Elevated arsenic concentrations have been reported in a drinking water and irrigation-supply aquifer of Stuarts Point, New South Wales, Australia. Arsenic occurrence in such aquifers is potentially a major issue due to their common use for high yield domestic and irrigation water supplies. Ten multi-level piezometers were installed to depths of approximately 30 m in the sand and clay aquifer. Sediment samples were collected at specific depths during drilling and analysed for chemical and mineralogical composition, grain size characteristics, potential for arsenic release from solid phase and detailed microscopic features. From this data, a full geomorphic reconstruction allowed the determination of source provenance for the aquifer sediments. The model proposed herein provides evidence that the bulk of the aquifer was deposited under intermittent fluvial and estuarine conditions; and that all sediments derive from the regional arsenicmineralised hinterland. More than 200 groundwater samples were collected and analysed for over 50 variables. The heterogeneity of the aquifer sediments causes redox stratification to occur, which in turn governs arsenic mobility in the groundwater. The bulk of the aquifer is composed of fluvial sand deposits undergoing reductive dissolution of iron oxides. Arsenic adsorbed to iron oxide minerals is released during dissolution but re-adsorbs to other iron oxides present in this part of the aquifer. The deeper, more reducing fluvial sand and estuarine clay groundwaters have undergone complete reductive dissolution of iron oxides resulting in the subsequent mobilisation of arsenic into groundwater. Some of this arsenic has been incorporated into iron sulfide mineral precipitates, forming current arsenian pyrite sinks within the aquifer. The extraction of groundwater from the aquifer for irrigation and drinking water supply induces seawater intrusion of arsenic-rich estuarine water, bringing further dissolved arsenic into the aquifer. A greater understanding of the source, sinks and mobilisation of arsenic in this aquifer contributes to our broad understanding of arsenic in the environment; and allows aquifer specific management procedures and research recommendations to be made. Any coastal or unconsolidated aquifer that has sediments derived from mineralised provenances should consider monitoring for arsenic, and other potentially toxic trace elements, in their groundwater systems.

Elevated arsenic concentrations have been reported in a drinking water and irrigation-supply aquifer of Stuarts Point, New South Wales, Australia. Arsenic occurrence in such aquifers is potentially a major issue due to their common use for high yield domestic and irrigation water supplies. Ten multi-level piezometers were installed to depths of approximately 30 m in the sand and clay aquifer. Sediment samples were collected at specific depths during drilling and analysed for chemical and mineralogical composition, grain size characteristics, potential for arsenic release from solid phase and detailed microscopic features. From this data, a full geomorphic reconstruction allowed the determination of source provenance for the aquifer sediments. The model proposed herein provides evidence that the bulk of the aquifer was deposited under intermittent fluvial and estuarine conditions; and that all sediments derive from the regional arsenicmineralised hinterland. More than 200 groundwater samples were collected and analysed for over 50 variables. The heterogeneity of the aquifer sediments causes redox stratification to occur, which in turn governs arsenic mobility in the groundwater. The bulk of the aquifer is composed of fluvial sand deposits undergoing reductive dissolution of iron oxides. Arsenic adsorbed to iron oxide minerals is released during dissolution but re-adsorbs to other iron oxides present in this part of the aquifer. The deeper, more reducing fluvial sand and estuarine clay groundwaters have undergone complete reductive dissolution of iron oxides resulting in the subsequent mobilisation of arsenic into groundwater. Some of this arsenic has been incorporated into iron sulfide mineral precipitates, forming current arsenian pyrite sinks within the aquifer. The extraction of groundwater from the aquifer for irrigation and drinking water supply induces seawater intrusion of arsenic-rich estuarine water, bringing further dissolved arsenic into the aquifer. A greater understanding of the source, sinks and mobilisation of arsenic in this aquifer contributes to our broad understanding of arsenic in the environment; and allows aquifer specific management procedures and research recommendations to be made. Any coastal or unconsolidated aquifer that has sediments derived from mineralised provenances should consider monitoring for arsenic, and other potentially toxic trace elements, in their groundwater systems.

