A finite element model is developed for multiphase flow through soil involving three immiscible fluids: namely air, water, and an organic fluid. A variational method is employed for the finite element formulation corresponding to the coupled differential equations governing the flow of the three fluid phase porous medium system with constant air phase pressure. Constitutive relationships for fluid conductivities and saturations as functions of fluid pressures which may be calibrated from two-phase laboratory measurements, are employed in the finite element program. The solution procedure uses iteration by a modified Picard method to handle the nonlinear properties and the backward method for a stable time integration. Laboratory experiments involving soil columns initially saturated with water and displaced by p-cymene (benzene-derivative hydrocarbon) under constant pressure were simulated by the finite element model to validate the numerical model and formulation for constitutive properties. Transient water outflow predicted using independently measured capillary head-saturation data agreed well with observed outflow data. Two-dimensional simulations are presented for eleven hypothetical field cases involving introduction of an organic fluid near the soil surface due to leakage from an underground storage tank. The subsequent transport of the organic fluid in the variably saturated vadose and ground water zones is analysed. / Ph. D.

This study contributes a procedure, based on data analysis and geostatistical methods, to evaluate the distribution of chemical ratios and differentiate natural and anthropogenic contaminant sources of groundwater quality in the East Texas Basin. Four aquifers were studied, Sparta, Queen City, Carrizo and Wilcox. In this study, Carrizo- Wilcox is considered as one aquifer, and Sparta-Queen City as another. These aquifers were divided into depth categories, 0-150 feet for Sparta-Queen City and 300-600 feet and 600-900 feet for Carrizo-Wilcox in order to identify individual sources of contamination. Natural sources include aquifer mineral make up, salt domes and lignite beds. Major anthropogenic sources include lignite and salt dome mining and oil-gas production. Chemical ratios selected were Na/Cl, Ca/Cl, Mg/Cl, SO4/Cl, (Na+Cl)/TDS, SO4/Ca and (Ca+Mg)/(Na+K). Ratio distributions and their relationships were examined to evaluate physical-chemical processes occurring in the study area. Potential contaminant sources were used to divide the Basin into three areas: Area 1 to the east, Area 2 in the west and Area 3 in the center. Bivariate analysis was used to uncover differences between the areas. The waters in Area 1 are potentially impacted primarily from oil field waters. Sources present in Area 2 include lignite beds and oil field operations. Area 3 is the cap rock of salt domes that can contain gypsum and anhydrite. Based on the exploratory data analysis (Na+Cl)/TDS, (Ca+Mg)/(Na+K), and SO4/Ca ratios were chosen for geostatistical analysis. Chemical ratios that provided indications of cation exchange, salt domes and oil fields were (Na+Cl)/TDS, (Ca+Mg)/(Na+K) and SO4/Ca. In the Sparta-Queen City 150 zone the procedure did not provide a good method for differentiating between contaminant sources. However, the procedure was effective to indicate impacted ground water in the Carrizo-Wilcox 600 and 900 foot zones.

ArcView and ArcInfo were used to identify and delineate areas contaminated by fluoride, sulfate, chloride, and nitrate in the Woodbine Aquifer. Water analysis data were obtained from the TWDB from the 1950s to 1990s covering 9 counties. 1990s land use data were obtained to determine the relationship with each contaminant. Spearman's rank correlation coefficients and Kruskal-Wallis tests were used to calculate relationships between variables. Land uses had little effect on distributions of contaminants. Sulfate and fluoride levels were most problematic in the aquifer. Depth and lithology controlled the distributions of each contaminant. Nitrate patterns were controlled mainly by land use rather than geology, but were below the maximum contaminant level. In general, contaminant concentrations have decreased since the 1950s.

