No description available.

<p>Owing to the lack of knowledge pertaining to the fate and transport of microorganisms in fractured aquifers, the research presented in this thesis was designed to improve the mechanistic understanding of particulate transport in fractures by conducting tracer experiments in natural and epoxy replica fractures. This research demonstrated that particulate retention within fractures is heavily dependent on the equivalent mass balance aperture, followed by the coefficient of variation of the aperture field, and then by the flow conditions. It was also shown that the fracture aperture field alone, not the flow rate or the matrix properties, determines the number of fracture volume flushes required to achieve a 2-3 log decrease in effluent concentration. Moreover, a statistical model was developed that identifies the most important factors affecting particulate retention as the ratio of the ionic strength of solution to the charge of the collector, the ratio of the particle to collector charges, and the Peclet number. The model is able to reasonably predict particulate retention. Finally, tracer experiments conducted in a natural fracture and an epoxy replica of that fracture isolated the effects of matrix properties on attachment, and hence, retention. The transparent nature of the replica fracture was exploited to capture images of <em>E. coli</em> RS2-GFP transport. These images reveal preferential transport within the fracture, and also show that the preferential pathway broadens slightly under increasing flow conditions. This broadening is likely due to higher fluid pressures associated with larger specific discharges. In the groundwater field, there is so little fracture-specific information available that coupling the understanding of a critical environmental setting (fractures) with high-quality particulate tracer experiments and associated modeling represents a significant contribution to the body of science.</p> / Doctor of Philosophy (PhD)

Verunreinigtes Grundwasser stellt eine ernsthafte Bedrohung für die Trinkwasser-Ressourcen auf der ganzen Welt dar. Verunreinigte Grundwasser können zwar in Brunnen detektiert werden, eine ordnungsgemäße Sanierung ist jedoch häufig nur erfolgreich, wenn die Quelle der Verunreinigung erfasst und entfernt wird. Wenn von Anbeginn eines Sanierungsprojektes ein Schwerpunkt auf die Erkennung und Eingrenzung des Verunreinigungsherdes gelegt wird, kann die Sanierung direkt an dieser Stelle ansetzen und zudem hohe Grundwasser-Sanierungskosten verringert werden. ModBack ist eine Software, die mehrere bestehende Modellierungs-Werkzeuge in einer, ein-fach zu verwendenden, ESRI ArcGIS 10-basierten Schnittstelle vereinigt und hilft mögliche Schadstoffquelle Zonen im Untergrund abzugrenzen. Diese Software ist in Visual Basic 3.5 geschrieben und verwendet ArcObjects Bibliotheken, um die erforderlichen GIS-Anwendungen zu implementieren. Es kann ohne Änderung auf allen Microsoft Windows-basierten PC‘s mit ausreichend RAM und mindestens Microsoft. NET Framework 3.5 verwendet werden. Die Nutzung von ModBack erfordert zusätzliche Installation der folgenden Software: Processing Modflow Pro 7.0 (PMWin), MODPATH, CSTREAM (Bayer-Raich et al., 2003a, Bayer-Raich et al., 2003b, Bayer-Raich et al., 2004), Golden Software Surfer, Microsoft Excel und NAS (eine Software zur Berechnung des natürlichen Schadstoffabbaus). Die grafische Benutzeroberfläche (GUI) von ModBack ist in vier Verfahrensschritte Dateneingabe, Grundwassermodellierung, Partikel Backtracking und Analysen getrennt. Geographischen Eingangsdaten werden für eine geografische Übersicht des Testfeldes benötigt. Sie bestehen meist aus georeferenzierten Informationen des Testfeldes und Informationen zur unterirdischen Grundwasserverunreinigungen. Grundwasseranalysen werden entweder durch konventionelle Probennahme aus Grundwassermessstellen oder durch die Durchführung integraler Pumpversuche an Kontrolleben mit eine bestimmten Konzentration/Zeit- Serie (CT-series) gesammelt. Aus den Pumpversuchen resultierende hydraulische Daten werden zusammen mit allen anderen verfügbaren Informationen zur Erstellung eines grundlegenden Grundwasserströmungsmodells des Testfeldes verwendet. Nachfolgende Backtracking Verfahren, als auch die Berechnung von advektivem Schadstofftransport beziehen sich auf die-ses Strömungsfeld und werden entlang einer zuvor definierten Kontrollebene berechnet. Eine Analyse der Backtracking-Ergebnisse erfolgt innerhalb ModBack. Die