Chromium is a common groundwater pollutant originating from industrial processes such as metal plating, leather tanning and pigment manufacturing. Permeable reactive barriers (PRBs) have proven to be viable and cost-effective systems for remediation of chromium contaminated groundwater at many sites. The purpose of this research presented in this thesis is to focus on two parameters that affect the performance of PRB on chromium removal, namely the concentration of reactive media and groundwater flux by analyzing the data obtained from laboratory column studies. Laboratory scale columns packed with different amounts of iron powder and quartz sand mixtures were fed with 20 mg/l chromium influent solution under different fluxes. When chromium treatment efficiencies of the columns were compared with respect to iron powder/quartz sand ratio, the amount of iron powder was found to be an important parameter for treatment efficiency of PRBs. The formation of H2 gas and the reddish-brown precipitates throughout the column matrix were observed, suggesting the reductive precipitation reactions. SEM-EDX analysis of the iron surface after the breakthrough illustrated chromium precipitation. In addition to chromium / calcium and significant amount of iron-oxides or -hydroxides was also detected on the iron surfaces. When the same experiments were conducted at higher fluxes, an increase was observed in the treatment efficiency in the column containing 50% iron. This suggested that the precipitates may not be accumulating at higher fluxes which, in turn, create available surface area for reduction. Extraction experiments were also performed to determine the fraction of chromium that adsorbed to ironhydroxides. The analysis showed that chromium was not removed by adsorption to oxyhydroxides and that reduction is the only removal mechanism in the laboratory experiments. The observed rate of Cr(VI) removal was calculated for each reactive mixture which ranged from 48.86 hour-1 to 3804.13 hour-1. These rate constants and complete removal efficiency values were thought to be important design parameters in the field scale permeable reactive barrier applications.

<p>At present the automotive industry is due to an EU directive, replacing hexavalent chrome on vehicles. This is an extensive job as hexavalent chrome is used all over the vehicle and to large extent on fasteners (screws, nuts, rivets etc.). Chrome (VI) is used as a passivating layer on mainly zinc-iron. When replacing the hexavalent chrome with a chrome (VI) free product, the passivating properties are reduced. One of the alternatives is to replace the zinc-iron coating with a zinc-nickel coating. This coating shows great promise from the corrosion resistance point of view. Zinc-nickel is a cathodically protecting coating, and will in principle dissolve to protect the substrate from corrosion. It is therefore important to understand how, and at what rates nickel is released from zinc-nickel coatings when exposed to a chloride-rich automotive environment. The potential environmental impact of nickel needs to be evaluated before Scania can introduce this alternative as corrosion protection. Tests by Scania have previously shown that contact allergy is not an issue for zinc-nickel coatings with Cr (III) passivation.</p><p>Nickel release rates corresponding to 0,12 mg m^-2yr^-1 for zinc-15 % nickel coatings at a pH of 4,2 were determined from an accelerated corrosion test. Based on these values, less than 1 kg of nickel per year would be released from the Scania rolling stock if Scania were to introduce zinc-nickel coatings preferably on fasteners. This value is low compared to other sources of nickel release. In order to evaluate the toxicity of the released nickel, information about the chemical speciation, i.e. chemical forms, is needed.</p><p>Total or dissolved metal are not good predictors of ecotoxicity of metals. Chemical speciation and bioavailability must be incorporated in toxicity testing. Total or dissolved metal may be used as a worst case approximation.</p>

