Thesis (M. S. in Environmental Engineering)--Vanderbilt University, Dec. 2008. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

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Doctor of Philosophy(PhD) / Soil contamination with heavy metal(loid)s is a major environmental problem that requires effective and affordable remediation technologies. The utilisation of plants to remediate heavy metal(loid)s contaminated soils has attracted considerable interest as a low cost green remediation technology. The process is referred to as phytoremediation, and this versatile technology utilises plants to phytostabilise and/or phytoextract heavy metal(loid)s from contaminated soils, thereby effectively minimising their threat to ecosystem, human and animal health. Plants that can accumulate exceptionally high concentrations of heavy metal(loid)s into above-ground biomass are referred to as hyperaccumulators, and may be exploited in phytoremediation, geobotanical prospecting and/or phytomining of low-grade ore bodies. Despite the apparent tangible benefits of utilising phytoremediation techniques, a greater understanding is required to comprehend the ecophysiological aspects of species suitable for phytoremediation purposes. A screening study was instigated to assess phytoremediation potential of several fern species for soils contaminated with cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn). Hyperaccumulation was not observed in any of the studied species, and in general, species excluded heavy metal uptake by restricting their translocation into aboveground biomass. Nephrolepis cordifolia and Hypolepis muelleri were identified as possible candidates in phytostabilisation of Cu-, Pb-, Ni- or Zn-contaminated soils and Dennstaedtia davallioides appeared favourable for use in phytostabilisation of Cu- and Zn-contaminated soils. Conversely, Blechnum nudum, B. cartilagineum, Doodia aspera and Calochlaena dubia were least tolerant to most heavy metals and were classified as being least suitable for phytoremediation purposes Ensuing studies addressed the physiology of arsenic (As) hyperaccumulation in a lesser known hyperaccumulator, Pityrogramma calomelanos var. austroamericana. The phytoremediation potential of this species was compared with that of the well known As hyperaccumulator Pteris vittata. Arsenic concentration of 3,008 mg kg–1 dry weight (DW) occurred in P. calomelanos var. austroamericana fronds when exposed to 50 mg kg–1 As without visual symptoms of phytotoxicities. Conversely, P. vittata was able to hyperaccumulate 10,753 mg As kg–1 DW when exposed to 100 mg kg–1 As without the onset of phytotoxicities. In P. calomelanos var. austroamericana, As was readily translocated to fronds with concentrations 75 times greater in fronds than in roots. This species has the potential for use in phytoremediation of soils with As levels up to 50 mg kg–1. Localisation and spatial distribution of As in P. calomelanos var. austroamericana pinnule and stipe tissues was investigated using micro-proton induced X-ray emission spectrometry (µ-PIXE). Freeze-drying and freeze-substitution protocols (using tetrahydrofuran [THF] as a freeze-substitution medium) were compared to ascertain their usefulness in tissue preservation. Micro-PIXE results indicated that pinnule sections prepared by freeze-drying adequately preserved the spatial elemental distribution and tissue structure of pinnule samples. In pinnules, µ-PIXE results indicated higher As concentration than in stipe tissues, with concentrations of 3,700 and 1,600 mg As kg–1 DW, respectively. In pinnules, a clear pattern of cellular localisation was not resolved whereas vascular bundles in stipe tissues contained the highest As concentration (2,000 mg As kg–1 DW). Building on these µ-PIXE results, the chemical speciation of As in P. calomelanos var. austroamericana was determined using micro-focused X-ray fluorescence (µ-XRF) spectroscopy in conjunction with micro-focused X-ray absorption near edge structure (µ-XANES) spectroscopy. The results suggested that arsenate (AsV) absorbed by roots was reduced to arsenite (AsIII) in roots prior to transport through vascular tissues as AsV and AsIII. In pinnules, AsIII was the predominant species, presumably as aqueous-oxygen coordinated compounds. Linear least-squares combination fits of µ-XANES spectra showed AsIII as the predominant component in all tissues sampled. The results also revealed that sulphur containing thiolates may, in part sequester accumulated As. The final aspect of this thesis examined several ecophysiological strategies of Ni hyperaccumulation in Hybanthus floribundus subsp. floribundus, a native Australian perennial shrub species and promising candidate in phytoremediation of Ni-contaminated soils. Micro-PIXE analysis revealed that cellular structure in leaf tissues prepared by freeze-drying was adequately preserved as compared to THF freeze-substituted tissues. Elemental distribution maps of leaves showed that Ni was preferentially localised in the adaxial epidermal tissues and leaf margin, with concentration of 10,000 kg–1 DW in both regions. Nickel concentrations in stem tissues obtained by µ-PIXE analysis were lower than in the leaf tissues (1,800 mg kg–1 vs. 7,800 mg kg–1 DW, respectively), and there was no clear pattern of compartmentalisation across different anatomical regions. It is possible that storage of accumulated Ni in epidermal tissues may provide Ni tolerance to this species, and may further act as a deterrent against herbivory and pathogenic attack. In H. floribundus subsp. floribundus seeds, µ-PIXE analysis did not resolve a clear pattern of Ni compartmentalisation and suggests that Ni was able to move apoplastically within the seed tissues. The role of organic acids and free amino acids (low molecular weight ligands [LMW]) in Ni detoxification in H. floribundus subsp. floribundus were quantified using high performance liquid chromatography (HPLC) and ultra performance liquid chromatography (UPLC). Nickel accumulation stimulated a significant increase in citric acid concentration in leaf extracts, and based on the molar ratios of Ni to citric acid (1.3:1–1.7:1), citric acid was sufficient to account for approximately 50% of the accumulated Ni. Glutamine, alanine and aspartic acid concentrations were also stimulated in response to Ni hyperaccumulation and accounted for up to 75% of the total free amino acid concentration in leaf extracts. Together, these LMW ligands may complex with accumulated Ni and contribute to its detoxification and storage in this hyperaccumulator species. Lastly, the hypothesis that hyperaccumulation of Ni in certain plants may act as an osmoticum under water stress (drought) was tested in context of H. floribundus subsp. floribundus. A 38% decline in water potential and a 68% decline in osmotic potential occurred between water stressed and unstressed plants, however, this was not matched by an increase in accumulated Ni. The results suggested that Ni was unlikely to play a role in osmotic adjustment in this species. Drought stressed plants exhibited a low water use efficiency which might be a conservative ecophysiological strategy enabling survival of this species in competitive water-limited environments.

