Au cours des dernières décennies, l’intérêt pour la gazéification de biomasses a considérablement augmenté, notamment en raison de la grande efficacité de recouvrement énergétique de ce procédé par rapport aux autres procédés de génération de bioénergies. Les composants majoritaires du gaz de synthèse, le monoxyde de carbone (CO) et l’hydrogène (H2) peuvent entre autres servir de substrats à divers microorganismes qui peuvent produire une variété de molécules chimiques d’intérêts, ou encore produire des biocarburants, particulièrement le méthane. Il est donc important d'étudier les consortiums méthanogènes naturels qui, en syntrophie, serait en mesure de convertir le gaz de synthèse en carburants utiles. Cette étude évalue principalement le potentiel de méthanisation du CO par un consortium microbien issu d’un réacteur de type UASB, ainsi que les voies métaboliques impliquées dans cette conversion en conditions mésophiles. Des tests d’activité ont donc été réalisés avec la boue anaérobie du réacteur sous différentes pressions partielles de CO variant de 0.1 à 1,65 atm (0.09 à 1.31 mmol CO/L), en présence ou absence de certains inhibiteurs métaboliques spécifiques. Dès le départ, la boue non acclimatée au CO présente une activité carboxidotrophique relativement intéressante et permet une croissance sur le CO. Les tests effectués avec de l’acide 2- bromoethanesulfonique (BES) ou avec de la vancomycine démontrent que le CO est majoritairement consommé par les bactéries acétogènes avant d’être converti en méthane par les méthanogènes acétotrophes. De plus, un plus grand potentiel de méthanisation a pu être atteint sous une atmosphère constituée uniquement de CO en acclimatant auparavant la boue. Cette adaptation est caractérisée par un changement dans la population microbienne désormais dominée par les méthanogènes hydrogénotrophes. Ceci suggère un potentiel de production à large échelle de biométhane à partir du gaz de synthèse avec l’aide de biofilms anaérobies. / Syngas produced through the thermal gasification of biomass for energy recovery has received increased attention in the past decades due to its higher efficiency compared to other bioenergy processes. The gas components of syngas, CO and H2, can serve as substrates for the conversion of desirable chemicals and fuels, namely methane, by a wide range of microorganisms. Meanwhile, anaerobic wastewater-treating sludges have been reported as good sources of carboxidotrophic microorganisms which can be exploited for methane production. Thus it is important to investigate existing methanogenic consortiums which, in syntrophy, are able to convert syngas into useful fuels. This study is mainly focused on the assessment of the carboxidotrophic methanogenic potential present in a natural consortium of microorganisms from a UASB reactor and the identification of CO conversion routes to methane under mesophilic temperatures. To achieve this, a series of kinetic-activity tests with the anaerobic sludge were performed under CO partial pressures varying from 0.1 to 1.65 atm (0.09-1.31 mmol/L) in both the presence and absence of specific metabolic inhibitors. The non-adapted sludge presented an interesting carboxidotrophic activity potential for growing conditions on CO alone. Inhibition experiments with 2- bromoethanesulfonic acid (BES) and vancomycin showed that CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens. Moreover, it was possible to achieve higher methanogenic potential under 100% CO by acclimation of the sludge. This adaptation led to a shift in the microbial population predominated by hydrogenophilic methanogens. This suggests a possible enrichment potential with anaerobic biofilms for large scale methane production from CO-rich syngas, and further advances the knowledge base for anaerobic reactor development.