Ce travail de thèse porte sur la synthèse de matériaux hybrides organiques-inorganiques obtenus par greffage contrôlé d'oligomères ou de polymères pi-conjugués, à base de thiophène ou d'aniline, sur la surface de nanocristaux de semi-conducteurs II-VI, et plus précisément sur du CdSe. <br />La réaction de greffage est assurée par une fonction d'ancrage, de type carbodithioate, présente sur les ligands et ayant une grande affinité pour la surface des nanocristaux. On distingue deux méthodes de greffage : une voie directe par simple échange de ligands et une voie indirecte comprenant une étape de post-fonctionnalisation de nanocristaux enrobés par des ligands bi-fonctionnels, en l'occurrence par le 4-formyldithiobenzoate. Cette dernière méthode est très générale et permet en outre de co-déposer un mélange nanocristaux / oligomère et d'effectuer la réaction de couplage en phase solide en chauffant.<br />De manière générale, les propriétés électrochimiques des nanocristaux et des ligands greffés sont principalement conservées et les études spectroélectrochimiques démontrent que le mécanisme de dopage des ligands conjugués greffés reste inchangé en présence du nanocristal. <br />La position des niveaux énergétiques des ligands, par exemple du tétramère d'aniline, par rapport au nanocristal est telle qu'une séparation des charges est possible après une excitation, ce qui est confirmé par la diminution forte de la photoluminescence. Des études de photoluminescence résolue dans le temps montrent une corrélation directe entre la longueur de conjugaison des ligands et l'efficacité du transfert. Dans le cas du tétramère d'aniline, plus aucun signal n'est mesurable. Mais le transfert de charges dans le cas du thiophènedithiobenzoate est également très efficace. Les premières mesures de photocourant sont également prometteuses. Les matériaux développés, qui peuvent être préparés de manière contrôlée et variée, possèdent un potentiel d'application dans les cellules photovoltaïques.

This study examines painted leaves and fragments that were extracted from a set of choir books created in the last decade of the fifteenth century for the basilica of Santa Maria in Aracoeli in Rome. These remnants are currently housed within various library and museum collections throughout Europe and the United States. The set is agreed upon generally by scholars to have been commissioned by Alexander VI (Rodrigo Borgia, 1431-1503), who was pope from 1492 to 1503, as a gift to the church during his time as pontiff. The choir books for Santa Maria in Aracoeli contain the bulk of the known body of work by the enigmatic illuminator Fra Antonio da Monza. The best known items from this set of choir books are a complete gradual (or book of chants for the Mass) currently housed in the Getty Museum, called the Ludwig Aracoeli Manuscript, and a montage of cuttings in the Albertina Museum, Vienna, that features a miniature of the Pentecost. These are studied in the context of the artistic patronage of Alexander VI, and political and diplomatic gift cultures in papal Rome during the last decade of the Quattrocento. Alexander VI's gift to Santa Maria in Aracoeli served multiple functions. It advanced church music, but is also an example of a pontiff using custom luxury books for cultural diplomacy. The intent of the choir books was to build social relationships and augment the prestige of Alexander VI's regime with a local audience. Alexander VI sought to acknowledge the symbolic resonance of Santa Maria in Aracoeli and attempted to recuperate the site's importance for his reign through the gift. This study argues that the choir books were commissioned by the pontiff to promote his cultural and religious authority through abbellimento or "embellishment", the practice of commissioning ostentatious liturgical objects and additions to religious ceremonies for the purpose of developing esteem for an ecclesiastical office. This thesis argues that another purpose of the bestowment was to appease the Observant Franciscans in charge of the basilica in anticipation of Alexander VI's reforms of the Franciscan order.

No description available.

<p>The goal of this study is to understand how residents may benefit from living in a mixed income, HOPE VI development in the South. This analysis focuses on a former housing project and its immediate neighborhood in the aftermath of HOPE VI revitalization. I conducted a case study by utilizing original data collected from in-depth, semi-structured interviews and unstructured interviews, along with administrative records, evaluation data, media accounts, observation, and casual encounters. A unique contribution of this study of a HOPE VI development is that it also addresses the surrounding neighborhood. Furthermore, this case study offers a unique lens for examining contemporary black gentrification in a publicly constructed space. </p><p>A major finding of this study is that complex intra-racial social dynamics among African American community members may stem from HOPE VI intervention. Specifically, there may be limited positive interaction among residents in the development, and between them and residents of the proximate exterior neighborhood. Further, the nature of constrained interaction manufactures divisive processes for claiming space and community identity that may potentially have negative consequences for renters. </p><p>These consequences stem from a reproduction of space and community, which shapes social control, policing, and exclusion contests, among other tensions. Overall, this study brings to bear some unimagined consequences of HOPE VI that potentially neutralize anticipated benefits of mixed income living for the poor, based on real and perceived alterations of class, mobility, and shared identity in and around the development site.</p> / Dissertation

