruik moet volgens die Nasionale Waterwet van 1998 gelisensieer word. 'n Ruimtelike Besluitnemings Ondersteuning Stelsel (RBOS) kan as 'n hulpmiddel gebruik word in die lisensiëringsproses van die Departement van Waterwese en Bosbou. Die hoofdoel van hierdie studie was om 'n RBOS, genoem Groundwater Abstraction & Licence Evaluation Tool (GALET), te ontwikkel wat as hulpmiddel gebruik kan word in die allokeringsproses van watergebruiklisensies en die bepaling van die impak van grondwateronttrekking op die omgewing, gebaseer op bestaande teorie en data. Die ontwikkeling is in ArcView 3.2 met die programmeringstaal Avenue gedoen. Die Sandveld, 'n ariede streek aan die weskus van Suid-Afrika wat onderhewig is aan grootskaalse grondwateronttrekking, is gekies as die studie area. Die data wat vir hierdie studie ingesamel is sluit bestaande boorgat, grondwateraanvulling, reënval en geologiese inligting in. GALET was in staat om belangrike inligting aangaande die evaluering van grondwateronttrekking te bereken, o.a. die daling van die grondwatervlak, die impaksone en die moontlike effekte op landvorms soos riviere en vleilande. Die teikengroep potensiële gebruikers het GALET as 'n nuttige hulpmiddel in die proses van lisensiëring en grondwateronttrekking impakbepaling beskou en planne is onderweg om dit of 'n aangepaste program by die streekskantore van die Departement van Waterwese en Bosbou te implementeer.

MESHWR / See the attached abstract below

Thesis (MSc)--University of Stellenbosch, 2004 / ENGLISH ABSTRACT: The Sandveld, a potato growing area of the Western Cape is subject to significant groundwater abstraction for both municipal and agriculture purposes. The climate is arid and sensitive and important ecosystems in the area are showing varying degrees of impact. Management measures are needed to ensure ongoing sustainable development of the area. In this study, different interpolation techniques were evaluated to calculate values for unsampled variables rainfall and groundwater elevation. Local deterministic techniques as well as geostatistical techniques were used. It was found that geostatistical techniques, especially with collateral information, such as topography, provided a more accurate result. For environmental studies of this nature, Kriging is recommended as interpolation technique. The underlying data will determine the selection of the particular type of Kriging. Data was extracted from a customized relational database, geoMon, used for data capture, retrieval, processing and reporting. Ease of data extraction facilitated analysis. The interpolated grids were applied in two scenarios: Recharge calculations and quantification as well as a new classification approach according to Resource Directed Measures (RDM). Management classes were defined based on GIS-derived data. / AFRIKAANSE OPSOMMING: Die Sandveld, ‘n aartappelverbouingsgebied in die Wes-Kaap, ondergaan aansienlike grondwateronttrekking vir beide munisipale sowel as landbou doeleindes. Die klimaat is dor en droog en sensitiewe en belangrike ekosisteme in die area ondervind wisselende impakvlakke. Bestuursmaatreëls word benodig om volhoubare ontwikkeling van die area te verseker. In hierdie studie is verskillende interpolasie tegnieke om onbekende waardes vir veranderlikes gebruik in grondwater evaluasie te bereken, evalueer. Lokale deterministiese tegnieke sowel as geostatistiese tegnieke is gebruik. Geostatistiese tegnieke, veral gebruik saam met addisionele inligting soos topografie, bereken meer akkurate resultate. Vir omgewingsstudies van hierdie aard, word Kriging aanbeveel as interpolasie tegniek. Eienskappe van die onderliggende data word gebruik om die tipe Kriging aan te dui. Data is onttrek uit ‘n gebruikersaangepaste databasis, geoMon, wat gebruik is vir datavaslegging, onttrekking, prosessering en verslaggewing. Die gemak waarmee data onttrek kon word het analise vergemaklik. Geïnterpoleerde data is gebruik vir grondwateraanvullingsberekeninge en -kwantifisering sowel as ‘n nuwe benadering tot klassifikasie volgens hulpbron gerigte maatreëls. Bestuursklasse gebaseer op GIS-afgeleide data, is gedefinieer.