Population exposure to traffic pollution is a rapidly developing, multi-disciplinary scientific field. While the link between long-term exposure and respiratory issues is well-established, there are probable links to a number of more serious health effects, which are still not fully understood. In the interests of protecting human health, it is prudent that we take a cautionary approach and actively seek to reduce exposure levels, especially in the home environment where people spend a significant portion of their time. In many large cities, a substantial number of homes are situated on land immediately adjacent to busy freeways and other heavily-trafficked roads. Characterising exposures of local residents is incredibly challenging but necessary for advancing epidemiological understandings. While existing studies are plentiful, the results are mixed and generally not transferable to other urban areas due to the localised nature of the built environment and meteorological influences. This thesis aimed to employ a variety of methods to develop a holistic understanding of the influence of traffic emissions on near-highway residents' exposure in two communities of South Auckland, New Zealand, where Annual Average Daily Traffic (AADT) is as high as 122,000 vehicles. First, ultrafine particles (UFPs), nitrogen oxides (NOx), carbon monoxide (CO) and particulate matter ≤ 10 μm (PM₁₀) were continuously monitored using a series of fixed stations at different distances from the highways, over several months during the winters of 2010 and 2011. Emissions modelling output (based on traffic composition), was used within a dispersion model to compare modelled concentrations with monitored levels. In addition, community census meshblock units were mapped by level of social deprivation in order to assess potential inequities in highway emissions exposure. The second layer of local air quality investigation involved using a bicycle platform to systematically measure concentrations of UFPs, CO and PM₁₀ using the entire street-grid network throughout each community. This was done forty times - five times at four times of day (07:00, 12:00, 17:00 and 22:00), for each study area, with the aim of mapping the diurnal fluctuation of microspatial variation in concentrations. Using global positioning system (GPS) data and geographical information system (GIS) software, spatially-resolved pollutant levels were pooled by time of day and the median values mapped, providing a visualisation of the spatial extent of the influence of emissions from the highways compared to minor roads. The third layer involved using data from multiple ambient monitors, both within the local areas and around the city, to simulate fifty-four residents' personal exposure for the month of June, 2010. This required collecting timeactivity information which was carried out by door-to-door surveying. The time-activity data were transformed into microenvironment and activity codes reflecting residents movements across a typical week, which were then run through the US-EPA's Air Pollution Exposure Model (APEX). APEX is a probabilistic population exposure model for which the user sets numerous microenvironmental parameters such as Air Exchange Rates (AERs) and infiltration factors, which are used in combination with air pollutant concentrations, meteorological, and geospatial data, to calculate individuals' exposures. Simulated exposure outputs were grouped by residents' occupations and their home addresses were artificially placed at varying distances from the highways. The effects of residential proximity to the highway, occupation, work destination and commute distance were explored using a Generalised Linear Model (GLM). Surveyed residents were also asked a series of Likert-type, ordered response questions relating to their perceptions and understandings of the potential impacts of living near a significant emissions source. Their response scores were explored as a function of proximity to the highway using multivariate linear regression. This formed the final layer of this investigation into air quality throughout these South Auckland communities of Otahuhu and Mangere Bridge. Results show that concentrations of primary traffic pollutants (UFPs, NOx, CO) are elevated by 41 - 64% within the roadside corridor compared to setback distances approximately 150 m away and that the spatial extent of UFPs can reach up to 650 m downwind early in the morning and late in the evening. Further, social deprivation mapping revealed that 100% of all census meshblocks within 150 m either side of both highways are at the extreme end of the deprivation index (NZDep levels 8 - 10). Simulations for residents dispersed across the community of Otahuhu estimated daily NOx and CO exposure would increase by 32 and 37% (p<0.001) if they lived immediately downwind of the highway. If they were to shift 100 m further downwind, daily exposure would decline by 56 - 70% (p<0.001). The difference in individuals' exposure levels by occupation varied across the same distance by a factor of eight (p<0.05), with unemployed or retired persons the most exposed due to having more free time to spend outdoors at home (recreation, gardening, etc.). Those working in ventilated offices were the least exposed, even though ambient concentrations - likely due to a strong urban street canyon effect - were higher than the nearest highway monitor (5 m downwind) by 25 - 30% for NOx and CO, respectively. Inverse linear relationships were identified for distance from highway and measures of concern for health impacts, as well as for noise (p<0.05). Positive linear relationships were identified for distance from highway and ratings of both outdoor and indoor air quality (p<0.05). Measures of level of income had no conclusive statistically significant effect on perceptions (p>0.05). The main findings within this thesis demonstrate that those living within the highway corridor are disproportionately exposed to elevated long-term average concentrations of toxic air pollutants which may impact on physical health. While the socioeconomic characteristics could also heighten susceptibility to potential health impacts in these areas, certain activity patterns can help mitigate exposure. This thesis has also shown that there may be quantifiable psychological benefits of a separation buffer of at least 100 m alongside major highways. These results enhance a very limited knowledge base on the impacts of near-roadway pollution in New Zealand. Furthermore, the results lend additional support to the international literature which is working to reduce residential exposures and population exposure disparities through better policies and improved environmental planning. Where possible, the placement of sensitive population groups within highway corridors, e.g. retirement homes, social housing complexes, schools and childcare centres, should be avoided.

