The elimination of natural organic matter (NOM) is an important aim of water treatment in demineralisation plants of power stations. NOM is regarded as corrosion risk factor in the steam water cycle because of its potential to decompose into low-molecular-weight (LMW) acids and carbon dioxide. Further, the removal of NOM is also one of the main objectives in the drinking water production, since it can cause i) colour, taste and odour problems, ii) formation of carcinogen halogenated disinfection by-products (DBPs) after disinfection with chlorine and iii) bacterial growth in the water distribution system. In earlier studies, it was found that anion exchange is a successful method to remove NOM fractions. However, NOM fractions with low charge density (LMW neutrals and hydrophobic organic carbon (HOC)) and/or large molecular size (biopolymers and particulate organic carbon (POC)) could not be removed in some cases in satisfying quantities. The aim of the present work was to investigate the uptake performance of different anion exchange resins (AERs) in regard to problematic NOM fractions. The AERs differ especially in their functional groups (tertiary versus quaternary amines) and matrix material (polystyrene versus polyacrylic resins). The use of different AERs provides an option to identify possible interactions between adsorbate (NOM fractions) and adsorber (AERs) as well as the mechanism which determine the removal efficiency. The NOM fraction adsorption onto AERs was studied in equilibrium and fixed-bed experiments with three types of starch with different molecular size distributions (model substances for biopolymer fraction) as well as 2-naphthol (model substance for the LMW neutral fraction) at acidic pH (relevant for water in demineralisation plants of power stations) and neutral pH (covering most raw waters). Furthermore, the NOM fraction uptake from “real” acidic and neutral water samples, obtained from a demineralisation plant of a power station, was estimated for different AERs. Results were discussed in terms of size-exclusion, anion exchange and hydrophilic/hydrophobic repulsion. In case that size-exclusion influences the NOM uptake onto AERs, it was found that the smaller the size of the NOM molecules and the higher the water content of the AERs, the more effective the uptake is. Thus, for the removal of biopolymers and POC, polyacrylic resins with high water content could be a good choice. Contrary, polystyrene AERs are the most effective resins in the removal of NOM fractions, if no size-exclusion occurs. They seem to be able to uptake more hydrophilic NOM fractions by polar/ionic interactions between acids/acidic components and tertiary/quaternary amines as well as to remove more hydrophobic NOM fractions by π-π stacking and/or hydrophobic interactions on the polystyrene matrix. Further, it was found that the higher the total volume (anion exchange) capacity of an AER, the higher its NOM removal by polar/ionic interactions can be. At acidic pH, weak/medium base AERs have higher total volume (anion exchange) capacities than strong base AERs, whereas, at neutral pH, strong base AERs have the highest ones. In view of these results, the application of polyacrylic AERs with high water content can be recommended to remove NOM components with large molecular size in demineralisation and drinking water plants. If there is a higher amount of smaller NOM fractions, especially LMW neutrals, than polystyrene weak/medium base AERs should be favoured in demineralisation plants and polystyrene strong base AERs in drinking water treatment plants. From the engineering point of view, breakthrough curve (BTC) prediction models are important for the design of fixed-bed filter. Therefore, two different BTC model approaches were tested in the present study to describe the single-solute adsorption onto AERs: i) the homogenous surface diffusion model (HSDM) with linear driving force (LDF) approach for surface diffusion, known from activated carbon adsorption, and ii) the Glueckauf/Helfferich formulae as an extension of the height equivalent to a theoretical plate (HETP) model, initially used to describe ion exchange processes. It was found that the Glueckauf/Helfferich approach is not only a suitable tool for the fast calculation of BTCs for ionic components, but it can also successfully be applied, after considering the Freundlich model for the mass balance, for the rapid prediction of BTCs for single-solute organic molecules. For competitive BTC predictions, the ideal adsorbed solution theory (IAST) within the LDF model was applied. All calculated BTCs fit the experimental data in a good manner. Thus, the investigated BTC models can be applied for estimating the breakthrough bed volumes of different AERs to avoid leakage of NOM in the drinking or demineralised water caused by overloading. / Die Entfernung von natürlichen organischen Substanzen (NOM) ist ein wichtiges Ziel für die Herstellung von Reinstwasser im Kraftwerksbetrieb, da diese sich im Wasser/Dampf-Kreislauf zu niedermolekularen Säuren und Kohlenstoffdioxid zersetzen können und so ein potentielles Korrosionsrisiko darstellen. Außerdem ist die Elimination von natürlichen organischen Substanzen einer der Schwerpunkte in der Trinkwasseraufbereitung, da NOM im Trinkwasser folgende Konsequenzen verursachen können i) Farb-, Geschmacks- und Geruchsprobleme, ii) Bildung von kanzerogen halogenierten Desinfektionsnebenprodukten nach der Desinfektion mit Chlor und iii) Bakterienwachstum im Wasserverteilungssystem. In früheren Untersuchungen wurde festgestellt, dass Anionenaustauscherharze (AERs) die NOM-Fraktionen in der Regel erfolgreich aufnehmen können. Nur NOM-Fraktionen mit geringer