Ces travaux de thèse ont débuté par la présentation des propriétés physico-chimiques du chrome, ses principaux domaines d'application. On a aussi indiqué les problèmes posés et les risques associés à l'emploi des dérivés chromiques qui s'expriment essentiellement au niveau cutané, respiratoire et même immunologique. Ensuite, on a cité les différents procédés d'élimination tels que les procédés membranaires, procédés chimiques, procédés biologiques et procédés physiques en précisant les avantages et inconvénients de chacun de ces procédés. Après, on a présenté le procédé d'adsorption sur alumine activée, en rappelant brièvement les différents adsorbants utilisés ainsi que les modèles thermodynamiques et cinétiques utilisés pour décrire ce phénomène. Enfin, on a rappelé quelques généralités sur les membranes échangeuses d'ions et sur le procédé de dialyse ionique croisée. Dans une seconde étape, on a étudié la validation de la technique analytique selon la norme Française XPT 90-120, ensuite une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation factorielle afin de montrer l'influence de chaque paramètre indépendamment et leurs dépendances aussi. Ces facteurs sont les suivants : pH, quantité de l'adsorbant, concentration du métal initial et de la température. Cette étude a porté sur l'effet du pH mais aussi l'effet de la masse de l'alumine activée et l'effet de la concentration initiale du chrome afin d'optimiser ces paramètres, les résultats expérimentaux ont montré que l'adsorption du chrome dépend essentiellement du pH et de la concentration du chrome initiale. Dans les conditions optimales, les taux d'élimination du chrome VI peuvent attendre 98 % pour une concentration initiale de 10 mg/L en chrome. Les résultats expérimentaux ont été appliqués aux modèles de Freundlich, Langmuir, Dubinin-Redushkevich et Temkin. Des études cinétique et thermodynamiques suivront pour déterminer l'ordre de la réaction d'adsorption des métaux lourds et nature exothermique du mécanisme. La troisième partie a porté sur la Dialyse Ionique Croisée, dans un premier temps on a développé une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation effectué afin d'identifier et d'évaluer l'influence de chaque paramètre sur les taux d'élimination de l'ion métallique. Ces facteurs sont la concentration initiale de l'ion métallique, la concentration initiale de l'ion de substitution, le type de la membrane et l'agitation magnétique. Cette démarche est nécessaire afin de fixer les paramètres optimaux et évaluer leurs interactions mutuelles. Cette étude a permis de montrer que le type de membrane échangeuse d'anions est le plus important paramètre influant sur l'élimination du chrome et ceci peut s'expliquer par les valeurs élevées de la capacité d'échange et de la teneur en eau de la membrane AFN. La modélisation du transfert des ions HCrO4- en dialyse ionique croisée a montré la présence de deux phases : la couche limite de diffusion du côté de l'alimentation (solution à traiter contant les ions HCrO4-) et la membrane. En deuxième étape, nous avons effectué une étude du vieillissement des membranes, qui consiste à faire un suivie de l'épaisseur membranaire, de la conductivité membranaire et de leur morphologie par MEB. Nous avons montré que les membranes AMV et AFN se dégradent peu à priori de la même manière. Finalement, nous avons effectué un nouveau montage qui couple les deux procédés et ceci dans le but d'améliorer le taux d'élimination. Ce couplage a permis d'augmenter l'efficacité et la cinétique d'échange de la dialyse, en plus une réduction considérable de la quantité d'alumine activée à régénérer et l'amélioration de la cinétique de transfert transmembranaire

Integreringsprocessen för utländska barn i den svenska skolan är huvudpunkten i denna systematiska litteraturstudie. Syftet är att undersöka vilka problem som vanligtvis uppkommer i skolan för nyanlända barn med utländsk bakgrund men även deras och föräldrarnas egna önskningar om förbättring eller tillvägagångssätt i integrationsprocessen. Utöver detta analyseras hur skolan arbetar för att integrera eleverna i skolan och in i den ordinarie undervisningen. Resultaten visar att det är många problem som uppstår men de mest återkommande är språket, utanförskap samt ständiga omflyttningar. Vidare visar resultaten att det optimala tillvägagångssättet för en sund integrering i skolan är när eleverna kan knyta an till något och känna samhörighet genom att skolan värnar om deras språk, kultur och familj. Lärarens betydelse för integreringen av de utländska eleverna är även en viktig faktor. Det teoretiska perspektivet som studien grundar sig på är det interkulturella perspektivet.