La gazéification est aujourd'hui l'une des stratégies les plus prometteuses pour valoriser les déchets en énergie. Cette technologie thermo-chimique permet une réduction de 95 % de la masse des intrants et génère des cendres inertes ainsi que du gaz de synthèse (syngaz). Le syngaz est un combustible gazeux composé principalement de monoxyde de carbone (CO), d'hydrogène (H2) et de dioxyde de carbone (CO2). Le syngaz peut être utilisé pour produire de la chaleur et de l'électricité. Il est également la pierre angulaire d'un grand nombre de produits à haute valeur ajoutée, allant de l'éthanol à l'ammoniac et l'hydrogène pur. Les applications en aval de la production de syngaz sont dictées par son pouvoir calorifique, lui-même dépendant de la teneur du gaz en H2. L’augmentation du contenu du syngaz en H2 est rendu possible par la conversion catalytique à la vapeur d’eau, largement répandu dans le cadre du reformage du méthane pour la production d'hydrogène. Au cours de cette réaction, le CO est converti en H2 et CO2 selon : CO + H2O → CO2 + H2. Ce processus est possible grâce à des catalyseurs métalliques mis en contact avec le CO et de la vapeur. La conversion catalytique à la vapeur d’eau a jusqu'ici été réservé pour de grandes installations industrielles car elle nécessite un capital et des charges d’exploitations très importantes. Par conséquent, les installations de plus petite échelle et traitant des intrants de faible qualité (biomasse, déchets, boues ...), n'ont pas accès à cette technologie. Ainsi, la seule utilisation de leur syngaz à faible pouvoir calorifique, est limitée à la génération de chaleur ou, tout au plus, d'électricité. Afin de permettre à ces installations une gamme d’application plus vaste de leurs syngaz, une alternative économique à base de catalyseur biologique est proposée par l’utilisation de bactéries hyperthermophiles hydrogénogènes. L'objectif de cette thèse est d'utiliser Carboxydothermus hydrogenoformans, une bactérie thermophile carboxydotrophe hydrogénogène comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène. Pour cela, l’impact d'un phénomène de biominéralisation sur la production d’H2 a été étudié. Ensuite, la faisabilité et les limites de l’utilisation de la souche dans un bioréacteur ont été évaluées. Tout d'abord, la caractérisation de la phase inorganique prédominante lorsque C. hydrogenoformans est inoculé dans le milieu DSMZ, a révélé une biominéralisation de phosphate de calcium (CaP) cristallin en deux phases. L’analyse par diffraction des rayons X et spectrométrie infrarouge à transformée de Fourier de ce matériau biphasique indique une signature caractéristique de la Mg-whitlockite, alors que les images obtenues par microscopie électronique à transmission ont montré l'existence de nanotiges cristallines s’apparentant à de l’hydroxyapatite. Dans les deux cas, le mode de biominéralisation semble être biologiquement induit plutôt que contrôlé. L'impact du précipité de CaP endogène sur le transfert de masse du CO et la production d’H2 a ensuite été étudié. Les résultats ont été comparés aux valeurs obtenues dans un milieu où aucune précipitation n'est observée. Dans le milieu DSMZ, le KLa apparent (0.22 ± 0.005 min-1) et le rendement de production d’H2 (89.11 ± 6.69 %) étaient plus élevés que ceux obtenus avec le milieu modifié (0.19 ± 0.015 min-1 et 82.60 ± 3.62% respectivement). La présence du précipité n'a eu aucune incidence sur l'activité microbienne. En somme, le précipité de CaP offre une nouvelle stratégie pour améliorer les performances de transfert de masse du CO en utilisant les propriétés hydrophobes de gaz. En second lieu, la conversion du CO en H2 par la souche Carboxydothermus hydrogenoformans fut étudiée et optimisée dans un réacteur gazosiphon de 35 L. Parmi toutes les conditions opérationnelles, le paramètre majeur fut le ratio du débit de recirculation du gaz sur le débit d'alimentation en CO (QR:Qin). Ce ratio impacte à la fois l'activité biologique et le taux de transfert de masse gaz-liquide. En effet, au dessus d’un ratio de 40, les performances de conversion du CO en H2 sont limitées par l’activité biologique alors qu’en dessous, elles sont