Spelling suggestions: "subject:"chlorine."" "subject:"cholorine.""
531 |
Caractérisation des eaux de l'aquifère du complexe terminal : approche multi-isotopiques (234U / 238U, 36CI,14C, δ18O, δ2H) / Characterization of the complexe terminal groundwater : multi- isotope approach (234U / 238U, 36Cl, 14C, δ18O, δ2H)Hadj Ammar, Friha 12 January 2016 (has links)
La caractérisation géochimique et isotopique des aquifères du Complexe Terminal (CT) du sud tunisien a été effectuée sur la base d'une approche multi isotopique. Cette étude a mis en évidence la continuité hydrogéologique des aquifères du CT en dépit de la variabilité lithologique latérale des formations aquifères et à travers les grands accidents tectoniques. La minéralisation des eaux est acquise par les processus d’interactions eau / roche, la dissolution des évaporites associés à la précipitation de la calcite. Les teneurs en δ18O et δ2H, montrent un fort contraste entre les eaux du CT. La signature isotopique traduit l’effet de l’évaporation manifesté par un enrichissement en δ18O et δ2H. Le marquage isotopique atteste aussi d’un effet de paléorecharge. En outre, les teneurs en 14C couplées aux teneurs en δ13C, ont soutenu la recharge de la nappe au cours de l’Holocène. Le déséquilibre 234U / 238U a été aussi utilisé. Les eaux du CT ont enregistré des teneurs qui varient de 1.5 à 19.5 ppb et des rapports 234U / 238U qui varient de 1.1 à 3.2. La mise en solution de l’uranium est contrôlée par la dissolution de la matrice aquifère. Cette étude a mis en évidence aussi des conditions oxydantes régnant au sein des aquifères du CT. Ces conditions sont propices au lessivage préférentiel de l’234U et dont l’effet marquant les rapports 234U / 238U qui sont >1. L’étude des teneurs en 36Cl et du rapport 36Cl / Cl montre que leur variation est liée aux processus d’évaporation et de dissolution. Les taux d’évaporation et de dissolution calculés sont > 50% traduisant l’effet marquant de ces deux processus sur la variation des teneurs en chlore des eaux du CT. / The geochemical and isotopic characterization of CT aquifers of southern Tunisia was conducted on the basis of a multi isotopic approach. This study highlighted the hydrogeological continuity of the CT aquifers despite the lateral lithological variability of aquifers and through major tectonic accidents. Groundwater mineralization is controlled by water rock interaction and the dissolution of evaporate minerals associated with the calcite precipitation. The δ18O and δ2H composition, show a strong contrast. The isotopic signature reflects the evaporation effect shown by stable isotope enrichment. Isotopic composition also demonstrates a paleorecharge effect. In addition, the 14C content coupled with the contents δ 13C, supported the groundwater recharge in the Holocene period. 234U / 238U disequilibrium was also used. Results indicate a range in 238U concentration and 234U/238U activity ratios of 1.5 to 19 ppb and 1.1 to 3.2 respectively. Our results show that groundwater geochemistry is ultimately a result of lithologic variations associated with water / rock interaction. Results elucidate also the mixing relationships between the different aquifer horizons.In this study, we used also chlorine-36 (36Cl) as a groundwater tracer. The variation in 36Cl content and 36Cl / Cl ratio is essentially related to both evaporation and dissolution processes. Evaporation and dissolution rates recorded values that exceed 50 % showing the major effect of these processes on the change of chloride contents in CT groundwater.
