This dissertation presents the results of laboratory experiments in which essential aspects of the movement of F- in saturated media have been addressed. The interactions between F-solutions and quartz, vermiculite, and kaolinite were studied through batch and column experiments. Quartz was found to react slightly with F⁻ , giving data described by a quasi-linear isotherm. Vermiculite adsorbed only minute amounts of F. A large uptake of F⁻ by kaolinite was measured. Ion exchange F⁻ by 0H⁻. may not have been the exclusive mechanism operating under the experimental conditions. The kinetics of the dissolution of fluorite (CaF₂) were investigated by means of batch and column tests. There appears to be a relationship between the dissolution rate and the mean flow velocity. Solution pHs greater than 5-6 may accelerate the dissolution process. For temperatures between 15 and 30°C, the dissolution is characterized by an activation energy of about 7 Kcal/mole, which would indicate that both surface reaction and transport are the rate-limiting step. The percolation of columns containing quartz, vermiculite, and kaolinite with multi-component solutions (including F⁻) resulted in a late breakthrough of F⁻ when compared with that of the other species. Circulation of distilled water led to an almost complete recovery of the F⁻ injected, which exited the column with relative concentrations greater than 1. When the packing included fluorite and distilled water was flushed through the column for 2 days, a concentration of F⁻ of about 1.3 pprn was rapidly reached and remained constant throughout the run. Multivariate analysis techniques (factor and correspondence analyses) were applied to data from two aquifers known to carry high F-waters. Although helpful in discriminating major and minor associations of species, none of those techniques could help unravel the behavior of F⁻ in the study aquifers. It is suggested that laboratory and field studies be continued and that, for the successful modeling of the movement and distribution of F⁻ in aquifers, non-linear source/sink terms should be included in the pertinent differential equation governing the transport of solutes.

Recent years have seen increasing use of atmospheric radionuclides for dating and tracing hydrogeologic processes. Hydrologists often assume that meteoric sources of these nuclides are dominant in ground water and that age-dating methods are limited primarily by analytical detection capability. However, in some cases, subsurface production may also limit the usefulness of these nuclides for dating. Equilibrium radionuclide concentrations are calculated as a function of depth for a variety of rock types. Production mechanisms include fissioning of heavy radionuclides; spallation by cosmic-ray nucleons; capture of neutrons, a-particles, muons and protons; and photonuclear reactions. Calculations indicate that deep subsurface production of ³H, ¹⁴c, ⁸⁵Kr and ⁹⁹Tc is generally below detection but that deep production of ³⁶C1, ³⁹Ar, ⁸¹Kr and ¹²⁹I establishes limits to age-dating of water in most rocks. Parameters for estimating production of ¹⁰Be, ²²Na, ²⁶Al, ³⁷Ar, ³²Si, ⁴¹Ca and ⁷⁹Se are included in appendices. Evidence for in-situ production of ³⁶C1 and ¹²⁹I is presented for two field studies. Concentrations in ground water from the Stripa granite, Sweden, were determined by accelerator mass spectrometry. ¹²⁹I values range from 1,000 to 200,000 atoms/ml, compared to an estimated background concentration in pre-1945 water of 20 atoms/ml. The high levels are attributed to production by spontaneous fission of ²³⁸U in the granite (44 ppm U). ³⁶C1/C1 ratios range from 50-200 x 10 -15 compared to about 40 x 10⁻¹⁵ in meteoric recharge. An increase in ratios with depth has been attributed to production of ³⁶C1 by neutron- capture on ³⁵C1 and is used to set upper limits on the residence time of water in the granite. The validity of using ³⁶C1/C1 ratios as a monitor of deep lithospheric neutron fluxes was tested by measuring the ratios in Cl extracted from Stripa granite. The average ratio, 190 x 10⁻¹⁵, agrees with ratios calculated based on rock chemistry, 190 x 10⁻¹⁵, and on the measured neutron flux, 220 x 10⁻¹⁵. ¹²⁹I and ³⁸C1 were also measured in uranium ores from the Koongarra and Ranger deposits, N.T., Australia. Samples from the oxidized ore zone contain only 6-23% of the ¹²⁹I contents predicted for equilibrium, suggesting preferential loss of ¹²⁹I relative to U during weathering. ³⁶C1 is produced as a result of high neutron fluxes in the ore. Measured ³⁶C1/C1 ratios range from 3 x 10 -12 to 1 x 10⁻¹⁰, corresponding to apparent neutron fluxes of 2 x 10⁵ to 1 x 10⁷/cm²/yr.