Ladungsdichte (niedermolekulare Neutralstoffe und hydrophober organischer Kohlenstoff) und/oder großer Molekülgröße (Biopolymere und partikulärer organischer Kohlenstoff) können unter bestimmten Bedingungen nicht in zufriedenstellender Menge entfernt werden. Ziel dieser Arbeit war es, das Aufnahmeverhalten unterschiedlicher AERs hinsichtlich problematischer NOM-Fraktionen zu untersuchen. Die AERs unterscheiden sich vor allem in ihren funktionellen Gruppen (tertiäre versus quaternäre Amine) und ihrer Matrix (Polystyren- versus Polyacryl-Harze). Die Verwendung unterschiedlicher AERs erlaubt es, mögliche Wechselwirkungen zwischen Adsorbat (NOM-Fraktionen) und Adsorber (AERs) und die Mechanismen, die die NOM-Aufnahme entscheidend bestimmen, zu identifizieren. Die Entfernung von NOM-Fraktionen durch AERs wurde in Gleichgewichts- und Festbett-versuchen mittels dreier Stärketypen mit unterschiedlicher Molekülgrößenverteilung (Modellsubstanzen für die Biopolymere) und 2-Naphthol (Modellsubstanz für die Neutralstoffe) unter sauren pH-Bedingungen (relevant für die Herstellung von Reinstwasser im Kraftwerksbetrieb) und neutralen pH-Bedingungen (bedeutsam für die meisten Rohwässer) untersucht. Außerdem sollte das Adsorptionsverhalten von AERs bezüglich verschiedener NOM-Fraktionen unter Einsatz von „real“ neutralen und sauren Wasserproben aus einer Wasseraufbereitungsanlage eines Kraftwerksbetriebes eingeschätzt werden. In dieser Arbeit konnte gezeigt werden, dass falls Größenausschluss die NOM-Aufnahme von AERs beeinflusst, dann ist die Adsorption der NOM-Fraktionen umso größer, je kleiner die NOM-Moleküle sind und je höher der Wassergehalt der AERs ist. Daher kann für die Entfernung von größeren Biopolymeren, der Einsatz von AERs mit Polyacryl-Matrix und hohem Wassergehalt die beste Option sein. AERs mit Polystyren-Matrix besitzen die höchste Aufnahmekapazität für NOM-Fraktionen, falls kein Größenausschluss auftritt. Es scheint für sie möglich zu sein, sowohl hydrophile NOM-Fraktionen durch polare/ionische Wechselwirkungen zwischen NOM Säuren/sauren Komponenten und tertiären/quaternären Aminen aufzunehmen als auch hydrophobe NOM-Fraktionen durch π-π Anziehungen und/oder hydrophobe Interaktionen an die Polystyren-Matrix zu binden. Weiterhin konnte gezeigt werden, dass je höher die Gesamtvolumenkapazität eines AERs, desto größer ist die NOM-Entfernung auf Grund von polaren/ionischen Wechselwirkungen. Es gilt, dass schwach/mittel basische AERs im Vergleich zu stark basischen AERs höhere Gesamtvolumenkapazitäten unter sauren pH-Bedingungen besitzen und stark basische AERs die höchsten Gesamtvolumenkapazitäten unter neutralen pH-Bedingungen aufweisen. Auf Grund dieser Ergebnisse ist es möglich, die Verwendung von AERs mit Polyacryl-Matrix und hohem Wassergehalt für die Entfernung von NOM-Fraktionen mit großer Molekülgröße in Reinst- und Trinkwasseraufbereitungsanlagen zu empfehlen. Falls es einen höheren Anteil von kleineren NOM-Fraktionen, im Besonderen Neutralstoffen, gibt, sollte die Verwendung von schwach/mittel basischen AERs in Vollentsalzungsanlagen von Kraft-werksbetrieben und stark basischen AERs in Trinkwasseraufbereitungsanlagen bevorzugt werden. Vor allem im Hinblick auf technische Anwendungen ist es wichtig, Durchbruchskurven (BTC) vorausberechnen zu können. In der vorliegenden Arbeit wurden zwei Modellansätze für die Berechnung von BTCs für die Einkomponentenadsorption getestet: i) das homogene Oberflächendiffusionsmodell mit linearer Triebkraft (LDF), bekannt aus Untersuchungen zur Aufnahme von NOM an Aktivkohle, und ii) die Glueckauf/Helfferich-Formeln, primär verwendet für die Beschreibung von Ionenaustauschprozessen. Es konnte gezeigt werden, dass das Glueckauf/Helfferich-Verfahren nicht nur ein geeignetes Instrument für die schnelle Berechnung von BTCs für ionische Komponenten ist, sondern dass dieses, nach Berücksichtigung des Freundlich-Ansatzes in der Massenbilanz, auch erfolgreich angewendet werden kann, um BTCs für Einkomponentenadsorption von Organika zu berechnen. Für die Vorausberechnung von BTCs für Mehrkomponentensysteme wurde die Theorie der idealen adsorbierten Lösung im LDF-Modell genutzt. Die berechneten BTCs stimmen in guter Qualität mit den experimentell ermittelten BTCs überein. Die Ergebnisse verdeutlichen, dass die untersuchten BTC-Modelle eingesetzt werden können, um Durchbruchspunkte für die jeweiligen AERs zu bestimmen und damit die Gefahr des Schlupfes von NOM ins Trink- bzw. Reinstwasser zu minimieren.

Ion-exchange membranes, conventionally utilized in separation processes of electrolyte solutions, are electroactive polymers that display a unique coupling between electrochemistry and mechanics. Previous experimental studies have demonstrated the possibility of actuating cation-exchange membranes in salt solution through the application of a remote external electric field. The use of anion-exchange membranes as contactless actuators, however, has never been documented and little is known about the physics of their actuation. Here, it is reported for the first time the possibility of contactless actuating anion-exchange membranes in salt solutions; such an actuation is mediated by the selection of anions in the external salt solution and the membrane. Actuation is attributed to the physical phenomenon of solvation, the interaction between ions and solvent in solution. Contrary to previous studies with cation-exchange membranes, the results show that anion-exchange membranes consistently bend toward the anode. The integration of anion-exchange and cation-exchange membranes in composites promises innovative programmable contactless actuators, with applications in underwater robotics and biomedical engineering.