|
532 |
Inhibition de souches bactériennes par de nouveaux composés photosensibles conjugués à la Polymyxine B / Bacterial inhibition through innovative photosensitizers conjugated to polymyxin BLe Guern, Florent 10 November 2017 (has links)
L’émergence de nouvelles souches bactériennes résistantes a signé la fin de l’« âge d’or » des antibiotiques. L’organisation mondiale de la santé a reconnu l’imminence des problèmes associés à ces nouvelles bactéries, qui engendrent de nouveau une mortalité en augmentation. Afin de palier à ce problème, de nouvelles alternatives aux antibiotiques sont envisagées par les chercheurs à travers le monde. La thérapie photodynamique antimicrobienne est l’une de ces alternatives. Elle a su se démarquer grâce à son incapacité à induire la résistance bactérienne. Alors que les résultats furent initialement très prometteurs contre les bactéries Gram positif, une moins bonne sensibilité fut rapidement observée de la part des bactéries Gram négatif. Afin d’augmenter le potentiel antibactérien de cette technique, diverses stratégies furent élaborées comme l’utilisation de photosensibilisateurs cationiques, l’ajout d’un agent de ciblage, ou la présence d’un agent de perméabilisation membranaire. L’un de ces agents est la polymyxine B, un peptide antimicrobien qui arbore une très bonne affinité avec les bactéries Gram négatif. Dans cette étude, nous avons voulu associer chimiquement différents photosensibilisateurs avec des dérivés de polymyxines B de façon covalente, par l’intermédiaire d’un bras « spacer » ou d’une plateforme. L’association de ces deux familles de molécules a permis d’élaborer de nouveaux composés qui ont démontré une activité photobactéricide accrue contre un large spectre de bactérie. De plus, ces composés ont montré une affinité augmentée pour les bactéries, ce qui permettra de réduire les effets secondaires sur les cellules humaines. Cette étude confirme l’importance d’utiliser des peptides antimicrobiens afin d’améliorer la thérapie photodynamique. Ces travaux seront approfondis afin de permettre la création de nouveaux traitements dermatologiques basées sur cette nouvelle thérapie et efficaces contre un large spectre de souche bactérienne / Despite advances achieved over the last decade, infections caused by multi-drug resistant bacterial strains are increasingly important societal issues that need to be addressed. New approaches have already been developed in order to overcome this problem. Photodynamic antimicrobial chemotherapy (PACT) could provide an alternative to fight infectious bacteria. Interesting results have been obtained against Gram-positive bacteria, but it also appeared that Gram-negative strains were less sensitive to PACT. Enhanced efficacy against Gram-negative bacteria had been previously obtained following three differents strategies, which are respectively the use of cationic photosensitizers, photosensitizers bound to antimicrobial peptides, or a membrane disrupting agent. Polymyxin B is an antimicrobial peptide, known as the “last-line” treatment against Gram-negative resistant strains, which has already been used as a disrupting agent in order to improve PACT. In addition of this enhancement, this peptide is known for its strong interaction for Gram-negative bacteria. Thus, in this work, we designed differents coumpounds, consisting of a photosensitizer covalently attached to derivatives of polymyxin B, through a spacer or a chemical platform. These combinations have led to the creation of novel compounds which have shown highly photobactericidal activities against a wide spectrum of bacteria. Moreover, these compounds present enhanced affinity for bacteria, which should significantly reduce side effects on mammalian cells. This study confirmed the importance of using antimicrobial in order to target bacterial strains. Thus, such results may allow the creation of novels PACT-based dermatological treatments efficient against a wide spectrum of bacterial strains.