potenzielle Quelle von Kontaminationen oder deren Abwesenheit werden basierend auf dem Verfahren nach Jarsjö et al. (2005) bestimmt. Die Länge einer Schadstofffahne kann anhand von Fahnenlängen Statistiken und /oder dem Abbau erster Ordnung Abbau Gleichungen oder Berechnungen auf ortsspezifische hydraulischen und chemischen Parametern beruhen. Ferner ist ein analytisches Instrument enthalten, um die Verteilung der Verunreinigungen über eine Steuerebene zu identifizieren. Alle relevanten Ergebnisse können als Vektordaten in ModBack graphisch dargestellt und gespeichert werden und sind somit kompatibel mit weiteren GIS-Software Produkten. ModBack wurde bereits an Testgebieten in Slowenien und Süddeutschland angewendet, um die möglichen Zonen der Verunreinigungsquelle oder deren Abwesenheit zu begrenzen. Auf dem Testgelände in Süddeutschland sind diese Abgrenzungen vergleichbar mit früheren Untersuchungen vor Ort und unterstützt somit die Funktionalität der Software ModBack. Mit ModBack, steht ein Werkzeug zur Verfügung, die bereits jetzt Um-welt-Beratern, Ingenieuren und Umwelt-Agenturen ermöglicht denkbare Quellen der Verunreinigung bei der Planung der Untersuchungen vor Ort und Sanierungsmaßnahmen abzugrenzen, und hilft Kosten deutlich zu senken.

Contaminated land is a widespread, global issue affecting millions of people. Atrazine is a commonly used herbicide which often contaminates groundwater and drinking water supplies and is associated with adverse health outcomes. Biochar is the solid product of pyrolysis and is associated with several environmental benefits. It may be an effective remediation tool when used as a soil amendment. This thesis investigates the mechanisms through which biochar can immobilise atrazine, and the implications of the mechanisms for remediating contaminated land. Nine biochar samples were obtained from the United Kingdom Biochar Research Centre , which were produced from softwood pellets (SWP), wheat straw pellets (WSP), miscanthus straw pellets (MSP), rice husk (RH) and oil seed rape (OSR) each at pyrolysis temperatures of 550°C and 700°C (excluding OSR at 700°C). The sorption mechanisms controlling atrazine sorption to these biochars were determined through various characterisation methods and batch sorption experiments. The sorption tests showed that sorption to each of the standard biochars occurs via multiple simultaneously occurring mechanisms, which are each promoted under certain conditions. Studies investigating sorption kinetics, isotherms and interactions with humic acids showed that for all biochars in this study, pore filling was a significant process through which atrazine is transported to adsorption sites, although poor intraparticle diffusion for softwood and oil seed rape biochars can prevent efficient transport. Wheat straw and rice husk biochars showed effective pore diffusion, resulting in high sorption capacities. Partitioning was associated with poor remediation outcomes and was significant to softwood biochars, although adsorption dominated overall sorption for all other biochars. pH was shown to significantly influence the occurrence of various sorption mechanisms. At low pH values, most biochars showed evidence of electrostatic repulsion between positive atrazine species and the positively charged biochar surface. At intermediate pH values, all biochars showed strong hydrogen bonding between H+ groups on the surface of the biochar and atrazine. A meta-analysis of previous relevant studies provided further evidence for hydrogen bonding of atrazine to biochar and showed that hydrophobic effects likely play little role in adsorption after accounting for the effects of surface area. Varying contributions of π-π EDA interactions, hydrogen bonding involving biochar O- groups, and interactions with ash minerals resulted in different sorption profiles for each biochar at high pH values. In order to further determine the mechanisms controlling sorption at high pH, surface compositions of SWP550, RH700 and OSR550 biochars were modified using hydrofluoric acid. Modification with hydrofluoric acid successfully removed the ash contents of rice husk and oil seed rape biochars and reduced atrazine removal at high pH values. This suggested that the ash fraction increases atrazine removal at high pH through complexation or catalytic hydrolysis. The roles of the various mechanisms are related to remediation outcomes in a novel manner allowing for the improved design of biochar for environmental remediation.