limitées par le transfert de masse. Cela se concrétise par une efficacité de conversion maximale de 90.4 ± 0.3 % et une activité spécifique de 2.7 ± 0.4 molCO·g–1VSS·d–1. Malgré des résultats prometteurs, les performances du bioréacteur ont été limitées par une faible densité cellulaire, typique de la croissance planctonique de C. hydrogenoformans. Cette limite est le facteur le plus contraignant pour des taux de charge de CO plus élevés. Ces performances ont été comparées à celles obtenues dans un réacteur à fibres creuses (BRFC) inoculé par la souche. En dépit d’une densité cellulaire et d’une activité volumétrique plus élevées, les performances du BRFC à tout le moins cinétiquement limitées quand elles n’étaient pas impactées par le transfert de masse, l'encrassement et le vieillissement de la membrane. Afin de parer à la dégénérescence de C. hydrogenoformans en cas de pénurie de CO, la croissance de la bactérie sur pyruvate en tant que seule source de carbone a été également caractérisée. Fait intéressant, en présence simultanée de pyruvate et de CO, C. hydrogenoformans n’a amorcé la consommation de pyruvate qu’une fois le CO épuisé. Cela a été attribué à un mécanisme d'inhibition du métabolisme du pyruvate par le CO, faisant ainsi du pyruvate le candidat idéal pour un système in situ de secours. / Gasification is today one of the most promising strategies to recover energy from waste. This thermo-chemical technology allows a 95% weight reduction of the input and generates inorganic inert ashes as well as a synthesis gas (syngas). Syngas is a gaseous fuel mainly composed of carbon monoxide (CO), hydrogen (H2) and carbon dioxide (CO2). Syngas can be burned to produce heat and electricity. It is also the building block of many high added- value products ranging from ethanol to ammonia and pure hydrogen. Downstream applications of syngas production will depend on its heating value, which is determined by its content in H2. Upgrading the H2 content in syngas is performed by the water-gas shift (WGS) reaction, widely utilized during methane reforming for hydrogen production. During the WGS reaction CO is converted to H2 and CO2 according to: CO + H2O → CO2 + H2. This process is achieved using a metallic catalyst in a heterogeneous gas-phase reaction with CO and steam. The WGS reaction has so far been reserved for large-scale gasification plants and requires high capital and operational expenditures. Hence, smaller scale plants that process low-grade materials (biomass, waste, sludge...), would not have access to such technology. The only possible outcome with the synthesis gas (syngas) produced and which generally has a poor heating value, is to generate heat or at best, electricity. In order to offer small plants access to the WGS reaction and to a higher range of products from their syngas, an alternative to the expensive and energy-intensive established catalyst-based WGS is here considered, such as extreme-thermophilic microbial processes carried out by hydrogenogens. The goal of this thesis was to use Carboxydothermus hydrogenoformans, a thermophilic carboxydotrophic hydrogenogenic bacterium as a biological catalyst for the WGS reaction. This was done by characterizing the impact of a growth-associated biomineralization phenomenon on H2 production and assessing the feasibility and limitations of using the strain in a bioreactor. First, characterization of the predominant inorganic phase when Carboxydothermus hydrogenoformans was inoculated in the DSMZ medium revealed the biomineralization of two crystalline CaP phases. The X-ray diffractometry peaks and Fourier transform infrared spectroscopy spectrum of this biphasic material consistently showed features characteristic of Mg-whitlockite, whereas transmission electron microscopy analysis showed the existence of hydroxyapatite-like nanorods crystals. In both cases, the mode of biomineralization appears to be biologically induced rather than biologically controlled. The impact of the endogenous CaP precipitate on CO mass transfer and H2 production was thus assessed and compared to a medium where no precipitation was observed. In the DSMZ medium, the apparent