Volcanic tuffs and tuffaceous sediments are frequently associated with elevated As groundwater concentrations even though their bulk As contents (~ 5 mg kg-1; Savoie, 2013) are only marginally greater than the average crustal abundance of 4.8 mg g-1 (Rudnick & Gao, 2003). Thus, As mobilization must be facilitated by conditions particular to these rocks. Alkaline desorption, anionic competition, reactive glass dissolution, and reductive dissolution of iron oxides are proposed processes of As release from volcanic rocks. Geogenic As contamination of groundwater in the southern Willamette Valley in western Oregon has been well-documented since the early 1960s, and previous studies have identified the Little Butte Volcanics Series and Fisher and Eugene Formations as the source of As contamination. This study examines 19 samples from 10 units of ash flow tuffs and tuffaceous sediments within the Fisher Formation and Little Butte Volcanics Series, representing a range of weathering and devitrification, to determine conditions of mobilization and mineralogical constraints that control As release into solution. Leachate studies were conducted over a range of pH from 7 to 11, phosphate concentrations from 10 μM to 100 mM, and in time series from 4 to 196 hours. Results demonstrate that silicic volcanic tuffs are capable of mobilizing As in concentrations above regulatory limits at pH conditions produced naturally by the tuffs (pH 8-9) or with moderate concentrations of P (10-100 μM). Alteration products, e.g. zeolites and clays, appear to be the primary host phases for mobile As. Samples that do not contain these alteration products tend to produce concentrations of As well below regulatory limits and often below the instrument detection limits of this study. The type of alteration may influence As mobilization: tuffs containing more clays tend to mobilize As through surficial desorption, and tuffs containing more zeolites tend to mobilize As by dissolution or formation of colloids. Additionally, one volcaniclastic sample demonstrates that extremely elevated concentrations of As, up to 1000 μg/L are possible as a result of oxidative dissolution of As-bearing sulfide phases.

Groundwater aquifers are precious resources that has been serving human consumption for many centuries. This resource is pristine in comparison with surface waters such as lakes and canals, however, as population grows exponentially so does the demand for groundwater and the need to study the potential of groundwater replenishment programs. The injection of treated water or wastewater into an aquifer is a method to protect this resource for current and future generations. Health concerns would be expected since migration of water of “impaired quality” can affect the drinking water by contamination. Regulatory barriers resulting from the perceived risks of adverse health effects from pathogens such as viruses have limited the concept of this impaired water resources from being used for groundwater replenishment programs. The objective of this study is to examine the risk assessment using computational modeling with MODFLOW and MT3D groundwater transport simulation. The results from the simulation showed that after two years, the risk of contamination based on concentration contours from the injection well to the production wellfields for the City of Hollywood stabilized below 10- 6. The risk assessment provided important aspect to demonstrate the concept of using injection of treated water as an option for groundwater replenishment. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2014. / FAU Electronic Theses and Dissertations Collection

