The nitroaromatic explosive 2,4,6-trinitrotoluene is a widespread, toxic groundwater contaminant. The objective of this work was to describe TNT fate in contaminated aquifer sediments. A series of bench scale experiments and model simulations were performed to evaluate the fate of TNT in historically contaminated aquifer sediments. A TNT contaminated site on the National Priorities List, Former Nansemond Ordnance Depot (FNOD), Suffolk, VA, served as the model site for this work. To describe desorption rate in contaminated sediments, two approaches for a first order single-site desorption were evaluated. In Model 1, the driving force for desorption is mathematically related to the sorbed phase concentrations, whereas in Model 2 the rate is based on aqueous phase concentrations. Two data sets were used to evaluate the models: (1) batch draw-and-fill experiments using FNOD sediment and (2) results from a previously published report from the Louisiana Army Ammunition Plant. Both models provided adequate fit, but Model 2 was better behaved and first order parameters fell within a smaller confidence interval. Draw-and-fill experiments were observed to yield first-order mass transfer coefficients well aligned with those derived from column experiments. The effect of organic amendments on anaerobic TNT degradation rate and microbial community structure in culture enriched from the FNOD site was studied in batch anaerobic microcosms. TNT readily degraded under all experimental conditions. A reductive pathway of TNT degradation was observed across all conditions, however, denaturing gradient gel electrophoresis (DGGE) analysis revealed distinct bacterial community compositions. In all microcosms, Gram-negative γ- or β-Proteobacteria and Gram-positive Negativicutes or Clostridia were observed. According to non-metric multidimensional scaling analysis of DGGE profiles, the microcosm communities were most similar to field site sediment corresponding to the highest TNT concentration, relative to moderately and uncontaminated sediments, suggesting that TNT contamination itself is a major driver of microbial community structure. Candidate degraders were identified and a Pseudomonas sp. was observed to be stimulated under all conditions, which was confirmed to rapidly degrade TNT in pure culture. Mathematical modeling of the batch microcosm results revealed that TNT degraded 1.7 times faster in lactate amended microcosms than in ethanol amended microcosms, which degraded 3.0 times faster than natural organic matter amended microcosms. Simulation of the TNT degradation pathway included determination of branching coefficients representing whether the first reduction of nitro group occurred in the ortho or para position or whether TNT was removed from the aqueous phase (i.e. bound to dissolved organic matter). Branching coefficients were greater for initial reduction of para (17-27% initial TNT concentration) over ortho (3-9% initial TNT concentration) for all test conditions. However, a greater degradate recovery and a different (lower para/ortho) ratio was observed for ethanol compared to lactate and un-amended conditions. Given the difference in sorption parameters between degradate isomers, these results suggest that differences in pathway branching stimulated by different electron donors are potentially relevant to long term site models. This work provides parameter values and model simulations of desorption relevant to other TNT contaminated sites, qualitative observations of how TNT-reducing bacterial community structure changes in response to electron donor addition, and quantitative comparison of the effect of electron donor addition on biodegradation rate with cultures relevant to field conditions; in addition, this work serves as a feasibility study demonstrating biodegradation as well as biostimulation potential at FNOD. / Ph. D.

Plutonium (Pu) is one of the key elements in high-level radioactive waste due to its long half-life. Understanding the sorption behavior of key radionuclides such as Pu and U is important to the safety assessment calculation for a deep geological repository for high-level radioactive waste. Europium (III) (Eu(III)), a chemical analogue of Pu, has shared similar sorption behaviors as Pu. The aim of this study is to investigate the sorption properties of europium onto MX-80 bentonite and crystalline rock (granite), a potential host rock for a deep geological repository for some countries, as a function of pH and ionic strength using batch experiment technique and surface complexation modeling. The experiments are conducted in Ca-Na-Cl solutions. For granite, the sorption coefficient Kd showed proportionate dependence on the pH. The sorption of Eu is dependent on ionic strength at near neutral to low pH region while not dependent on ionic strength at higher pH. For MX-80 bentonite, the sorption of Eu has little dependence on the ionic strength. A surface complexation modeling is also being carried out to examine the experimental results and identify the possible mechanism of the sorption. / Thesis / Master of Applied Science (MASc)

Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the "natural greensand effect," in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Merkle et al. (1997) by either neglecting the empirically determined available fraction of sorption sites (referred to as the "simple" model), which took into account the fact that some adsorption sites in the porous media were inaccessible, or by explicitly accounting for the transport and reaction processes within the porous structure of the MnOx(s) coating (referred to as the "mechanistic" model). Both models were applied to experimental data and used to evaluate the oxidation rate constant, which was the only unknown parameter. An inverse relationship between the fitted reaction rate constant and chlorine concentration was observed, showing that the oxidation reaction does not depend on chlorine concentration for the experimental conditions considered. In a sensitivity analysis, the adsorption isotherm and reaction rate were found to have the greatest impact on predicted Mn removal. The simple model should prove useful for designing contactor units for manganese removal, provided its limitations are clearly understood, while the mechanistic model should be able to resolve differences in the various types of oxide coating (internal porosity, surface area and coating thickness) and will allow a more fundamental and mechanistically-consistent evaluation of the appropriate form of the oxidation rate expression. However, further research is needed to more completely characterize the adsorption and reaction mechanisms over the range of conditions commonly encountered in water treatment plants. / Master of Science

The organoarsenical roxarsone is added to poultry feed to increase weight gain. Studies have shown that roxarsone does not accumulate in poultry tissue but is excreted, resulting in elevated arsenic concentrations (~40 mg/kg) in poultry litter. However, there is little understanding of the fate of roxarsone once it is introduced into agricultural watersheds. Using batch experiments, I investigated the sorption characteristics of roxarsone to Ap and Bt soils of the Frederick series, common in the Shenandoah Valley of Virginia, an area of intense poultry production. Results demonstrate that roxarsone sorbs strongly to Bt soils, but only showed moderate to low sorption onto Ap soils. Sorption to the Ap soils demonstrated stronger pH dependence than did sorption to the Bt soils. Removing organic matter (OM) from Ap soils significantly changed the sorption characteristics, suggesting that OM may be coating mineral surfaces in these soils. Results of this study have implications for roxarsone transport in agricultural watersheds. For soils that have had years of poultry litter application, there will be both sorption and subsequent leaching of roxarsone. In the OM-rich Ap horizon, OM controls sorption. Because roxarsone is loosely bound to OM, it would be rapidly leached into water after a recharge event or field irrigation. Once roxarsone reaches the Bt soils, it is strongly sorbed into iron oxides or clays, decreasing the potential for leaching. However, competition from phosphate or organic acids for sorption sites on mineral surfaces may affect roxarsone retention in the Bt soils. / Master of Science

The work presented in this thesis is divided into two parts. The first part is the sorption of Ni and Eu to granitic materials, and cation exchange capacity measurements for powdered and intact samples. The second part is method development on autoradiography. In the first part, static batch sorption experiments were carried out to study the relative sorption properties of different granitic rocks and minerals. Experimental data were described using non-electrostatic correction models such as the Langmuir, Freundlich and Linear models. Sorption data obtained for sorption in a constant pH environment and variable metal concentration were used to test the Component Additive Model (CAM). Sorption test studies carried out using energy dispersive X-ray microanalysis were used to map the sorption of Eu on an intact sample. The results showed the CAM was applicable for Ni sorption to BG but that it was not applicable for Eu sorption to any of the granitic rocks studied. The sorption data fitted the CAM in the following order; BG (1) > GA (0.7) > RG (0.5) > GG (0.2), GrG (0.2) for Ni sorption and RG (0.7) > BG (0.4) > GA (0.2), GG (0.2), GrG (0.2) for Eu sorption to the different granitic rocks. Values in brackets represent the ratio of Rd-predicted/Rd-calculated. Results from the application of the CAM showed it was not possible to predict the Rd of the bulk sample from the component minerals. Desorption studies at constant pH were analysed by calculating the hysteresis H. The results showed that the higher the Rd the higher the hysteresis. Surface complexation using JChess Geochemical Code was used to obtain surface complexation parameters for the metal-solid complex for sorption in variable pH and constant metal concentration. Experimental data were described by the mass action law to obtained proton stoichiometry at which the sorption edge is defined. Results showed the presence of NaCl decreased the sorption of Ni, and increased the sorption of Eu. Sorption kinetics experiments in different carbonate complexing environments were carried out to study the effect of carbonate on Eu sorption capacity and rate of sorption. Data were fitted to first and second order kinetic models to investigate the sorption rates. Results showed the sorption to be fast initially before reaching a steady state after more than 200 hours of equilibration. Kinetic data confirmed the low sorption capacity observed for quartz. Data obtained for sorption in a mixed radionuclide system were modelled using the Linear model and the surface complexation model. The surface complexation constants are correlated to the Rd values obtained from the linear sorption isotherms. Modelling the results using Rdmix and Rdsing showed that sorption was suppressed in a mixed system, with no effect observed for sorption to feldspar in single and mixed systems. Cation exchange capacity (CEC) measurements were undertaken to deduce a correlation between the CEC of powdered rock samples and intact sample using rock beakers developed from the British Geological Survey by applying the Bascomb method in which the pH was buffered to pH 8.1. Normalising the results using the surface area showed that the CEC of the rock beakers was 6 orders of magnitude greater than that of the powdered sample. In the second part, a method for differentiating two or more radionuclides using storage phosphor imaging plates coupled with the Storm Scanner system was tested. Initial results showed that it is possible to differentiate one radionuclide from another in a mixed system using different levels of shielding.