KLa (0.22 ±0.005 min-1) and H2 production yield (89.11 ±6.69%) were higher than the ones obtained in the modified medium (0.19 ±0.015 min-1 and 82.60 ±3.62% respectively). The presence of the precipitate had no impact on C. hydrogenoformans CO uptake. Overall, the CaP precipitate offers a novel strategy for gas-liquid mass transfer enhancement using CO hydrophobic properties. Second, the conversion of CO into H2 by C. hydrogenoformans was investigated and optimized in a 35 L gas-lift reactor. Upon all operational conditions, the ratio of gas recirculation over CO feed flow rates (QR:Qin) was the major parameter that impacted both biological activity and volumetric gas-liquid mass transfer. The CO conversion performance of the gas lift reactor was kinetically limited over a QR:Qin ratio of 40, and mass transfer limited below that ratio, resulting in a maximum conversion efficiency of 90.4±0.3% and a biological activity of 2.7±0.4 molCO· g–1VSS· day–1. Despite very promising results, CO conversion performance was limited by a low cell density, typical of C. hydrogenoformans planktonic growth. This limitation was found to be the most restrictive factor for higher CO loading rates. Results were compared to the performance of the strain inoculated in a hollow fiber membrane bioreactor where performance, despite the higher cell density and volumetric activity, was biokinetically limited, when not limited by gas–liquid mass transfer, membrane fouling and aging. To avoid any C. hydrogenoformans decay during potential CO shortages, growth of the bacterium on pyruvate as a sole carbon source was characterized. Interestingly, when grown simultaneously on pyruvate and CO, pyruvate consumption was initiated upon CO depletion. This was attributed to the inhibition of pyruvate oxidation by CO, making pyruvate the ideal candidate for an in-situ back-up system.

Emissions from light-duty passenger vehicles represent a significant portion of total criteria pollutant emissions in the United States. Since the 1970s, emissions testing of these vehicles has been required in many major metropolitan areas, including Atlanta, GA, that were designated to be in non-attainment for one or more of the National Ambient Air Quality Standards. While emissions inspections have successfully reduced emissions by identifying and repairing high emitting vehicles, they have been increasingly inefficient as emissions control systems have become more durable and fewer vehicles are in need of repair. Currently, only about 9% of Atlanta area vehicles fail emissions inspection, but every vehicle is inspected annually. This research addresses explores ways to create a more efficient emissions testing program while continuing to use existing testing infrastructure. To achieve this objective, on road vehicle emissions data were collected as a part of the Continuous Atlanta Fleet Evaluation program sponsored the Georgia Department of Natural Resources. These remote sensing data were combined with in-program vehicle inspection data from the Atlanta Vehicle Inspection and Maintenance (I/M) program to establish the degree to which on road vehicle remote sensing could be used to enhance program efficiency. Based on this analysis, a multi-parameter model was developed to predict the probability of a particular vehicle failing an emissions inspection. The parameters found to influence the probability of failure include: vehicle characteristics, ownership history, vehicle usage, previous emission test results, and remote sensing emissions readings. This model was the foundation for a proposed emissions testing program that would create variable timing for vehicle retesting with high and low failure probability vehicles being more and less frequently, respectively, than the current annual cycle. Implementation of this program is estimated to reduce fleet emissions of 17% for carbon monoxide, 11% for hydrocarbons, and 5% for nitrogen oxides in Atlanta. These reductions would be achieved very cost-effectively at an estimated marginal cost of $149, $7,576 and $2,436 per-ton-per-year for carbon monoxide, hydrocarbons, and nitrogen oxides emissions reductions respectfully.

