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In the first phase of the study, the effect of five Safol surfactants on the aqueous solubility of phenanthrene and acenaphthene was determined. The fixed variables were temperature and ionic strength, while surfactant concentration and pH were varied. Quantification of the polyaromatic hydrocarbons (PAHs) was conducted by UV-Visible spectrophotometry. The surfactants had little or no effect on analyte solubilisation below the critical micelle concentration (CMC) while a linear relationship between surfactant concentration and amount of solubilised phenanthrene was observed above CMC concentrations. Safol 45E5 had the highest phenanthrene molar solubilisation ratio (0.83) of the five surfactants tested. The solubilisation of phenanthrene increased marginally (4.1 % for Safol 45E12 and 15.2 % for Safol 45E7) by decreasing the pH from 8 to 5. The concentration of solubilised acenaphthene was 8.4 % higher than phenanthrene in a 1 mM solution of Safol 45E7. The aqueous solubility of phenanthrene was enhanced 11.0, 21.2, 19.6, 15.9 and 14.7 times in 1 mM solutions of Safol 45E3, 45E5, 45E7, 45E9 and 45E12 respectively. Seasand, Longlands sand, Longlands soil and a standard soil sample were spiked with the two PAHs and aged for two weeks. API sludge provided by Sasol and unspiked samples of the above mentioned sorbents were subjected to determinations of organic matter content, particle size distribution and moisture content. The spiked soils and sands and the sludge samples were then washed in various concentrations of Safol 45E7 (0.5, 1.0 and 2.0 mM) at the same temperature used in the solubility studies. A soil mass to solution volume of lg to 10 mL was used. Analyses of the soil and sand samples were conducted by High Pressure Liquid Chromatography (HPLC). Using a 2 mM Safol 45E7 surfactant solution, 100 % and 90 % of phenanthrene and acenaphthene were respectively extracted from Longlands sand and 88 % and 100 % of phenanthrene and acenaphthene were removed from seasand. 8.4 % phenanthrene and 8.17 % of acenaphthene was removed from Longlands soil, while 7.03 % phenanthrene and 6.64 % acenaphthene was removed from the standard soil sample. In the sand desorption studies, the amount of desorbed contaminants initially increased rapidly with increasing surfactant concentration, before levelling off at equilibrium. The amount of desorbed acenaphthene and phenanthrene increased exponentially with increasing surfactant concentration while contaminant concentrations decreased with increasing time in the Longlands soil and standard soil desorption experiments. Dry API sludge samples were also subjected to soil washing studies. The washed samples were Soxhlet extracted and analysed by gas chromatography. The 0.5 mM and 1 mM Safol 45E7 washed sludge samples showed respective phenanthrene peak area percent reductions representing a 44 % and 47 % extraction of phenanthrene from the API sludge. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2005.

There are two main components to the research: the theoretical and the experimental. Chapter 2 contains an analysis of the state of soil quality guidelines and the scientific methods used to determine them. A number of recommendations to improve soil quality criteria for trace metals are offered including the importance of considering bioavailability and the need to use realistic conditions, trace metal sources and organisms. / A critical review of the literature dealing with predicting the availability of trace metals to plants is presented in Chapter 3. We found little agreement among hundreds of similar studies which relate plant metal uptake to the amount of metal extracted by selective chemical dissolution procedures. An extensive summary of the data shows clearly that the extraction methods are not widely applicable. Differences between individual soils, their metal retention capacities, as well as plant factors and environmental conditions contribute to the variability of the results. Alternative ways of assessing bioavailability are suggested. / The experimental component of the thesis focuses on the availability of trace metals to plants. In Chapter 4 the uptake of Cu from different soil pools was examined and the free metal ion (Cu2+) was found to be the best predictor of uptake by lettuce (Latuca sativa cv. Buttercrunch), ryegrass (Lolium perenne cv. Barmultra) and radish (Raphanus sativus cv. Cherry Belle). / In Chapters 5 and 6 we examined the effect of low-cost in-situ treatments on the availability of metals to plants in greenhouse and field experiments. Synthetic zeolites, P amendments, organic matter and clean soil were used and their effect on the bioavailability of Cd, Cu, Pb, Ni and Zn evaluated. The plants for the experimental work were lettuce and perennial ryegrass. Only the clean soil treatment was consistently effective in reducing the concentration of metals in the plant. We also wanted to determine whether the trace metals in the plant tissue came from the soil or from direct deposition of pollutants on the leaf surfaces. We found little evidence that metals in plants were a result of atmospheric fallout. / A method for the accurate analysis of total metal concentrations in a range of contaminated soils including those containing oil and grease was developed (Chapter 7). For this research the trace metals of concern are Cd, Cu, Ni, Pb and Zn---all commonly found in urban/industrial soils. The proposed method using HNO3/HClO4 has several advantages over the common HNO3/H2O2 procedure. We were able to digest larger soil samples and hence the final concentration of trace metals was usually in the range for analysis by inductively coupled plasma atomic absorption spectrometry or flame atomic absorption spectrometry.

