Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Surface Waters are generally used as support for disposal of waste generated by man. The effluents from dairy industries are characterized by high volume presents, but mainly because of its high concentration of organic load. The evolution of agro-industrial systems wastewater treatment offers the application of eficiente technologies of the environmental impact is kept to a maximum. The UASB (upflow anaerobib sludge blanket) reactor is considered one of the most representative anaerobic systems, due to its high biomass concentration and a rich microbial diversity. This study aimed to initiate and control their operation in the anaerobic digestion process to the treat wastewater from a dairy plant evaluating the removal of control parameters (temperature, pH, COD, BOD5, TKN, TS and VST) beside the design parameters (HRT, HLR and VOL). The reactor was operated with the HRT of 0,085 d-1, and VOLs ranging from 12,58 to 29,2 kg.m-3.d-1, which influenced the high HLR value. To start, the inoculum used was from a septic tank. The temperature oscillations due to the presented experimental period. As for the control parameters, the system showed a significant difference in the removal of organic matter. The removal of BOD5 by the system obtained a removal efficiency of 42,7%. For COD, removal was 58,6%. The removal efficiency was related by large sludge production, indicating the time of withdrawal of excess. The concentration of excess sludge was analyzed, which showed significant 17.538 mg.L-1, being the explicit need for disposal of the sludge during operation. / As águas superficiais geralmente são utilizadas como suporte para eliminação de resíduos produzidos pelo homem. Os efluentes das indústrias de laticínios são caracterizados por apresentarem elevados volumes, mas principalmente por sua elevada concentração de carga orgânica. A evolução dos sistemas de tratamento de efluentes agroindustriais disponibiliza a aplicação de tecnologias eficientes para que o impacto ambiental seja reduzido ao máximo. O reator UASB (upflow anaerobic sludge blanket) é considerado um dos mais representativos sistemas anaeróbios, devido a sua alta concentração de biomassa e uma rica diversidade microbiana. Este trabalho objetivou dar início ao processo bem como controlar sua operação no processo de digestão anaeróbia para o tratamento de efluentes de uma usina de laticínios avaliando a remoção dos parâmetros de controle (temperatura, pH, DQO, DBO5, NTK, ST e SVT), além dos parâmetros de projeto (TDH, TCH e COV). O reator foi operado com um TDH de 0,085 d-1, e COV variando de 12, 58 a 29,2 kg.m-3.d-1, os quais influenciaram no alto valor da TCH. Para a partida, o inóculo utilizado foi proveniente de uma fossa séptica. A temperatura apresentou oscilações devido ao tempo experimental. Quanto aos parâmetros de controle, o sistema apresentou diferença significativa na remoção da matéria orgânica. A remoção de DBO5 pelo sistema obteve-se uma eficiência de remoção de 42,7%. Para a DQO, a remoção foi de 58,6%. A eficiência de remoção foi relacionada pela grande produção de lodo, indicando o momento da retirada do excesso. A concentração do excesso de lodo foi analisada, onde apresentou expressivos 17.538 mg.L-1, ficando explícita a necessidade de descarte do lodo durante a sua operação.