A preocupação com a contaminação das águas subterrâneas está relacionada principalmente aos aquíferos não confinados, especialmente nos casos em que o nível freático é raso. Para evitar o escoamento subterrâneo lateral através de aterros de resíduos sólidos, o objetivo deste trabalho é avaliar &#8211; teoricamente e experimentalmente &#8211; uma técnica alternativa de encapsulamento, que consiste em uma barreira vertical de alta permeabilidade. Foi desenvolvida uma solução analítica para modelar o escoamento em uma barreira vertical cilíndrica instalada no entorno de um aterro localizado abaixo do nível d\'água, em um campo de fluxo uniforme, onde cada domínio (aquífero, barreira e área encapsulada) possui uma condutividade hidráulica diferente. Os resultados do estudo teórico mostram que nos casos em que o maciço de resíduos possui condutividade hidráulica maior do que o aquífero, a barreira de alta permeabilidade é a solução mais eficaz. Já nos problemas em que o aterro possui condutividade hidráulica menor do que o aquífero, a técnica mais indicada é a barreira de baixa permeabilidade. A partir do experimento em escala reduzida, conclui-se que a barreira de alta permeabilidade é uma técnica de encapsulamento eficiente para impedir o transporte advectivo através de determinada região. Segundo os resultados, a velocidade média do fluido na área encapsulada é consideravelmente menor do que a velocidade média no aquífero. Comparando com a barreira de baixa permeabilidade, a vantagem da barreira de alta permeabilidade é que o seu preenchimento é muito menos sensível às falhas, resultando em um melhor desempenho em longo prazo. / The concern about groundwater contamination is mainly related to unconfined aquifers, especially in the cases where the water table is shallow. Therefore, in order to prevent the groundwater lateral flow through landfills, this research evaluates &#8211; theoretically and experimentally &#8211; an alternative encapsulation technique, which consists in a vertical barrier of high permeability. An analytical solution was developed to model the flow for a cylindrical barrier installed around a landfill located below the groundwater table, in a field of uniform flow, where each domain (aquifer, barrier and encapsulated area) has a different hydraulic conductivity. The results from the theoretical study show that in situations where the landfill has a hydraulic conductivity higher than the aquifer, the high permeability barrier is more efficient. In contrast, in the cases where the landfill has a hydraulic conductivity lower than the aquifer, the lw permeability barrier is a more suitable technique. From the small-scale experiment, it is possible to conclude that the permeable barrier is an efficient encapsulation technique to prevent the advective transport through a certain region. According to the results, the fluid mean velocity at the encapsulated area is considerably lower than the aquifer mean velocity. Comparing to the low permeability barrier, the advantage of the high permeability barrier is that its backfill material is less sensitive to defects, resulting in a better long-term performance.