Avloppsreningsverk är en spridningsväg för läkemedelsrester och per- och polyfluorerade alkylsubstanser (PFAS) till miljön. Genom en pågående revidering av avloppsdirektivet, vilket är ett genomförandedirektiv från EU, kommer det införas krav på reduktion av läkemedelssubstanser för att minska denna spridning. Kolonnförsök i bänkskala och pilotförsök i containerskala genomförs av Uppsala Vatten och Avfall AB och IVL Svenska Miljöinstitutet på Kungsängsverket i Uppsala för att testa tekniker för avskiljning av läkemedelsrester och andra mikroföroreningar. Syftet med detta examensarbete var att utvärdera de pågående försöken utifrån reningseffektivitet, kostnader, klimatpåverkan och utifrån de krav som kan komma att ställas i det reviderade avloppsdirektivet.  Avskiljningsgrad i avloppsvatten av perfluoroktansulfonsyra (PFOS), citalopram, diklofenak, metoprolol, oxazepam och summan av 14 svårnedbrytbara substanser vid singel- och seriedrift av granulerat aktivt kol (GAK) i kombination med efterföljande anjonbytare (AIX) undersöktes baserat på analysdata från provtagningar. För läkemedel sker reduktionen huvudsakligen med GAK. Efterföljande AIX bidrar med en kompletterande reduktion av diklofenak och PFOS. Vid byte av kol i GAK-filtret i kolonnförsöken påverkas reduktionen över efterföljande AIX, vilket syns genom desorption av diklofenak över AIX. Vid jämförelse mellan GAK-filtren i kolonnförsöken och GAK-filtren i pilotförsöken kunde liknande trender ses gällande hur snabbt avskiljningsgraden för olika substanser avtar vid ett ökat antal behandlade bäddvolymer (BV). Utvärdering av de substanser som ingår i förslaget till reviderat avloppsdirektiv utifrån de krav som ställs visade en genomsnittlig reduktion på över 80 % av sex utvalda substanser (amisulprid, citalopram, diklofenak, venlafaxin, ∑6&4-metylbenxotriazol and benzotriazol), och därmed uppfyllda reduktionskrav, fram till minst 24 000 behandlade BV i GAK-filtren och 60 300 behandlade BV i AIX-filtret. Av de undersökta teknikerna förväntas lägst kostnad och klimatpåverkan vid seriedrift av GAK i två steg om målet med reningen är att avskilja läkemedel. Om reningsmålet även inkluderar reduktion av PFOS förväntas lägst kostnad och klimatpåverkan vid seriedrift av GAK i två steg följt av AIX. / Wastewater treatment plants contribute to the spread of pharmaceuticals and per- and polyfluoroalkyl substances (PFAS) to the environment. The urban wastewater treatment directive from the European Union is under revision, and requirements for reduction of pharmaceutical substances will be introduced to reduce the spread. Column tests in bench scale, and pilot tests in a shipping container, are being conducted by Uppsala Vatten och Avfall AB and IVL Svenska Miljöinstitutet at Kungsängsverket in Uppsala with the aim of evaluating techniques to reduce pharmaceuticals and other micropollutants. This master thesis was aimed to evaluate the tests based on treatment efficiency, costs, climate impact and based on the requirements that may be set in the revised urban wastewater treatment directive.    Reduction of perfluorooctanesulfonic acid (PFOS), citalopram, diclofenac, metoprolol, oxazepam and the sum of 14 persistent pharmaceuticals in wastewater, with granulated activated carbon (GAC) in single- and two-stage series operation in combination with a following anion exchange resin (AE), were evaluated based on data from analyzed samples. The reduction of pharmaceuticals was mostly done by GAC. AE after GAC contribute with a complementary reduction of diclofenac and PFOS. When changing the resin in the GAC-filter in the column tests, the reduction over the subsequent AE-filter was affected, which could be seen by desorption of diclofenac from AE. A comparison between the GAC-filter in the column tests and the GAC-filter in the pilot test showed similar trends regarding how fast the treatment efficiency for different substances decreased with an increased number of treated bed volumes (BV). An evaluation of the substances that are included in the proposal to the revised directive showed an average reduction of six selected substances (amisulprid, citalopram, diclofenac, venlafaxine, ∑6&4-metylbenxotriazol and benzotriazol) over 80 % for 24 000 treated BV in the GAC-filter and 60 300 treated BV in the AE-filter. GAC in a two-step series operation was the technique with lowest expected cost and climate impact if the aim of the treatment was to reduce pharmaceuticals. If the aim of the treatment also includes reduction of PFOS, the lowest expected cost and climate impact was achieved with GAC in two-step series operation followed by AE.

Per- and polyfluorinated substances (PFAS) are used in many areas of application due to their many beneficial properties such as heat resistance. insulator and water- and oil repellent. PFAS containing products can often be found in landfills and their leachate. This study compares the two common treatment techniques granulated activated carbon (GAC) and anion exchange (AIX) for treating groundwater at a landfill site. The removal efficiencies of the PFAS found at the site were determined for both methods as well as the cost of treatment for removal efficiencies at 99, 95, 90, 85, 80 and 50 % for one cubic metre of groundwater. Twenty different PFAS were found and the removal efficiency of ∑PFAS ranged between 4 – 90 % for two stage GAC and 30 – 100% for AIX. Within the groups perfluoroalkyl carboxylic acid (PFCA) and perfluorosulfonic acid (PFSA), both methods were most efficient in removing long chains. PFSA generally had a higher removal efficiency than PFCA. The cost of removing PFAS was related to the removal efficiency. Since AIX had a higher removal efficiency the cost became lower, despite the filter media costing nearly seven times more than GAC’s. The costs of removing PFCA and PFSA were 3.1 – 32 and 2.3 – 6.5 euros/m3 groundwater for removal of 50 – 99% using AIX. For GAC, the cost could not be calculated for 99 % removal since the removal efficiencies were too low for the Lin and Huang adsorption model to work. For 50 – 95% removal the costs for PFCA and PFSA were 2.9 – 23.1 and 2.8 – 6.9 euros/m3 groundwater.

