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.

Monitored natural attenuation has been particularly used at sites where petroleum hydrocarbons and chlorinated solvents have contaminated soil and groundwater. One of the important aspects of the methodology that has been recognized recently is that the mass removal rates, the most important parameter to determine effectiveness of the methodology, is controlled by the groundwater flow regime and the aquifer heterogeneity. Considering this recognition, the primary objective of this study is to quantitatively describe the relationship between the natural attenuation rates and aquifer heterogeneity using numerical simulation techniques. To represent different levels of aquifer heterogeneity, the hydraulic conductivity distribution (ln K) is statistically simulated with the numerical algorithm, Turning Bands Random Field Generator, by changing the statistical parameters, Coefficient of Variation (CV) and correlation length (h) and Visual MODFLOW and RT3D software programs are used for the simulation of groundwater flow and chlorinated solvent transport. Simulation results showed that degradation rates and the shape of the contaminant plumes show variations for different heterogeneity levels. Increasing CV resulted in the decrease in the transport of the plume and shrinkage in the areal extend. On the other hand, &ldquo / h&rdquo / determined the shape and the size of the plume through its affect on mechanical dispersion. For a given &ldquo / h&rdquo / , degradation rates increased with increasing CV, but change in &ldquo / h&rdquo / did not show a regular trend. Such findings are expected to be beneficial when assessing the effectiveness of natural attenuation process for a selected site during the feasibility studies without need for detailed site characterization.

Low-lying coastal plains comprised of unconsolidated infill are internally complex hydrogeological settings, due to the high level of heterogeneity in the infill material. In order to resolve the hydrogeological processes active in these complex settings, an integrated multi-disciplinary, geoscientific approach is required. This research determines quantitatively, the effects of sedimentary aquifer heterogeneity on groundwater flowpaths and groundwater processes within a heavily laterised, coastal plain setting. The study site is the Bells Creek catchment in southeast Queensland, Australia. The methodology developed in this study provides a new approach to enable the determination of groundwater flowpaths and groundwater processes at macroscale resolution within other shallow alluvial and coastal plain aquifers. The multi-disciplinary approach utilises sedimentological, geophysical, chronological and hydrogeological techniques (including hydrochemistry and groundwater flow modelling) to develop a high-resolution aquifer framework, and to determine accurately, both groundwater flowpaths and relative flow rates. Sedimentary framework is confirmed to be the principal factor controlling the distribution of aquifer permeability pathways in any given setting, and is therefore, the dominant control over groundwater flow and processes. For the Bells Creek catchment, interpretation of stratigraphic and sedimentary data allowed the compilation of a detailed sedimentary framework. This interpretation demonstrated that weathering of the low-lying arkose sandstone bedrock has developed thick lateritic profiles. Within the weathering profiles, cemented, iron-rich horizons have resisted erosion and developed raised and elongated ridges in the modern landscape, while other clay-rich weathered layers have submitted to erosion and downgraded around those iron-rich ridges. Consequently, alluvial deposition throughout the Late Quaternary has been restricted to narrow, and relatively deep valleys containing sandrich channels, and thin floodplains at shallow depth. From a hydrogeological perspective, there is significant macroscopic aquifer heterogeneity between fine-grained lateritic mixed clay layers, floodplain clays, ironcemented ferricrete horizons, and permeable sand-rich alluvial aquifers. This variability of aquifer material has created a complex subsurface arrangement of permeability pathways. Application of Ground Penetrating Radar (GPR) in this setting enabled accurate definition of alluvial channel boundaries and the high degree of connectedness within the channels themselves. Interpretation of a comprehensive GPR dataset (that covered the entire catchment) allowed refinement of the sedimentary framework previously established to develop a detailed threedimensional aquifer framework. Finite-difference groundwater modelling and particle tracking analysis (using MODFLOW and MODPATH) has clearly demonstrated that the macroscopic heterogeneity within the various aquifer materials of the plain has marked impacts on groundwater pathways, and especially groundwater travel times. The variability between a maximum residence time of 18 months for groundwater within the alluvium, compared to hundreds of years for groundwater within the mixed clay layers of the laterite, clearly demonstrates the importance of accurately defining the spatial distribution of the various aquifer materials in a groundwater flow investigation. In this setting, the interconnection of the narrow alluvial channels feeding into a deeper alluvial delta has provided an effective conduit for shallow groundwater flow. The role of the alluvial delta in discharging the bulk of fresh groundwater from the central plain into the coastal and estuarine aquifers to the east, is certainly critical in preventing saline intrusion from encroaching further west. Hydrochemical and isotopic indicators have identified the dominant recharge processes and groundwater flowpaths within the plain, and indicated that the processes are strongly related to sub-surface permeability distributions determined in the aquifer framework (and groundwater modelling), as well as seasonal fluctuations in rainfall. In the northwest of the plain, sandstone hills provide a delayed and slightly mineralized component of groundwater recharge into adjacent highly permeable, unconfined alluvial aquifers; these aquifers also recharge directly via precipitation. Aluminosilicate weathering in the bedrock hills and eastern peripheries of the laterised bedrock are a source of excess Na, SiO2, and HCO3 to the alluvial groundwater. As this groundwater flows down-gradient to the east, however, its chemical composition evolves by sulfate reduction, silica equilibrium and ion exchange processes into a more mature Na-Cl type. Within the shallow coastal aquifers proximal to the eastern shoreline, sulfate enrichment is occurring (associated with increases in Ca, HCO3, Fe and Al) resulting in major deterioration in groundwater quality. The deterioration is produced by saline intrusion from the adjacent estuary coupled with oxidation of sulfide materials in shallow marine and estuarine clays. Reverses in salinity in those coastal aquifers have been correlated with surges in fresh recharge waters from unconfined coastal dunes and semi-confined landward alluvium, following significant rainfall events. The multi-disciplinary methodology developed, provides an effective approach for accurately defining the three-dimensional distribution of shallow aquifer material of varying permeability via detailed stratigraphic interpretation and GPR analysis. Utilising this aquifer framework, finite-difference groundwater modelling aided by hydrogeological data and hydrochemical analysis, allows accurate determination of groundwater flowpaths and groundwater processes. This research provides a new hydrogeological analogue for alluvial channel aquifers within a laterised coastal plain setting. Key Words: groundwater flow, aquifer heterogeneity, numerical modelling, hydrochemistry, recharge, ground penetrating radar, coastal plain aquifers, weathering, alluvial channels.