Anthropogenic environmental changes can serve as drivers for evolutionary responses in wild populations. To predict the long-term impact of anthropogenic changes on populations, it is crucial to understand the genetic effects caused by these disturbances. The Baltic Sea is considered to be one of the world’s most contaminated seas, and the increase of anthropogenic chemical pollution is a major threat to its ecosystems. This thesis assesses the impact of harbors and sewage treatment plants on physiological traits and genetic structure of resident populations of blue mussels at replicated sites in the Baltic Sea. The initial evaluation of the overall genetic pattern in blue mussel populations in the Swedish West Coast, the Baltic Proper and the Bothnian Sea found genetic differentiation between the three water basins and a low genetic differentiation within each basin, especially within the Baltic Proper. Despite the low genetic differentiation among blue mussels within the Baltic Proper, a parallel genetic differentiation associated with sewage treatment plant effluents was found in this basin. This included genomic regions with a high degree of differentiation between reference sites and sites affected by sewage plants effluent. This genetic differentiation is suggested to be due to post-dispersal selection acting in each generation. In contrast, no parallel genetic differentiation was associated with harbors. We identified five genomic regions in blue mussels, showing strong signs of selection, shared among three out of four replicated reference sites and sites affected by sewage effluents in the Baltic Proper i.e. Askö, Tvärminne and Karlskrona. An initial characterization of these genomic regions revealed functions related to immune and endocrine responses, oxidative stress and shell formation. Our results indicate that selection caused by sewage effluents involves multiple loci. The same genomic regions are found across different locations in the Baltic Proper but there are also unique genomic regions at each location. No genotoxic or histopathological effects were found among blue mussels from sewage effluent-affected areas but a higher frequency of histological abnormalities in the digestive gland were observed in mussels from harbors. / Evolutionära anpassningar till miljöstörningar i marina ekosystem: genetisk ekotoxikologi i Östersjön

Les effluents de distillerie de mélasse de canne à sucre génèrent une pollution environnementale due à, d’une part de grands volumes et d’autres part à la présence de composés de couleur brune foncée, connus sous le nom de mélanoïdines. Dans cette étude, un consortium bactérien CONS8 isolé dans des sédiments de chute d'eau a été choisi comme consortium apte à la décoloration de la mélasse. On a montré que le consortium CONS8 pouvait décolorer, trois eaux usées synthétiques différentes, élaborées respectivement à base de Viandox (13,48% v/v), d’eau usée de mélasse de betterave (41,5% v/v) ou d’eau usée de mélasse de canne à sucre (20% v/v). Les décolorations obtenues en 2 jours seulement, en fioles d’Erlenmeyer sont respectivement de 9,5, à 8,02 et à 17,5%. Quatre bactéries prédominantes ont été identifiées dans le consortium CONS8 par l'analyse de l'rADN 16S. Sur la base de cette identification, et afin de réaliser la décoloration la plus élevée, un consortium bactérien artificiel MMP1 a été reconstruit avec Klebsiella oxytoca, Serratia mercescens (T2) et la bactérie inconnue DQ817737 (T4). Dans des conditions optimisées (aération, pH) le consortium bactérien MMP1 a permis de décolorer l'eau usée synthétique contenant de la mélanoidine à 18,3% en 2 jours. La comparaison de la décoloration par le consortium MMP1 avec un milieu abiotique a démontré que la décoloration était principalement due à l'activité biotique des cellules bactériennes, sans aucun phénomène d'adsorption. Un complément en minéraux et vitamines B n'a pas amélioré la décoloration de mélanoïdines avec le consortium bactérien MMP1. Enfin, les performances d'un bioréacteur à membrane pour traiter les eaux résiduaires synthétiques contenant de la mélanoïdine ont été évaluées à l’échelle du laboratoire. L'ensemencement du réacteur a été réalisé avec un inoculum sur la base du consortium MMP1. Le réacteur a fonctionné sous plusieurs conditions de temps de séjour hydrauliques (HRT) de 15, 20, et 40 heures. Les performances ont été analysées en termes de DCO (demande chimique en oxygène), décoloration et croissance de biomasse. Les résultats ont indiqué qu’une efficacité accrue d’élimination de la DCO et de la couleur ont été obtenues avec le HRT le plus long. / Distillery effluent from sugarcane molasses leads to an environmental pollution due to its large volume and the presence of dark brown colored compounds, known as melanoidins. In this study, a bacterial consortium CONS8 isolated from waterfall sediments in Maehongsorn province was selected as a molasses-decolorizing consortium. Consortium CONS8 was able to decolorize, only within 2 days, in Erlenmeyer flasks, three different synthetic wastewaters containing either Viandox sauce (13.5% v/v), beet molasses wastewater (41.5% v/v) or sugarcane molasses wastewater (20% v/v) at 9.5, 8.0 and 17.5%, respectively. Four predominant bacteria present in the consortium CONS8 were identified by the 16S rDNA analysis. To achieve the highest decolorization, the artificial bacterial consortium MMP1 comprising Klebsiella oxytoca, Serratia mercescens (T2) and unknown bacterium DQ817737 (T4), was constructed. Under optimized conditions (aeration, pH), the bacterial consortium MMP1 was able to decolorize the synthetic melanoidins-containing wastewater at 18.3% within 2 days. The comparison of decolorization by the consortium MMP1 with abiotic control proved that the color removal for synthetic melanoidins-containing wastewater medium was mainly due to biotic activity of bacterial cells, without any adsorption phenomena. Supplement of nutrients and vitamin B did not promote melanoidins decolorization by bacterial consortium MMP1. Finally, the performance of a membrane bioreactor (MBR) for synthetic melanoidins-containing wastewater treatment was investigated at laboratory scale, with a mineral membrane. The reactor seeding was made with the MMP1 bacterial consortium inoculum. The reactor was performed with several hydraulic retention times (HRT) of 15, 20, and 40 hours. The performances were analyzed in terms of COD, color removal and biomass in the reactor. The results indicated that the higher COD and color removal efficiency were achieved with the longer HRT.