Ce travail constitue une contribution à l'étude de l'influence de la déformation libre des fibres textiles sous l'effet des contraintes hydriques sur la structure globale d'un tricot Jersey et d'un tissu Toile en coton, ayant subi les mêmes traitements de finition. Une comparaison entre les capacités de sorption du Jersey et des fils défilés de leur structure montre que le serrage géométrique limite les capacités de sorption du Jersey. Les coefficients du tenseur déformation plane du Jersey sous l'effet d'un cycle d'adsorption/désorption montre un gonflement croissant en fonction de l'humidité au moment de l'adsorption et un rétrécissement presque linéaire au moment de la désorption pour reprendre ses valeurs initiales marquant ainsi l'effet mémoire de l'état relaxé de la structure. L'influence du repassage sur le comportement de la Toile en coton sous l'effet de deux cycles continus successifs d'adsorption/désorption est étudiée. Les résultats montrent que l'aplatissement des fils dans la structure génère une amplification de la déformation plane résultante. Un deuxième cycle d'adsorption successif montre l'annulation complète de l'effet de repassage. Une comparaison entre les isothermes d'adsorption et de désorption d'un tissu Toile repassé et non repassé montre que les isothermes de sorption de la Toile repassée et non repassée se collent dés la troisième zone de l'isotherme du premier cycle d'adsorption, ce qui explique que l'encombrement stérique des molécules d'eau dans la structure de la Toile repassée génère un réarrangement stéréochimique de la structure supramoléculaire pour reprendre une forme similaire à la Toile non repassée. / The 2D deformation of bleached plain weave and Jersey cotton ready to wear clothing was measured during adsorption and desorption cycles. The strain along warp and weft directions and the shear deformation were evaluated by image correlation process. The dimensional variations are explained by geometrical consideration of the structure at microscopic (fibers scale) and macroscopic levels (yarns scale). Indeed, the reaction between water vapor molecules and material enlightens two steps. At first, the swelling fibers fill the micro pores inside the yarns. Then, the yarns swell and push on their neighbors to fill up the macro pores and cause the macroscopic swelling of the overall structure. During the desorption phase, the fibers shrink to create a free space inside the plain weave structure that will be relaxed to find its initial state. The shear deformation is related to the cohesion by twist between cotton fibers. The ironing generates flattened yarns and increases their friction which amplifies the deformation during the first adsorption cycle. However, this effect is cancelled at the end of the first adsorption / desorption cycle with no memory effect of the ironing process. These results are confirmed by comparison between sorption isotherms of ironed and not ironed plain weave samples. A comparison between the sorption capacity of Jersey and yarn made of the same structure shows that the geometric form decreases the sorption capacity of jersey especially at high humidity. Then knitting infects the swelling of yarns and decreases their sorption capacity.