The study presents the spatio-temporal assessment of groundwater-surface water (GW-SW) interaction aspects in the Schoonspruit River catchment, North West of South Africa. The research study aimed at improving understanding of groundwater and surface water interaction through assessing its location and time when such interaction occurs. GW-SW interaction sites were identified using principal aquifer type characterization methods. The occurrence of the interaction was established using hydrochemistry methods and the effectiveness of the existing monitoring methods were evaluated in their consideration of GW-SW interaction within the study area. The main results from the study showed that there was GW-SW interaction in the Schoonspruit River catchment which was not affected by seasonal changes. The result further showed that existing monitoring methods in the study catchment were not effective in addressing GW-SW interaction. The study concluded that qualitative methods are essential in studying GW-SW interaction and that monitoring methods for such interactions are required / Centre for Sustainable Agriculture and Environmental Sciences / M. Sc. (Environmental Management)

No description available.

An investigation into the quality of surface water and ground water was conducted during 1988 in the 38,8 km² Hout Bay River catchment near Cape Town. The main objective of the study was to determine those areas and activities which constitute a pollution source and to ascertain the relative proportion which each contributes to the pollution problem and health risk of the surf zone of the beach at Hout Ba . The objective was achieved by monitoring the chemical and microbiological attributes of the Hout Bay River, its tributaries and stormdrains in wet and dry conditions on a routine basis and during storm events. Hout Bay is a rapidly developing residential area in which sewage disposal occurs by means of septic tank soakaway systems. Ground water quality was monitored to investigate the contribution to contamination by septic tank effluent. Results showed that stormdrain effluent in dry and wet conditions and surface runoff during rainfall were the main vectors of pollution. Although the pollution concentration was high during dry conditions the greatest pollution discharge to the surf zone of Hout Bay occurred during storm events. In view of the proposed residential development it is imperative that pollution control measures be undertaken so as to secure the future recreational and aesthetic value of Hout Bay

Hydrogeologists have faced serious challenges worldwide in the characterization of fractured rock aquifers due to the heterogeneous nature of the imbedded geology. The bulk flow parameters in the Karoo strata in South Africa are specifically uncertain since most models are based on homogenous block systems. As part of a WRC research project, entitled “Measurement of the bulk flow and transport characteristics of selected fractured rock aquifer systems in South Africa”, this study focuses on the characterization, borehole drilling, flow parameter measurements and groundwater quality assessment of the Balfour Formation in the Beaufort Group of the Karoo Supergroup in the Eastern Cape, South Africa, which is seriously heterogeneous in deposition and has also been largely neglected as drilling targets for groundwater. The Balfour Formation comprises mostly mudstone, shale and sandstone, formed in a braided and meandering river system. In addition to the heterogeneous deposition, the flow pathways in this aquifer system are not fully understood due to lack of actual measurement data. The methods used in this study include field mapping, site characterization, borehole drilling, and pumping and tracer testing in order to obtain the borehole yield, aquifer transmissivity, storativity and groundwater flow velocity. In addition, the groundwater chemistry was also studied to determine quality for use and possible connectivity with the nearby Tyume River and to determine potential sources of groundwater contamination. The results obtained include: 1) The study area is predominantly mudstone/shale with thin layers and lenses of siltstone and sandstone, which are interbedded; 2) Two boreholes were successfully drilled, which had yields in excess of 10 l/s in four water levels (at 7, 22, 54 and 65 m); 3) The estimated average transmissivity is 246 m 2/day according to the recovery test; 4) The estimated seepage velocity is 120 m/day according to tracer tests in the aquifer between the two boreholes which are 5 m apart; and 5) The water chemical type is the combination of HCO3-, Cl-and SO42- , which is distinguishable from that of the Tyume river; 6) There is no evidence for groundwater recharge to the deep aquifers from the Tyume river, based on the differences of the water chemistry; 7) The elements Ca, Cl, Na and C are distributed more than 90% as free ion species in BH2 borehole water; and 8) The groundwater in BH2 borehole is undersaturated (negative SI) with respect to some minerals (for example: anhydrite, fluorite, gypsum and halite), oversaturated (positive SI) with respect to some minerals (for example: aragonite, calcite and dolomite). It is concluded that there is a great potential to obtain drilling targets for high yielding boreholes in the sedimentary rocks of the Balfour Formation in the Karoo Supergroup.