Thesis (Ph.D.)--University of Melbourne, School of Chemistry, 2007. / Typescript. Includes bibliographical references (leaves 151-169).

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More and more attention has been paid to the research on phytoremediation and hyperaccumulators. Arsenic (As) uptake by hyperaccumulator plant species depends on many different environmental factors. Fertilizer is one of the most important factors because the plant growth needs nutrients. In this study, the pot experiments were conducted in 12 weeks to understand the effect of different fertilizer on As removal capacity of Pityrogramma calomelanos and Pteris vittata. The results showed that, Arsenic concentration in the frond is higher than that in the root of the fern. As removal efficiency of the ferns from the soil amended with both inorganic and organic fertilizer is highest. The ferns removed As content in soil up to 7.4 and 12.6 mg As per kg DW soil, respectively. For the control experiments without adding fertilizers, As removal ability of the ferns from the soil is lowest that was only 2.1 mg As per kg DW soil. / Trên thế giới đã và đang có nhiều nghiên cứu, ứng dụng phương pháp sử dụng thực vật để xử lýônhiễm, đặc biệt là các loài thực vật siêu tích tụ kim loại nặng. Sự tích lũy Asen (As) trong các loài thực vật siêu tích lũy phụ thuộc vào rất nhiều yếu tố môi trường và dinh dưỡng khác nhau. Phân bón là một trong những yếu tố quan trọng nhất vì sự phát triển cây rất cần chất dinh dưỡng. Trong nghiên cứu này, các thí nghiệm được tiến hành trong 12 tuần để đánh giá về ảnh hưởng của các loại phân bón khác nhau đến khả năng xử lý ô nhiễm As trong đất của dương xỉ. Kết quả thu được cho thấy, nồng độ As tích lũy trong phần thân của dương xỉ cao hơn rất nhiều so với phần rễ của cây. Hiệu quả loại bỏ As ra khỏi đất của dương xỉ trong các thí nghiệm bổ sung cả phân bón vô cơ và phân bón hữu cơ là cao nhất. Pityrogramma calomelanos và Pteris vittata có thể loại bỏ hàm lượng As trong 1 kg trọng lượng khô đất tương ứng lên đến 7,4 và 12,6 mg. Các công thức thínghiệm đối chứng không bổ sung phân bón thì cho hiệu quả loại bỏ As ra khỏi đất là thấp nhất chỉ 2,1 mg As trên 1 kg trọng lượng khô đất.

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