Le travail de thèse présenté dans ce manuscrit a pour objectif de mettre en place un nouveau procédé d’élaboration de membranes à base de chitosane pour le traitement d’effluents acides contenants des ions métallique. Soluble en milieu aqueux acide, le chitosane présente la propriété de gélifier lorsque le pH devient basique, ce qui permet d’envisager l’élaboration de membrane sans solvant organique contrairement aux polymères synthétiques classiques. Par ailleurs, ce travail de thèse s’est intéressé à un procédé original de gélification par voie enzymatique, dans lequel la gélification in-situ de la solution de chitosane permet une structuration contrôlée de la membrane contrairement aux procédés classiques qui donnent lieu à un front de gélification. Une étude des cinétiques de gélification en fonction des paramètres d’élaboration (température et concentration en urée) a mis en évidence que seule la température est significativement influente sur le temps de gélification dès lors que la concentration en urée n’est pas limitante. Un modèle a été mis en place pour décrire la gélification enzymatique du chitosane afin de comprendre les mécanismes des cinétiques réactionnelles et de transferts lors de la formation du gel. Des membranes de chitosane ont ainsi été élaborées par le procédé par voie enzymatique, la porosité de ces membranes ayant été générée avec un agent porogène (PEG 6000) et une réaction d’acétylation du chitosane ayant permis d’obtenir des membranes insolubles en milieu acide. Les membranes obtenues ont été caractérisées en termes de morphologie et de propriétés fonctionnelles (filtration, sorption du Cu(II) comme élément métallique modèle). / The Ph-D work presented in this manuscript aims to develop a new process for elaborate chitosan membranes for treatment of acidic media containing metal ions. Soluble In acidic aqueous media, gelation occurs when the pH becomes basic, allowing elaboration of membrane without the use of organic solvents unlike classical synthetic polymers. Moreover, this Ph-D work has focused on an original process enzymatic gelation which the in-situ gelation of chitosan solution allows a controlled structuration of the membrane unlike conventional processes which leads to a front gelling.A study of gelation time as a function of the elaboration parameters (temperature and urea concentration) highlighted that only the temperature is a main parameter on gelation time since the urea concentration is not limiting. A model was developed to describe the chitosan enzymatic gelation in order to understand mechanisms of reaction kinetics and transfers during the gel formation.Chitosan membranes have been prepared by enzymatic process, the porosity of such membranes have been generated with a blowing agent (PEG 6000) and an acetylation of chitosan having yielded insoluble membranes in acid medium. The resulting membranes were characterized by their morphology and functional properties (filtration, sorption of Cu (II) as model metal element).

L'irrigation par les eaux usées est une pratique intéressante dans les régions arides et semi-arides où la ressource en eau subit une pression accrue. Cependant, cette pratique risque de contaminer les sols par des contaminants chimiques tels que les polluants organiques émergents comme les médicaments. Les mécanismes de transfert et de transformation de ces molécules sont encore peu connus. L'objectif de cette thèse a été d'étudier les processus de biodégradation et de sorption des médicaments en conditions contrôlées, avec une réflexion dans le contexte de la réutilisation des eaux usées pour l'irrigation. Nous avons exploité la signature chirale de l'antidépresseur venlafaxine (VEN) et de son métabolite humain majeur O-desméthyl venlafaxine (ODV) afin de discriminer le processus biologique et les processus abiotiques. Les résultats au laboratoire ont montré une corrélation entre le taux de biodégradation et le changement de fraction énantiomérique. La fraction énantiomérique de la VEN a été ensuite suivie à la sortie d'une STEP et dans une rivière recevant ce rejet, où un changement de la fraction énantiomérique a été observé, montrant l'intérêt de mieux développer cette approche pour des études de biodégradation in situ. Le processus de sorption des molécules cationiques VEN et ODV a été étudié avec deux approches, statique en batch et dynamique en colonne de lixiviation, avec une comparaison avec les molécules neutres carbamazépine et son métabolite trans-10,11-dihydro-10,11-dihydroxy carbamazepine. L'étude en batch a montré que pH et force ionique a influencé la sorption des molécules cationiques mais pas celle des molécules neutres. L'échange cationique pourrait ainsi jouer un rôle important dans la sorption des molécules cationiques. L'étude de la lixiviation a montré que les molécules neutres ont été plus mobiles que les molécules cationiques et elles sont susceptibles de contaminer l'eau souterraine dans le cas de l'irrigation par des eaux usées. / Wastewater irrigation represents great interest in arid and semi-arid regions where water demand is important. However, wastewater irrigation results in, for example, soil contamination by emerging organic pollutants such as pharmaceuticals. Transport and transformation mechanisms of these substances are still poorly understood. The objective of this thesis was to study the processes of biodegradation and sorption of pharmaceutical products in laboratory experiments, with a special reflection in the context of wastewater irrigation. Firstly, we exploited the chiral signature of the antidepressant venlafaxine (VEN) and its major human metabolite O-desmethyl venlafaxine (ODV) in order to discriminate the biological processes from other processes. Laboratory experiment showed a correlation between the biodegradation rate and the change in enantiomer fraction. The VEN was then monitored at the outlet of a WWTP and in the river receiving the discharge. A change in enantiomer fraction showed the interest for a better development of this application to investigate in situ biodegradation. Secondly, the sorption of cationic molecules VEN and ODV, as well as the neutral molecules antiepileptic carbamazepine and its human metabolite trans-10,11-dihydro-10,11-dihydroxy carbamazepine, was studied in batch and soil column leaching experiments. The pH and ionic strength conditions in batch experiment influenced the sorption of VEN and ODV, while there was little impact for neutral compounds. The cationic exchange should play an important role in the sorption process of cationic molecules. Leaching study showed that neutral compounds are much more mobile than cationic compounds; therefore they may contaminate groundwater in the case of wastewater irrigation.