|
533 |
Isotope effects in atomic spectroscopy of negative ions and neutral atoms: a theoretical contribution / Effets isotopiques en spéctroscopie atomique d'ions négatifs et d'atomes neutres: une contribution théoriqueCarette, Thomas 15 December 2010 (has links)
<p>Cette thèse est consacrée à l'étude des effets isotopiques dans les atomes neutres et ions négatifs. En particulier, nous ciblons notre recherche sur le calcul ab initio des déplacements isotopiques (DI) sur les électroaffinités des éléments des blocs p des deuxième et troisième périodes (B à F et Al à Cl). Ces derniers sont les systèmes les plus susceptibles d'être l'objet d'études expérimentales de haute précision.</p><p><p><p>Le premier chapitre se concentre sur une étude didactique du problème atomique et des effets isotopiques. Nous concluons par une description détaillée des motivations de notre thèse.</p><p><p><p>Le second chapitre présente le modèle Hartree-Fock (HF) et son extension multi-configurationelle (MCHF). Nous y énonçons le théorème de Brillouin et sa généralisation à un ansatz MCHF. Pour ce faire, nous formulons de manière originale le principe d'invariance d'une fonction d'onde CAS (Complete Active Set) par rapport aux rotations d'états d'orbitales. De cette formulation, nous caractérisons la famille des solutions CAS n'interagissant pas avec une fonction d'état de configuration (CSF) particulière et démontrons sa multiplicité. Finalement, nous appliquons notre technique d'analyse à l'étude de modèles concrets et prédisons l'apparition de minima locaux correspondant à chacune de ces solutions GBT. Introduisant le concept de quasi-symétrie de la fonctionnelle d'énergie, nous expliquons l'origine de fortes perturbations du "coeur" atomique dans des modèles particuliers.</p><p><p><p>Les troisième et quatrième chapitres fournissent les outils méthodologiques de base utilisés dans la deuxième partie de notre thèse qui présente des résultats quantitatifs originaux.</p><p><p><p>Le cinquième chapitre traite des DI et structures hyperfines des termes les plus bas de S, S-, Cl, Cl-, Si et Si-.</p><p><p><p>Dans le sixième chapitre, nous rapportons un profond désaccord entre théorie et expérience au sujet de la structure hyperfine de transitions de l'azote dans le infrarouge lointain. Nous montrons que les simulations basées sur nos valeurs de constantes isotopiques sont compatibles avec les spectres enregistrés moyennant une réassignation des raies faibles à des signaux de "cross-overs". Sur cette base, nous déduisons un nouvel ensemble de constantes hyperfines pour les états considérés, en bon accord avec nos valeurs théoriques, en nous basant uniquement sur les données expérimentales.</p><p><p><p>Le septième chapitre est une étude globale des configurations de plus basse énergie du C et C- (i.e. tous les états liés de ce dernier). Par une étude détaillée de nos incertitudes, nous obtenons des estimations très fiables et de grande précision pour un ensemble de propriétés. En particulier, nous présentons les valeurs de structure fine et hyperfine du C-, ainsi que les probabilités de transitions intra-configurationelles fournissant une base solide pour l'étude spectroscopique de ce système.</p><p><p><p>Dans le huitième chapitre, nous étudions la périodicité du déplacement spécifique de masse sur l'électroaffinité dans le Tableau Périodique des Eléments. Nous avançons les contributions dominantes qui interviennent dans cette grandeur et analysons les principales limitations des techniques de calcul actuelles dans ce contexte.</p><p><p><p>Nous présentons nos conclusions générales et les perspectives de notre travail dans le neuvième chapitre.</p><p><p><p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished
|
534 |
Étude de la réaction d’hydrogénation du CO sur des catalyseurs à base de cobalt supporté par DRIFTS operando / Study of CO hydrogenation reaction on supported cobalt catalysts by operando DRIFTSParedes-Nunez, Anaëlle 25 October 2016 (has links)