Bioavailability of trace metals in urban contaminated soils was investigated to relate chemical extraction efficiencies with biological effects. / Results from a Collembola reproduction bioassay showed minimal toxicity suggesting limited bioavailability. Chemical extractions were carried out on these urban soils. The sodium acetate extraction was the best predictor of the biological effects of Cd while the biological effects of Zn were best explained by a water extraction. / An earthworm uptake bioassay was done to quantify the bioavailable fractions. Cadmium, Cu, Pb and Zn accumulated in Lumbricus terrestris L. The sodium acetate extraction was the best predictor of Cd uptake while calcium chloride extraction best predicted Zn uptake by earthworms. / Treatments were made to urban soils to immobilize the metals and reduce their bioavailability. The metal concentrations were so low in the soils that the effects of the treatments could not be measured. / Collembola and earthworms are good indicators of trace metal bioavailability and should be included in the evaluation of contaminated soils.

The efficacies ofsoil extraction methods, namely, Soxhlet, sonication, agitation, alkaline digestion and the ethyl acetate micro-method, for monitoring soil bioremediation were evaluated using three soil types, Swartland, Rensburg and Hutton, encompassing the mineralogical range prevalent in Kwa Zulu Natal. Phenol, atrazine and the BTEX component of petrol were the molecules used in this study and were extracted under different spiking concentrations, after prolonged ageing times up to 21 days and after changing the composition of the spiking solution. It was concluded that extraction methods must be validated for the specific conditions under which they would be used, taking into consideration, soil type, spiking solutions, moisture content, weathering times and the analyte(s) in question. A preliminary appraisal of atrazine degradation in a Hutton soil was then made under the conditions of sterilized, fertilized/non-fertilized and non-sterilized, fertilized/nonfertilized soils. The predominant pathway of atrazine degradation was deemed to be chemically/abiotically mediated due to the soil pH and the presence of iron and aluminium oxides as well as the high levels of manganese in the soil. The results obtained prompted further study into atrazinecatabolism using soil-slurry reactors, under the conditions of carbon-limitation, nitrogen limitation, carbon/nitrogen non-limitation and carbon/nitrogen limitation. A comparison was made between inoculated and non-inoculated bioreactors. The ability of the indigenous microbial population to return the Hutton soil to its original pristine state was confirmed. The expense of inoculation and culture maintenance could be avoided since carbon and nitrogen supplementation would be as equally effective as inoculation. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 2002.