The transport of contaminants in groundwater system is strongly influenced by various aquifer heterogeneity factors such as spatial aquifer heterogeneity of hydraulic conductivity and reactive substances distribution. The contaminants transport can be simulated by using numerical reactive transport models, and their fate can be possibly even predicted. Furthermore, reactive transport modeling is an essential tool to get a profound understanding of hydrological-geochemical complex processes and to make plausible predictions of assessment. The goal of this work is to improve our understanding of the groundwater contaminants fate and transport processes in heterogeneous aquifer systems, with a focus on nitrate problems. A large body of knowledge of the fate and transport of nitrogen species has been achieved by previous works, however, most previous models typically neglect the interrelation of physical and chemical aquifer heterogeneities on the contaminant fate and redox transformation, which is required for predicting the movement and behavior of nitrate and quantifying the impact of uncertainty of numerical groundwater simulation, and which motivates this study. The main research questions which are answered in this work are how aquifer heterogeneity influences on the nitrate fate and transport and then, what is the most influential aquifer heterogeneity factor must be considered. Among the various type of aquifer heterogeneity, physical and chemical aquifer heterogeneities are considered. The first part of the work describes groundwater flow system and hydrochemical characteristics of the study area (Hessian Ried, Germany). Especially, data analyses are performed with the hydrochemical data to identify the major driving force for nitrate reduction in the study area. The second part of the work introduces a kinetic model describing nitrate removal by using numerical simulation. The resulting model reproduces nitrate reduction processes and captures the sequence of redox reactions. The third and fourth parts show the influence of physical and chemical aquifer heterogeneity with varying variance, correlation length scale, and anisotropy ratio. Heterogeneous aquifer systems are realized by using stochastic approach. Results, in short, show that the most influential aquifer heterogeneity factors could change over time. With abundant requisite electron donors, physical aquifer heterogeneity significantly influences the nitrate reduction while chemical aquifer heterogeneity plays a minor role. Increasing the spatial variability of the hydraulic conductivity increases the nitrate removal efficiency of the system in addition. If these conditions are reversed, nitrate removal efficiency varies by the spatial heterogeneity of the available initial electron donor. The results indicate that an appropriate characterization of the physical and chemical properties can be of significant importance to predict redox contamination transport and design long-term remediation strategies and risk assessment.

The transport of contaminants in groundwater system is strongly influenced by various aquifer heterogeneity factors such as spatial aquifer heterogeneity of hydraulic conductivity and reactive substances distribution. The contaminants transport can be simulated by using numerical reactive transport models, and their fate can be possibly even predicted. Furthermore, reactive transport modeling is an essential tool to get a profound understanding of hydrological-geochemical complex processes and to make plausible predictions of assessment. The goal of this work is to improve our understanding of the groundwater contaminants fate and transport processes in heterogeneous aquifer systems, with a focus on nitrate problems. A large body of knowledge of the fate and transport of nitrogen species has been achieved by previous works, however, most previous models typically neglect the interrelation of physical and chemical aquifer heterogeneities on the contaminant fate and redox transformation, which is required for predicting the movement and behavior of nitrate and quantifying the impact of uncertainty of numerical groundwater simulation, and which motivates this study. The main research questions which are answered in this work are how aquifer heterogeneity influences on the nitrate fate and transport and then, what is the most influential aquifer heterogeneity factor must be considered. Among the various type of aquifer heterogeneity, physical and chemical aquifer heterogeneities are considered. The first part of the work describes groundwater flow system and hydrochemical characteristics of the study area (Hessian Ried, Germany). Especially, data analyses are performed with the hydrochemical data to identify the major driving force for nitrate reduction in the study area. The second part of the work introduces a kinetic model describing nitrate removal by using numerical simulation. The resulting model reproduces nitrate reduction processes and captures the sequence of redox reactions. The third and fourth parts show the influence of physical and chemical aquifer heterogeneity with varying variance, correlation length scale, and anisotropy ratio. Heterogeneous aquifer systems are realized by using stochastic approach. Results, in short, show that the most influential aquifer heterogeneity factors could change over time. With abundant requisite electron donors, physical aquifer heterogeneity significantly influences the nitrate reduction while chemical aquifer heterogeneity plays a minor role. Increasing the spatial variability of the hydraulic conductivity increases the nitrate removal efficiency of the system in addition. If these conditions are reversed, nitrate removal efficiency varies by the spatial heterogeneity of the available initial electron donor. The results indicate that an appropriate characterization of the physical and chemical properties can be of significant importance to predict redox contamination transport and design long-term remediation strategies and risk assessment.