As indústrias químicas são consideradas como o segmento industrial que gera os efluentes mais perigosos ao meio ambiente. Em virtude das concentrações expressivas de poluentes, tanto orgânicos quanto inorgânicos, os efluentes dessas indústrias podem interferir na atividade da biomassa de estações de tratamento de efluentes (E.T.E.), diminuindo sua eficiência e gerando efluentes tratados, porém em desacordo com a legislação pertinente. Para prevenir tais efeitos, o recebimento de efluentes industriais em E.T.E.s pode ser precedido por pré-tratamento, dentre os quais, o biológico, otimizado pela adição de microrganismos com capacidade de degradar poluentes. Foram isolados microrganismos com capacidade de degradar os compostos identificados como responsáveis pela toxicidade do efluente final da E.T.E.: benzeno, clorofórmio, 1,2-dicloroetano, pentaclorofenol, tricloroeteno, tolueno e p-xileno. Foram realizados testes de bioaumentação para pré tratar o efluente industrial, que foram avaliados através de ensaios físico-químicos e de toxicidade aguda para Vibrio fischeri e Daphnia similis. Os resultados obtidos demonstraram que o pré tratamento reduziu a toxicidade do efluente final da estação de tratamento. / Chemical industries are considered the industrial sector that generates the most dangerous effluents to the environment. Due to the high pollutant concentration, either organics or inorganics, the chemical industries effluents may interferer in the biomass activity in wastewater treatment plants (WWTP), what may reduce its efficiency and generate treated effluents in disagreement to the concerned law. In order to prevent such effects, the industrial effluents disposal in WWTPs can be preceded by biological pretreatment, which can be optimized by adding microorganisms capable of pollutants degradation. Microorganism strains that are able to degrade the compounds identified as the responsible for toxicity levels in the WWTP final effluent: benzene, chloroform, 1,2-dichloroethane, pentachlorophenol, trichloroethene, tolune and p-xylene were isolated. Bioaugmentation tests aiming the chemical effluent pretreatment were performed and they were evaluated through physical-chemical analysis and acute toxicity tests for Vibrio fischeri and Daphnia similis. The results showed that the industrial effluent pretreatment reduced the toxicity levels in the WWTP final effluent.

