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published_or_final_version / Radioisotope / Master / Master of Philosophy

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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.

Chlorinated aromatic compounds are an important group of compounds. Many of them have been produced in large quantities and they are indispensable to technological and societal benefits. But regulatory agencies have tightened regulations on the use and release of chlorinated aromatic compounds because of the scientific understanding of their toxicity, persistence, behavior in the environment and their potential to cause adverse effects on the ecosystem and human health. / Pentachlorophenol (PCP), octachloronaphthalene and decachlorobiphenyl are all highly chlorinated aromatic compounds, of which, PCP has been used mainly as a biocide. Octachloronaphthalene and decachlorobiphenyl don't have practical use, but their congeners have been used widely as chemicals in industry. These compounds are toxic, recalcitrant and bio-accumulated within organisms. As the conventional treatment, incineration of these compounds can cause more serious problems, so that suitable alternatives need to be developed for their detoxification. / When compared with biodegradation or the thermal treatment of these compounds, chemical degradations have several merits. (Abstract shortened by UMI.)

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Phytoextraction is an innovative method that can be implemented to remove lead (Pb), cadmium (Cd), and zinc (Zn) from contaminated soil. A two-year field and growth chamber study was conducted to determine the effectiveness of several soil amendments in the phytoextraction or stabilization of Pb, Cd and Zn. Field plots were established at the Memorial Drive Dump site (Muncie, IN). Amendments included composted municipal solid waste (MSW) (25 Mg/ha), dried sewage sludge (SS) (25 Mg/ha), citric acid (2 mmol/kg soil), ethylenediaminetetraacetic acid (EDTA) (2 mmol/kg soil), and a control. A mixed grass crop was capable of survival and growth in the contaminated soil; in contrast, Helianthus annuus (sunflower) and Ambrosia artemisiifolia (ragweed) failed to become established. Soil Pb and Zn occurred primarily in the carbonate, organic-bound and residual forms (23.1%, 31.8%, and 44.4%, Pb, respectively and 11.4%, 26.5%, and 60.2% Zn, respectively). Soil Cd occurred primarily in the soluble, carbonate, and residual forms (21.8%, 21.3%, and 27.4%, respectively). In a growth chamber leaching study, soil Pb was most rapidly leached from the 0.1 M EDTA treatment (51.7 mg Pb over 200 pore volumes); the 0.001M resulted in the lowest leaching. Soil Pb was most rapidly leached using 0.1 M HEDTA (52.1 mg Pb over 200 pore volumes). The 0.001 M HEDTA rate resulted in lowest Pb leaching. Addition of an NPK solution resulted in minimal Pb leached. The MSW and dried sludge treatments resulted in the greatest dry matter production on the plots. Dry matter production was significantly (p >0.05) higher in the MSW (1.09 MT/ha) and SS (95 MT/ha) treatments. Addition of EDTA, citric acid and MSW significantly (p < 0.05) increased the amount of Cd uptake into plant tissue. The study also demonstrated the ability of vegetation to establish and grow on toxic soil and to uptake Pb, Cd, and Zn. / Department of Natural Resources and Environmental Management