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

This study utilized GIS and statistical methods to map the spatial variability of nitrate and related groundwater constituents in 30 counties above the Seymour Aquifer, analyze temporal patterns of nitrate pollution, identify probable sources of pollution, and recommend water development strategies to minimize exposure to nitrate and reduce future aquifer contamination. Nitrate concentrations in excess of 44 mg/L (US EPA limit) were commonly observed in the Seymour Aquifer region, especially in the central agricultural belt. Data indicated that this is an ongoing problem in the Seymour Aquifer and that agricultural activity and rural septic systems are the likely sources of the nitrate. Inconclusive results emphasized the need for a more comprehensive spatial and temporal water quality monitoring.

M.S.

Excessive nitrates in drinking water pose a human health threat, especially to infants. Methemoglobinemia, or blue-baby syndrome, is a potentially fatal condition that inhibits the ability of red blood cells to bind and transport oxygen. Nitrates/nitrites have also been linked to such conditions as cancer, birth defects, and behavioral and developmental abnormalities. Nitrates are frequently found in wells in rural farming areas because synthetic fertilizers (containing nitrates) leach from the soil into the groundwater. The Lower Umatilla Basin (LUB) in Morrow and Umatilla counties of Oregon represents an intensively farmed and irrigated area in which relatively high amounts of nitrates are present in the groundwater and domestic well water. This study investigated population demographics for the rural Lower Umatilla Basin, comparing these data to identified well-water nitrate levels for the purpose of estimating nitrate exposures and potential risk of adverse health effects in the survey area. Results of the investigation revealed that 25 percent of the domestic-use wells in the survey area had nitrate levels that were in excess of the 10 ppm nN MCL for drinking water, as established by the U.S. Environmental Protection Agency. From access to these wells, 23 percent of the surveyed population was exposed to nitrate concentrations in excess of the MCL standard. However, resident infants were neither exposed to well-water nitrates in excess of the standard, nor were they exposed to illness that could have increased the risk of methemoglobinemia. The LUB survey population was generally older than the populations from cities in the LUB or the combined populations of rural areas of Morrow and Umatilla counties. The population included few women of childbearing age, and it was not subject to an appreciable increase in the proportion of younger to older families. These factors reduced the likelihood of a significant increase in the infant population, which also minimized the risk of methemoglobinemia to this population. Even though the risk of methemoglobinemia to infants was low in the LUB area, it is recommended that exposures to well-water nitrates be prevented, if possible even for adults, to reduce the potential for chronic, adverse health effects from excess nitrate ingestion. Continued monitoring of private wells by state agencies is recommended, with attention directed at domesticuse wells with nitrate levels in excess of 10 ppm nN. This information should be shared with local health departments for follow-up, investigation, and educational efforts as needed. Future studies by the Oregon DEQ, or other agencies which seek to document the sources of well-water nitrate contamination in the LUB, should include an investigation of the influence of local sources of nitrate contamination. / Graduation date: 1993

The purpose of this study was to evaluate the level of nitrate contamination in the water in Cherry Valley. It examines the theory that human effluent is the source of the nitrate and evaluates the role of politics in the nitrate issue.