This thesis applies the ab initio techniques of computational chemistry to studies of molecular clusters containing covalent (strong) or van der Waals (weak) bonds formed in chemistry and biochemistry in the temperature range 10-300 K. Van derWaals complexes with an enthalpy of formation from reactants of less than 25 kJ mol-1 and covalent clusters are described in this thesis. The first group of van der Waals complexes involved the molecule carbon monoxide that possesses a small permanent dipole that could lead to dipole - induced dipole interaction and dipole - dipole interaction with another reactant in addition to dispersion. The substrates investigated were methanimine and cyanogen where endergonic unstable molecules were formed, and the clustering of carbon monoxideon a porphin surface leading to the formation of carbon - carbon fragments. TheFaraday effect was invoked to suggest that this was the original method by which thechirality of the D-sugars was selected. Coordination of imino-compounds on thesame surface involving induction and electrostatic interactions could lead to the preferential formation of L-aziridones, hydrolysable to L-amino-acids.The preferred formation of D-ribose, and the more stable D-2-deoxyribose, andnucleotides polymerisable to deoxyribonucleic acids was described. The second group of van der Waals complexes involved the polymerisation of acetylene molecules, to di- and tri-acetylene complexes where the exchange interaction involved the quadrupole moment of the acetylene radical reacting with acetylene or diacetylene. The reaction of carbon monoxide was extended to include its interaction with diacetylene. The entire potential energy surface for the interaction with diacetylene was investigated. The reaction was shown to be endergonic to produce a reactive species, here postulated to rearrange with a reasonable activation energy toform an aldehyde. The energetics of the formation of diacetylene, triacetylene andhigher polymers was briefly investigated. The reactivity of the acetylene polymeraldehydes with other substrates was briefly investigated. This work has apparently laid a firm basis both, qualitative and quantitative, tounderstand some of the weakest interactions in nature involving the simplest ofreactions that have been important in atmospheric chemistry.

No description available.

La cytochrome c oxydase (CcO) est un complexe protéique commun à tous les organismes aérobies. Elle catalyse la réduction de l’oxygène en eau au niveau d’un site catalytique qui contient un atome de fer hémique et un atome de cuivre (CuB). La famille de ces oxydases est ainsi appelée super famille des oxydases à "hème-cuivre". Malgré le grand nombre d’études réalisées au sujet de l’activité catalytique des CcO, le déroulement exact des étapes de leur mécanisme reste encore mal connu. Afin de mieux cerner le problème de la relation structure-activité de cette hémoprotéine, deux approches distinctes et complémentaires ont été abordées : l’étude du système naturel et l’approche biomimétique. Les propriétés électroniques et vibrationnelles de certains intermédiaires du cycle catalytique de la cytochrome c oxydase ont été caractérisées par spectroscopies UV-Visible, de fluorescence résolue en temps et infrarouge. L’analyse du site actif de la CcO par des substitutions isotopiques du CuB, ainsi que l’influence du pH sur la structure de cet enzyme sont discutées. La deuxième partie de ce travail concerne l’étude du rôle de l’environnement proche de l’hème sur la réactivité des complexes FeII-CO et FeII-O2 grâce à une série de modèles superstructurés du centre binucléaire Fe/Cu de la CcO. Ces analogues synthétiques conservent l’hème, la ligation fer-histidine du site proximal et le ligand complexant le cuivre du site distal de la CcO, mais se différencient notamment par leur environnement autour de l’atome de cuivre et par leur rigidité. Deux techniques ont été utilisées: la spectroscopie