A preocupação com a contaminação das águas subterrâneas está relacionada principalmente aos aquíferos não confinados, especialmente nos casos em que o nível freático é raso. Para evitar o escoamento subterrâneo lateral através de aterros de resíduos sólidos, o objetivo deste trabalho é avaliar &#8211; teoricamente e experimentalmente &#8211; uma técnica alternativa de encapsulamento, que consiste em uma barreira vertical de alta permeabilidade. Foi desenvolvida uma solução analítica para modelar o escoamento em uma barreira vertical cilíndrica instalada no entorno de um aterro localizado abaixo do nível d\'água, em um campo de fluxo uniforme, onde cada domínio (aquífero, barreira e área encapsulada) possui uma condutividade hidráulica diferente. Os resultados do estudo teórico mostram que nos casos em que o maciço de resíduos possui condutividade hidráulica maior do que o aquífero, a barreira de alta permeabilidade é a solução mais eficaz. Já nos problemas em que o aterro possui condutividade hidráulica menor do que o aquífero, a técnica mais indicada é a barreira de baixa permeabilidade. A partir do experimento em escala reduzida, conclui-se que a barreira de alta permeabilidade é uma técnica de encapsulamento eficiente para impedir o transporte advectivo através de determinada região. Segundo os resultados, a velocidade média do fluido na área encapsulada é consideravelmente menor do que a velocidade média no aquífero. Comparando com a barreira de baixa permeabilidade, a vantagem da barreira de alta permeabilidade é que o seu preenchimento é muito menos sensível às falhas, resultando em um melhor desempenho em longo prazo. / The concern about groundwater contamination is mainly related to unconfined aquifers, especially in the cases where the water table is shallow. Therefore, in order to prevent the groundwater lateral flow through landfills, this research evaluates &#8211; theoretically and experimentally &#8211; an alternative encapsulation technique, which consists in a vertical barrier of high permeability. An analytical solution was developed to model the flow for a cylindrical barrier installed around a landfill located below the groundwater table, in a field of uniform flow, where each domain (aquifer, barrier and encapsulated area) has a different hydraulic conductivity. The results from the theoretical study show that in situations where the landfill has a hydraulic conductivity higher than the aquifer, the high permeability barrier is more efficient. In contrast, in the cases where the landfill has a hydraulic conductivity lower than the aquifer, the lw permeability barrier is a more suitable technique. From the small-scale experiment, it is possible to conclude that the permeable barrier is an efficient encapsulation technique to prevent the advective transport through a certain region. According to the results, the fluid mean velocity at the encapsulated area is considerably lower than the aquifer mean velocity. Comparing to the low permeability barrier, the advantage of the high permeability barrier is that its backfill material is less sensitive to defects, resulting in a better long-term performance.

Multiphase flow and transport in fractured rock is of importance to many practical and engineering applications. In the field of groundwater hydrology an issue of significant environmental concern is the release of dense non-aqueous phase liquids (DNAPLs) which can cause long-term groundwater contamination in fractured aquifers. This study deals with two fundamental processes – fluid displacement and interphase mass transfer – concerning the behavior of the multiphase contaminants in fractured media. The focus of this work has been placed on improving the current understanding of small-scale (single fracture) physics by a combined effort of numerical modeling analysis, laboratory experiments and model development. This thesis contributes to the improved understanding through several aspects. Firstly, the effect of aperture variability, as characterized by geostatistical parameters such as standard deviation and correlation length, on the DNAPL entrapment, dissolution and source-depletion behaviors in single fractures was revealed. Secondly, a novel, generalized approach (adaptive circle fitting approach) to account for the effect of in-plane curvature of fluid-fluid interfaces on immiscible fluid displacement was developed; the new approach has demonstrated good performance when applied to simulate previously published experimental data. Thirdly, the performance of a continuum-based two-phase flow model and an invasion percolation model was compared for modeling fluid displacement in a variable-aperture fracture and the