Interactions between plant roots and soil microorganisms in the rhizosphere are critical for plant growth. However, understanding of precisely how root exudates influence the diversity and activity of rhizosphere microorganisms is limited. The main objective of this study was to investigate the effect of radiata pine (Pinus radiata) root exudates on rhizosphere soil microbial communities, with an emphasis on the role of low molecular weight organic anions. The study involved the development and validation of new methods for investigating rhizosphere processes in a purpose-built facility. This included development of an in situ sampling technique using an anion exchange membrane strip to collect a range of organic anions exuded from radiata pine roots grown in large-scale rhizotrons. These included tartarate, quinate, formate, malate, malonate, shikimate, lactate, acetate, maleate, citrate, succinate and fumarate. Soil microbial activity and diversity were determined using dehydrogenase activity and denaturing gradient gel electrophoresis. Links between organic anions in root exudates and rhizosphere soil microbial community structures were investigated by comparing wild type and genetically modified radiata pine trees which were grown in rhizotrons for 10 months. As expected, there was considerable temporal and spatial variability in the amounts and composition of organic anions collected, and there were no consistent or significant differences determined between the two tree lines. Significant differences in rhizosphere microbial communities were detected between wild type and genetically modified pine trees; however, they were inconsistent throughout the experiment. The shifts in microbial communities could have been related to changes in exudate production and composition. Based on results from the main rhizotron experiment, a microcosm study was carried out to investigate the influence of selected pine root exudate sugars (glucose, sucrose and fructose) and organic anions (quinate, lactate and maleate) on soil microbial activity and diversity. Soil microbial activity increased up to 3-fold in all of the sugar and organic anion treatments compared to the control, except for a mixture of sugars and maleate where it decreased. The corresponding impacts on soil microbial diversity were assessed using denaturing gradient gel electrophoresis and 16S rRNA phylochips. Addition of the exudate compounds had a dramatic impact on the composition and diversity of the soil microbial community. A large number of bacterial taxa (88 to 1043) responded positively to the presence of exudate compounds, although some taxa (12 to 24) responded negatively. Organic anions had a greater impact on microbial communities than sugars, which indicated that they may have important roles in rhizosphere ecology of radiata pine. In addition, a diverse range of potentially beneficial bacterial taxa were detected in soil amended with organic anions, indicating specific regulation of rhizosphere microbial communities by root exudates. This project highlighted the considerable challenges and difficulties involved in detailed investigation of in situ rhizosphere processes. Nonetheless, the findings of this study represent a significant contribution to advancing understanding of relationships between root exudates and soil microbial diversity, which will be further enhanced by refinement and application of the specific methodologies and techniques developed.

L'analyse chimique est indispensable à de nombreuses étapes de la mise au point et dusuivi des procédés de retraitement des combustibles nucléaires usés, de la gestion des déchetsnucléaires, ou encore de l’optimisation des combustibles du futur. Le cycle global d’analysecomprend généralement plusieurs étapes de séparations chimiques longues, manuelles etdifficiles à mettre en oeuvre en raison de leur confinement en boite à gants. Il apparaîtaujourd’hui nécessaire de proposer des solutions innovantes et viables dans le butd’automatiser ces étapes mais aussi de réduire le volume de déchets radioactifs en fin de cycleanalytique. Une solution est alors la conception de plateformes analytiques miniaturiséesautomatisées et jetables.L’objectif de cette thèse est de concevoir un système miniaturisé alternatif à lapremière étape actuelle d’analyse des combustibles usés séparant, par chromatographied’échange d’ions, l’Uranium et le Plutonium des autres éléments constituant l’échantillon. Cesystème doit permettre à la fois de conserver les performances analytiques du processusactuel, de réduire drastiquement l’exposition des expérimentateurs par l’automatisation, ainsique le volume de déchets produits en fin de cycle analytique. Ainsi, la séparation a étéimplantée sur un microsystème jetable en plastique (COC), au design spécialement adapté àl’automatisation : un lab-on-CD.Le prototype développé intègre une micro-colonne séparative d’échange d’anionsremplie d’un polymère monolithique dont la synthèse in-situ ainsi que la fonctionnalisation desurface ont été optimisées spécifiquement pour la séparation voulue. Le développement duprotocole de séparation adapté à ces micro-colonnes a été réalisé à l’aide d’un outil desimulation de l’élution des différents éléments d’intérêts. Cet outil permet de prévoir lagéométrie de la colonne (section et longueur) afin d’obtenir, en fonction de l’échantillon, desfractions de collecte de l’Uranium et du Plutonium pures.Finalement, le prototype actuel est capable de conduire simultanément 4 séparationsde façon automatisée et permet de réduire à la fois le nombre de manipulations, le tempsd’analyse mais aussi de diviser approximativement par 1000 le volume des déchets liquidesgénérés. / The chemical analysis of spent nuclear fuels is essential to design future nuclear fuelscycle and reprocessing methods but also for waste management. The analysis cycle consistsof several chemical separation steps which are time consuming and difficult to implement dueto confinement in glove boxes. It is required that the separation steps be automated and thatthe volume of radioactive waste generated be reduced. The design of automated, miniaturizedand disposable analytical platforms should fulfill these requirements.This project aims to provide an alternative