Abstract This research work details a systematic study of the structure and function of supramolecular host-guest systems. Host-guest inclusion complexes were formed between β-Cyclodextrin (β-CD) and its copolymers (as hosts), with several types of guest molecules both in aqueous solution and the solid state. The research is divided into two themes; (1) structural characterization and dynamic properties of the inclusion compounds of β-CD with various guest systems in aqueous solution and the solid phase, and (2) heterogeneous adsorption and structural studies of β-CD based copolymers with various guest systems in aqueous solutions. The guest systems include alkyl and perfluoroalkyl carboxylates, perfluoroalkyl sulfonate, and p-nitrophenol (PNP) at variable experimental conditions. In the first theme (chapter 2-5), host-guest complexes in the solid state were prepared using dissolution and slow cool methods at variable host/guest mole ratios (i.e., 1:1 and 2:1). The complexes were further characterized using 19F/13C DP/MAS and CP/MAS solid-state NMR spectroscopy. The solution state complexes were prepared in D2O for structural characterization using 1H/19F NMR spectroscopy. The NMR studies were complemented using FT-IR, thermal analyses (DSC, and TGA), and powder X-ray diffraction (PXRD). Evidence for the formation of host-guest inclusion compounds (ICs) was provided using CP/MAS solids NMR spectroscopy and complexation-induced chemical shift (CIS) values of 1H/19F nuclei in aqueous solution. The β-CD/PFC ICs displayed variable guest geometry and hydration states as determined by the host-guest stoichiometry and the conformation of the guest. PFOA and SPFO form 1:1 and 2:1 ICs with β-CD, wherein the guest adopts a range of gauche and trans conformations, respectively. 1:1 host-guest complexes were concluded for short perfluorocarbon chains (i.e., PFBA) where the gauche conformation of the PFC guest in the bound state was favoured. In the second theme (chapters 6–8), β-CD based copolymers were used as host materials. The structural characterization of a soluble poly-CD material (known as HDI-1) revealed that the solution behaviour of such polymeric hosts are sensitive to the presence of guest compounds such as p-nitrophenol (PNP) (i.e. chemo-responsive), as well as temperature variations (i.e. thermo-responsive). The host-guest chemistry of the soluble poly-CD material, as studied by 2-D solution NMR and induced circular dichroism (ICD) spectroscopy, indicates that PNP was bound within the cavity sites of β-CD and the interstitial domains of the copolymer (cf. Scheme 1.6 and chapter 6). The observed responsive nature of such polymeric host materials to temperature variation and chemical potential resembles behaviour characteristic of ‘smart materials’. Herein, ‘smart materials’ refer to systems which are responsive to external stimuli (e.g. temperature and chemical). The adsorption properties of the soluble (HDI-1) and insoluble (HDI-3 and -6) poly-CD adsorbents with octyl and perfluorooctyl carboxylate and sulfonate anions were estimated using the Sips and BET models. The hydrocarbon (HC) and fluorocarbon (FC) anions form monolayer and multilayer structures at the surface of the polymeric adsorbents, respectively. The formation of layered structures was controlled by the relative hydrophobicity of the alkyl/perfluoroalkyl chains and their mutual miscibility with the adsorbent surface. Other factors include the inductive effects of the alkyl/perfluoroalkyl head groups and their interactions with aqueous solvent or dipolar domains of the adsorbent surface. The adsorbed species at the liquid-solid interface were characterized using FT-IR spectroscopy, thermal analyses, and contact angle.

No description available.