ATR-IRTF et la photochimie dans le cas d’espèces carbonylées. / Cytochrome c Oxidase (CcO), a member of the heme-copper oxidase superfamily, is a membrane protein in many aerobic organisms, that catalyses the reduction of dioxygen to water. Dioxygen binding and reduction occurs at a heterobinuclear site that is comprised of a heme a3, and a copper atom (CuB) in close proximity. Despite, the CcO has been the subject of numerous biophysical and spectroscopic investigations, the detailed molecular mechanism of CcO remains still elusive. In order to better define the structure-function relationship for this hemoprotein, two distinct and complementary approaches have been employed: the study of the natural system and the biomimetic approach.Structural changes accompanying the change in the redox state of some CcO intermediates have been characterised by UV-Visible, ATR-FTIR and time-resolved fluorescence spectroscopies. The study of the cytochrome c oxydase active site modified with isotopic substitutions of CuB, and the effect of pH on the structure are discussed. The second part of this work is related to study the role of environment on the reactivity of FeII-CO et FeII-O2 complexes by exploiting a series of superstructured models of the binuclear Fe/Cu active site of CcO. Based upon a porphyrin core, all these models have the iron-histidine ligation of the proximal site and the copper ligand of the distal site of CcO but they differ strongly by the environment around the copper and their rigidity.

Made available in DSpace on 2014-10-09T12:26:36Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:22Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-12-17T14:57:49Z (GMT). No. of bitstreams: 1 CelitonS.pdf: 1872654 bytes, checksum: 0e3a2fa3a25b2b0d3f6314fb9f1b6ab9 (MD5) Previous issue date: 2009-07-13 / The vehicles are the main mobile sources of carbon monoxide (CO) and unburned hydrocarbons (HC) released into the atmosphere. In the last years the increment of the fleet of vehicles in the municipal district of Natal-RN it is contributing to the increase of the emissions of those pollutants. The study consisted of a statistical analysis of the emissions of CO and HC of a composed sample for 384 vehicles with mechanization Gasoline/CNG or Alcohol/Gasoline/CNG of the municipal district of Natal-RN. The tests were accomplished in vehicles submitted to Vehicular Safety's Inspection, in the facilities of INSPETRANS, Organism of Vehicular Inspection. An partial gases analyzer allowed to measure, for each vehicle, the levels of CO and HC in two conditions of rotation of the motor (900 and 2500 rpm). The statistical analysis accomplished through the STATISTICA software revealed a sensitive reduction in the efficiency of the converters catalytic after 6 years of use with emission average it is of 0,78% of CO and 156 (ppm) of HC, Which represents approximately 4 (four) times the amount of CO and the double of HC in comparison with the newest vehicles. The result of a Student s t-test, suggests strongly that the average of the emissions of HC (152 ppm), at 900 rpm, is 40% larger than at 2500 rpm, for the motor without load. This result reveals that the efficiency of the catalytic conversion is limited kinetically in low engine speeds. The Study also ends that when comparing the emissions of CO and HC considering the influence of the fuels, it was verified that although the emissions of CO starting from CNG are 62% smaller than arising from the gasoline, there are not significant differences among the emissions of HC originating from of CNG and of the gasoline. In synthesis, the results place the current criteria of vehicular inspection, for exhaust gases, in doubt, leading the creation of emission limits of pollutant more rigorous, because the efficiency of the converters catalytic is sensibly reduced starting from 6 years of use. It is also raised the possibility of modifications in the test conditions adopted