http://hdl.handle.net/10092/23 2013-05-18T08:07:24Z http://hdl.handle.net/10092/4509 Title: Geomorphological and geophysical investigation of the effects of active tectonic deformation on the hydrogeology of North Culverden Basin, North Canterbury Authors: Armstrong, Mark James Abstract: This thesis examines the complex interaction between the tectonic evolution of Culverden Basin and the Late Quaternary sediments, which form the aquifer-bearing deposits, using geological and geomorphological mapping as well as near-surface geophysical investigations. Along the eastern margin of Culverden Basin, the deformation associated with the actively widening Australian-Pacific plate boundary zone, has resulted in the evolution of Culverden Basin and the progressive inversion of the basin floor. The eastern margin of the basin is structurally controlled by a NE trending, complexly segmented range-front fault system and associated thrust-propagated anticlines forming the basin boundary. Basin inversion is driven by the westward propagation of footwall imbricate thrusts and associated folds. The inversion of the basin floor lead to the creation of sub-basins within the larger basin, which have controlled the distribution and architecture of the Late Quaternary stratigraphy. The Late Quaternary sedimentary record documents periods of climatically induced aggradation during cold conditions and degradation in the intervening warmer times. The interaction between the sedimentation and ongoing tectonic deformation has resulted in complex lithological relationships between the locally sourced alluvial fans and the glacial outwash deposits of the major rivers entering the basin. The architecture of the aquifers is therefore controlled by the changing fluvial regime and its interaction with the evolving sub-basins. The progressive evolution of the sub-basins leads to increasing complexities in the facies relationships and to the confinement of the deposits into progressively smaller portions of the sub-basins. Once the basin boundaries become emergent, the basin becomes isolated, and potentially cut-off from its groundwater recharge source. Leonard Mound is an actively evolving imbricate thrust system along the eastern margin of Culverden Basin that has isolated the Wynyard sub-basin from the central portion of Culverden Basin, during the Late Pleistocene and present. The emergence of Leonard Mound is preventing the recharge to the Wynyard sub-basin from the high yielding aquifers of the central portion of the basin. In the central portion of Culverden Basin, high natural recharge combined with an irrigation scheme has allowed for transformation of the basin into a major dairy farming centre. In contrast, the Wynyard sub-basin is still subjected to frequent summer droughts, making it desirable to find a better source of groundwater for the eastern margin of the basin. The hydrogeological model provided by the Culverden Basin almost certainly has wider implications to the groundwater resources of other basins in similar active tectonic settings. 2000-01-01T00:00:00Z http://hdl.handle.net/10092/7735 Title: The constitution of the aldobionic acid from phormium hemicellulose Authors: Mauger, R. P. Abstract: The term “Hemicellulose” is applied to the cell-wall constituents extracted from plant tissues by cold 4% sodium hydroxide, after preliminary extractions with cold water and 0.5% ammonium oxalate to remove pectic substances and water-soluble materials. The originator of the name was Schultze who, in 1891 and succeeding years, isolated there substances from a number of plant materials by extraction with dilute alkali and precipitation with acid. He observed that they were far more susceptible to dilute acid hydrolysis than cellulose, and believed them to be in some way related to cellulose, probably as intermediates in its formation. Although the eludication of the structure of cellulose and the analysis of hemicellulose have shown that there is little foundation for this belief, the name “hemicellulose” still persists. Hemicelluloses are polysaccharides which generally contain uronic acid. One of the few well-authenticated true hexosans that may be removed by alkali from the cell-wall of a higher plant is the mannan of the ivory nut. When dried by alcohol, hemicellulose preparations are obtained as fine, white or cream, amorphous powders; whereas, if dried from water, they form an extremely hard, horny mass, which will redissolve only with difficulty even if finely ground. The hemicelluloses are optically active, and usually more or less strongly laevo-rotatory. The majority of hemicellulose preparations give either no colour or a slightly greenish colour with iodine. The hemicellulose “A” of black-locust and of English oak sap-woods, precipitated by hydrochloric acid, was found to give a strong blue colouration with iodine. Anderson (1940) found that those hemicelluloses which are coloured by iodine