Most natural products and xenobiotic molecules, irrespective of their molecular or structural complexity, are degradable by some microbial species/associations within particular environments. Atrazine- and selected petroleum hydrocarbon (benzene, toluen~ and 0-, m- and p-xylene (BTX))-degrading associations were enriched and isolated"trom atrazine- and petroleum hydrocarbon (PHC)-contaminated KwaZuluNatal loamy and sandy soils, respectively. In total, eight pesticide- and forty BTXcatabolizing associations were isolated. Electron microscopy revealed that, numerically, rods constituted the majority of the populations responsible for both atrazine and PHC catabolism. Cocci and, possibly, spores or fungal reproductive bodies were observed also. For the BTX-catabolizing associations, the population profiles appeared to be dependent on the enrichment pH and the molecule concentration. After combining selected associations, to ensure that all the isolated species were present, batch cultures were made to determine the optimum pH and temperature for growth; With an atrazine concentration of 30 mgr1, the highest specific growth rates, as determined by biomass (OD) changes, were recorded at 30DC and pH 4 although the rate§ at 25DC and pH 5 were comparable. For the BTX (50 mgr1)-catabolizing associations, the highest growth rates were recorded at pH 4 for the four temperatures (15, 20, 25 and 30DC) examined. The sole exception was p-xylene with the highest specific growth rate recorded at pH 5 and 30De. Batch and continuous (retentostat) cultivations in the presence/absence of methanol and under C- and N-limited conditions were used to investigate the impacts of the solvent and the catabolic potentials of a combined atrazine-catabolizing culture (KRA30). In general, different degradation rates were recorded for the culture in response to element limitation. Addition of citrate as the primary carbon source / effected atrazine (100 mg!"l) degradation rates comparable to that of Pseudomonas sp. strain ADP while succinate addition effected herbicide co-metabolism. Carbon supplementation may, therefore, be considered for site amelioration practices. To complement conventional culture-based microbiological procedures, molecular techniques were employed to explore the diversities and analyze the structures of the microbial communities. In parallel, anaerobic microbial associations which targeted atrazine were also characterized. The soil DNA isolation/characterization protocol adopted consisted of a clean-up step followed by the polymerase chain reaction (peR) and 16S rDNA fingerprinting by denaturing-gradient gel electrophoresis (DGGE). The preliminary results suggested that despite different, but chemically similar, petroleum hydrocarbon molecules, the common selection pressures of the primary enrichments effected the isolation of similar and complex aerobic microbial associations. Some similar numerically-dominant bands characterized the aerobic and anaerobic atrazine-catabolizing associations although distinct differences were also recorded on the basis of the enrichment/isolation pH value and the concentration of the herbicide. Cloning and sequencing were then used to identify some of the numerically-dominant and non-dominant association members. Community-level physiological profiling (CLPP) for physiological fingerprinting was made with Biolog EcoPlates and highlighted the differences in the isolated aerobic atrazine-catabolizing associations depending on the enrichment pH and molecule concentration. Logarithmic-phase cultures of the combined atrazine- and BTX-catabolizing associations were used to explore the association profiles following pH and temperaiure optImIzation. Although some common numerically-dominant components were maintained, differences in numerical and, possibly, activity dominance were observed in the 16S rDNA profiles in response to changes in pH and temperature. This indicated that environmental parameter optimization and characterization of catabolic association structure must precede bioaugmentation so that control of key variables will facilitate maintenance of the dominant site-specific species. Following KRA30 cultivation in the presence/absence of methanol and under carbon and nitrogen-limited conditions, the population fingerprints showed that the presence of methanol effected shifts in species numerical dominance and, possibly, changes in atrazine catabolic capacity. Also, Coulter counter results, optical density readings and 16S rDNA characterization by DGGE indicated that degradation rate changes were accompanied by shifts in species numerical/activity dominance within the association. Although N-limitation effected the highest rates of herbicide catabolism, a potential versatility of the combined association for bioaugmented and/or biosupplemented remediation with acceptable rates regardless of any elemental limitation was recorded. To determine if the contaminated and pristine source soils contained comparable catabolic populations and, thus, offered potential for intrinsic bioremediation, PCRDGGE was used to characterize the populations in comparison with the enriched/isolated associations. Some similar dominant bands characterized the contaminated soils and the enriched/isolated associations. The significance of this, in relation to a possible correlation between numerical and activity dominance in the component species, is discussed with respect to the use of PCR-DGGE to identify natural attenuation potential and monitor sustained intrinsic and enhanced (bioaugmented and biosupplemented) bioremediation. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 2001.

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The work in this thesis demonstrates whether resins are better than conventional soil extractants at predicting plant metal concentrations, and whether low-cost soil treatments can effectively reduce metal content and concentrations in lettuce leaves. / Researchers have shown that ion exchange resins can simulate root metal uptake behaviour by acting as ion sinks. Chemical extractants on the other hand, generally do not behave in this manner. Thus, we would expect resins (in either bead or membrane form) to predict plant metal concentrations better than conventional extractants. For the first study, a procedure using anion exchange resin membranes (AEM) treated with either EDTA or DTPA chelators was chosen, since previous studies showed this method to be effective at predicting plant metal uptake, and practical for routine laboratory use. In addition, several conventional extractants were selected for comparison. / For the second part of the thesis, a study was undertaken to test the effectiveness of various food processing byproducts to stabilize metal contaminants in soils, and compare the results with those of a Na-based aluminosilicate (zeolite). (Abstract shortened by UMI.)

Urban soils are often contaminated with trace metals and the toxicity of the metals depends, in part, on their speciation in soil solutions. The objectives of this project were to estimate the metal speciation in urban soils and to evaluate the predictability of soil metal pools on plant uptake. The chemical speciation of Cd, Cu, Ni, Pb and Zn was estimated by using the Windermere Humic Aqueous Model (WHAM). In soil solutions, Cd, Ni and Zn were present mainly as free ions when the solutions were acidic and their organic complexes were dominant as the pH was over 7.5. The other two metals mostly formed complexes with organic ligands. The activities of Cd2+, Cu2+, Ni2+, Pb2+ and Zn 2+ were affected by soil pH and total soil metal burdens. All five metals were under-saturated with respect to the minerals which could potentially control the metal solubility. / Metal uptake by plants in the contaminated railway yards was generally not correlated with free, dissolved and total soil metal pools. A pot experiment demonstrated better correlations between the metal pools and the metal content in wild chicory. Multiple regression analysis showed that the metals in the leaves and roots of wild chicory could be adequately predicted by the soil total metals and soil properties such as pH and exchangeable Ca.