Geological carbon sequestration, as a method of atmospheric greenhouse gas reduction, is at the technological forefront of the climate change movement. During sequestration, carbon dioxide (CO���) gas effluent is captured from coal fired power plants and is injected into a storage saline aquifer or depleted oil reservoir. In an effort to fully understand and optimize CO��� trapping efficiency, the capillary trapping mechanisms that immobilize subsurface CO��� were analyzed at the pore-scale. Pairs of proxy fluids representing the range of in situ supercritical CO��� and brine conditions were used during experimentation. The two fluids (identified as wetting and non-wetting) were imbibed and drained from a flow cell apparatus containing a sintered glass bead column. Experimental and fluid parameters, such as interfacial tension, fluid viscosities and flow rate, were altered to characterize their relative impact on capillary trapping. Computed x-ray microtomography (CMT) was used to identify immobilized CO��� (non-wetting fluid) volumes after imbibition and drainage events. CMT analyzed data suggests that capillary behavior in glass bead systems do not follow the same trends as in consolidated natural material systems. An analysis of the disconnected phases in both the initial and final flood events indicate that the final (residual) amount of trapped non-wetting phase has a strong linear dependence on the original amount of non-wetting phase (after primary imbibition), which corresponds to the amount of gas or oil present in the formation prior to CO��� injection. More importantly, the residual trapped gas was also observed to increase with increasing non-wetting fluid phase viscosity. This suggests that CO��� sequestration can be optimized in two ways: through characterization of the trapped fluid present in the formation prior to injection and through alterations to the viscosity of supercritical CO2. / Graduation date: 2013

<p>The aim of this study was to test whether one could use the same methods as used for sampling heavy metals and apply them to radioactive elements. Furthermore a sampling protocol was developed, the first of its kind, for the sampling of radioactive elements in fractured rock aquifers. This was achieved by initially examining local as well as international manuals and methods. The aforementioned was done in conjunction with a literature review of the movement of radioactive elements in these fractured rock aquifers. Beaufort West was utilised as a study area and the geology, hydrogeology and topography was outlined. Background radioactivity was generally acceptable except for two samples which were anomalously high. Taking cognisance of the methods used, as well as those previously applied in the area and abroad, a sampling protocol for radioactive elements in fractured rock aquifers was developed and attached as an appendix. In conclusion it was suggested that multiple methods be tested on one well in order to check whether similar results would occur. This would thus determine the best applicable methods. Also it was proposed that a new method, called DGT sampling, be applied in order to gain a time weighted average of the heavy metals and radioactive elements in groundwater. It could also be clearly seen, by comparing historical data and the current data, that the methods used for sampling heavy metal can be applied to radioactivity.</p>

Although deep saline aquifers are found in all sedimentary basins and provide very large storage capacities, a little is known about them because they are rarely a target for the exploration. Furthermore, nearly all the experiments and simulations made for CO2 sequestration in deep saline aquifers are related to the sandstone formations. The aim of this study is to create a predictive model to estimate the CO2 storage capacity of the deep saline carbonate aquifers since a little is known about them. To create a predictive model, the variables which affect the CO2 storage capacity and their ranges are determined from published literature data. They are rock properties (porosity, permeability, vertical to horizontal permeability ratio), fluid properties (irreducible water saturation, gas permeability end point, Corey water and gas coefficients), reaction properties (forward and backward reaction rates) and reservoir properties (depth, pressure gradient, temperature gradient, formation dip angle, salinity), diffusion coefficient and Kozeny-Carman Coefficient. Other parameters such as pore volume compressibility and density of brine are calculated from correlations found in literature. To cover all possibilities, Latin Hypercube Space Filling Design is used to construct 100 simulation cases and CMG STARS is used for simulation runs. By using least squares method, a linear correlation is found to calculate CO2 storage capacity of the deep saline carbonate aquifers with a correlation coefficient 0.81 by using variables found from literature and simulation results. Numerical dispersion effects have been considered by increasing the grid dimensions. It has been found that correlation coefficient decreased to 0.77 when the grid size was increased from 250 ft to 750 ft. The sensitivity analysis shows that the most important parameter that affects CO2 storage capacity is depth since the pressure difference between formation pressure and fracture pressure increases with depth. Also, CO2 storage mechanisms are investigated at the end of 300 years of simulation. Most of the gas (up to 90%) injected into formation dissolves into the formation water and negligible amount of CO2 reacts with carbonate. This result is consistent with sensitivity analysis results since the variables affecting the solubility of CO2 in brine have greater affect on storage capacity of aquifers. Dimensionless linear and nonlinear predictive models are constructed to estimate the CO2 storage capacity of all deep saline carbonate aquifers and it is found that the best dimensionless predictive model is linear one independent of bulk volume of the aquifer.