Modern pig farming production may over burden the environment with organic substances, exposure of bacterial pathogens and introduction of resistance gene. This may be caused by the pig’s droppings, lack of seepage management or accidental spillage of seepage which may impact on the environment and its physicochemical parameters. The objective of this study is to determine and assess the level of bacteriological pollution emanating from the pig farm and their impact on the physicochemical parameters of soil and water as well as to identify the presence of antibiotic resistance gene of these prevailing bacteria. Soil and water samples were collected monthly for a period of six months (March- August 2013). Samples were collected at pig enclosures, soil 20 m and 100 m away from pig enclosures, constructed wetland used for treating pig farm wastewater, soil 20m and 100 m away from constructed wetland. Procedure followed for analysing soil and water samples includes physicochemical analyses, viable cell counts of 10-1 to 10-8 dilutions, identification of bacteria using API 20E test kit, antibiotic susceptibility analyses, and identification of resistance gene using molecular procedures. The media that were used for viable cell counts were, Nutrient agar, MacConkey Agar, Xylose Lysine Deoxycholate agar (XLD agar), and Eosin Methylene Blue (EMB). Physicochemical parameters of water showed unacceptable high levels of analysed parameters for BOD (163 mg/L to 3350 mg/L), TDS (0.77 g/L to 6.48 mg/L), COD (210 mg/L to 9400 mg/L), NO3 (55 mg/L to 1680 mg/L), NO2 (37.5 mg/L to 2730 mg/L), and PO43− (50 mg/L to 1427 mg/L) were higher than the maximum permissible limits set by Department of Water Affairs and Forestry (DWAF). For soil samples TDS (0.01g/L to 0.88 g/L), COD (40 mg/L to 304 mg/L), NO3 (32.5 mg/L to 475 mg/L), and NO2 (7.35 mg/L to 255 mg/L) and PO43- (32.5 mg/L to 475 mg/L ) were observed to be higher than recommended limits set by Federal Ministry for the Environmental (FME). The viable cells in soil samples 30cm depth ranged from 0 cfu/mL to 2.44 x 1010cfu/mL, in soil 5cm depth ranged from 1.00 x 101 cfu/mL to 1.91 x 1010 cfu/mL, and in water samples viable cells ranged from 5.00 x 101 to 5.05 x 109. Pseudomonas luteola (Ps. luteola), Escherichia vulneris (E. vulneris), Salmonella choleraesuis spp arizonae, Escherichia coli 1(E. coli 1), Enterobacter cloacae, Pseudomonas flourescens/putida (Ps. flourescens/putida), Enterobacter aerogenes, Serratia ordoriferal, Pasteurella pneumotropica, Ochrobactrum antropi, Proteus vulgaris group, Proteus vulgaris, Salmonella spp, Aeromonas Hydrophila/caviae/sobria1, Proteus Mirabillis, Vibrio fluvials, Rahnella aquatillis, Pseudomonas aeruginosa (Ps. aeruginosa), Burkholderia Cepacia, Stenotrophomonas maltophilia (St. maltophilia), Shwenella putrefaciens, Klebsiela pneumonia, Cedecea davisa, Serratia liquefaciens, Serratia plymuthica, Enterobacter sakaziki, Citrobacter braakii, Enterobacter amnigenus 2, Yersinia pestis, Serratia ficaria, Enterobacter gergoriae, Enterobacter amnigenus 1, Serratia marcescens, Raoutella terrigena, Hafnia alvei 1, Providencia rettgeri, and Pantoa were isolated from soil and water samples from the pig farm. Isolates were highly resistant to Penicillin G, Sulphamethaxazole, Vancomycin, Tilmocozin, Oxytetracycline, Spectinomycin, Lincomycin, and Trimethoprim. The most resistance genes detected in most isolates were aa (6’)-le-aph (2”)-la, aph (2”)-lb, aph (3”)-llla, Van A, Van B, Otr A and Otr B. Pig farm seepage is causing bacterial pollution which is impacting negatively on the natural environment in the vicinity of pig farm by introducing bacterial pathogens that have an antibiotic resistance gene and is increasing the physicochemical parameters for soil and water in the natural environment at the pig farm. It is therefore recommended that pig farms should consider the need to implement appropriate regulatory agencies that may include the regular monitoring of the qualities of final effluents from waste water treatment facilities. In addition there is a need to limit soil pollution in order to safe guard the natural environment in the vicinity of pig farm from bacteriological pollution and introduction of antibiotic resistance gene. It is also recommended that more advanced technologies should be introduced that will assist pig farms to manages the seepage properly. / Environmental Sciences / M. Sc. (Environmental Sciences)

Light Non-Aqueous Phase Liquids (LNAPLs) are used throughout the world for numerous applications, the most well-known being automotive fuels, such as petrol and diesel. The widespread production, distribution, storage and use of LNAPLs results in the ubiquitous occurrence of spillage to ground (Geller et al, 2000). Considering the hazardous nature of most LNAPLs due to their explosive and toxic characteristics, releases of LNAPLs to ground have well documented human health and ecological consequences. The occurrence of leaking underground and above-ground storage tanks at service stations and consumer installations is a common cause of contamination; and is described in literature for various countries of the world (Dietz et. al., 1986; Moschini et al, 2005; Mulroy and Ou, 1997; Harris, 1989; The Institute of Petroleum, 2002). Little failure data are however available for the South African context. In addition to this, data concerning the location and characteristics of sites storing LNAPLs in South Africa is similarly scarce. The study analysed data from three sources, namely the eThekwini Fire and Emergency Services data, GIS data and data from a local consultancy, in order to determine whether certain factors increased contamination risk posed by these facilities. The results indicated that contamination may be a result of numerous factors, but primarily line and tank failure. The type of installation was also found to have a significant influence on whether a site would be contaminated or not. In addition to the above, the results indicated that certain circumstances increase the severity of loss. The results indicated the need for more investigation to be performed into contamination as a result of LNAPL loss to ground, and the need for protective measures to be implemented for high risk sites where the likelihood and severity of a potential loss is high. Focus should then be centred on the probability of failure of non-ferrous pipework and GRP tanks to ensure adequate protective mechanisms are in place in the event of a failure of this newer infrastructure. In addition, a review of regulatory control of LNAPL storage in South Africa and the eThekwini Municipality, with reference to the international context, indicated the need for a specific department within the local government structure that manages LNAPLs with the objective of reducing contamination incidents. The continued use of underground storage of LNAPLs will always present a risk of failure/contamination due to the unseen nature of the installations and related infrastructure. It is this risk that requires regulatory management. Details of contaminated sites in South Africa should be within the public domain. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2011.

