Thesis (Ph. D.)--University of Hong Kong, 2001. / Includes bibliographical references.

Thesis (Ph. D.)--Mississippi State University. Department of Engineering. / Title from title screen. Includes bibliographical references.

No description available.

The research used dendro-chemical analysis of ash tree rings and current year leaf litter to track Cd, Pb, Zn, Cu, Mn, Cr, and Sn spread and cycling from a closed garbage dump-toxic waste site. This technique allowed for determination of areal extent, contaminant levels and time period of initial contaminant contact. Only Zn, Sn, and Cu were found in elevated quantities in the xylem wood and Pb in the leaf litter. Elemental concentrations of Pb, Sn and Cd in xylem wood and leaves of ash were positively correlated. Tin was the only element to demonstrate a clear initial contact period and elemental accumulation with age. Significant levels of Cu accumulated in the heartwood while Zn revealed significant but inconsistent accumulated patterns. Expected attenuation zones associated with municipal solid waste landfill leachate dispersion were not found; thus the pathway for contaminant dispersion was likely through groundwater flow. / An elemental index was developed to facilitate the use of dendro-chemical analysis in periods of suppressed tree growth resulting from environmental pollution.

An important task of research on trace metals in soils is to evaluate how much metals are potentially bioavailable and may cause toxic effects. In this thesis, the chemical speciation and complexation of cadmium (Cd), copper (Cu), mercury (Hg) and lead (Pb) were examined in eastern Canadian soils collected from different locations around smelters. Our goal is to be able to predict metal binding in the soil solution and on the solid phase under a wide range of field conditions. / In Chapter 2, speciation of Cd, Cu and Pb in the lysimeter soil solutions was determined using an ion exchange technique (IET) involving a resin column. The IET-speciation data were used to estimate the metal-dissolved organic carbon (DOC) binding constants using the non-ideal competitive adsorption (MICA)-Donnan model, which assumed a continuous distribution of binding affinities on the DOC molecule. The published Cd and Pb speciation data in a variety of soils (Chapter 3) were also used to test the effectiveness of two speciation models, the MICA-Donnan model and WinHumicV. Both models satisfactorily predicted the concentrations of Cd2+ and Pb2+. The two chapters of metal speciation demonstrated that the NICA-Donnan model could estimate the binding strength of organic matter in soil solutions. / Proton and metal complexation to the surface of soil particles (Chapters 4 and 5) was investigated using back-titration and batch adsorption procedures. It was shown that the surface binding of H+, Cd2+, Hg2+ and Pb2+ was significantly related to soil organic matter (SOM). Though the soil particle surface was covered by a mixture of organic and mineral components, a two-site distribution could be identified from the titration curves. With the parameters derived from the back-titration and adsorption data, the MICA-Donnan model reasonably predicted the surface complexation of proton and metals. Furthermore, the statistically significant relationships between the model parameters and soil organic matter supported the assumptions in this thesis: (1) Organic matter was the most important sorbent on the particle surface; (2) The MICA-Donnan model may be used to interpret the surface binding data in these soils.

No description available.

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 use of standard soil tests to assess waste materials has become a common practice in waste management. However, the suitability of using standard soil tests on waste materials is questionable. Therefore, this investigation was undertaken to compare commonly used chemical extraction methods for their ability to extract elements from soil, waste, and soil-waste mixtures. This was carried out by: · Assessing the effects of extraction time on the extractability of Al,Ca, Co, Cu, Fe, Mg, Mn, Ni, Pb, S, Si, and Zn; · Assessing the comparability between single and sequential extraction. Two manganese rich wastes namely electro-winning waste (EW) and silicate-rich smelter slag (SS) and an acid soil (Inanda, Ia) were used for this study. Waste amended soils were obtained by incubating the EW and SS with Ia soil at field capacity at a rate of 20 g kg-1 and 120 g kg-1 soil respectively, and were sampled at day 0, 7, 28, 56, and 140. The effect of extraction time was assessed on the EW, SS, and Ia soil with carbonated water used in the acid rain test conducted at 16, 20, 30, and 50 hours. The equilibration time was different for different materials and elements. The concentration of Al and Zn did not change appreciably with increasing extraction time in the EW. Similar results were found for Mg, S, and Si in the SS and S in the Ia soil. This was attributed to ‘equilibrium’ being reached before 16 hours. The equilibration time of 20 hours which would release the exchangeable and specifically adsorbed elements was obtained for Co, Mg, Si, S, and Mn in the EW. The concentration of Ca decreased with extraction time in the EW and was attributed to readsorption. The concentration of Ca and Mn in the SS and Al, Fe, and Si in the Ia soil increased with extraction time and the ‘equilibrium’ was not reached even after 50 hours. This was attributed to the release of elements due to dissolution of minerals. In the comparison between Community Bureau of Reference (BCR) sequential and batch extraction, the concentrations of Ca, Co, Mg, Mn, and S were higher in batch extraction than in sequential extraction, particularly for the EW and the EW treated soils. This was possibly caused by the readsorption of released elements during water extraction. On the contrary, sequential extraction had higher concentration of Al and Fe compared to batch extraction for the EW, Ia soil, SS treated soils, and EW treated soils. These were attributed to a continued desorption of elements and dissolution of minerals due to exposed surfaces which occurs in sequential extraction. The comparison between single and sequential extraction for the BCR sequential extraction showed that hydroxylammonium chloride (HAC) applied in sequential extraction had higher concentration of Al, Co, Fe, Pb, and Zn than the single HAC extraction. This was probably due to incomplete dissolution of minerals, precipitation of amorphous minerals, and readsorption of released elements occurring for a single HAC extraction. These were minimised for hydrogen peroxide (H2O2) extraction and hence comparability between single and sequential H2O2 extraction was observed. This was probably due to the presence of complexing agent in the extracting reagent which would minimise the formation of secondary precipitates and hence, improved dissolution of minerals was obtained. Similarly, the concentrations of elements were comparable between single and sequential aqua regia extraction. These results indicated that comparability is improved between single and sequential extraction when aggressive conditions are used. The results from this investigation indicated that when chemical extraction methods are applied to wastes, the effects of the waste properties on the results of extraction need to be well understood. Consequently, when the chemical extraction methods are used in waste management scenarios certain modifications might have to be made. These modifications include the use of a high solution:solid ratio and an extracting solution which has high complexing ability / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2010.

