The advancement in synthetic chemicals commonly referred to as contaminants of emerging concern (CECs) and their application has led to an increase in environmental pollution. The use of septic tanks otherwise referred to as onsite water treatment systems (OWTS), promotes the introduction of CECs into the environment while allowing little in the way of remediation. In order to study the impacts of CECs from OWTS as they infiltrate the environment and the aquifer system, water, sediment, and vegetation samples were collected around a sinkhole lake surrounded by residential housing using OWTSs. The main question of this research project is what is the fate of CECs from OWTSs effluent within the catchment of a sinkhole lake? Liquid chromatograph mass spectrometry was used to analyze the samples for the presence of CECs. It was found that the relative quantity of CECs in the individual constituents is dependent upon 1) the hydrophobicity and polarity of the individual compound, 2) the specific sampling site, 3) the topography gradient, and 4) for vegetation the connectedness of the sample type to the sediment. The implications derived from this study can be applied in environmental engineering, urban and suburban planning, environmental monitoring, and should be considered when residents use well water as their source of potable water.

This study utilized GIS and statistical methods to map the spatial variability of nitrate and related groundwater constituents in 30 counties above the Seymour Aquifer, analyze temporal patterns of nitrate pollution, identify probable sources of pollution, and recommend water development strategies to minimize exposure to nitrate and reduce future aquifer contamination. Nitrate concentrations in excess of 44 mg/L (US EPA limit) were commonly observed in the Seymour Aquifer region, especially in the central agricultural belt. Data indicated that this is an ongoing problem in the Seymour Aquifer and that agricultural activity and rural septic systems are the likely sources of the nitrate. Inconclusive results emphasized the need for a more comprehensive spatial and temporal water quality monitoring.

>Magister Scientiae - MSc / The need to improve groundwater security remains critical especially in urban areas where demand for groundwater as an alternative source of water supply increases. Declining trends in availability of surface water because of climate change effects further exacerbates problems of water supply shortage to meet the increasing demand for water, hence the need for groundwater sources. The use of hydrogeophysics data and derivative analysis in understanding aquifer dynamics remains limited and poorly understood therefore, the study argues that when hydrogeophysics data and derivative analysis are not used in aquifer characterization, it results in models that are not solution-based and cannot guide groundwater management. The study was aimed at providing improved understanding on characterization of aquifer dynamics for solution-based modelling while addressing the importance of integrating hydrogeophysics data and derivative analysis in amplifying the heterogeneities that exist in aquifer system.

Water volume in the shallow alluvial aquifer in the Mississippi Delta region is subject to seasonal declines and annual fluctuations caused by both climatological variability and crop water use variations from year-to-year. The most recently documented water volume decline in the aquifer is estimated at 500,000 acreeet. Available climate, crop acreage, irrigation water use, and groundwater decline data from Sunflower County, MS are used to evaluate the climate-groundwater interactions in the Mississippi Delta region. This research produced a model that simulates the effects of climatic variability, crop acreage changes, and specific irrigation methods on consequent variations in the water volume in the aquifer. Climatic variability is accounted for in the model by predicative equations that relate annual measured plant water use (irrigation) to growing season precipitation amounts. This derived relationship allows the application of a long-term climatological record to simulate the cumulative impact of climate on groundwater used for irrigation.

The design of effective quality management strategies in groundwater systems is crucial, as clean water is essential for livelihood, health, and development. Colloids represent a class of contaminants that might be pathogenic or benign. Colloids can also enhance or inhibit the transport of dissolved contaminants in groundwater, which has inspired the use of benign colloids in the remediation of contaminated aquifers. Reliable modelling of colloid behavior is therefore essential for the design of effective remediation strategies, both those employing benign colloids and those aiming at the removal of pathogenic colloids. While colloid transport is controlled by groundwater velocity, colloid retention is governed by the physical and chemical properties of the aquifer together with those of the colloid. The present study aims at enhancing the reliability of modelling colloid behavior in fractured aquifers through: i) developing a synchronization-based framework that can effectively identify hydraulic connections within the aquifer; ii) developing a mathematical model for the relationship between the fraction of colloids retained along a fracture (Fr) and the parameters describing the aquifer’s physical and chemical properties; iii) developing an analytical model for the relationship between Fr and the coefficient describing irreversible colloid deposition in single fractures; and, iv) developing a numerical technique that can efficiently simulate colloid behavior in single fractures and fracture networks under different physical, chemical, and matrix conditions. The performance of the synchronization-based framework, mathematical and analytical models, and the numerical technique was assessed separately for different verification cases, and the corresponding efficacy was confirmed. Coupling the tools developed in the present study enables the reliable prediction of colloid behavior in response to changes in the groundwater-colloid-fracture system’s physical and chemical properties, which can aid in understanding how to manipulate the system’s properties for the effective design of groundwater quality management and remediation strategies. / Thesis / Doctor of Philosophy (PhD) / Microorganisms, microplastics, clay, and fine silt are classified as colloids within the spectrum of contaminants that might exist in groundwater. Although some colloids are benign (e.g., clay and fine silt), they can still affect the groundwater quality and aquifer porosity. Colloids can also enhance or inhibit the migration of other contaminants in groundwater because of their high adsorption capacity. Several remediation strategies are being envisioned to remove pathogenic colloids and eliminate other contaminants adsorbed onto benign colloids, where effective design of such strategies requires reliable models of colloid behavior. The present study aims at enhancing the reliability of simulating colloid behavior in fractured aquifers through: i) developing models that capture the effects of the aquifer’s physical and chemical properties on colloid behavior; and, ii) designing a framework that improves the reliability of aquifer conceptualization. Effective remediation strategies can then be designed for contaminated fractured aquifers based on the developed tools.