Excessive pumping in coastal aquifers results in seawater intrusion where optimal and efficient planning is essential. In this study, numerical solution of single potential solution by Strack is combined with genetic algorithm (GA) to find the maximum extraction amount in a coastal aquifer. Seawater intrusion is tracked with the potential value at the extraction well locations. A code is developed by combining GA and a subroutine repeatedly calling MODFLOW as a numerical solver to calculate the potential distribution for different configurations of solution (trial solutions). Potential distributions are used to evaluate the fitness values for GA. The developed model is applied to a previous work by Mantoglou. Another heuristic method, simulated annealing (SA) is utilized to compare the results of GA. Different seawater prevention methods (i.e. injection wells, canals) and decision variables related to those methods (i.e. location of the injection wells or canals) are added to model to further prevent the seawater intrusion and improve the coastal aquifer benefit. A method called &ldquo / Alternating Constraints Method&rdquo / is introduced to improve the solution for the cases with variable location. The results show that both proposed method and the regular solution with GA or SA prove to be successful methods for the optimal management of coastal aquifers.

Concerns about elevated atmospheric carbon dioxide (CO 2 ) and the effect on global climate have created proposals for the reduction of carbon emissions from large stationary sources, such as power plants. Carbon dioxide capture and sequestration (CCS) in deep geologic units is being considered by Florida electric-utilities. Carbon dioxide-enhanced oil recovery (CO 2 -EOR) is a form of CCS that could offset some of the costs associated with geologic sequestration. Two potential reservoirs for geologic sequestration were evaluated in south-central and southern Florida: the Paleocene Cedar Keys Formation/Upper Cretaceous Lawson Formation (CKLIZ) and the Lower Cretaceous Sunniland Formation along the Sunniland Trend (Trend). The Trend is a slightly arcuate band in southwest Florida that is about 233 kilometers long and 32 kilometers wide, and contains oil plays within the Sunniland Formation at depths starting around 3,414 meters below land surface, which are confined to mound-like structures made of coarse fossil fragments, mostly rudistids. The Trend commercial oil fields of the South Florida Basin have an average porosity of 16% within the oil-producing Sunniland Formation, and collectively have an estimated storage capacity of around 26 million tons of CO 2 . The Sunniland Formation throughout the entire Trend has an average porosity of 14% and an estimated storage capacity of about 1.2 billion tons of CO 2 (BtCO2 ). The CKLIZ has an average porosity of 23% and an estimated storage capacity of approximately 79 BtCO 2 . Porous intervals within the CKLIZ and Sunniland Formation are laterally homogeneous, and low-permeability layers throughout the units provide significant vertical heterogeneity. The CKLIZ and Sunniland Formation are considered potentially suitable for CCS operations because of their geographic locations, appropriate depths, high porosities, estimated storage capacities, and potentiallyeffective seals. The Trend oil fields are suitable for CO 2 -EOR in the Sunniland Formation due to appropriate injected-CO 2 density, uniform intergranular porosity, suitable API density of formation-oil, sufficient production zones, and adequate remaining oil-in-place following secondary recovery. In addition to these in-depth investigations of the CKLIZ and Sunniland Formation, a more-cursory assessment of deep geologic units throughout the state of Florida, which includes rocks of Paleocene and Upper Cretaceous age through to rocks of Ordovician age, shows additional units in Florida that may be suitable for CO 2 -EOR and CCS operations. Furthermore, this study shows that deep geologic units throughout Florida potentially have the capacity to sequester billions of tons of CO 2 for hundreds of fossil-fuel-fired power plants. Geologic sequestration has not yet been conducted in Florida, and its implementation could prove useful to Florida utility companies, as well as to other energy-utilities in the southeastern United States.

