The indirect aerosol effect contributes to major uncertainties in determining the radiation budget of the earth. A large uncertainty is due to the formation of ice clouds onto natural or anthropogenic aerosols. Field studies have shown that mineral type particles are often associated with ice crystals in the mid-upper troposphere and given the long residence time in the atmosphere of dust particles (~2 weeks in the absence of precipitation), their contribution to ice formation processes is not fully defined. In order to probe ice formation onto natural mineral dust in a setting where it could be suspended as aerosol, a new continuous flow diffusion chamber (CFDC) was built. This allowed investigations of the effects of total aerosol surface area and particle size. The CFDC was also used in an international inter-comparison of ice nucleation instrumentation to compare efficiencies of soot, biological aerosol (bacteria) and samples of natural desert dusts from different regions of the world. The laboratory observations were parameterized using nucleation rates (Jhet) and contact angles () as described by classical nucleation theory. For both this experimental technique and a static one developed during the candidate’s Masters degree, mineral dust particulate proved to be the most efficient ice nuclei (IN) activating at RH with respect to ice (RHi) as low as 105% at T = 233 K. The efficiency varied with particle size and aerosol surface area (SA). Large particles or higher SA activated at lower RHi than small particles or lower SA. The static chamber was sensitive to the first ice event out of a large SA and therefore gave true onset RHi, which was lower than the onset defined by the CFDC studies, which was not sensitive to a single ice event. In addition the static chamber used a broader size range of particulate matter, including super micron particles while the CFDC particles sizes were restricted to below 0.5 µm. Soot and organic coated dust particles were inefficient IN compared to pure dust. Soot aerosols showed some efficiency at T < 233K where deposition ice formation was apparent. The hygroscopic organics had intermediate ice activity between dusts and alkyl-organics and soot. Bacteria aerosols were active in the deposition mode for T as high as 247 K. Contact angles () computed for ice germs forming onto natural mineral dust were small, 7<  < 29, at 223 K for RH ranging from ice to water saturation. It was concluded that there is no single value for the onset of ice formation in the atmosphere via deposition freezing. The associated contact angles show that there is a distribution of active sites on IN and that not all active sites have the same affinity for initiation of ice formation even within the same aerosol type. This work provides evidence that deposition mode nucleation can be an alternate pathway to homogeneous nucleation when mineral aerosols are present in the troposphere since the high T - low RH conditions required for deposition mode nucleation are more easily encountered in the atmosphere than the low T - high RH required for homogeneous nucleation.

Examination of Chrysotile Asbestos from the Eastern Townships of Quebec using optical and electron microscopic methods has shown that Chrysotile fibres are intimately associated with minute particles of magnetite. / Measurements were made using a fluxgate magnetometer of the remnant magnetic fields of bulk commercial fibres and of airborne total dust and of the respirable fraction of airborne dust collected in Quebec asbestos mines and mills using a Hexhlet horizontal eleutriator. The validity of the Hexhlet horizontal eleutriator for respirable fibre collection in the mill environment was determined. It was observed that the remnant magnetic field intensities of airborne dust in laboratory generated dust clouds, and in the work places were related in a meaningful way to the magnetite content of the dust and to the total mass and respirable mass fractions of airborne dust, and also, to the concentrations of fibre greater than 5 micrometre length (aspect ratio > 3:1) measured using phase contrast microscopy. Calibration curves were developed for each of 9 Quebec mills. Repeat calibrations showed the lines to be reproducible within (+OR-) 10 percent. The accuracy of the method for mass dust determination was dependent on sample size with errors as low as (+OR-) 7.5 percent for samples larger than 3 milligrams, and as large as (+OR-) 40 percent for samples of mass smaller than 0.5 milligrams. The relationships between fibre concentrations and remnant magnetic fields were less reproducible and the lower detection limit was limited by the sensitivity of the fluxgate magnetometer. Although the measured remnant magnetic field varied as the magnetite content varied between different mills and commercial fibre products, magnetite to chrysotile ratio remained constant for a given mill and commercial product. Measurements of the remnant magnetic fields of airborne dusts collected in mill environments can thus provide the possibility of the rapid determination of airborne chrysotile fibre concentrations both in terms of mass and number of fibres per litre of air sampled as well as their iron content. / Measurement of the magnetic content of specimens of autopsied lung tissue from asbestos exposed workers indicated that the residual estimated fibre content measured by electron microscopy was less than estimated using magnetic field measurements. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UMI

No description available.

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.

Diss. (sammanfattning) Linköping : Linköpings universitet, 2008. / Härtill 4 uppsatser.

Thesis (M.S.)--Villanova University, 2008. / Chemistry Dept. Includes bibliographical references.

Thesis (M.S. in Meteorology)--Naval Postgraduate School, Dec. 2004. / Thesis Advisor(s): Carlyle H. Wash. Includes bibliographical references (p. 99-101). Also available online.

Thesis (Honors)--College of William and Mary, 2009. / Includes bibliographical references (leaves 75-78). Also available via the World Wide Web.

Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Diss. (sammanfattning) Göteborg : Univ. , 2010.