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Thesis (Ph.D. (Biochemistry)) --University of Limpopo, 2010 / A heavy-metal resistant bacterium (GM 16) was isolated from a South African antimony mine, and the non-viable cells of the isolate were used to investigate its biosorption capacity for Cd(II) and Cu(II) from aqueous solution in a batch process. The biosorption of both metals were found to be influenced by factors such as pH of the metal solution, initial metal ion and biomass concentrations, rate of agitation, presence of other metal ions, contact time of the metal solution with the biomass and temperature. The initial biosorption of both Cd(II) and Cu(II) was rapid and equilibrium was reached within 1 hour of biomass contact with the metal solutions. The sorption of both metal ions was higher in weak acid than in strong acid conditions and the optimum pH values for Cd(II) and Cu(II) biosorption were 7 and 6, respectively. The presence of the other metal ions in the metal adsorption media influenced the biosorption of both Cd(II) and Cu(II). Mg2+ ions decreased the uptake of Cu(II) and Cd(II) by 4.7 and 6.5 %, respectively. Whereas K+, Na+ and Ca2+ ions increased the uptake of Cd(II) by 12.3, 8.7, and 3.2 %, respectively, they slightly decreased the sorption Cu(II) (2-6.4 %). Increases in initial metal ion (40-120 mg L-1) and biomass (0.8-4.8 g L-1) concentrations enhanced the sorption of Cd(II) and Cu(II) by GM16 biomass. When the biomass concentration was increased from 0.8 to 4.8 g L-1, the biosorption capacity of Cd(II) increased from 5.5 to 14.5 mg g-1 while that of Cu(II) increased from 2.8 to 14.7 mg g-1 at optimum pHs and a temperature of 40 °C. Maximum adsorption of both metals occurred at an agitation rate of 100 rpm. In addition, increase in initial metal ion concentration from 40-120 mg L-1 increased the initial adsorption rates (h) and the equilibrium metal sorption capacity (qe) of the GM 16 biomass from 6.07 to 16.51 mg g-1 for Cu(II) and 8.9 to 17.9 mg g g-1 for Cd(II). Adsorption equilibrium data for both metal ions fitted well to the Langmuir adsorption model with high correlation coefficients (r2 > 0.90) but the data for Cu(II) could also be described by the Freundlich adsorption model. Increase in temperature from 25-40 °C only caused marginal increases in maximum metal sorption capacities (qmax). The results on kinetic analysis showed that the biosorption processes of Cd(II) and Cu(II) ions by the non-viable GM 16 cells followed pseudo-second order kinetic model betterthan the pseudo-first order model, although the calculated metal sorption capacities obtained with the model were overestimated. The calculated thermodynamic parameters showed that the biosorption of Cd(II) and Cu(II) ions was feasible, spontaneous and slightly endothermic for Cd(II) but slightly exothermic for Cu(II) under examined conditions. Based on 16S ribosomal DNA sequencing, the bacterial isolate (GM 16) was identified as a Bacillus sp. and is closely related to Bacillus thuringiensis and Bacillus cereus strains. The biosorption capacity of the non-viable GM 16 biomass was higher than the biosorption capacity reported for the viable GM 16 cells, 65 % of Cd(II) was removed by non-viable biomass whereas 48 % was removed by the viable biomass. For the biosorption of Cu(II), the % metal ion adsorbed for the non-viable GM 16 cells was slightly higher than the % adsorbed for the viable cells although not statistically significant. Only 67 % of Cu(II) was removed by the non-viable cells whereas 65 % was removed by the viable cells. / National Research Foundation

Heavy metal pollutants are a worldwide concern. It causes negative effects on aquatic organisms and human health. Heavy metals concentration and transport of copper, zinc and cadmium were investigated in high and low flow conditions in Trönningeån River, southern Sweden. A total of 33 surface water samples collected from the river and Kistingebäcken tributary were analyzed. Concentration (high to low) of heavy metals in the Trönningeån   river and its tributary were- copper(Cu) > zinc (Zn) > cadmium (Cd). The concentration of Copper was found to be high in low flow condition whereas in the case of zinc, high concentrations were found in both the flows (high and low). Study further showed that, the tributary has high pH and conductivity. And finally, the study concluded that there is high concentration and transport of heavy metals in the above-mentioned industrial tributary.