Resumo: A indústria sucroalcooleira gera uma grande quantidade de lodo, o qual deve ser descartado de forma adequada. Na indústria sucroalcooleira o tratamento de efluentes pode ser realizado com o auxilio de um reator anaeróbio (Upflow Anaerobic Sludge Blanket- UASB). Este sistema produz aglomerados compactos de microrganismos anaeróbios em formato de grânulos, sendo estes os responsáveis pela decomposição da matéria orgânica em biogás. Assim, os microrganismos atuam como um poderoso biocatalisador capaz de converter altas taxas de matéria orgânica em metano. Devido a melhorias para o sistema UASB, uma nova série de reatores chamados Expanded Granular Sludge Bed (EGSB) foram desenvolvidos, entre as quais a tecnologia do reator de circulação interna (IC), que permite uma diluição eficaz de mistura e do efluente que entra no reator, ou seja, um melhor condicionamento da matéria orgânica a ser processada. Tendo em vista estes resíduos, aeróbio e anaeróbio, amostras destes lodos foram analisadas. Ambas as amostras foram caracterizadas, utilizando termogravimetria (TG), análise térmica diferencial (DTA), calorimetria exploratória diferencial (DSC), espectroscopia na região do infravermelho (FTIR), microscopia eletrônica de varredura (MEV), difratometria de raios X pelo método do pó (DRX), absorção atômica e outras técnicas analíticas de bancada (pH, DQO, temperatura, oxigênio dissolvido e resíduos sedimentáveis) . Os resultados a partir das curvas TG-DTA e DSC forneceram informações a respeito da desidratação e decomposição térmica destas amostras. Os espectros de FTIR sugerem a presença de grupos hidroxila devido à hidratação destes compostos; grupos carboxilatos e carboidratos proveniente de ácidos húmicos. Os difratogramas de raios X mostraram linhas de difração, sugerindo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The sugarcane industry in the Brazil show a great amount of generated sludge which should be utilized adequately. In the sugarcane industry, the effluents can be treated within of an anaerobic reactor (Up flow Anaerobic Sludge Blanket - UASB). This system produces granules agglomerated compact of anaerobic microorganisms (granules) which are responsible for the decomposition of the organic matter in biogas. Like this, these act as a powerful biocatalyst. Due to improvements for the system UASB, a new series of reactors called Granular Expanded Sludge Bed (EGSB) were developed, with technology for internal circulation (IC), which allows an effective dilution of mixture and of the effluent that enters in the reactor. In other words, a better conditioning of the organic matter is obtained. Then, two sludge samples, aerobic and anaerobic, were obtained. Both samples were characterized, using thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), spectroscopic of absorption in infrared (FTIR), scanning microscopy electronic (SEM), X-ray diffraction patterns (DRX) and atomic absorption. The results obtained from TG-DTA and DSC curves, supplied information on the dehydration and thermal decomposition of these samples. The infrared absorption suggest that the are hydroxyl groups due to hydration of these compounds and carboxylic, and carbohydrates originating from humics. The X-ray diffraction patterns showed that these sludge's have diffraction lines, suggesting that these compounds are crystalline due to presence of different metal oxides. The values of the activation energy (Ea) of these compounds were obtained from thermogravimetric curves ... (Complete abstract click electronic access below) / Orientador: Clovis Augusto Ribeiro / Coorientador: Marcelo Kobelnik / Banca: José Paschoal Batistuti / Banca: Lidia Maria de Almeida Plicas / Mestre

[pt] cádmio é um dos maiores agentes contaminantes do meio ambiente devido à sua alta toxicidade, ameaçando às plantas, animais e seres humanos. O uso de biomassas como material sorvente para a remoção do cádmio de efluentes líquidos aparece como uma alternativa promissora às tecnologias existentes. O objetivo desta tese foi determinar a capacidade de adsorção do pó de casca de coco verde (Cocos nucifera) para cádmio num sistema contínuo de biossorção, assim como a dessorção do metal da biomassa, para que esta possa ser utilizada num ciclo de biossorção-dessorção. O equipamento escolhido foi uma coluna de leito fixo. Foram avaliadas a influência da vazão, altura de leito, sentido do fluxo e a eficiência do processo com colunas em série. Os grupos funcionais presentes na superfície da biomassa foram estudados através de análises de espectroscopia no infravermelho. Os experimentos num sistema contínuo com diferentes alturas de leito e concentrações iniciais revelaram que a melhor eficiência do processo foi obtida com maiores alturas de leito (18 cm) e concentrações iniciais baixas (19 mg/l). Obtiveram-se tempos de ruptura de 150 minutos para soluções com vazão de 22 ml/min, obtendo-se uma solução com concentração final de 2,6 