to the first analytical step of the spent fuelsanalysis: the chromatographic separation of Uranium and Plutonium from the minor actinidesand fission products.The goal is to design a miniaturized platform showing analytical performancesequivalent to the current process, and to reduce both the exposure of workers throughautomation, and the volume of waste produced at the end of the analysis cycle. Thus, theseparation has been implemented on a disposable plastic microsystem (COC), specificallydesigned for automation: a lab on a Compact Disk or lab-on-CD.The developed prototype incorporates an anion-exchange monolithic micro-columnwhose in-situ synthesis as well as surface functionalization have been optimized specificallyfor the desired separation. The development of an adapted separation protocol was carried outusing a simulation tool modeling the elution of the various elements of interest. This tool isable to predict the column geometry (length and cross section) suited to obtain pure fractionsof Uranium and Plutonium as a function of the sample composition.Finally, the prototype is able to automatically carry out four separationssimultaneously reducing the number of manipulations, the analysis time and reducing thevolume of liquid waste by a factor of 1000.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-10T12:37:20Z No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T15:04:53Z (GMT) No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) / Made available in DSpace on 2017-05-17T15:04:53Z (GMT). No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) Previous issue date: 2011-07-29 / Os hidróxidos duplos lamelares (HDL) ou compostos tipo-hidrotalcita vêm sendo muito estudados devido a suas inúmeras aplicações. No campo da catálise, estes compostos podem atuar como catalisadores, suportes para catalisadores ou precursores de catalisadores. É sabido que a morfologia do suporte tem grande influência sobre a dispersão, a atividade e a seletividade apresentada pelo catalisador. Nestes caso, o conhecimento detalhado dos efeitos do suporte e dos sítios catalíticos exigem a compreensão da estrutura do HDL. Entretanto, por causa da desordem estrutural, muitas vezes inerente ao material, torna-se a determinação completa da estrutura, via difração de raios X, raramente possível. As bandas largas presentes na análise do IV, fazem a atribuição das mesmas ambígua. Devido à complexidade dos HDL e à dificuldade de se adquirir ou interpretar os resultados experimentais, foi proposto um modelo para simular as características estruturais dos compostos tipo-hidrotalcita com o politipo 3R1, usando condições periódicas de contorno e cálculos ab initio dentro da teoria do funcional da densidade (DFT). As informações estruturais da hidrotalcita, obtidas experimentalmente, foram usadas para verificar a validade do modelo teórico. Os resultados mostraram boas concordâncias com os padrões de raios X do pó experimentais. O espectro na região do infravermelho, a entalpia e energia livre de Gibbs, também foram calculadas. Os cálculos de frequências vibracionais mostraram que as moléculas de água intercaladas são altamente organizadas devido às fortes interações intermoleculares com outras moléculas de água, com ânions interlamelares e com as hidroxilas das lamelas. A presença destas interações é refletida na presença do estiramento O-H das moléculas de água deslocadas para baixas frequências. A perda da degenerescência dos modos vibracionais v3 e do v4 foi observada, indicando a redução da simetria do íon carbonato. As modificações termodinâmicas e estruturais resultantes da substituição do íon presente no HDL Zn-Al-Cl também formam analisadas. O íon Cl- do HDL precursor foi trocado por uma série de ânions como o F-, Br-, OH-, NO3-, ClO4-, CO32- e SO42-. Os resultados mostraram que a intercalação do HDL com diferentes íons, afeta o gap de energia e a basicidade da lamela tipo-brucita. A entalpia e a energia livre de Gibbs, a densidade de estados (DOS) e a densidade de estados projetada (PDOS) foram avaliadas para todos os HDL. / The layered double hydroxide (LDH) or hydrotalcite-like compounds have been widely studied due to many applications they have. In catalysis field these compounds can act as catalyst, catalyst support or precursor for supports and catalysts. It is well known that the support morphology has larger influence on the dispersion, activity and selectivity of catalysts. In this case, detailed knowledge about support effects and catalytic sites requires understanding the LDH structure. However, because of the inherent structural disorder, complete structure determination using X-ray diffraction is rarely possible. The IR analysis present broad bands, which makes their assignment ambiguous. Due to the complexity of the LDH and the difficult of acquiring experimental data, we proposed a model to simulate structural features of the hydrotalcite-like compounds with 3R1 polytypes using periodic boundary conditions and ab initio density functional theory (DFT) calculations. The structural information of hydrotalcite from experiments were used to verify the validity of theoretical model. Our results showed good agreements to the powder X-ray patterns. The infrared spectroscopy, enthalpy and Gibbs free energy, also was calculated. The IR calculations showed that intercalated water molecules are highly ordered due the strong intermolecular interactions with other water molecules, interlayer anions and layer hydroxyls. These interaction is reflected by the presence of downshift vibrational frequencies of OH-stretching of interlayer water. The loss of degeneracy of the v3 and v4 vibrational modes are observed, indicating the reduction of the carbonate anion symmetry. The thermodynamic and structural modifications derived from anion exchange on a LDH containing Zn-Al-Cl was also analyzed. The Cl- ion to the LDH precursor was exchanged for a series of anions as F-, Br-, OH-, NO3-, ClO4-, CO32- and SO42-. The resulted show that intercalation of LDH with different anions affect their gap energy and basicity of brucite-like layer. The enthalpy and Gibbs free energy, density of charge, density of state (DOS) and projected density of state (PDOS) were evaluated for all substituted materials.