Groundwater arsenic contamination is currently a global problem, and also a concern at numerous former industrial sites, agricultural sites, landfill sites and mining operations in the U.S. This dissertation aims to develop improved strategies of remediating these arsenic contaminated aquifers. It focuses on two distinct approaches of remediation: (1) mobilizing arsenic from contaminated aquifer sediments to decrease the quantity of arsenic at the source of contamination; and (2) immobilizing arsenic in situ, to decrease the mobility and bioavailability of this arsenic. Optimal remediation may well involve combinations of these two approaches. Arsenic mobilization using oxalic acid is effective because oxalic acid dissolves arsenic host minerals and competes for sorption sites on those minerals. In this dissertation, oxalic acid treatment was tested using sediments with contrasting iron mineralogies and arsenic contents from the Dover Municipal Landfill and the Vineland Chemical Company Superfund sites. Oxalic acid mobilized arsenic from both sites and the residual sediment arsenic was less vulnerable to microbial reduction than before the treatment. Oxalic acid thus could improve the efficiency of widely used pump-and-treat remediation. Oxalic acid did not remove all of the reactive iron(III) minerals in Vineland sediment samples, and thus released significant quantities of arsenic into solution under reducing conditions than the Dover samples. Therefore, the efficacy of pump-and-treat must consider iron mineralogy when evaluating its overall potential for remediating groundwater arsenic. Arsenic immobilization occurs by changing the chemical state, or speciation, of arsenic and other elements in the system. Arsenic is often assumed to be immobile in sulfidic environments. In this dissertation, sulfate reduction was stimulated in sediments from the Vineland Superfund site and the Coeur d'Alene mining district. Sulfate reduction in the Coeur d'Alene sediments was more effective at removing arsenic from solution than the Vineland sediments. The Vineland sediments initially contained abundant reactive ferrihydrite, and underwent extensive sulfur cycling during incubation. As a result, arsenic in the Vineland sediments could not be effectively converted to immobile arsenic-bearing sulfides, but instead a part of the arsenic was probably converted to soluble thioarsenates. Therefore, coupling between the iron and sulfur redox cycles must be fully understood for arsenic immobilization by sulfate reduction to be successful. Arsenic can also be immobilized by retention on magnetite (Fe3O4). Magnetite is stable under a wide range of aquifer conditions including both oxic and iron(III)-reducing environments. In this dissertation, a series of experiments were performed with sediments from the Dover and Vineland Superfund sites, to examine the potential of magnetite for use in arsenic immobilization. Our data suggest that the formation of magnetite can be achieved by the microbial oxidation of ferrous iron with nitrate. Magnetite can incorporate arsenic into its structure during formation, forming a stable arsenic sink. Magnetite, once formed, can also immobilize arsenic by surface adsorption, and thus serve as a reactive filter when contaminated groundwater migrates through the treatment zone. Reactive transport modeling is used for investigating the magnetite based arsenic immobilization strategy and for scaling laboratory results to field environments. Such modeling suggests that the ratio between iron(II) and nitrate in the injectant regulates the formations of magnetite and ferrihydrite, and thus regulates the long-term evolution of the effectiveness of the strategy. The results from field-scale models favor scenarios that rely on the chromatographic mixing of iron(II) and nitrate after injection. The studies in this dissertation demonstrate that the environmental fate of arsenic depends on the biogeochemical cycling of arsenic, iron, and to a lesser extent, sulfur. The development of effective groundwater arsenic remediation strategies depends on a good understanding of each of the involved processes, and their combinations.

Fault zones are potential paths for release of radioactive nuclides from radioactive-waste repositories in granitic rock. This research considers detailed maps of en echelon fault zones at two sites in southern Sweden, as a basis for analyses of how their internal geometry can influence groundwater flow and transport of radioactive nuclides. Fracture intensity within these zones is anisotropic and correlated over scales of several meters along strike, corresponding to the length and spacing of the en echelon steps. Flow modeling indicates these properties lead to correlation of zone transmissivity over similar scales. Intensity of fractures in the damage zone adjoining en echelon segments decreases exponentially with distance. These fractures are linked to en echelon segments as a hierarchical pattern of branches. Echelon steps also show a hierarchical internal structure. These traits suggest a fractal increase in the amount of pore volume that solute can access by diffusive mass transfer, with increasing distance from en echelon segments. Consequences may include tailing of solute breakthrough curves, similar to that observed in underground tracer experiments at one of the mapping sites. The implications of echelon-zone architecture are evaluated by numerical simulation of flow and solute transport in 2-D network models, including deterministic models based directly on mapping data, and a statistical model. The simulations account for advection, diffusion-controlled mixing across streamlines within fractures and at intersections, and diffusion into both stagnant branch fractures and macroscopically unfractured matrix. The simulations show that secondary fractures contribute to retardation of solute, although their net effect is sensitive to assumptions regarding heterogeneity of transmissivity and transport aperture. Detailed results provide insight into the function of secondary fractures as an immobile domain affecting mass transfer on time scales relevant to field characterization and repository safety assessment. In practical terms, secondary fractures in these en echelon zones are not indicated to limit release of radiation to the surface environment, to a degree that is significant for improving repository safety. Thus en echelon zones are to be regarded as detrimental geologic features, with potentially complex transport behavior which should be considered in the interpretation of in-situ experiments. / Graduation date: 2005