This master thesis is a study of the feasibility of in situ soil remediation techniques in Dar es Salaam, Tanzania. It first looks at the existing on site remediation techniques and assesses how feasible they appear in the conditions of Dar es Salaam. Two methods were interpreted as more feasible than others, namely reactive zone remediation and phytoremediation. The feasibility of phytoremediation was assessed by sampling locally occurring plants and comparing their content of Cu, Pb and Zn with the respective content of the soil they grew in. If the content in the plants were elevated as compared to the soil content, the plant was deemed interesting from a phytoremediation point of view.

Magister Scientiae - MSc / The aim of this study was to use plants to determine the degree of heavy metal contamination in water and sediments in order to effectively monitor and provide possible recommendation to improve the water quality in the aquatic ecosystem of the Bottelary River.

Polygonum hydropiper L. was cultivated on alluvial soil (Pb = 2.6 mg/kg, dry weight) and Pb contaminated soil (Pb = 1,380 mg/kg dry weight) without and with amendment of 2 g organic fertilizer/kg soil and 2.5; 5.0; 10.0 g NPK fertilizer/1kg soil. After 45 days of cultivation, the growth in height and biomass of P. hydropiper in Pb contaminated soil without amendment of fertilizer was lower than that in alluvial soil, but the Pb content in the above-ground part of the P. hydropiper was higher. In the formula 4, on Pb contaminated soil (Pb = 1,380 mg/kg dry weight), when amending 2 g of microbiological organic fertilizer + 5 g NPK fertilizer per 1 kg of soil (with the total nutrients amended were: N = 0.25, P2O5= 0.52, K2O = 0.15, and organic matter = 0.21 g/kg soil), growth of P. hydropiper was optimal (its height and biomass were up to 244.0% and 284.9% in comparison to that of before experiment) and their Pb extraction potential was promoted to the highest level among the formulae used. The average level of Pb accumulated in the above-ground part of P. hydropiper cultivated at formula 4 was 1,098.3 mg/kg dry weight (DW) after 45 days of cultivation that was 1.6 time higher than the one of formula 2 without fertilizer amendment (687.8 mg/kg DW). The potential of Pb extracted and stored in the above-ground part of P. hydropiper cultivated at formula 4 after 45 days was 479.2 g/ha that was 2.85 time higher than the one of formula 2 without fertilizer amendment (168.02 g/ha). / Nghể răm Polygonum hydropiper L. được trồng theo 5 công thức trên đất phù sa không ô nhiễm chì (Pb = 2,6 mg/kg khô) và đất ô nhiễm chì (Pb = 1380 mg/kg khô)không bón phân và có bón phân với các liều lượng 2 g phân hữu cơ vi sinh/1 kg đất và 2,5; 5,0; 10,0 g phân NPK /1 kg đất. Sau 45 ngày thí nghiệm trồng cây, tăng trưởng về chiều cao và sinh khối của cây trên đất ô nhiễm Pb không bón phân thấp hơn trên đất phù sa, nhưng hàm lượng Pb trong phần trên mặt đất của cây cao hơn. Ở công thức (CT) 4, trên đất ô nhiễm chì (Pb = 1380 mg/kg khô) khi bón phân với liều lượng 2 g hữu cơ + 5 g NPK/1 kg đất (với tổng hàm lượng dinh dưỡng được bón là: N = 0,25, P2O5= 0,52, K2O = 0,15, và chất hữu cơ = 0,21 g/kg đất) thì tăng trưởng của câynghể răm đạt tối ưu (chiều cao và khối lượng đạt 244,0 % và 284, 9% so với trước thí nghiệm) và tiềm năng hút thu Pb của chúng cũng được thúc đẩy cao nhất trong số các công thức được sử dụng. Lượng Pb trung bình tích lũy trong phần trên mặt đất của nghể răm ở CT 4 đạt 1.098,3 mg/kg khô sau 45 ngày trồng, cao gấp 1,6 lần so với cây ở công thức 2 không bón phân (687,8 mg/kg khô). Khả năng loại bỏ Pb từ đất ô nhiễm của nghể răm khi được bón phân ở CT4 đạt 479,2 g/ha sau 45 ngày trồng, cao gấp 2,85 lần so với cây ở CT 2 không bón phân (168,02 g/ha).

Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The terrestrial Oligochaete species Eisenia andrei and Enchytraeus doerjesi were exposed to different concentration series of Cd and Zn, both separately and in mixtures for 28 days in artificial OECD soil at 15, 20 and 25°C. At the end of the four week exposure period, survival and reproduction were assessed in E. doerjesi and survival, reproduction, biomass change, metal uptake and biomarker responses (MTT and comet assays) in E. andrei. Survival results for both E. andrei and E. doerjesi indicated that the lethality of Cd increased at higher temperatures, whereas the opposite was observed for Zn.Cadmium LC50 values were the highest at 15°C and the lowest at 25°C. In the Zn exposures LC50 increased with increasing temperature. Mixture results in both test organisms indicated that mixtures were less lethal than the metals separately. Effects of mixtures on survival, nonetheless, increased with increasing temperature. In the Cd experiment, reproduction in E. andrei was only recorded in the control treatments at the three temperatures investigated. However, the deleterious effect of Zn on the reproduction of both E. andrei and E. doerjesi decreased with increasing temperature and Zn EC50 for reproduction increased with increasing temperature. Results for exposures to mixtures indicated in both test organisms that the interaction between Cd and Zn were antagonistic. In both E. andrei and E. doerjesi, the effect of mixture exposures on reproduction decreased with increasing temperatures. The highest mixture EC50 values for reproduction were found at higher temperature. In E. doerjesi (using reproduction results in MixToxModules) Cd and Zn interactions were dose level dependent at the three temperatures investigated. Antagonism was the predominant interaction at lower mixture concentrations whereas synergism occurred at mixture concentrations equal to or higher than the mixtures’ EC50 values. Biomass loss increased with increasing temperature in the Cd exposures (p 9 0.05) but not in the Zn exposures in E. andrei. In this species mixture results indicated antagonistic interactions between Cd and Zn at all temperatures investigated. The deleterious effect of mixtures on the biomass of E. andrei increased with increasing temperature. When Cd and Zn interactions were further investigated in E. andrei (using biomass results in MixToxModules) it was found that they were dose level dependent at the three temperatures investigated. Antagonism was the predominant interaction at lower mixture concentrations whereas synergism occurred at mixture concentrations higher than the mixtures EC50 values. The assessment of metal uptake in E. andrei revealed a temperature dependent Cd uptake with higher Cd body burdens occurring at higher exposure concentrations and temperatures (p ≤ 0.05). In the case of Zn, although uptake was lower at higher temperature, there was no statistical difference in uptake between exposure concentrations and between temperatures. Mixture results however indicated that in mixture exposures less Cd was accumulated by E. andrei than in single Cd exposures (p ≤ 0.05). Inversely, in mixture exposures more Zn was accumulated by E. andrei than in single Zn exposures (p ≤ 0.05). Biomarker studies revealed that Cd and Zn were both cytotoxic and genotoxic whether in single or mixture exposures. Factorial ANOVA analyses of the effects of temperature and metals on the reduction of MTT by E. andrei indicated that temperature rather than the metals was the most important factor controlling mitochondrial activity (p < 0.001). In both Cd and Zn exposures significant deleterious metal effects on mitochondrial processes were found to increase with temperature (p ≤ 0.01). Mixture exposures indicated decreasing cytotoxicity with increasing temperature (p ≤ 0.05) and possible antagonism between Cd and Zn at cellular level. Results of the comet assay showed that the genotoxic profile of Cd was the opposite of the genotoxic profile of Zn. Cd was less genotoxic at lower temperature and increasingly deleterious at higher temperature while Zn was more genotoxic at lower than higher temperature (p ≤ 0.05). The results of mixture exposures indicated decreasing mixture genotoxicity with increasing temperature and suggested that the interactions between Cd and Zn at molecular level were probably antagonistic. / AFRIKAANSE OPSOMMING: Eisenia andrei en Enchytraeus doerjesi is aan verskillende konsentrasiereekse van Cd en Zn, afsonderlik en in mengsels, vir 28 dae in