Per- and polyfluorinated substances (PFAS) are compounds that consist of a carbon chainbackbone that is partially or entirely fluorinated, with an addition of a functional group. SomePFAS are known as persistent organic pollutants (POPs) and have therefore been drawing a lot ofattention as well as increased concerns. PFAS have been detected in humans, wildlife and theenvironment and some have exhibited toxic effects such as hepatotoxicity, immunotoxicity,reproductive toxicity and endocrine disruption as well as being persistent and bioaccumulative.Serum, plasma and whole blood have been used as biomonitoring matrices in many studies toevaluate human exposure to PFAS. Restrictions have been applied to some PFAS, but thesecompounds are still ubiquitous. This study will investigate the performance (recovery, matrixeffect (ME) in terms of intra-/inter-day repeatability) of ion-pair extraction (IPE) and solid phaseextraction with weak anion exchange (SPE-WAX). The extraction methods were adapted fromliterature and 13 PFAS were selected for this work based on prior biomonitoring studies. Thetarget PFAS content was analyzed with liquid chromatography coupled with tandem massspectrometry (LC-MS/MS). The extraction methods were also compared for extractableorganofluorine (EOF) extraction in terms of blank levels as well as the amount extracted withdifferent methods; the EOF content was measured with combustion ion chromatography (CIC).The EOF levels were used to estimate the amount of unidentified organofluorine (UOF), to avoidunderestimating potential health hazards. Samples extracted using IPE had an average ionizationenhancement of 9%, while SPE-WAX showed an average ionization suppression of -1%. SPEWAXshowed higher average recoveries for procedural blanks (78%), horse serum (96%) andhuman serum (95%) in comparison to IPE (69%, 36%, 88%, respectively). The CIC analysis forEOF content was observed to be below MDL (<50 ng/mL F) with some contaminations observedin the procedural blanks.

Avloppsreningsverk utgör en viktig spridningsväg för läkemedelsrester till den akvatiska miljön. Även per- och polyfluorerade alkylsubstanser (PFAS) har påvisats i utgående vatten från avloppsreningsverk. För att minska utsläpp av dessa krävs ett kompletterande reningssteg. Syftet med denna studie var att utvärdera utökad rening av avloppsvatten med granulerat aktivt kol (GAK) och anjonbytare (AIX, Anion exchange resin). Underlag för utvärdering utgjordes av resultat från pågående pilotstudie vid Kungsängsverket i Uppsala, vilken består av kolonnförsök samt pilotförsök i större skala. I kolonnförsöken testas kombinationen GAK (Cyclecarb 401 eller Filtrasorb 400) i fixerade bäddar, följt av AIX (Purolite 694E) i fixerade samt fluidiserade bäddar i olika driftlinjer. Kontakttiden (EBCT, Empty Bed Contact Time) var cirka 15 minuter för GAK respektive 5 minuter för AIX. I pilotförsöken inkluderas även tvåstegsdrift av GAK med EBCT på cirka 14 minuter per filter. Vid slutet av denna studie hade cirka 36 000 till 37 000 bäddvolymer (BV) behandlats med GAK, respektive 98 000 till 116 000 BV med AIX i kolonnförsöken. I pilotförsöken hade cirka 5 000 till 10 000 BV behandlats med GAK samt cirka 8 000 till 31 000 BV med AIX. Reningseffektivitet utvärderades avseende avskiljning av diklofenak, oxazepam, metoprolol, citalopram samt PFOS eftersom dessa i tidigare studie pekats ut som mest utmanande för mottagande vattenmiljö. En högre avskiljning av oxazepam, metoprolol och citalopram uppnåddes med GAK än med AIX, där Cyclecarb 401 uppvisat högst reduktion. För diklofenak och PFOS uppnåddes en högre avskiljning med kombinationen GAK följt av AIX än med enbart GAK. Driftkostnad och klimatpåverkan utvärderades för samtliga adsorbenter samt för specifika scenarion vid Kungsängsverket. Scenarierna inkluderar olika reningsmål för avancerad rening med singel- respektive tvåstegsdrift av GAK samt GAK följt av AIX. Reningsmålen avser en 80 procentig genomsnittlig reduktion över tid av diklofenak, oxazepam, PFOS eller en kombination av dessa. Vid ekvivalent dos av adsorbenterna resulterade Cyclecarb 401 i den lägsta driftkostnaden och klimatpåverkan. Lägst driftkostnad för samtliga reningsmål erhölls med tvåstegsdrift av GAK. För avskiljning av PFOS eller PFOS och diklofenak erhölls lägst klimatpåverkan med kombinationen GAK följt av AIX. För resterande reningsmål erhölls lägst klimatpåverkan med tvåstegsdrift av GAK. I tillägg utfördes en regressionsanalys för att undersöka om enkla mätningar av löst organiskt kol (DOC) eller ultraviolett absorbans (UVA) kan användas som uppföljningsmetod för reningseffektiviteten. Ingen korrelation kunde dock fastställas mellan skillnaden i ingående och utgående koncentration eller absorbans av DOC, UVA och diklofenak, oxazepam eller PFOS. / Wastewater treatment plants are an important source for the spread of pharmaceuticals to the aquatic environment. Per- and polyfluorinated alkyl substances (PFASs) have also been detected in outgoing wastewater. To reduce emissions of these micropollutants, an advanced treatment process is required.  This study aimed to evaluate advanced treatment with granular activated carbon (GAC) and anion exchange resin (AIX), using results from an ongoing pilot study at the wastewater treatment plant Kungsängsverket in Uppsala, Sweden. The pilot study consists of column tests and pilot tests in larger scale. The column tests consist of the combination of GAC (Cyclecarb 401 or Filtrasorb 400) in fixed beds, followed by AIX (Purolite 694E) in fixed or fluidized beds in different operating lines. Contact time (EBCT, Empty Bed Contact Time) was 15 minutes for GAC and 5 minutes for AIX. The pilot tests include two-stage operation of GAC with EBCT of 14 minutes per filter. At the end of this study, in the column tests, approximately 36 000 bed volumes (BV) had been treated with GAC and 98 000 to 116 000 BV with AIX. In the pilot tests, 5 000 to 10 000 BV had been treated with GAC and 8 000 to 31 000 BV with AIX. Treatment efficiency was evaluated for diclofenac, oxazepam, metoprolol, citalopram and PFOS, since these were identified as prioritized substances in a previous study. A higher reduction of oxazepam, metoprolol and citalopram were obtained using GAC compared to AIX, where Cyclecarb 401 showed the highest reduction. For diclofenac and PFOS, a higher reduction was achieved for the combination of GAC followed by AIX compared to GAC alone.  