The cycling of water in the landscape is influenced by climate change on different time scales and in different directions regarding warming or cooling trends. Along with a changing climate, also the landscape and subsurface conditions, such as permafrost extent, may change in a long-term perspective. Permafrost and hydrology are intimately connected but the interactions between them are poorly understood, and the hydrological response to climate change is complex. The first part of this thesis investigates the effects of different drivers of future changes in hydrological flow and water storage components in the present day temperate Forsmark catchment in Sweden. The role of taliks and their influence on the exchange of deep and shallow groundwater in permafrost environments are also studied. This is done by a simulation sequence where the site is exposed to the landscape, climate and permafrost changes expected from site-specific numerical modeling. In the second part of this thesis, present day periglacial hydrological processes are studied in the Two Boat Lake catchment in western Greenland by field and model investigations of the site. The presence of a through talik below the Two Boat Lake, and data from a deep bedrock borehole into the talik, enable studies of the hydrological interactions between the lake and the talik. The spatial and temporal variability of the different water balance components of the catchment are quantified and the interactions between the surface water and the supra- and sub-permafrost groundwater are analyzed. The results show that the investigated changes in climate and permafrost influence hydrology more than the investigated landscape changes. Under permafrost conditions, the general direction of the exchange between deep and shallow groundwater may change relative to unfrozen conditions. The simulation studies of Forsmark show that the relative topography between taliks governs the recharging and discharging conditions, which is consistent with results from Two Boat Lake. The lake is located at high altitude relative to other taliks and hydraulic measurements indicate recharging conditions. The talik recharge is small compared to other water balance components and does not influence the lake level, which instead is found to be controlled by evapotranspiration and water inflow from the active layer. This is concluded from numerical simulations that take into account and combine evapotranspiration with other surface and subsurface hydrological processes. This thesis highlights the need to integrate surface and subsurface process modelling in order to quantitatively understand and represent the dynamics and complexity of hydrological interactions in periglacial catchments.

The Palm Valley oasis in arid central Australia is characterised by stands of palm trees (Livistona mariae). How these unique plants, separated by nearly a 1000 kilometres of arid country from their nearest relatives persist, has long fascinated visitors. Defining the hydrogeology of the Hermannsburg Sandstone, a regionally extensive and thick Devonian sequence of the Amadeus Basin that underlies Palm Valley, is the major thrust of investigation. Appraisal of drilling data shows this aquifer to be a dual porosity fractured rock aquifer which, on a regional scale, behaves as a low permeability, hydraulically continuous resource. Groundwater is low salinity (TDS &lt1000 mg/L) and bicarbonate rich. Slight variations in cation chemistry indicate different flow paths with separate geochemical histories have been sampled. Stable isotope (????H, ???????O) results from Palm Valley show groundwater to have a uniform composition that plots on or near a local meteoric water line. Radiocarbon results are observed to vary from effectively dead (&lt 4%) to 87 % modern carbon. To resolve groundwater age beyond the radiocarbon window the long lived radioisotope 36Cl was also used. Ratios of 36Cl/Cl range from 130 to 290 x 10-15. In this region atmospheric 36Cl/Cl ratio is around 300 x 10-15. Thus an age range of around 300 ka is indicated if, as is apparent, radioactive decay is the only significant cause of 36Cl/Cl variation within the aquifer. A review of previous, often controversial, 36Cl decay studies shows results are usually ambiguous due to lack of certainty when factoring subsurface Cl- addition into decay calculations. Apparently, due to the thickness of the Hermannsburg Sandstone, no subsurface sources of Cl- such as aquitards or halites, are encountered along groundwater flow paths, hence the clear 36Cl decay trend seen. The classic homogenous aquifer with varying surface topography, the &quotToth&quot flow model, is the simplest conceptual model that need be invoked to explain these isotope data. Complexities, associated with local topography flow cells superimposed on the regional gradient, signify groundwater with markedly different flow path lengths has been sampled. The long travel times (&gt 100 ka) indicate groundwater discharge would endure through arid phases associated with Quaternary climate oscillations. Such a flow system can explain the persistence of this arid zone groundwater-dependent ecosystem and highlight the possibility that Palm Valley has acted as a flora refuge since at least the mid- Pleistocene.

Meteorological and environmental (i.e. soil water content) data measured from semiarid watersheds (Lucky Hills and Kendall) during the summer rainy and winter periods were used to study the interrelationships between variables, and to evaluate the effects of variables on the daily estimation of actual evapotranspiration (AET). The relationship between AET and potential evapotranspiration (PET) as a function of an environmental factor was the major consideration of this research. The relationship between AET and PET as a function of soil water content as suggested by Thornthwaite-Mather, Morton and Priestley-Taylor was studied to determine its applicability to the study area. Furthermore, multiple linear regression (MLR) analysis was employed to evaluate the order of importance of the meteorological and soil water factors involved. Finally, the information gained was used for MLR model development. The results of MLR analysis showed that the combined effects of available energy, soil water content and wind speed were responsible for 77 % of the observed variations in AET at Lucky Hills watershed and 70 % at Kendall watershed during the summer rainy period. The analyses also indicated that the combined effects of available energy, vapor pressure deficit and wind speed were responsible for 70 % of the observed variations in AET at Lucky Hills watershed and 72 % at Kendall watershed during the winter period. However, the test results of three different approaches, using the relationships between AET and PET as a function of soil water content indicated some inadequacy. The low correlation between PET, AET, and soil moisture conditions raised some doubt concerning the validity of methods developed elsewhere, and indicated the effects of energy availability on the relationship between PET, AET, and soil water content regardless of the soil water condition. In contrast, agreement between observed AET and estimated AET from MLR models during the summer rainy and winter periods at both watersheds indicated that MLR models can give reasonable estimates of AET, at least under the climatic conditions in which the formulae were developed.