OECD kunsmatige grond onderskeidelik by 15, 20 en 25°C blootgestel Die volgende eindpunte is aan die einde van die vier weke blootstellingsperiode gemeet: oorlewing en voortplanting (by E. doerjesi) en oorlewing, voortplanting, biomassaverandering, metaalopname, MTT en komeettoetse (by E. andrei). Oorlewingsresultate by beide E. andrei en E. doerjesi het getoon dat toenemende temperatuur die letale toksisiteit van Cd laat toeneem terwyl die teenoorgestelde waar was vir Zn. By die Cd blootstellings was die LK50 waardes die hoogste by 15°C en die laagste by 25°C. By die blootstellings aan Zn het die LK50 waardes toegeneem by hoër temperatuur. Resultate by die mengsels by beide toestspesies het aangetoon dat die mengsels minder letaal was as die afsonderlike metale. Effekte van mengsels op oorlewing het nietemin toegeneem met toenemende temperatuur. By die Cd blootstellings is voortplanting slegs by die kontroles en in die geval van E. andrei by die drie onderskeie temperature ondersoek. Die nadelige uitwerking van Zn op voortplanting by beide E. andrei en E. doerjesi het afgeneem met stygende temperatuur en die Zn LK50 vir voortplanting het toegeneem met toenemende temperatuur. Resultate van die blootstellings aan mengsels het getoon dat die wisselwerking tussen Cd en Zn by beide spesies antagonisties was. By beide spesies het die invloed van die mengsels op voortplanting afgeneem met stygende temperatuur. Die hoogste mengsel LK50 waardes vir voortplanting is by hoër temperature gevind. By E. doerjesi was Cd en Zn wisselwerkings by blootstelling aan mengsels (voortplantingsresultate ondersoek deur van MixToxModules gebruik te maak) dosisvlak verwant by die drie temperature wat ondersoek is. Antagonisme was die oorwegende wisselwerking by laer mengsel konsentrasies terwyl sinergisme voorgekom het by mengsel konsentrasies gelyk aan of hoër as die LK50 waardes van die mengsels. In die geval van die Cd blootstellings by E. andrei het biomassaverlies toegeneem met toenemende temperatuur (p ≤ 0.05) maar nie by die Zn blootstellings nie. Resultate van blootstellings aan mengsels het getoon dat die uitwerking van mengsels op die biomassa van E. fetida toegeneem het met toenemende temperatuur. By die verdere ondersoek van Cd en Zn wisselwerkings, waar gekyk is na dosis verhouding of dosisvlak antagonisme (deur van biomassa resultate in MixToxModules gebruik te maak), is gevind dat Cd en Zn wisselwerkings dosisvlak afhanklik was by die drie temperature wat ondersoek is. Antagonisme was die oorwegende wisselwerking by laer mengselkonsentrasies terwyl sinergisme voorgekom het by mengselkonsentrasies hoër as die mengsel EK50 konsentrasies. Die bepaling van metaalopname deur E. andrei het ’n temperatuurafhanklike opname van Cd getoon met hoër Cd liggaamskonsentrasies by hoër blootstellingskonsentrasies en temperature (p ≤ 0.05). Alhoewel Zn opname laer was by hoër temperatuur was daar geen statisties betekenisvolle verskille in opname tussen blootstellingskonsentrasies of temperature nie. Die bepaling van metaalopname by wurms wat aan mengsels blootgestel is, het getoon dat minder Cd deur E. andrei opgeneem is as waneer die wurms aan Cd as enkelmetaal blootgestel is (p ≤ 0.05), Daarteenoor het die teenoorgestelde gebeur in die geval van Zn, Meer van die metaal is opgeneem wanneer E. andrei aan mengsels blootgestel is as aan die enkelmetaal. Biomerkerstudie het getoon dat Cd en Zn beide sito- en genotoksies kan wees ongeag of dit as enkelmetale of in mengsels toegedien is. Faktoriale ANOVA analises van die effekte van temperatuur en metale op die verlaging van MTT by E. andrei het getoon dat temperatuur ’n belangriker faktor was as metaalbesoedeling by die kontrole van mitochondriale aktiwiteit. (p ≤ 0.001). By beide Cd en Zn blootstellings was daar in elk geval statisties betekenisvolle metaaleffekte op mitochondriale prosesse met toename in temperatuur (P ≤ 0.01). By blootstellings aan mengsels is gevind dat sitotoksisiteit afgeneem het met toenemende temperatuur (p ≤ 0.05) asook ’n moontlike antagonisme tussen Cd en Zn op sellulêre vlak. Resultate van die komeettoets het getoon dat die genotoksiese profiel van Cd die teenoorgestelde was as die van Zn. Cd was minder genotoksies by laer temperature en meer en meer skadelik by hoër temperature terwyl Zn meer genotoksies was by laer as by hoër temperature (p ≤ 0.05). Die resultate van blootstlling aan mengsels het laer genotoksisiteit getoon met toename in temperatuur. Dit dui daarop dat wisselwerkings tussen Cd en Zn op molekulêre vlak moontlik antagonisties was.