solution usually give some d-glucose along with d-xylose in the products of hydrolysis. O’Dwyer suggests that in these hemicelluloses, anhydro-glucose units form a part of the molecule. It is more probable however, that they are derived from starch associated with it. 1943-01-01T00:00:00Z http://hdl.handle.net/10092/7734 Title: Vibrational spectral studies and crystal analysis of coordination complexes Authors: Janson, V. Abstract: There are many physical or physico-chemical methods available for studying the various properties of chemical compounds. These methods can be conveniently classified into classes which are determined by the purpose of the investigation. Those used to elucidate molecular structure fall into two classes. The first, which includes x-ray, neutron, and electron diffraction yields detailed information about the whole structure of the molecule. These techniques introduce a metrical element into the understanding of the complex, revealing the lengths of the chemical bonds, the angles between them, and other structural details such as the various forms of isomerism in the topological and conformational arrangements of polydentate ligands about the metal centre. The second gives fragmentary information concerning individual bonds of a particular group of atoms in the molecule. This class includes optical rotatory dispersion, circular dichrosism, the measurement of electric and magnetic moments, and various kinds of spectroscopy of the region ranging from microwave to ultraviolet. The last two groups should yield information mostly in the area of the electronic structure of the molecule. The last group covers vibrational spectroscopy which originates in the vibrations of the nuclei constituting a molecule. Vibrational spectra are observed both as infrared and Raman spectra, and the frequencies of the vibrational transitions are determined by the masses of the constituent atoms, the molecular geometry and the interatomic forces. The intensities of infrared and Raman spectra are related to the changes in dipole moment and polarisability, respectively. Attempts have been made to analyse the vibrational spectra quantitatively. Though there has been some success, work on many aspects (such as intensity in relation to bonding) is sparse. Nevertheless, the understanding of the molecular and the electronic structure of some molecules can be much extended by employing a combination of methods. This thesis consists of two main sections. The first describes the vibrational spectral studies of diarsine complexes. Most of the spectral work is centred around the low infrared frequency region. Raman spectra of two complexes are reported and characterised by their metal-ligand sensitive absorptions. The frequencies of these assignments are used to calculate the frequencies of the infrared active metal-ligand vibrations. The frequencies assigned to the metal-ligand vibration of diarsine complexes are analysed in terms of the change in electronic configuration of the transition element. It is hoped that the inferences obtained from the vibrational may elucidate the bonding in these complexes. These results are checked against those derived from the data given in x-ray and electron spin resonance (e.s.r.) spectral studies. The second main section gives a description of the crystal and the molecular structure of cobalt triethylenetetramine glycinato dichloride, 𝚫-𝛃2'-(RS)-(Co(trien)(gly)) Cl2.H2O. It belongs to a series of cobalt(III) polyamino compounds containing asymmetric nitrogen centres. These polyamino complexes can display various forms of isomerism in their topological and confrontational arrangements. The reasons for the study of this particular complex are many, and are given in the Introduction to Crystal Studies. However, the primary reason is that precise molecular geometry is of great importance as a check on the predicted molecular geometry derived from energy minimisation techniques. 1972-01-01T00:00:00Z http://hdl.handle.net/10092/7733 Title: The solubility of silver chloride in a mixed solvent from 15°C to 45°C Authors: Davis, D. J. O'D Abstract: The qualitative parallelism between the solubility of ionic crystals and the dielectric constant of the solvent medium has long been recognised and the more recent development of theories regarding the interaction between ions and solvent has lead to increasing use of solubility data for the estimation of ionic diameters and the degree of solvation of ions. A quantitative expression for this relation may be found from Born's equation, which gives the work of transfer of an ion, assumed spherical, carrying charge ziε, from a medium of dielectric constant D1‚ to a medium of dielectric constant D2‚ as [equation] where a1 is the ionic radius. This work of transfer can be equated to a free energy change, whose value [equation] Per ion, where f1‚ and f2‚ are the activity coefficients of the ion in the two media. 1940-01-01T00:00:00Z