Notre dépendance à l'égard des combustibles fossiles et la diminution des ressources pétrolières nous imposent la recherche de sources renouvelables d'énergie et de produits chimiques. La synthèse Fischer-Tropsch permet de répondre à la demande en carburants propres et renouvelables grâce à l'utilisation de gaz de synthèse issu de la biomasse. L'objectif de ce travail est de contribuer à la compréhension du mécanisme de l'hydrogénation du CO sur des catalyseurs au cobalt et à l'identification du site actif par des études spectroscopiques DRIFTS operando. Ce système permet d'observer les différentes espèces adsorbées à la surface du catalyseur pendant la réaction : CO pontés et linéaires, formiates, carboxylates et hydrocarbures. Nos travaux ont montré qu'une fraction des formiates dits « rapides» peut expliquer la formation du méthanol dans nos conditions de réaction. L'ajout dans le mélange H2+CO d'un élément minéral typique de la biomasse, le chlore sous forme de trichloréthylène, a révélé que, l'activité diminuait. La bande des CO pontés étant la plus impactée et se déplaçant vers les hauts nombres d'onde, l'effet du chlore a été notamment associé à un effet électronique sur le cobalt. L'adsorption du chlore étant réversible, nous avons également étudié l'effet de l'étain. Ce métal n'adsorbe pas le CO dans nos conditions et peut s'adsorber à la surface du cobalt. L'étain empoisonne sélectivement la formation des CO pontés et limite fortement la chimisorption de l'hydrogène. Une relation linéaire entre la vitesse de formation des produits et la proportion de CO pontés est observée, révélant l'importance des CO pontés pour la réaction d'hydrogénation du CO / Our dependence on fossil fuels and the decrease of oil resources warrant the search for renewable energy sources and chemicals. Fischer-Tropsch synthesis enables meeting the requirements for cleaner and renewable fuels through the use of syngas obtained from biomass.The objective of this work was to contribute to the understanding of the mechanism of CO hydrogenation on cobalt-based catalysts and the identification of the active site by operando DRIFT spectroscopy. Different species were adsorbed on the surface of the catalyst under reaction conditions: bridged and linear CO, formates, carboxylates and hydrocarbons. Our resutls shows that so-called “fast formate” can account for the formation of methanol under our reaction conditions. The study of a typical biomass element, chlorine, revealed that the activity decreased under trichloroethylene,. The CO bridged band being the most affected band and shifting to higher wavenumber, the chlorine effect was partly associated with an electronic effect on cobalt. Chlorine adsorption being reversible, tin poisoning was also studied. This metal does not adsorb CO under our conditions. Tin addition to cobalt selectively poisons bridged CO and greatly limits the chemisorption of hydrogen. A linear relationship between the rate of formation of products and the proportion of CO bridged is observed, highlighting the importance of CO bridged
|
535 |
Suivi de l'état viable non cultivable de souches de Legionella pneumophila soumises à différents stress (thermique ou chloré) : Evaluation de leur pouvoir pathogène / Monitoring state of viable but non culturable legionella pneumophila strains after different stress (heat shock or chlorine treatment) : Evaluation of their pathogenicityEpalle, Thibaut 09 February 2015 (has links)
Legionella pneumophila, l’agent responsable de la légionellose est transmissible à l’Homme par les aérosols environnementaux et infecte les macrophages pulmonaires. Après l’exposition à différents stress L. pneumophila est capable de d’entrer dans un état Viable Non Cultivable (VBNC) qui semble être une stratégie de survie. L’objectif de nos travaux était d’étudier l’état VBNC de différentes souches de L. pneumophila après des traitements thermique et chimique et d’évaluer le pouvoir infectieux des formes VBNC envers les macrophages et les cellules épithéliales alvéolaires. Nous avons étudié les profils physiologiques de L. pneumophila de trois souches différentes. Les résultats montrent que pour chaque souche 3 populations peuvent être identifiées, les légionelles viables cultivables, les VBNC et les bactéries mortes. Lorsque soumises aux stress, chaque souche possède un profil physiologique propre et la présence ou non de bactéries VBNC était dépendante du traitement appliqué et de la souche utilisée. La deuxième partie fut relative à l’étude des traitements thermiques de 70°C pendant 30 min et des chocs au dioxyde de chlore de 4, 6 et 7 mg/L pendant 60 min à température ambiante sur ces VBNC. Aucune légionelle VBNC n’est capable de se développer au sein des cellules et aucune croissance sur milieu BCYE n’a été observée après co-culture. La suite de notre étude a été d’étudier le comportement, envers les macrophages, de L. pneumophila revivifiées après culture sur amibes. Les résultats montrent que les légionelles VBNC induites par choc thermique et revivifiées par co-culture sur Acanthamoeba polyphaga sont capables d’infecter de nouveau les macrophages. En conclusion, ces