mg/l. Uma eficiência de remoção de 46% foi obtida quando se trabalhou com concentrações iniciais de 19 mg/l e o processo torna-se mais eficiente quando é utilizado um sentido de fluxo ascendente.O EDTA mostrou-se como um excelente eluente ao realizar a dessorção dos íons metálicos contidos na biomassa, num processo em batelada. A biomassa foi submetida a quatro ciclos de biossorção-dessorção, apresentando em cada um deles eficiências de dessorção superiores a 70% e uma posterior eficiência de remoção superior a 85% em todos os ciclos. Os grupos funcionais presentes na superfície da biomassa são principalmente grupos carboxila, hidroxila, amina e amida. Os resultados apresentados mostram que o pó de casca de coco verde apresenta as características adequadas para o processo de biossorção de cádmio num processo contínuo utilizando colunas de leito fixo, e que pode ser utilizado como uma alternativa aos processos clássicos de tratamento de efluentes. / [en] Cadmium is one of the greatest actors of environmental pollution due to its high toxicity, threatening plants, animals and humans beings. The use of biomass as a sorbent material for cadmium removal seems to be a promising alternative to existing technologies. The objective of this work was to determine the adsorption capacity of coconut shell powder (Cocos nucifera) for cadmium in a continuous system of biosorption, and also the desorption of the metal from the biomass, so that this material could be used in a new cycle of biosorptiondesorption. A fixed bed column was chosen, as it does not present clogging problems and is easy to operate. The influence of flow rate and its direction, bed height and the efficiency of the process with series columns were evaluated. The functional groups present on the surface of the biomass were studied by infrared spectroscopy analysis.The column experiments with different bed heights and initial concentration revealed that the best efficiency was obtained with higher bed heights (18 cm) and lower initial concentrations (19 mg/l). Breakthrough time of 150 minutes was obtained for solutions with a flow rate of 22 ml/min, generating a solution with final concentration of 2.6 mg/l. A removal efficiency of 46% was obtained when working with initial concentrations of 19 mg/l. The process becomes more efficient when the solution is pumped upward through the columnEDTA was an excellent elutant for desorption of metal ions in the biomass in a batch system. The biomass was subjected to four biosorption-desorption cycles, presenting higher than 70% desorption efficiencies and removal efficiencies of more than 85% in all cases.The functional groups presents on the particle surface of the biomass are mainly carboxyl, hydroxyl, amine and amide groups. The results show that the powder of coconut shell has the appropriate characteristics for biosorption of cadmium in a continuous process using columns of fixed bed, which can be used as an alternative to conventional processes for effluent decontamination.

The aquaculture industry has experienced a great expansion in recent years. Along with this growth, increased regulatory attention has been directed towards aquacultural effluents. The problem with the majority of these discharges is the solids and nutrient spikes that occur during times of high farm activity. Several studies have proven that these discharges have the potential to adversely affect downstream water quality. Although several treatment options are currently in use, the use of Best Management Practices (BMPs)has been recommended in recent years to improve the quality of these discharges. The implementation of one of these BMPs, the use of a high energy feed, was the focus of this study. In two separate experiments at trout raising facilities, the effluents of basins receiving a high energy feed were compared to similar basins receiving a standard trout grower feed. The water quality parameters of main concern were total suspended solids, total Kjeldahl nitrogen (TKN) and total ammonia nitrogen (TAN). The results of these studies showed that the effluents of basins receiving a high energy feed generally contained significantly lower concentrations of TSS, but higher amounts of TKN than those receiving a standard grower feed. / Master of Science