Texas water resources are under pressure due to population growth expected in the coming decades, increasing industrial demands, and frequent periods of drought. With this increasing demand for limited water resources it is important to explore alternative water sources within the State. One of those resources that can be developed is the many small aquifers which have never been well-characterized but could be an alternative source of fresh and brackish water for agriculture, municipal, and industrial applications. The natural gas industry’s demand for water is growing in Texas as new drilling techniques such a hydraulic fracturing have opened new reserves previously considered economically non-viable. The development of smaller aquifers containing brackish water is a viable alternative to the gas industry’s current reliance on fresh (potable) groundwater resources. The aquifer sections containing brackish water need to be mapped and characterized so they can be developed as an alternative water resource by the gas industry. The Barnett Shale in North-central Texas is one of the first major gas plays in the United States to use the technique of hydraulic fracturing in field development. This technique requires large quantities of water to create the required hydraulic pressure down the gas well to fracture the normally low permeability shale. A typical horizontal well completion consumes approximately 3.0 to 3.5 million gallons (11,400 to 13,200 m3) of fresh water. Projections of future groundwater demand for the Barnett Shale gas play total 417,000 AF (5.1x108 m3), an annual average of 22,000 AF (2.7x107 m3) over the expected 2007-2025 development phase. This level of water demand has the gas industry and groundwater managers exploring alternative sources of water for future development of the Barnett Shale. One alternative source of water for the expanding footprint of the Barnett Shale gas play are the smaller local Paleozoic aquifers on the western edge of the play. These small aquifers are underutilized and contain waters with higher levels of TDS. These levels are, however, acceptable to the drilling industry. In order to characterize theses aquifers, TWDB databases were utilized to analyze water chemistry and well productivity. / text