Bioremediation is the process whereby the degradation of organic polluting compounds occurs as a result of biochemical activity of macro- and microorganisms. Bioremediation of hydrocarbon contaminated soils can be practised in situ or ex situ by either stimulating the indigenous microorganisms (biostimulation) or introducing adapted microorganisms which specifically degrade a contaminant (bioaugmentation). This investigation focused on ex situ remediation processes with special attention to the processes and microbiology of landfarming and thermal bioventing. Landfarming was investigated at pilot-scale and full-scale, and thermal bioventing at laboratory and pilot-scale. This study indicated that pilot-scale bioremediation by landfarming was capable of effecting a total petroleum hydrocarbon concentration (TPHC) reduction of 94% (m1m) from an initial concentration of 320 gkg-I soil to 18 gkg-I soil over a period of 10 weeks. Reactors receiving biosupplements showed greater rates of bioremediation than those receiving nutrients. Promotion of TPHC catabolism by addition of a commercial or a site-specific microbial biosupplement was similar. Seedling experiments proved that bioremediation did not necessarily leave the soil in an optimal condition for plant growth. The full-scale landfarming operation reduced the TPHC concentrations from 5 260 - 23 000 mgkg- I to 820 - 2335 mgkg- I soil over a period of 169 days. At full-scale, the larger fraction of more recalcitrant and weathered petroleums. and the less intensive treatment resulted in a slower rate of TPHC reduction than was found in the pilot-scale study. Three distinct decreases in the TPHC were observed during the full-scale treatment. These presented an ideal opportunity to investigate the microbiology of the soil undergoing treatment. The dominant culturable microorganisms were isolated and identified. The bioremediation process was dominated by Bacillus and Pseudomonas species. The method used to study the population was, however, biased to culturable, fast growing microorganisms which represent a small portion of the total microbial population. For this reason, a method to study the total eubacterial population in situ with rRNA targeted oligonucleotide probes was adapted and found to be a valuable technique. Soil microorganisms respiratory activity was investigated at different times in the full-scale treatment. A clear correlation between activity and degradation was recorded. The effect of a supplement. anaerobically digested sludge, was also assessed by this method. Thermal bioventing was investigated as an ex situ in-vessel treatment technology for small volumes of highly contaminated soils. This proved to be a viable technique for the bioremediation of petroleum hydrocarbons at laboratory-scale. Volatilisation contributed to at least 40% of the reduction. Of the two supplements evaluated. dried sludge promoted degradation to a greater extent than chicken manure. The pilot-scale study proved that a chemical contaminant reduction of at least 50% could be achieved in 13 weeks by thermal bioventing. Of the supplemented reactors. the presence of dried sludge and commercial biosupplement etfected the largest contaminant decrease. As a possible supplement to increase the rate of bioremediation. dried anaerobically digested sludge was more effective than chicken manure. A parallel laboratory-scale experiment gave similar results. Gravimetric analyses were found to be conservative indications of the remediation process. The results of this study shed some light on our. still. limited understanding of bioremediation. The gap between the technology in the laboratory and field was narrowed and a better understanding of the soil microbiology was achieved. Due to the limited control of environmental parameters in the case of landfarming. thermal bioventing was investigated and proved to be an effective alternative. The latter technology is novel in Southern Africa. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1996.