For this study, I have constructed a logistic regression model, using existing datasets of environmental parameters to predict the probability of As concentrations above 5 parts per billion (ppb) in Virginia groundwater and to evaluate if geologic or other characteristics are linked to elevated As concentrations. Measured As concentrations in groundwater from the Virginia Tech Biological Systems Engineering (BSE) Household Water Quality dataset were used as the dependent variable to train (calibrate) the model. Geologic units, lithology, soil series and texture, land use, and physiographic province were used as regressors in the model. Initial models included all regressors, but during model refinement, attention was focused solely on geologic units. Two geologic units, Triassic-aged sedimentary rocks and Devonian-aged shales/sandstones, were identified as significant in the model; the presence of these units at a spatial location results in a higher probability for As occurrences in groundwater. Measured As concentrations in groundwater from an independent dataset collected by the Virginia Department of Health were used to test (validate) the model. Due to the structure of the As datasets, which included As concentrations mostly (95-99%) = 5 ppb, and thus few (1-5%) data in the range > 5 ppb, the regression model cannot be used reliably to predict As concentrations in other parts of the state. However, our results are useful for identifying areas of Virginia, defined by underlying geology, that are more likely to have elevated As concentrations in groundwater. Results of this work suggest that homeowners with wells installed in these geologic units have their wells tested for As and regulators closely monitor public supply wells in these areas for As. / Master of Science

Karst aquifers host significant water supplies but are easily contaminated because highly conductive inlets can rapidly transmit water to depth. The epikarst, which is the region of vegetation, soil, and weathered bedrock above karst aquifers, is a critical zone as it regulates the quantity and quality of recharge to the aquifer. As the epikarst exhibits complex heterogeneity, characterization at the field scale can be challenging. The objective of this thesis was to develop a model of epikarst hydrodynamics using longterm field measurements. To meet this objective, continuous hydrologic data of precipitation, speleothem drips, and an underground stream in James Cave in Pulaski County, VA, were collected to delineate seasonal recharge patterns, estimate effective recharge and catchment areas, characterize the number and permeability of flow paths, and evaluate storativity in the epikarst. Results demonstrate that after significant seasonal recharge, which occurs in the late winter and early spring, the epikarst can temporarily store a significant portion of recharge in low permeability flow paths. Effective recharge was estimated to be approximately 30% of total precipitation (2008-2009). Hydrograph recession analysis aided in delineation of flowpaths in the epikarst, including quickflow, moderate flow, and baseflow components. Hydrograph shape analysis suggests flow restrictions at two of the drip sites that may reveal spatial differences in storage capacity and retention time. Results of this work are intended to aid karst aquifer management by providing a multitechnique approach that can be used to assess seasonal patterns of recharge, quantify flowpath and storage characteristics, and delineate recharge zones. / Master of Science