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Removal of wastewater pollutants is urgent as they are continuously defiling the limited freshwater resources, affecting the ecosystem, aquatic and terrestrial life. Carbon nanotubes-based adsorbent materials are effective for removal of wastewater pollutants owing to their large specific surface area. Surface modification of carbon nanotubes (CNTs) can mediate specific pollutant adsorption and increase CNTs colloidal stability and chemical reactivity. Heavy metal pollution of wastewater is one of the major threats, as this metals can be toxic to humans when present at certain concentrations in drinking water. This study report the synthesis of chlorine functionalized and nitrogen doped carbon nanotubes (ClNCNTs) loaded with iron oxide nanoparticles and their use as adsorbents for Pb2+ ions in aqueous solutions. Carbon nanomaterials that are functionalized with chlorine and doped with nitrogen were successfully synthesized. This was done through pyrolysis of a mixture of dichlorobenzene and acetonitrile (in a 1:1 volume ratio) over 10% Fe-Co/CaCO3 bi-metallic catalyst via chemical vapour deposition (CVD) method. Addition of chlorine and nitrogen to the CNTs was to enable defect and disorder creation on the surface of the nanotubes which is envisaged to create nucleation sites on the their surface for better adhesion of the iron oxide nanoparticles. Different loadings of magnetite (Fe3O4) nanoparticles on the surface of the ClNCNTs was achieved using a co-precipitation method. The synthesized materials were charaterized by Raman spectroscopy, Transmission electron microscopy (TEM), Powder X-ray diffraction (PXRD) spectroscopy, Thermal gravimetric analysis (TGA), Brunauer Emmett and Teller (BET) and X-ray photoelectron spectroscopy (XPS). Highly defected CNTs, some with hollow and others with bamboo-compartments due to nitrogen inclusion were obtained. The effect of metal salt concentration in wt.% (10, 20, 30 and 53 wt.%) was investigated. The increase in wt.% loading has resulted in an increase in surface area, and a decrease in thermal stability as a result of defected Fe3O4/ClNCNTs. In addition, agglomeration was observed at 30 and 53 wt.% loading, due to large amount of iron present. The identity of the Fe3O4 nanoparticles was confirmed by PXRD and XPS with two iron peaks deconvoluted at 725.6 eV and 721 eV respectively. The percentage loading of the Fe3O4 nanoparticles at the surface of the ClNCNTs was affirmed by TGA analysis, where the residual mass obtained from TGA were closely related to the mass percentages added. Different nitrogen environments namely, the quatenary, pyridinic, pyrollic and nitrogen oxides were also observed, whilst chlorine could not be deconvoluted because it was present in very limited amount probably it was masked by the iron oxide nanoparticle. Thus, a 20 wt.% Fe3O4/ClNCNTs was chosen as an optimum, due to uniform distribution of spherical nanopaticles observed along the radial length of ClNCNTs that had an average size of 10 ± 4.5 nm. The synthesized ClNCNTs and a nanocomposite made from a 20 wt.% Fe3O4/ClNCNTs were applied in the removal of Pb2+ ions from aqueous solution. The results obtained showed that a nanocomposite made from a 20 wt.% Fe3O4/ClNCNTs had a better adsorption capacity of 17.0 mg/g as compared with 14.8 mg/g for ClNCNTs.