résultats suggèrent que: (i) les formes VBNC de L. pneumophila ne sont pas spontanément infectieuses pour les macrophages et les cellules épithéliales alvéolaires in vitro et (ii) elles peuvent devenir pathogènes pour les cellules humaines après revivification préalable sur A. polyphaga / Legionella pneumophila, the causative agent of legionellosis is transmitted to human through aerosols from environmental sources and invades lung’s macrophages. It also can replicate within various protozoan species in environmental reservoirs. Following exposures to various stresses, L. pneumophila enters a Viable Non Cultivable state (VBNC) which is likely to be a survival strategy. The objective of our work was to study the VBNC forms of several strains of L. pneumophila serogroup 1 obtained after thermal and chemical treatments and to evaluate the infectivity of these VBNC forms against macrophages and alveolar epithelial cells. First we studied the physiological patterns of the three different strains (Philadelphia GFP 008, 044 clinical and environmental RNN). For all strains we observed the presence of VBNC bacteria in the native (non stressed) state. The results show that for each strain, three populations of Legionella can be identified: viable and culturable, VBNC and dead cells. Once submitted to the various stresses, we observed that each strain had its own physiological pattern and the presence (or not) of VBNC bacteria was dependent on the applied treatment and the strain used. The second part was related to the study of the pathogenicity of these VBNC forms against macrophages or epithelial cells. The study focused on heat shock treatment at 70°C for 30 min and chlorine dioxide treatment at 4, 6 and 7 mg/L for 60 min at room temperature. The results show that no Legionella VBNC forms were able to grow within the cells and no growth on BCYE medium was observed after co-culture. Then we investigated the behavior of L. pneumophila resuscitated after culture on ameba within macrophages. The results shows that Legionella VBNC induced by heat shock treatment and resuscitated by Acanthamoeba polyphaga co-culture are able to infect macrophages. In conclusion, these results suggest that: (i) the VBNC forms of L. pneumophila are not infectious for macrophages and alveolar epithelial cells in vitro and; (ii) they can be pathogenic for human cells after revivification by an amoeba (A. polyphaga)
|
536 |
Development and Application of Chlorine Solid-State Nuclear Magnetic Resonance and Quantum Chemical Calculations to the Study of Organic and Inorganic SystemsChapman, Rebecca January 2012 (has links)
Chlorine solid-state nuclear magnetic resonance (SSNMR) is an ideal site specific probe of chloride-containing solids as SSNMR tensor properties are sensitive to the local chlorine environment. In this thesis, the development and use of chlorine SSNMR as a method to characterize a wide variety of chemical environments was explored. Ultrahigh field, and multi-field studies were essential to overcome the difficulties associated with the collection of chlorine SSNMR spectra.
Benchmark chemical shift (CS) and electric field gradient (EFG) tensor data were collected for organic chloride systems, including several amino acid hydrochlorides. These experiments demonstrated the sensitivity of chlorine SSNMR to slight changes in chemical environment. Quantum chemical calculations were used to complement experimental data, with the gauge-including projector augmented wave DFT (GIPAW-DFT) method shown to yield better agreement than B3LYP or RHF methods. The GIPAW-DFT method was found to slightly, but systematically, overestimate the chlorine quadrupolar coupling constant and the CS tensor span. Other organic chlorides examined by chlorine SSMR included a known ion receptor, meso-octamethylcalix[4]pyrrole. This compound was found to have a very small quadrupole interaction (QI), but significant chemical shift anisotropy (CSA). GIPAW-DFT calculations were also utilized and, in combination with the experimental results, used to identify the solvate structure of the material analyzed by NMR.
Chlorine SSNMR was further used to study different solvate structures and polymorphism. The technique was an effective means to distinguish different room temperature polymorphs of benzidine hydrochloride, despite the similarities of the chloride environments. In the case of magnesium chloride, chlorine SSNMR was sensitive to the level of hydration and through the use of GIPAW-DFT calculations, the identity of an unknown hydrate was determined.