dependence of fracture-scale capillary pressure – saturation relationships on aperture variability was studied. Lastly, through experimental studies and mechanistic numerical modeling of DNAPL dissolution, kinetic mass transfer characteristics of two different entrapment configurations (residual blobs and dead-end pools) were investigated. The obtained understanding from this thesis will be useful for predictive modeling of multiphase contaminant behavior at a larger (fracture network) scale. / Flerfasflöde och ämnestransport i sprickigt berg är av betydelse för många praktiska och tekniska problem. Tunga, svårlösliga organiska vätskor (engelska: dense non-aqueous phase liquids: DNAPLs; t.ex. klorerade lösningsmedel) kan orsaka långvarig förorening av vattenresurser, inklusive akviferer i sprickigt berg, och utgör ett viktigt miljöproblem inom grundvattenhydrologin. Denna studie behandlar två fundamentala processer för spridning av flerfasföroreningar i sprickiga medier – utbredning av den organiska vätskan och massöverföring mellan organisk vätska och vatten. Arbetet har fokuserat på att förbättra nuvarande kunskap om de fysikaliska processerna på liten skala (enskilda sprickor) genom en kombination av numerisk modellering, laboratorieexperiment och modellutveckling. Avhandlingen har bidragit till utökad processförståelse i flera avseenden. För det första har arbetet belyst effekterna av sprickaperturens variabilitet, uttryckt med geostatistiska parametrar som standardavvikelse och rumslig korrelationslängd, på fastläggning och lösning av organiska vätskor i enskilda sprickor, samt utmattningsbeteendet hos dessa källor till grundvattenförorening. För det andra har en ny, generell metod (adaptiva cirkelpassningsmetoden) för att ta hänsyn till effekten av krökningen av gränsytan mellan organisk vätska och vatten i sprickplanet utvecklats; denna metod har visats fungera väl i simuleringar av tidigare publicerade experimentella data. För det tredje, har en jämförelse gjorts mellan en kontinuumbaserad tvåfasflödesmodell och en invasions-perkolationsmodell med avseende på hur väl de kan simulera tvåfasflöde i en spricka med varierande apertur. Här studerades även hur relationen mellan kapillärtryck och mättnadsgrad på sprickplansskala beror av variabiliteten i sprickapertur. Till sist undersöktes lösning av den organiska vätskan i grundvatten för två fastläggningsscenarier (fastläggning i immobila droppar och ansamling i fällor – ”återvändssprickor”) både genom experiment och mekanistisk numerisk modellering. Kunskapen som tagits fram i denna avhandling bedöms vara användbar även för att modellera spridningen av flerfasföroreningar på större (spricknätverks-) skalor.

The groundwater in agricultural karst areas is susceptible to contamination from organic soil amendments and pesticides. During major storm events during 2011, dye traces were initiated using sulphorhodamine-B, fluorescein and eosine in a groundwater recharge area where manure was applied to the ground. Fecal coliform samples were collected from significant storm events from January-September 2011. Water samples and geochemical data were collected every four hours before, during, and between the storm events from a waterfall in Crumps cave flowing from the known recharge area to track the transport and residence time of the epikarst water and organic soil amendments during variable flow conditions. Two dataloggers at the same waterfall were set up to collect 10-minute data, which included pH, specific conductivity, temperature, and discharge. Total rainfall amount and other surface meteorological data were collected from a rain station located above the cave. Cave water samples were collected for the analysis of anions, cations, bacterial count, and the presence of dye. The dye traces show variability in the characteristics of epikarstic response and flowpaths. The changes in geochemistry indicate simultaneous storage and transport of meteoric water through epikarst pathways into the cave, with rapid transport of bacteria occurring through the conduits that bypass storage. Fecal coliform counts were elevated all through the study period indicating survivability in soils through the seasons. The results indicate that significant precipitation events affect the storage properties and rapidly impact the various pathways and timing of contaminant transport through the epikarst zone, eventually allowing these contaminants to be transported unfiltered in to the groundwater supply. This study shows that current best management practices in karst lands need to be revisited to incorporate areas that do not have surface runoff but where contaminants are transported by seepage into local aquifer.