Bank storage is defined as a volume of water that periodically infiltrates a river's banks during increases in stream stage. It is a potentially critical variable for accurately modeling the water budget in semi-arid riparian systems, but is particularly difficult to assess and quantify. It is especially essential for understanding ground-water/surface-water interactions. In collaboration with other projects, a field-scale vadose monitoring effort took place in the San Pedro Riparian National Conservation Area (SPRNCA), Arizona. The San Pedro River flows north from Mexico into the United States, and SPRNCA is a 60 km stretch of U.S.-protected ecosystem north of the border. In addition to a progressive climate of ecological conservation, hydrological research that leads to an improved understanding of the water budget will ultimately improve the prospects for improved water policy decisions. Soil moisture, stream stage, and soil tension data were collected for over 8 consecutive months in both 1997 and 1998, and the data were used as input into a software program called HYDRUS-2D (§imiinek et al. 1996), which models two-dimensional, variably saturated flow. Field-collected data and subsequent modeling efforts suggest that the effects of bank storage were estimated to contribute approximately 8.5% of the river's total flow for 147 days in 1997. Accordingly, bank storage and its effects should be considered in future water-balance simulations of stream-aquifer interaction, and of the San Pedro River in particular. In addition, model estimates of root water uptake match favorably with other estimates of evapotranspiration in the cottonwood-willow forest gallery of the SPRNCA.

The Palm Valley oasis in arid central Australia is characterised by stands of palm trees (Livistona mariae). How these unique plants, separated by nearly a 1000 kilometres of arid country from their nearest relatives persist, has long fascinated visitors. Defining the hydrogeology of the Hermannsburg Sandstone, a regionally extensive and thick Devonian sequence of the Amadeus Basin that underlies Palm Valley, is the major thrust of investigation. Appraisal of drilling data shows this aquifer to be a dual porosity fractured rock aquifer which, on a regional scale, behaves as a low permeability, hydraulically continuous resource. Groundwater is low salinity (TDS &lt1000 mg/L) and bicarbonate rich. Slight variations in cation chemistry indicate different flow paths with separate geochemical histories have been sampled. Stable isotope (????H, ???????O) results from Palm Valley show groundwater to have a uniform composition that plots on or near a local meteoric water line. Radiocarbon results are observed to vary from effectively dead (&lt 4%) to 87 % modern carbon. To resolve groundwater age beyond the radiocarbon window the long lived radioisotope 36Cl was also used. Ratios of 36Cl/Cl range from 130 to 290 x 10-15. In this region atmospheric 36Cl/Cl ratio is around 300 x 10-15. Thus an age range of around 300 ka is indicated if, as is apparent, radioactive decay is the only significant cause of 36Cl/Cl variation within the aquifer. A review of previous, often controversial, 36Cl decay studies shows results are usually ambiguous due to lack of certainty when factoring subsurface Cl- addition into decay calculations. Apparently, due to the thickness of the Hermannsburg Sandstone, no subsurface sources of Cl- such as aquitards or halites, are encountered along groundwater flow paths, hence the clear 36Cl decay trend seen. The classic homogenous aquifer with varying surface topography, the &quotToth&quot flow model, is the simplest conceptual model that need be invoked to explain these isotope data. Complexities, associated with local topography flow cells superimposed on the regional gradient, signify groundwater with markedly different flow path lengths has been sampled. The long travel times (&gt 100 ka) indicate groundwater discharge would endure through arid phases associated with Quaternary climate oscillations. Such a flow system can explain the persistence of this arid zone groundwater-dependent ecosystem and highlight the possibility that Palm Valley has acted as a flora refuge since at least the mid- Pleistocene.

Australia is not only the driest continent, but its streams are among the most variable in the world. To date in Australia there has been no large-scale study of Australia’s low flow hydrologic characteristics, and consequently there is a fundamental need to develop methods that can be readily used to assess the hydrology during times of low flow. This thesis describes the development and derivation of a methodology for the estimation of low flow characteristics and yield in small ungauged rural catchments. The methodology has been applied to 184 catchments located in New South Wales and Victoria, in south-eastern Australia. A systems approach was adopted in which multivariate techniques were used to develop relationships between low flow parameters and climatic and land information data. The low flow and yield parameters considered include: descriptive statistics of monthly and annual flows, ratio of baseflow to total streamflow volumes, streamflow recession constants, flow duration curves for daily, monthly and annual durations, low flow frequency curves for durations from 1 to 284 days, duration of low flow spells below a given threshold, deficiency volume of low flow spells below a given threshold, estimate of storage to satisfy a specified draft at a given level of reliability, and parameters of a simple rainfall-runoff model for conversion of daily rainfall to monthly streamflow volumes.

Thesis (Ph. D. - Hydrology and Water Resources)--University of Arizona, 1986. / Includes bibliographical references (leaves 174-179).

Thesis (M.S.)--Oregon State University, 1988. / Typescript (photocopy). Includes bibliographical references (leaves 129-133). Also available on the World Wide Web.