School of Earth Sciences - Theses
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ItemDetection of uranium(VI) in groundwater using a field electroanalytical technique( 1999)In this thesis electroanalytical methods are investigated and a new method developed to determine uranium(VI) in groundwater samples. Differential pulse polarography, differential pulse voltammetry and adsorptive stripping voltammetry methods, with appropriate mercury drop electrodes, were optimised using the adsorptive chelate 2,5-dichloro-3,6-dihydroxy-l,4-benzoquinone (chloranilic acid). An alternative adsorptive stripping voltammetry method, with a hanging mercury drop electrode, was optimised using the chelate 8-hydroxyquinoline (oxine). The liquid mercury requirements of these techniques limit their use in the field. Therefore, mercury film electrode methods that are potentially better suited to field conditions are investigated. Chloranilic acid was found to be a suitable chelating agent for uranium determination in combination with a hanging mercury drop electrode, but the reduction of chloranilic acid was a concern. A new mercury film electrode determination method using chloranilic acid was developed but was found to result in the deterioration of the MFE to the extent of rendering the method unsuitable for uranium determination. An adsorptive stripping voltammetry, MFE method with oxine was investigated. The inability to remove the uranyl-oxine reaction products from the MFE created a memory effect that contributed to a lack of accuracy and precision when performing standard addition determinations. This interference was a significant factor in the inability to reliably measure a uranium response using an adsorptive stripping potentiometry method with oxine. The technique of square wave adsorptive stripping voltammetry with oxine in combination with a hanging mercury drop electrode was found to be the most appropriate method for uranium determination. The method was fast, sensitive, precise and accurate when analysing standard solutions. A low detection limit of 2.7 µg/L was achieved. Groundwater and surface water samples were analysed by the AdSV, HMDE method with oxine. The mineral spring water samples from Daylesford, Victoria, were high in ionic content and contained interfering ions. The unacidified samples contained high concentrations of dissolved C02 that needed to be removed prior to sample analysis to prevent pH changes during analysis. Of six unacidified samples uranium was found in only one sample, the Tipperary Spring sample at 4.9 µg/L U(VI). Interference prevented confirmation of this concentration in the acidified Tipperary Spring sample. The construction of a linear standard addition plot with a positive x-intercept was a common outcome for both the unacidified and the acidified spring samples. The uranium concentration was determined in three surface water samples collected from the Ranger Uranium Mine in the Northern Territory. Matrix interference in these surface water samples resulted in non-linearity for two standard addition determinations. A third sample was successfully analysed to give a concentration of 23 µg/L U(VI), which is in good agreement with an independent determination. The unselective nature of oxine was found to result in significant interference when analysing environmental samples by the AdSV, HMDE method with oxine. This method was found to be inappropriate for field analysis of environmental samples. However, in a laboratory environment the AdSV, HMDE method with oxine was the best performing method when determining uranium in standard solutions.
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ItemThe geology and hydrogeology of the Corangamite region( 1971)Tectonic activity after the early Cretaceous resulted in a complete change in the depositional environment in the sedimentary basin - the Otway Basin - located to the south of the Western Highlands of Victoria and to the west of Melbourne. ThiS Basin became subject to increasing marine influences and the sediments deposited include thick sequences of Miocene marls: the Gellibrand Marl. The water in the marls and in the underlying sands of the Dilwyn Formation is saline near Lake Corangamite but elsewhere water of good quality is found in the sand aquifers, indicating that tectonic activity has caused the local isolation of the lower formation from the effects of flushing by fresher groundwater. Continued tectonic activity and associated volcanic activity during the Miocene and Lower Pliocene resulted firstly in the regression of the sea then the development of the internal drainage characteristic of the Corangamite Region. The sea probably retreated to the southeast as indicated by the unusual parallel physiographic features which have influenced the flows of 'earlier' Newer Volcanic lavas in the Curdie River area and the subsequent development of this river's drainage system. These features are probably related to remanent coast strandlines. The quality of the groundwater found in the 'earlier' lavas is generally poor but the basalts and tuffs of the 'later' Newer Volcanic age often contain water of low salinity, particularly in the intake areas which are located in the ‘stony rises' or near the volcanic cones. The intake area water of the Mt. Warrion basalts is a low salinity calcium-magnesium-bicarbonate water, having an unusually high nitrate content. As the salinity of the water increases away from the intake area the chemical nature of the water approaches that of a dilute sea water. This has been interpreted as being the result of a release of 'oceanic' connate salts by weathering of the calcareous material found in the tuffs and scoria beds of the volcanic cones. The material has been derived from the underlying marl sequence and has been incorporated into the igneous rocks during eruption. The high nitrate concentration has been attributed to the effects of pollution, since there is some evidence that the nitrate values have increased over the last sixty years, but there is also probably an increased rate of fixation in the intake area due to the effects of cultivation. The high bicarbonate values are probably due to a high rate of absorption of carbon dioxide from the atmosphere in the intake areas. The hydraulic characteristic of the basalts ensures the rapid distribution at the high nitrate and bicarbonate waters of the intake area over large areas, hence the effects of pollution are more readily noticeable. The groundwater regime plays an important role in the transfer of dissolved salts in the mainly saline water domain of the Corangamite Region. The study of the water and salt content of some of the lakes of the area indicates that a balance exists that results in the maintenance of a specific lake salinity within narrow limits, and in which the groundwater regime is often involved. By considering the salt balance and water balance of a system as one parameter, referred to as the Hydro Salinity Factor, a simple mathematical model can be postulated to determine some of the unknown factors involved in the maintenance of an equilibrium salinity in a lake. The drilling programme and groundwater investigation outlined an important water resource located in the Warrion area. Already 40 bores have been drilled in this area and they produce 6.6 x 105m3 /year (800 acre feet/year). There is an annual underflow of about 1.5 x 107 m3 (12,000 acre feet). This quantity is well within the 'safe yield' of the area and further development should be encouraged, but because of the presence of the large number of saline lakes in the area, saline water intrusion into the basalts would rapidly occur if the groundwater levels are lowered beneath the lake levels.