Operating cost and climate impact were evaluated for the adsorbents as well as for specific scenarios at Kungsängsverket, that includes different treatment goals for single stage and two-stage operation of GAC, and GAC followed by AIX. Treatment goals consists of an 80 percent average reduction over time of diclofenac, oxazepam, PFOS, or a combination of these. For an equivalent dose of adsorbent, the lowest operating cost and climate impact was obtained with Cyclecarb 401. The lowest operating cost for all the treatment goals was obtained with two-stage operation of GAC. For reduction of PFOS or PFOS and diclofenac, the lowest climate impact was obtained with the combination of GAC followed by AIX. For the remaining treatment goals, the lowest climate impact was obtained with two-stage operation of GAC.   In addition, a regression analysis was preformed to evaluate whether measurements of dissolved organic carbon (DOC) or ultraviolet absorbance (UVA) could serve as a prediction method for the treatment efficiency of organic micropollutants. However, the regression analysis showed no correlation between the reduction of DOC, UVA, and diclofenac, oxazepam or PFOS.

RESUME La Trypanosomiase Humain Africaine (THA) demeure un problème de santé publique pour plusieurs pays en Afrique subsaharienne. Le contrôle de la THA est basé essentiellement sur la stratégie de dépistage actif suivi du traitement des personnes infectées. Le dépistage actif est réalisé par des unités mobiles spécialisées, bien que les services de santé fixes jouent un rôle important en détectant « passivement » des cas. Le dépistage reposait jadis sur la palpation ganglionnaire mais, depuis le développement du test d’agglutination sur carte (CATT), trois possibilités se sont offertes aux programmes de contrôle à savoir: i) continuer avec la palpation ganglionnaire ii) combiner la palpation ganglionnaire avec le CATT iii) recourir au CATT seul. Certains programmes comme celui de la République Démocratique du Congo (RDC) ont opté pour la combinaison en parallèle de la palpation ganglionnaire avec le CATT. Toute personne ayant une hypertrophie ganglionnaire cervicale et/ou un CATT positif est considéré comme suspecte de la THA. Elle sera soumise aux tests parasitologiques de confirmation à cause de la toxicité des médicaments anti-THA. Les tests parasitologiques classiques sont l’examen du suc ganglionnaire (PG), l’examen du sang à l’état frais (SF), la goutte épaisse colorée (GE). La sensibilité de cette séquence a été estimée insuffisante par plusieurs auteurs et serait à la base d’une grande perte de l’efficacité de la stratégie dépistage-traitement. D’autres techniques de concentration ont été développées comme la mini-Anion Exchange Concentration Technique (mAECT), la Centrifugation en Tube Capillaire (CTC) et le Quantitative Buffy Coat (QBC), mais ces techniques de concentration ne sont pas utilisées en routine. En RDC, une interruption des activités de contrôle en 1990 a eu comme conséquence une réémergence importante de la maladie du sommeil. Depuis 1998 les activités de contrôle ont été refinancées de manière structurée. Ce travail vise deux buts à savoir le plaidoyer pour la continuité des activités de contrôle et la rationalisation des stratégies de contrôle. Nous avons évalué l’évolution de la maladie du sommeil en rapport avec le financement, son impact sur les ménages ainsi que la communauté. L’exercice de rationalisation a porté sur les outils de dépistage et de confirmation. Nous avons d’abord évalué la validité des tests, leur faisabilité ainsi que les coûts et ensuite nous avons effectué une analyse décisionnelle formelle pour comparer les algorithmes de dépistage et pour les tests de confirmation. Pendant la période de refinancement structurel de la lutte contre la THA en RDC (1998-2003), le budget alloué aux activités a été doublé lorsqu’on le compare à la période précédente (1993-1997). Le nombre des personnes examinées a aussi doublé mais par contre le nombre des nouveaux cas de THA est passé d’un pic de 26 000 cas en 1998 à 11 000 en 2003. Le coût par personne examinée a été de 1,5 US$ et celui d’un cas détecté et sauvé à 300 US$. Pendant cette période, les activités ont été financées par l’aide extérieure à plus de 95%. Cette subvention pourrait laisser supposer que l’impact de la THA au niveau des ménages et des communautés est réduit mais lorsque nous avons abordé cet aspect, il s’est avéré que le coût de la THA au niveau des ménages équivaut à un mois de leur revenu et que la THA fait perdre 2145 DALYs dans la communauté. L’intervention par la stratégie de dépistage-traitement a permis de sauver 1408 DALYs à un coût de 17 US$ par DALYs sauvé. Ce coût classe l’intervention comme « good value for money ». Le recours au CATT seul s’est avéré comme la stratégie la plus efficiente pour le dépistage actif. Le gain marginal lorsque l’on ajoute la palpation ganglionnaire en parallèle est minime et n’est pas compensé par le coût élevé lié à un nombre important des suspects soumis aux tests parasitologiques. Les techniques de concentration ont une bonne sensibilité et leur faisabilité est acceptable. Leur ajout à l’arbre classique améliore la sensibilité de 29 % pour la CTC et de 42% pour la mAECT. Le