by the current norms, specifically in the speed engine, have seen that in the condition without load the largest emission indexes were registered in slow march. That fact that allows to suggest the dismissal of the tests in high speed engine, reducing the time of inspection in half and generating economy of fuel / Os ve?culos automotores s?o as principais fontes m?veis de Mon?xido de Carbono (CO) e Hidrocarbonetos n?o queimados (HC) lan?ados na atmosfera. Nos ?ltimos anos o acr?scimo da frota de ve?culos no munic?pio de Natal-RN vem contribuindo para o aumento das emiss?es desses gases poluentes. O estudo consistiu de uma an?lise estat?stica das emiss?es de CO e HC de uma amostra composta por 384 ve?culos com motoriza??o a Gasolina/GNV ou ?lcool/Gasolina/GNV do munic?pio de Natal-RN. Os testes foram realizados em ve?culos submetidos ? Inspe??o de Seguran?a Veicular, nas instala??es do INSPETRANS, Organismo de Inspe??o Veicular. Um analisador de gases parcial permitiu medir, para cada ve?culo, os n?veis de CO e HC em duas condi??es de rota??o do motor (900 e 2500 rpm). A an?lise estat?stica realizada por meio do software STATISTICA revelou uma sens?vel redu??o na efici?ncia dos conversores catal?ticos ap?s 6 anos de uso com a emiss?o m?dia de 0,78 % de CO e 156 (ppm) de HC, o que representa aproximadamente 4 (quatro) vezes a quantidade de CO e o dobro de HC em compara??o com os ve?culos mais novos. O resultado de um Teste-T de Student sugere fortemente que a m?dia das emiss?es de HC (152 ppm), a 900 rpm, ? 40% maior que a 2500 rpm, para o motor sem carga. Esse resultado revela que a efici?ncia da convers?o catal?tica ? limitada cineticamente em baixas rota??es. O Estudo conclui tamb?m que ao comparar as emiss?es de CO e HC, considerando a influ?ncia dos combust?veis, verificou-se que embora as emiss?es de CO a partir do GNV sejam 62% menores do que a partir da gasolina, n?o h? diferen?as significativa entre as emiss?es de HC oriundas do GNV e da gasolina. Em s?ntese, os resultados colocam os atuais crit?rios de inspe??o veicular, para gases da exaust?o, em d?vida, conduzindo a cria??o de limites de emiss?o de poluentes mais rigorosos, visto que a efici?ncia dos conversores catal?ticos ? sensivelmente reduzida a partir de 6 anos de uso. Suscita-se tamb?m a possibilidade de modifica??es nas condi??es de teste adotadas pelas normas atuais, especificamente na rota??o do motor, haja vista que na condi??o sem carga os maiores ?ndices de emiss?o foram registrados em marcha lenta. De ante disso, sugere-se a dispensa dos testes em altas rota??es, reduzindo ? metade o tempo de inspe??o e gerando economia de combust?vel

Background and aims: Treatment of acute fulminant liver damage arising as a result of various origins (ischemia-reperfusion injury, toxic shock, an infectious cause or cholestasis) still remains a major clinical problem. We currently do not have available clinically proven, pharmacologically effective and universal compound for the treatment of acute liver injury. The main aim of my research work was, therefore, to test the potential hepatoprotective effect of selected cytoprotective drugs and try to find out or suggest their mechanism of action, which we have examined in the systems for the intracellular gaseous signaling molecules NO and CO, where the key enzymes for their formation are NOS / HO respectively. My PhD study had two main directions: 1) Experimental study of the relationship between HO / CO and NOS / NO systems in the environment of hepatotoxic substances on isolated primary rat hepatocytes and in rat model, 2) Evaluation of ameliorative effect of selected substances in the hepatotoxicity models and to test the relationship of this effect on changes in some parameters of cytotoxicity / cytoprotection, antioxidant parameters, gene expression of mRNA for selected genes and histological changes in the state of cells / tissues / organs. Methods: We measured urea, bilirubin and liver...