Effluent from on-site sewage treatment and disposal systems (OSTDS) is generally known to impact groundwaters and surface waters with nitrogen (N) and phosphorus (P) and other contaminants. Little research has quantified this problem along the Indian River Lagoon (IRL), especially in Indian River County (IRC) where there are 26,660 active systems. This study assessed the effects of OSTDS on contamination of surface and groundwaters along three urbanized canals and the St. Sebastian River in IRC, all of which flow into the Central IRL. Multiple lines of evidence were used to define the source of the nutrient loadings including the novel approach of using the artificial sweetener, sucralose, as an indicator of human sewage impact. Results indicate that areas with high densities of OSTDS are contributing N to surface waters and elevating N:P ratios through submarine groundwater discharge and promoting eutrophication in the Central IRL. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2014. / FAU Electronic Theses and Dissertations Collection

Post-remediation soil, ground and surface water monitoring is essential to assess the effectiveness of remediation efforts undertaken to eliminate or minimize the risk of pollution to human health and valuable ecosystems. In that regard, comparison of pollution levels pre- and post-remediation is an effective way of evaluating the effectiveness of the remediation techniques used. Thus, this study sought to measure concentrations of pollutants in the soil, ground and surface water post remediation in Steel Valley, Vanderbijlpark and compare them to concentration levels prior to remediation, as well as compare them to internationally accepted standards with respect to risk to humans and the environment. Water samples were collected from three locations within the study site, in both the dry and rainy seasons and their physio-chemical and organic properties were tested. Soil samples were collected from six different locations within the study site and analysed for metal concentrations. The data was compared against that of the Iron and Steel Corporation (ISCOR) Vanderbijlpark Environmental Master Plan (EMP), water and soil guidelines of the World Health Organization (WHO) as well as South African water and soil guidelines. The study found that groundwater is generally safe for domestic use but Aluminium (Al), Iron (Fe) and Manganese (Mn) concentrations were above South African water quality guideline levels – with their concentrations ranging from 0.54 to 0.91 mg/L, 1.01 to 1.86 mg/L and 0.24 to 0.53 mg/L respectively. There were no traces of organic pollution in the water samples. Soil samples had levels of Al ranging from 1106 mg/kg to 1 3621 mg/kg, Mn concentrations in the range of 202.8 to 966.4 mg/kg and Fe ranging from 1 1587 to 23 201 mg/kg. Thus, water and soil at the selected sites are safe in terms of physico-chemical and organic quality. Natural attenuation should be able, over time, to further reduce the levels of parameters that are currently above the target range. Thus, there has been considerable reduction in pollutant concentrations, but as this study was limited in scope, additional research is needed to verify the results. / Environmental Sciences / M. Sc. (Environmental Science)

Spatially explicit ecosystem service valuation (ESV) allows for the identification of the location and magnitude of services provided by natural ecosystems to human activities along with a measure of their significance based upon economic valuation. While ESV has been used to provide new insight into land use management, few studies have identified the connections between the values of ecosystem services and ecological sensitivity to nitrogen loading despite a growing body of ecosystem service literature. This research combines a GIS-based, value transfer approach to map ecosystem services in the Lower Yakima River Basin (LYRB), Washington, USA, along with estimates of nitrogen loading to identify how nitrogen management may affect ecosystem services in the basin. This analysis combines values of ecosystem services with estimates of nitrogen loading and identifies subwatersheds and specific parcels within a Groundwater Management Area (GWMA) most susceptible to reductions in ecosystem services due to excess nitrogen loading. Based on the benefit transfer analysis, wetlands and forested areas have disproportionately high values of ecosystem services when compared to their land area in the LYRB, while pasture and cultivated crops contribute much less to the total value of ecosystem service flows in proportion to the total area in the LYRB. Across the study area estimated nitrogen loads are strongly driven by the location of concentrated animal feeding operations (CAFOs) and cultivated crops. Areas of particularly high nitrogen loading and high ESV may highlight specific areas for achieving immediate success in increasing or maintaining ecosystem services through appropriately focused regulatory mechanisms. The land cover analysis however, completely neglects the values and importance of subsurface processes and groundwater resources in ecosystem service assessment, and therefore an econometric model is applied to estimate willingness to pay (WTP) to maintain safe nitrate levels in private wells. Through the incorporation of WTP estimates for groundwater quality, a more complete economic and ecological perspective on the effects of landscape N loading in the study site is highlighted. The results of these estimates clearly indicate that ecosystem services from groundwater should be considered to have significant value in the LYRB. Further economic valuation data on specific land cover types and the value of groundwater quality, whether from primary studies or meta-analysis, is needed to refine relative measures of ecosystem service values and more confidently describe these values in specific dollar amounts. Additionally, limits in spatial data resolution may contribute to errors in location and magnitude of ecosystem services, and is an area in need of further development. Despite these potential limitations, this analysis highlights a promising direction for combining spatially explicit ecosystem service valuation with nutrient loading data to identify the location and potential magnitude of effects on ecosystem services from management practices. / Graduation date: 2013