Natural contamination of groundwater by arsenic (As) has become a critical public health threat in many parts of the world. The well-known regions associated with As contamination of groundwater are Bangladesh and West Bengal, India where approximately 100 million people are exposed to high levels of arsenic by drinking arsenic-contaminated groundwater and about 35 million are already affected. Long-term drinking of arsenic-contaminated water leads to arsenicosis, which is characterized by cancers of the skin, organ disease and certain other types of cancer. Affected developing communities are at higher risk because they may not have access to conventional water treatment facilities. This problem has focused research efforts on providing accessible arsenic removal technologies. In this study, cactus mucilage, an extract from the Opuntia ficus-indica (also known as Nopal and Prickly Pear cactus), is investigated as a natural agent for As removal from water. Cactus mucilage is a natural hydrocolloid with known flocculant abilities and a demonstrated interaction with As. Two mucilage fractions were extracted - a gelling extract (GE) and a non-gelling extract (NE). Two As removal systems were studied: the cactus mucilage acting alone and a hybrid mucilage and iron treatment system. The mechanism of action of the mucilage's interaction with arsenic was also studied. Batch experiments were used to study the arsenic removal systems. Total As was determined with Hydride Generation - Atomic Fluorescence Spectroscopy (HGAFS) and Inductively Coupled Plasma - Mass Spectroscopy (ICPMS). In the hybrid system, iron (Fe) was also determined by ICP-MS. Total Organic Carbon (TOC) analysis was used to determine mucilage concentration. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Ultraviolet-Visible Spectroscopy (UVVIS) were used to study the molecular composition. Additionally, the mucilage was characterized by Transmission Electron Microscopy (TEM) for physical morphology and by Laser-induced Breakdown Spectroscopy (LIBS) and High Performance Liquid Chromatography (HPLC) for inorganics and sugars composition. Both cactus extracts showed an interaction with As by binding and transporting As to the air-water interface of the treatment container, with GE and NE causing a 14% and 9% respective increase in As concentration at the air-water interface. TOC analysis showed that the mucilage migrated to the top of the treatment container but also settled on the bottom. This interaction with As was shown to be pH dependent - optimal performance was at pH 5.5 and 9. The mucilage interaction with As was also dependent on the ionic strength of the solution. ATR-FTIR showed the role of the carboxyl functional group as the binding site for the As(V). The hybrid iron-mucilage treatment system was studied in order to capitalize on the strong affinity of iron for As, as well as to exploit the flocculant properties of the mucilage. Mucilage was successfully applied as a coagulant aid in the removal of As by Fe(III) salt, achieving between 75% to 96% As removal. The process depended on the hydrolysis of the Fe(III) salt to form iron hydroxides and oxyhydroxides, which reacted with and adsorbed the dissolved As(V). The iron arsenate colloidal precipitate which formed was then adsorbed onto the mucilage surface forming larger, heavier, denser flocs. The As removal increased with increasing mucilage concentration reaching a maximum at 100 mg/L GE. Increasing Fe(III) concentration increased the As removal reaching an optimum concentration at 40 mg/L Fe. The As removal had rapid kinetics, achieving visual separation within 10 minutes and completing the majority of the removal within 30 minutes. These results are important because they demonstrate that the mucilage is the versatile basis for an As removal treatment, being able to interact as a complexant for the arsenic as well as an effective coagulant aid for iron arsenate precipitation.

Nearly 250,000 sites with past and present potentially polluting activities need urgent remediation within Europe. Major pollutants include organochlorines (OCls), e.g. chlorinated ethenes (CEs) and hexachlorocyclohexanes (HCHs), mainly used as industrial solvents and pesticides, respectively. Due to improper handling and disposal, OCls contaminants are present in the soil or groundwater surrounding sites, where they have been produced or used. CEs and HCHs can undergo degradation by microorganisms indigenous to the soil or groundwater. Therefore natural attenuation (NA), relying on the in situ biodegradation of pollutants, is considered as a cost effective remediation strategy, yet it requires accurate monitoring methods. Compound specific isotope analysis (CSIA) is a powerful tool to provide information on the extent of degradation and, when combining two isotope systems (2D-CSIA), such as carbon (δ13C) and chlorine (δ37Cl), on reaction mechanisms. The diagnostic reaction-specific isotope enrichment factors (εC and εCl) were determined in laboratory experiments for the anaerobic degradation of PCE, TCE (Paper II) and α-HCH (Paper III) by mixed bacterial cultures enriched from CEs and HCHs contaminated sites, respectively. The related mechanism-specific εCl/εC ratios were calculated as 0.35 ± 0.11 (PCE), 0.37 ± 0.11 (TCE) and 0.52 ± 0.23 (α-HCH). These values are smaller than previously reported values for pure cultures. This is explained by the microbial community composition changes observed during degradation of PCE and α-HCH, which also reflect the variability of the microbial community at the field level. Furthermore, εCl/εC ratio might be bacteria specific. These values allowed the estimation of the extent of contaminant degradation at the respective study sites (Paper III and IV). Application of both isotope systems (δ13C and δ37Cl) led to comparable estimates. However the choice of representative ε values is crucial for an accurate assessment. These studies show that CSIA is useful to quantify in situ degradation of OCls contaminants and identify reaction pathways, by combining δ13C and δ37Cl. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p>