Soils of 49 agricultural and 2 "native condition" sites in the Lower Umatilla Basin, Oregon were sampled for nitrate-nitrogen, ammonium-nitrogen, chloride, and pH beginning in Fall of 1992. Several sites were sampled in Spring and Fall 1993 in order to indicate movement or loss of residual soil nitrogen over time. This study was prompted by current concern over contamination of public drinking water supplies by nitrate and the designation of over 550 square miles of this region as a Ground Water Management Area. This study sought to identify links between agricultural management practices-primarily irrigation, fertilization, and crop rotation systems, and deep soil nitrate levels. Soil profiles were divided into 3 "management zones:" 0-3', 3-6', and beyond 6' in depth. These depths represent average rooting depths for the major agricultural crops of the study area. In general, the effective rooting depth of most area-crops does not extend beyond 6', therefore, it was determined that residual soil-nitrate found at this depth or beyond may be a potential source of ground water contamination if not managed correctly. Results of the study indicate that proper management of irrigation, fertilization, and cropping rotation can significantly reduce the potential for contaminating ground water. Deep soil nitrate levels under most agricultural fields were consistent with the concept that some loss of nitrate below the root zone is inevitable, however, this condition can be minimized through intensive crop management. This study concludes that responsible management of agriculture can minimize impacts on ground water, while providing quality food and fiber products to an ever-growing population. In addition, more research is needed in the area of crop physiology and response to intensively managed systems. Such research may provide insight into more efficient methods of crop production and environmental protection. / Graduation date: 1995

No abstract available. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 2002.

[Truncated abstract] It has become widely apparent throughout the world that the discharge of nitrogen contaminated groundwater is reducing surface water quality of marine coastal waters, and is subsequently contributing to the decline of benthic habitats such as seagrasses. A process-based understanding of submarine groundwater discharge (SGD) has lagged behind these impacts, and this lack of understanding is addressed by this thesis. This thesis, of the spatial and temporal complexity of SGD, has uncovered and answered questions regarding the sources, fate and transport of SGD in a complex coastal discharge environment. Radium isotope techniques, groundwater biogeochemical investigations and HAMSOM surface water modelling have identified the magnitude, transport and fate of SGD in Cockburn Sound, a semienclosed embayment in Western Australia. A temporal periodicity that encompassed end-of-winter, early-summer, late-summer and mid-winter regimes of hydrology and oceanography, was employed in field studies that spanned the years 2003, 2004 and 2005. ... The fate of the groundwater in the semi-enclosed embayment was investigated using knowledge of surface water currents. Localised regions of high groundwater influence were identified in the surface waters of the embayment, and through the application of a 3-dimensional hydrodynamic model (HAMSOM) it was discovered that, despite similar total volume residence times, variation in the surface flow regime resulted in very different fates for groundwater discharged to the embayment. For three of the four investigated seasonal regimes, groundwater discharged at the shoreline was shown to be rapidly exported out of the embayment (within approximately 1-3 days). During mid-winter very different wind and current regimes existed, resulting in the lateral transport of shoreline groundwater across the embayment, presenting potential for nutrient recirculation within the system for longer time periods (10+ days). Lateral transport of groundwater during mid-winter from the limestone region of the coastline, may contribute to peaks in phytoplankton biomass that have been reported to occur at this time. The investigations into spatial, temporal and biogeochemical dynamics of SGD provided for further dissertation of the processes that affect these dynamics, at a scale that was relevant to marine embayments, coastal aquifers and the coastal ecosystem. It is hoped that this thesis will contribute to a better understanding of the inputs, dynamics and impacts of SGD on coastal ecosystems and lead to improved management strategies for coastal zones.