Francisella tularensis is a highly virulent, intracellular pathogen that causes the disease tularaemia. Francisella species contain a cluster of genes referred to as the Francisella pathogenicity island (FPI). Several genes contained in the FPI encode proteins needed for the intracellular growth and virulence of Francisella tularensis. Pathogenicity determinant protein A (PdpA), encoded by the pdpA gene, is located within the FPI and has been associated with the virulence of Francisella species. The experiments outlined in this dissertation examine the properties of PdpA protein expression and localization as well as the phenotypes of non-polar F. novicida pdpA mutants. Monoclonal antibody detection of PdpA showed that it is a soluble protein that is upregulated in iron-limiting conditions and undetectable in an mglA or mglB mutant background. Deletion of pdpA resulted in a strain that was highly attenuated for virulence in chicken embryos and mice. The ΔpdpA strain was capable of a small amount of intracellular replication but, unlike wild-type F. novicida, remained associated with the lysosomal marker LAMP-1, suggesting that PdpA is necessary for progression from the early phagosome phase of infection. Infection of macrophages with the ΔpdpA mutant generated a host-cell mRNA profile distinct from that generated by infection with wild type F. novicida. The transcriptional response of the host macrophage indicates that PdpA functions directly or indirectly to suppress macrophage ability to signal via growth factors, cytokines and adhesion ligands. Experiments were designed to mutagenize a putative F-box domain within the amino terminus of PdpA. Deletion of amino acids 112-227 created a strain which was impaired in intracellular replication and exhibited severely reduced virulence. However, alanine mutagenesis of key conserved leucine residues required for the interaction of F-box domains with host proteins had no observed effect on bacterial growth in macrophages and did not affect virulence in chicken embryos or mice. Mono and polyubiquitinated proteins associated with both the wild type F. novicida and ΔpdpA bacterial strains early during the infection of J774A.1 macrophages. After 1 hour of infection the wild type strain developed a more intimate association with mono and polyubiquitinated proteins whereas the ΔpdpA strain did not. Inhibition of the host cell proteasome during infection did not affect the intracellular growth of wild type F. novicida. PdpA research concludes by examining the secretion patterns of F. novicida. PdpA was not detected as a surface exposed protein using biotinylation whereas IglA, IglB and IglC were found to be surface exposed in both wild type and ΔpdpA backgrounds. These observations suggest that PdpA is not involved in the assembly or function of the Francisella secretion system. FLAG tagged PdpA protein could not be detected in the TCA precipitated supernatant of broth grown cultures or in the immunoprecipitated cytosol of infected macrophages suggesting that PdpA is not a secreted protein.

Single crystals of GaSe were grown from the melt using 3-zone vertical Bridgman-Stockbarger system. In order to determine the doping effect, nitrogen and silicon ions were implanted to the grown crystals. Surface morphology and stoichiometry were examined using scanning electron microscope equipped with EDAX and structure properties were examined by x-ray diffraction technique. It was observed that the resulting ingot was stoichiometric and the structure was hexagonal. To identify the effects of ion implantation on the physical properties of the samples depending on annealing / electrical conductivity, hall measurements, current-voltage characteristics, photoconductivity and photoluminescence measurements were carried out in the temperature range of 100-450 K. Also spectral transmission measurements were carried out for all the samples at room temperature. It was observed that both N- and Si- implantation followed by annealing process decreased the resisitivity values from 107 to 103 (&amp / #61527 / -cm). Temperature dependent conductivity measurements were analyzed to deduce the dominant transport mechanisms. The trap levels were also investigated by the space charge limited currents (SCLC) measurements. The temperature dependence of hole concentrations showed that as-grown, N- and Si-implanted samples behave as partially compensated p-type semiconductors. Using suitable statistical method, transport parameters such as acceptor level, donor and acceptor concentrations were extracted from the experimental data. Trapping centers and recombination mechanisms were determined from the temperature dependent photoconductivity measurements by investigating the relation between photocurrent and illumination intensity. N- and Si- implantation effects on GaSe were also examined by spectral photoconductivity and transmission measurements. And lastly, radiative recombination mechanisms in as-grown GaSe were investigated through photoluminescence (PL) measurements and the information related to the structural defects, the exciton levels and the structure of the forbidden gap were investigated.