O estudo hidrogeoquímico dos aquíferos Tubarão (sedimentar, granular) e Cristalino (granítico, fissural) na Região de Salto (SP), tem como proposta avaliar os processos da interação água-solo-rocha que influem na composição química das águas e discutir a origem de anomalias de fluoreto e salinidade. Para averiguar a relação dessas anomalias com fontes naturais ou antropogênicas, foram estudados processos geoquímicos envolvidos nos níveis rasos e profundos de duas microbacias hidrográficas, onde se têm instaladas várias industriais. As águas dos aquíferos apresentam concentrações iônicas, pH e condutividade elétrica mais elevados em relação às águas subterrâneas rasas, sendo predominantemente bicarbonatadas cálcicas e sódicas no Aquífero Cristalino e bicarbonatadas e sulfatadas sódicas no Tubarão. A salinidade, pH e concentração de sódio destas águas tende a aumentar com a profundidade e no sentido do fluxo subterâneo das áreas de recarga para as de descarga nos principais rios da região. As anomalias geoquímicas ocorrem somente nas águas profundas. A origem do fluoreto é atribuída a alteração de biotita nos granitos e de micas e argilominerais nas rochas sedimentares. O F- está associado a águas bicarbonatadas e sulfatadas sódicas e a valores alcalinos de pH. Os focos de maior salinidade ocorrem em localidades próximas ao Rio Tietê e ao Rio Jundiaí. Ela pode estar associada a lineamentos estruturais de direção NE e NW, mas não se descarta a hipótese de águas residuais aprisionadas durante a deposição marinha dos sedimentos ou à circulação restrita da água subterrânea no Aquífero Tubarão. O sistema profundo encontra-se relativamente isolado em relação aos níveis subsuperficias rasos/superficiais, constatado pelos distintos fluxos subterrâneos e características físico-químicas e químicas. Os solos, sedimentos e águas superficiais e de poços cacimba apresentam evidências de degradação ocasionada por lançamento de esgotos e de um antigo lixão. / The hydrogeochemical study of Tubarão (sedimantary, granular) and Cristallyne (Granitic, fissural) aquifers in Salto Region, evaluates water-soil-rock interaction processes that have influence on water chemical composition and discuss the origin of fluoride and salinity anomalies in ground waters. To investigate the correlation between these anomalies with natural or antropogenic sources, geochemical process studies considering shallow and deep portions were conducted in two small watersheds, where several industries are installed. Deep ground waters present higher ionic concentrations, pH and electrical conductivity when compared to shallow ground waters; they are mainly bicarbonated calcic and sodic in the Crystalline Aquifer and bicarbonated or sulfated sodic in Tubarao Aquifer. The salinity, pH and sodium concentration of these water rise with deepness and from recharge to discharge areas in the main regional rivers. Geochemical anomalies only occur in deep waters. The origin of fluoride is attributed to biotite alteration in granites and to micas and clayminerals in sedimentary rocks. The fluoride is associated to bicarbonated and sulfated sodic waters and alcaline pH values. Focal points of high salinity occur in places near Tietê River and Jundiaí River. It can be associated to structural lineaments with NE and NW directions, but the hypothesis of residual waters that remained in the pore spaces of rocks during marine deposition of sediments cannot be rejected, as well as restrict portions of ground water circulation in the Tubarão Aquifer. The deep system is relatively isolated to the superficial and shallow subterraneous levels, verified by their distinct water flow and physicochemical and chemical properties. Soils, sediments and superficial waters and shallow groun dwater present evidences of degradation, caused by sewerage and an old waste dump.

A importância do estudo de aqüíferos livres e rasos se evidencia quando se leva em conta que tais aqüíferos são altamente vulneráveis a contaminação e que em geral se encontram em regiões densamente povoadas. Com o objetivo de melhor compreender a dinâmica do fluxo de água subterrânea na zona saturada destas formações aqüíferas, foi construído e calibrado um detalhado modelo tridimensional e transiente para representar o fluxo subterrâneo em uma porção de um aqüífero livre e raso que ocorre no Parque Ecológico do Tietê, no Município de São Paulo. Este modelo, baseado em dados de cargas hidráulicas de 81 poços de monitoramento instalados em uma área de 320m2 medidas diariamente, em valores diários de precipitação na área e em 75 determinações de condutividades hidráulicas, foi construído e executado através do software Visual MODFLOW e calibrado por meio do software PEST, através de um método de regressão não linear. Os resultados gerados por este modelo para um evento de recarga rápida indicam que a distribuição de cargas hidráulicas na área de estudo é governada pela recarga regional, pela distribuição das condutividades hidráulicas horizontais e pelas vazões específicas das camadas superiores da formação, mas é praticamente independente da intensidade e distribuição temporal da recarga local, que influencia apenas os níveis mais rasos da formação. Além disso, verifica-se o caráter extremamente dinâmico do fluxo, que responde rapidamente ao evento de recarga regional, apresentando alterações significativas de intensidade e direção no intervalo de apenas alguns dias. Tais resultados, verificados apenas por meio de um modelo tão detalhado como o produzido neste trabalho, sugerem que estratégias comuns de avaliação podem não ser capazes de avaliar suficientemente bem o comportamento deste tipo de aqüífero. / The importance of studying unconfined and shallow aquifers is verified when taking into account that these aquifers are highly vulnerable to contamination and that they are often located under heavily populated regions. A detailed three-dimensional and transient model, which represents the groundwater flow in an area of an unconfined and shallow aquifer at the Parque Ecológico do Tietê, in the Municipality of São Paulo, Brazil, was created and calibrated with the objective of enhancing the comprehension of the dynamics of the groundwater flow in the saturated zone of these formations. This model was based on hydraulic head data of 81 monitoring wells, which were installed in an area of 320 m2 and measured on a daily basis, on daily values of precipitation occurring in the area and 75 determinations of hydraulic conductivities. The model was created and run using the software Visual MODFLOW and calibrated using the software PEST, based on a non-linear regression method. The results generated by this method for an event of rapid recharge indicate that the distribution of the horizontal hydraulic conductivities and by the specific yield of the upper layers of the formation, but it is mostly disconnected from the intensity and temporal distribution of the local recharge, that only influences the shallowest levels of the formation. Furthermore, the extremely dynamic character of the flow can be verified, which responds rapidly to the regional recharge event, presenting significant changes of intensity and direction within only a few days. These results, which were only observable through a very detailed model such as the one produced and presented in this study, suggest that commonly employed evaluation strategies may not be capable of evaluating this kind of aquifer in a satisfactory way.