An analysis of several group thirteen chlorides demonstrated that chlorine SSNMR was also capable of characterizing the chlorine environment in cases where the QI is large, despite the resulting broad line widths. In these systems GIPAW-DFT calculations also yielded excellent agreement with experimental values.
Throughout this research, chlorine SSNMR has been shown to be a useful and effective means to study both organic and inorganic chlorides, with computational methods proving to be an important complement to experimental data.
|
537 |
Multinuclear Solid-State Magnetic Resonance Studies on ‘Exotic’ Quadrupolar Nuclei: Acquisition Methods, High-Order Effects, Quantum Chemical Computations, and NMR CrystallographyWiddifield, Cory January 2012 (has links)
This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.
|
538 |
Noble gas components in Martian meteoritesCartwright, Julia Ann January 2010 (has links)
This thesis focuses on the analysis of heavy noble gases (argon, krypton and xenon) and halogens (chlorine, bromine and iodine) in Martian meteorites. In the absence of a sample-return mission, Martian meteorite analysis is essential for establishing evidence for an active fluid system, evaluating the potential for life and understanding the formation and evolution of Mars. Noble gas analysis has multiple applications for Martian meteorite study, as described in this thesis. The noble gas isotopic signatures of Earth’s atmosphere, Martian atmosphere and Martian interior are sufficiently different that they can be distinguished through noble gas analysis. Analysis of bulk and mineral separates of shergottites showed that Martian atmospheric Xe was distributed evenly amongst samples, whilst terrestrially weathered samples contained elevated concentrations of terrestrial atmospheric Xe. Both atmospheric components were introduced by weathering. Shock redistribution is responsible for the distribution of Martian atmosphere into more retentive sites. Crustal contamination may be responsible for the presence or absence of detectable 129Xe from the Martian atmosphere. Halogen abundances can be determined as an extension of the Ar-Ar dating technique. As the halogen system on Earth acts as a tracer for important fluid related processes, Martian halogen abundances in meteorites may provide a tracer for the Martian fluid system. Analysis of bulk and mineral separates of nakhlites showed that halogens are distributed amongst minor phases and clear variation of Br/Cl and I/Cl ratios was observed amongst samples. Elevated I concentrations in low temperature releases of finds NWA 998 and MIL 03346 are consistent with terrestrial contamination. Analysis of Nakhla, (a meteorite fall), showed a trend of elevated Br/Cl and I/Cl ratios in crush and low temperature releases, consistent with Br/Cl ratios observed in Martian rocks, soils and weathering products. In contrast, high temperature releases had lower I/Cl and Br/Cl ratios, which are broadly comparable to the terrestrial mantle. This trend may represent mixing of hydrothermal fluids (low Br/Cl and I/Cl) and surface brines (high Br/Cl and I/Cl). An impact-induced hydrothermal system may provide a mechanism for mixing of both fluid types. The crystallisation ages of nakhlite meteorites were determined using the Ar-Ar dating technique. The apparent ages measured were similar to previous Ar-Ar analysis, and older than reported for other chronometers. Previously unrecognised components were observed, including evidence for a trapped hydrous fluid. This Cl-rich component showed strong correlation with 40Ar and had 40Ar/36Ar and 40Ar/129XeXS ratios consistent with Martian atmosphere. As this component was released during crush and low temperature analysis, fluid inclusions formed by percolation of brines from the Martian surface are likely hosts. Both finds showed clear evidence of a trapped component with 40Ar/36Ar ratios similar to either terrestrial atmosphere or the Martian interior. A further component observed in olivine phases had low 40Ar/36Ar ratios, and likely formed by the release of 36Ar formed by cosmic-ray spallation reactions on iron.