coût de la CTC a été de 0,76 € et celui de la mAECT de 2,82 €. Le SF a été estimé très peu sensible. L’algorithme PG- GE-CTC-mAECT a été le plus efficient avec 277 € par vie sauvée et un ratio de coût-efficacité marginal de 125 € par unité de vie supplémentaire sauvée. L’algorithme PG-GE-CATT titration avec traitement des personnes avec une parasitologie négative mais un CATT positif à un seuil de 1/8 devient compétitif lorsque la prévalence de la THA est élevée. Il est donc possible dans le contexte actuel de réduire la prévalence de la THA mais à condition que les activités ne soient pas interrompues. Le recours à un algorithme recourant au CATT dans le dépistage actif et à la séquence PG-GE-CTC-mAECT est le plus efficient et une efficacité de 80%. La faisabilité et l’efficacité peut être différent d’un endroit à l’autre à cause de la focalisation de la THA. Il est donc nécessaire de réévaluer cet algorithme dans un autre foyer de THA en étude pilote avant de décider d’un changement de politique. Le recours à cet algorithme implique un financement supplémentaire et une volonté politique. SUMMARY Human African Trypanosomiasis (HAT) remains a major public health problem affecting several countries in sub-Saharan Africa. HAT control is essentially based on active case finding conducted by specialized mobile teams. In the past the population screening was based on neck gland palpation, but since the development of the Card Agglutination Test for Trypanosomiasis (CATT) three control options are available to the control program: i) neck gland palpation ii) CATT iii) neck gland palpation and CATT done in parallel . Certain programs such as the one in DRC opted for the latter, combining CATT and neck gland palpation. All persons having hypertrophy of the neck gland and/or a positive CATT test are considered to be a HAT suspect. Confirmation tests are necessary because the screening algorithms are not 100 % specific and HAT drugs are very toxic. The classic parasitological confirmation tests are lymph node puncture (LNP), fresh blood examination (FBE) and thick blood film (TBF). The sensitivity of this combination is considered insufficient by several authors and causes important losses of efficacy of the screening-treatment strategy. More sensitive concentration methods were developed such as the mini Anion Exchange Concentration Techniques (mAECT), Capillary Tube Centrifugation (CTC) and the Quantitative Buffy Coat (QBC), but they are not used on a routine basis. Main reasons put forward are low feasibility, high cost and long time of execution. In the Democratic Republic of Congo, HAT control activities were suddenly interrupted in 1990 and this led to an important re-emergence or the epidemic. Since 1998 onwards, control activities were financed again in a structured way. This works aims to be both a plea for the continuation of HAT control as well as a contribution to the rationalization of the control strategies. We analyzed the evolution of sleeping sickness in the light of its financing, and we studied its impact on the household and the community. We aimed at a rationalization of the use of the screening and confirmation tools. We first evaluated the validity of the tests, their feasibility and the cost and we did a formal decision analysis to compare screening and confirmation algorithms. The budget allocated to control activities was doubled during the period when structural aid funding was again granted (1998-2003) compared with the period before (1993-1997). The number of persons examined per year doubled as well but the number of cases found peaked at 26 000 in 1998 and dropped to 11 000 in the period afterwards. The cost per person examined was 1.5 US$ and per case detected and saved was 300 US$. The activities were financed for 95 % by external donors during this period. This subvention could give the impression that the impact of HAT on the household and the household was limited but when we took a closer look at this aspect we found that the cost at household level amounted to one month of income and that HAT caused the loss of 2145 DALYs in the community. The intervention consisting of active case finding and treatment allowed to save 1408 DALY’s at a cost of 17 US$ per DALY, putting the intervention in the class of “good value for money”. The use of CATT alone as screening test emerged as the most efficient strategy for active case finding. The marginal gain when neck gland palpation is added is minor and is not compensated by the high cost of doing the parasitological confirmation test on a high number of suspected cases. The concentration methods have a good sensitivity and acceptable feasibility. Adding them to the classical tree improves its sensitivity with 29 % for CTC and with 42 % for mAECT. The cost of CTC was 0.76 US$ and of mAECT was 2.82 US$. Sensitivity of fresh blood examination was poor. The algorithm LNP-TBF-CTC-mAECT was the most efficient costing 277 Euro per life saved and a marginal cost effectiveness ratio of 125 Euro per supplementary life saved. The algorithm LNP-TBF-CATT titration with treatment of persons with a negative parasitology but a CATT positive at a dilution of 1/8 and more becomes competitive when HAT prevalence is high. We conclude that it is possible in the current RDC context to reduce HAT prevalence on condition that control activities are not interrupted. Using an algorithm that includes CATT in active case finding and the combination LNP-TBF-CTC-mAECT is the most efficient with an efficacy of 80 %. Feasibility and efficacy may differ from one place to another because HAT is very focalized, so it is necessary to test this novel algorithm in another HAT focus on a pilot basis, before deciding on a policy change. Implementation of this algorithm will require additional financial resources and political commitment.