Os metais são encontrados em todos os organismos vivos, sendo responsáveis por diversas funções e suas deficiências podem comprometer diversas funções biológicas, Mas, quando presentes em concentrações excessivas podem causar efeitos deletérios, modificando uma população ou um conjunto de espécies dentro de um ecossistema. O aquífero Bauru é predominantemente freático e grande parte do aquífero Guarani estudado neste trabalho localiza-se na sua faixa aflorante. Portanto apresentam vulnerabilidade alta, mostrando-se expostos ao risco de degradação antropogênicas, seja por atividades agrícolas ou uso do solo sem critérios em relação as suas aptidões. Os objetivos desse trabalho foram a validação da técnica de análise dos elementos químicos cobalto, estanho, fósforo, lítio, molibdênio, níquel, prata, tálio, titânio e vanádio por espectrometria de emissão atômica com plasma (ICP-OES) com nebulizador ultrassônico acoplado, avaliação da presença desses elementos em amostras coletadas nos aquíferos Bauru e Guarani, visando propor valores de referência para os elementos em estudo. Foram avaliados 57 e 34 pontos de coleta, respectivamente nos aquíferos Bauru e Guarani, em 88 municípios no Estado de São Paulo, em quatro campanhas distintas. As análises efetuadas nos pontos de coleta dos Aquíferos Bauru e Guarani, nas quatro campanhas de coleta (março e setembro de 2010 e 2011) apresentaram concentrações menores que o Limite de Quantificação do Método para os elementos químicos cobalto, estanho, molibdênio, prata, tálio e titânio. Para esses elementos químicos sugere-se que o Valor de Referência de Qualidade seja a metade do Limite de Quantificação do Método. Para os metais lítio e níquel não houve diferenças significativas nos resultados obtidos para a maioria dos pontos de coleta sendo que os valores das concentrações máximas e mínimas encontradas são próximas ao terceiro quartil calculado. A presença de vanádio nos poços cujas concentrações encontradas foram acima de 50?.L-1V deve ser avaliada de forma mais criteriosa para verificar se há tendência de aumento de concentração. Existe uma variação significativa nas concentrações de fósforo encontradas nos Aquíferos Bauru e Guarani. É necessário investigar a origem deste elemento químico, se é natural ou antrópica, a fim de propor ações de controle, bem como a gestão de recursos hídricos. / Metals are found in all living organisms and are responsible for various vital functions and its deficiencies can impair biological functions, but, when present in excessive concentrations can cause deleterious effects on human health or a group of species in an ecosystem. In the present work, we studied the Bauru aquifer that is predominantly freatic and a region of the Guarani Aquifer located in a strip outcropping. Considering that, these water bodies are vulnerable, being exposed to the risk of anthropogenic degradation, due to both agricultural activities and the use of land without criteria. The objectives of this study were to validate the technique for analysis of the chemical elements cobalt, tin, phosphorus, lithium, molybdenum, nickel, silver, thallium, titanium and vanadium using Inductively coupled plasma atomic emission spectroscopy (ICP-OES) with ultrasonic nebulizer; to determine the presence of these elements in samples collected from Bauru and Guarani aquifers and finally, we aimed to propose the Reference Quality Values (RQVs) for each chemical, based on our results. We analyzed 57 and 34 water samples collected from Bauru and Guarani aquifers, respectively, in a total of 88 municipalities in the State of São Paulo, in four distinct periods (March and September 2010 and 2011). Our results showed that the concentrations of the chemicals cobalt, tin, molybdenum, silver, thallium and titanium were below to the quantification limit of the method in all samples collected. For the metals lithium and nickel there were no significant differences between the results collected from the most sites, and the maximum and minimum concentrations are found near the third quartile calculated. The concentration of vanadium in the aquifer water samples was higher than 50?g.L-1V and we suggested that this concentration should be carefully evaluated, in order to verify an increase tendency. We detected a significant variation in phosphorus concentration found in Bauru and Guarani aquifers. So, we also suggested that the origin of this chemical should be investigated to determine if it is natural or anthropogenic in order to propose control actions, as well as the management of water resources.