|
539 |
Evaluating the Toxicity and Formation of Halobenzoquinones in Point-of-Use Chlorinated Drinking WaterHung, Stephanie 25 October 2018 (has links)
Chlorine has effectively reduced the prevalence of waterborne diseases, however there are secondary consequences to this public health advancement. Disinfection byproducts (DBPs) are chemicals formed when chlorine reacts with natural organic matter (NOM) in water. A new class of DBPs, halobenzoquinones (HBQs), has recently been identified and data suggests it could be potentially carcinogenic and up to 1000 times more toxic than some regulated DBPs. So far, in vitro studies have assessed HBQ toxicity without taking into account its transformation in cell media into potentially less toxic compounds. This study evaluated the toxic effects of one HBQ, 2,6-DCBQ, and its transformed derivatives on colon epithelial and liver hepatoma cell lines by measuring intracellular reactive oxygen species production and cell viability post-DCBQ exposure. In addition, to better quantify the trade-off between exposure to waterborne pathogens and 2,6-DCBQ, the inactivation of a virus indicator (MS2), and formation of DCBQ were determined in chlorinated surface waters. Dose-dependent toxic effects were observed in both cell lines and transformed DCBQs were observed to be less toxic than their parent compound. MS2 inactivation occurred immediately post-chlorination, but DCBQ was detected simultaneously. Such findings indicate that this compound is toxic to human cells, including colon epithelial cells, which may be pertinent due to the possible association between chlorinated waters and colon cancer. Findings also suggest this DBP may be relevant in developing countries because HBQs may form in point-of-use chlorinated drinking waters. Furthermore, observed reduction in toxicity of media-transformed DCBQs calls current literature on HBQ toxicity into question.
|
540 |
On the Process Development of an ECF Light Bleaching Sequence for the Production of High Quality Softwood Kraft Pulp and Low AOX FormationStarrsjö, Sara January 2021 (has links)
The aim of this work is to contribute to the process development of the ECF light bleaching sequence Q(OP)D(PO) by providing a better understanding of the bleaching of softwood kraft pulp. There are few published studies on this type of sequence, and more knowledge is needed on how to reduce environmental impact, improve cost-effectiveness and ensure a high pulp quality. Firstly, this research showed that using a pH buffer to stabilize the pH at a near-neutral level during bleaching with chlorine dioxide can lower the formation of adsorbable organically bound halogens (AOX) without altering the bleaching efficiency. A near-neutral pH decreases the formation of strongly chlorinating species so that the AOX content in the bleaching effluents is reduced by up to 30%. The increased pH in the near-neutral pH D stage compared with the reference lowered the chlorine dioxide consumption, resulting in a higher kappa number and viscosity. A lower degradation of hexenuronic acid correlated well with a lower AOX content in the effluents, affirming earlier theories that hexenuronic acid has an important impact on AOX formation. Secondly, this research aimed at studying bleachability in (OO)Q(OP)D(PO). The bleachability was defined as delignifying and brightness gain bleachability, which is suited to ECF light bleaching sequences. The delignifying and brightness gain bleachability were used to evaluate the stages in (OO)Q(OP)D(PO) in regard to the unbleached kappa number. When comparing different stages, it is possible to distinguish the bleaching efficiency in each stage. For this ECF light sequence, the bleachability depends on the purpose of the stage. It was found that in the stages that are mainly delignifying (OO and D), a higher unbleached kappa number is beneficial for the delignifying bleachability, although the brightness gain is not improved. However, in the stages that are mainly brightness increasing (OP and PO), the brightness gain bleachability is improved by a lower unbleached kappa number. Thirdly, the bleaching of the pulp samples in this study with the ECF light sequence was most effective with a kappa number around 32 after cooking. Although an even higher kappa number resulted in a higher yield after cooking, it seemed that this bleaching sequence cannot preserve the yield gain. Kappa number 32 also gave the best results in regard to brightness ceiling and viscosity. On the other hand, kappa number 27 was the most favourable with regard to yellowing and chemical charge. / <p>Examinator: Helena Håkansson, lektor, Karlstads universitet</p>
|
Page generated in 0.0477 seconds