Caves, the cornerstone feature of karst aquifers, are little understood in Florida. This dissertation, which analyzes the morphology, elevation, lithologic setting, and hydrology of caves in west-central Florida, demonstrates that the karst of the unconfined Floridan aquifer differs from the paradigm view of karst presented in modern geology textbooks. The differences reflect setting: eogenetic (west-central Florida) vs. telogenetic (conventional). Interpretations about the architecture of cavernous porosity in this dissertation come from detailed surveys (497 stations) of seven air-filled caves.The surveys reveal that solution cavities within the unconfined Floridan aquifer align along NE-SW and NW-SE fractures. The surveys further identify tabular zones of cavernous porosity that extend for tens of meters. Characteristic "plus-sign" passages occur at the intersection of solution-enlarged fractures and the tabular horizons. The caves, as surveyed, do not connect points of discrete aquifer input to springs. Rather, they are separated by intact bocks of aquifer matrix, ever- narrowing fissures, sediment fills, and breakdown. With an additional 574 spot elevations from 63 previously surveyed air-filled and submerged caves and 526 foot-length cavities encountered in 26 drilled wells, the assembled data reveal that cave passages above and below the watertable of the unconfined Floridan aquifer cluster at similar elevations throughout west-central Florida. At the largest scale, the levels of cavities cut across geologic structure, thus suggesting a water-table origin. The close linkage of the water table and sea level this coastal setting suggests the levels reflect positions of paleosea level. Given that the air-filled caves in west-central Florida reflect higher sea levels,the coastline would have been close when the air-filled caves formed. The levels organize according to a sea-level datum at elevations of 30 m, 20-22 m, 12-15 m,and 3-5 m. The levels are similar in elevation to nearby terraces evident in GIS and LIDAR topographic data. The terraces correspond to the classic, Quaternary marine terraces of the coastal plain of the southeastern U.S.A. Given that the now-submerged caves reflect lower sea levels, the coastline was far from the caves when they formed. They organize according to a watertable datum at depths of 15 m, 30-40 m, 60-70 m, and > 100 m with some correspondence to marine terrace and paleoshoreline features identified on the sea floor of the west florida shelf using GIS and multibeam bathymetry. The multigenerational origin of these deeper caves masks the correspondence. Although past water tables are seen to be the first-order control of cave passages regionally, lithology appears to play a significant role at the scale of an individual cave. Approximately 2,000 measurements of matrix permeability from more than 228 m of continuous core from the unconfined Floridan aquifer of west-central Florida reveal a wide-ranging facies-dependent matrix permeability[log k(m2)= -12.9 +/- 1.6, total range]. Solution passages tend to be wider where the matrix permeability is greater. Time-series analysis on measurements of spring discharge from 31 springs and published time series from 28 additional sites reveal key differences between eogenetic and telogenetic karst aquifers, reflecting the difference in matrix permeability of the eogenetic [log k(m2) from -14 to -11] and telogenetic[log k(m2) from -15 to -20] limestones. For instance, log Q/Qmin flow-duration curves have greater slopes at eogenetic karst springs, a manifestation of lowerratios between the maximum and mean discharge (Qmax/Qmean). Additionally,aquifer inertia as defined on auto correlograms is greater in eogenetic karst than telogenetic karst.Hydrographs of spring flow and water level vary on a seasonal or longertime scale. The localized, convective-style storm events typical of the Florida summer rainy season are not realized as individual peaks in these hydrographs.Apparently, large, widespread, storm events, such as hurricanes in the late summer and fall and frontal systems in the winter and spring, are necessary to produce significant changes in storage. Data from nine pressure transducers in caves and in the aquifer matrix across the unconfined Floridan aquifer all record immediate increases in the water level due to Hurricanes Frances and Jeanne in September of 2004. The increases are simultaneous over large regions. These changes do not propagate through the aquifer as a pulse like the classic scenario of conduit flow in telogenetic karst aquifers.

The assumption of perfect stratification in an aquifer has been widely used in solute-transport modeling studies. This assumption is especially useful for applied studies where limited site characterization data are available, but geologic well logs indicate significant layering. Chapter 3 investigates the issue of vertical sampling density via a sensitivity analysis of the number of aquifer layers used in a model of tracer transport through a heterogeneous synthetic aquifer. Tracer breakthrough in the synthetic aquifer is predicted by layered models. Given a variance of ln K of 2 and an exponential covariance function, sampling the synthetic aquifer at more than 12 elevations did not produce any significant improvement in the predictions. Even six sampling points, however, produced more accurate predictions of transport compared to a full-aquifer, homogeneous approach employing a local-scale dispersivity. Chapter 4 presents and interprets data from a dual-well, forced-gradient tracer experiment conducted in a confined aquifer underlying a contaminant source zone of a Superfund site. Tracer breakthrough was monitored at an extraction well and at four levels of a centerline monitoring well. A perfectly stratified numerical transport model based on multi-level data successfully predicted tracer breakthrough at the extraction well. Given the added vertical resolution associated with the layered model, it was possible to use dispersivity values more than an order of magnitude lower than the value used in a vertically integrated model. It is expected that the multi-layer model would allow for more robust analyses of solute transport at the site. In Chapter 5, TCE elution during the same dual-well experiment is predicted with a stratified numerical model incorporating rate-limited desorption, rate-limited diffusion, and rate-limited dissolution of nonaqueous phase liquid (NAPL). Based on model results, initial mass calculations, and other indirect lines of evidence, it is concluded that NAPL is the primary cause of rate limitations for TCE transport at the site. NAPL presence is the primary reason a large pump-and-treat system at the site has failed to reduce contaminant concentrations to federal drinking water standards. Alternative remediation technologies are thus necessary for restoring the aquifer, especially in the contaminant source zone.