Målet med den här studien är att förhindra effektivitetssänkningar i moderna biologiska reningsanläggningar för skogsindustriella avloppsvatten. Biologiska processer är vanligtvis effektiva när det gäller att reducera lättnedbrytbart organiskt material. Eftersom den utgörs av levande mikroorganismer (MO) är tekniken känslig. Toxiska ämnen kan döda en kultur av MO. Innan de har ökat i antal igen kommer reduktionseffektiviteten att vara påverkad för en ansenlig tid framöver. I ett pappers- och massabruk finns många typer av vätskor som oavsiktligt kan hamna i reningsanläggningen. I den här studien har svartluts inverkan på reduktionsgraden studerats. Biologiska reningsverk har använts under en lång tid. De har utvecklats från att vara generella reningsverk till att bli konceptanläggningar i flera steg, där varje steg har designats för sitt eget syfte med specifika MO. I det här arbetet har ett MultiBio-koncept vid Gruvön Bruk studerats. En anläggning i laboratorieskala har byggts för svartlutsförsöken. Resultatet har jämförts mot simulerade värden och värden från bruket. När ett spill av svartlut passerar genom en MultiBio späds det ut mellan varje steg. Halten av svartlut är hög i de första stegen vilka påverkas kraftigt. I de första stegen lever snabbväxande organismer som återhämtar sig på ett par dagar. De mer känsliga aktivslamstegen finns längre bak i reningsverket och är skyddade från toxiska koncentrationer av svartlut. Endast vid försök med 24-timmarstillsatser blev koncentrationen av svartlut så hög att den påverkade MO negativt. Den biologiska processen i ett reningsverk kan störas om MO förnekas något essentiellt behov. En biologisk process har ett flertal behov, bland annat behöver aeroba MO löst syre. Eftersom syresättning av vattnet är energikrävande och kostsamt är det inte problemfritt att skapa en omgivning som ger hög effektivitet samtidigt som man strävar efter att sänka energiförbrukningen. I avhandlingen beskrivs ett tillvägagångssätt för att studera energieffektiv syresättning. / The aim of this study is to prevent efficiency reduction in modern wastewater treatment plants for forest industry effluents. Biological processes are usually efficient in reducing biodegradable organic material. Since the technique depends on living microorganisms (MO) it is sensitive. Toxic substances can kill the population. It takes considerable time for the MOs to grow in number and the treatment efficiency will be affected accordingly. In a pulp and paper mill, a number of liquors are handled that can reach the treatment plant by accident. In this study the impact of black liquor spills on treatment efficiency has been studied. Biological treatment methods have been used for a long time. They have developed from general treatment plants to multiple stage concepts, where each stage is designed for its own purpose with specific MO cultures. In this thesis, a plant with the MultiBio concept, located at Gruvön Mill in Sweden has been studied. A laboratory scale MultiBio plant has been constructed for the trials in which efficiency during black liquor exposure has been measured. The measured laboratory results were evaluated by comparing them with simulated values and a mill case. When a shock of toxic black liquor passing through a MultiBio concept, the black liquor is diluted between the compartments. The first compartments that are exposed to high concentrations of black liquor are affected negatively. The MOs in the first compartment are fast growing and recover in a few days. The more sensitive activated sludge compartments are located further on in the plant. A toxic concentration is found in the activated sludge compartments only when the duration of the spill is 24 hours or more. Denying the MOs their needs can disturb biological treatments. Among many things, a biological process needs dissolved oxygen. Since aeration is energy consuming and expensive, there is a conflict between gaining high efficiency and, at the same time, decreasing the energy consumption. In this study, an approach to saving energy for aeration is initiated.

Avec les nouvelles lois et réglementations sur les émissions polluantes des moteurs à combustion, de plus en plus d’attention est portée sur la phase de démarrage à froid. La période de cette phase est une courte période de 2 minutes environ où la température de fonctionnement du catalyseur n’est pas encore suffisamment élevée et pendant laquelle 70-80% de la totalité des hydrocarbures émis par le moteur sont relâchés à l’atmosphère. La température minimale de fonctionnement, définie comme celle pour laquelle le catalyseur atteint une conversion de sortie du réacteur de 50%, est au-dessus de 200 ̊C. Pour pallier à l’inefficacité des catalyseurs trois voies dans la phase de démarrage à froid d’un moteur, une zéolithe, présentant des canaux unidimensionnels et une ouverture de pore avec un anneau à 12 atomes d’oxygènes, a été utilisée; on parle, dans ce cas, du processus "Single File Diffusion". Dans ce projet, une série de zéolithes ZSM-12 de structure MTW avec différents contre ions (Na⁺, H⁺ et Ag⁺) et avec différents rapports atomiques Si/Al (52, 64 et 80) ont été synthétisées. Ces échantillons zéolithiques ont été testés comme adsorbants pour la capture des hydrocarbures (HCs) en utilisant le toluène et l’éthylène comme modèles de grandes et de petites molécules des hydrocarbures présents dans les gaz d’échappement d’un moteur au démarrage à froid. Avec la collaboration de Phytronix Technologies, une nouvelle méthode expérimentale de thermodésorption a été développée qui permet des vitesses de montée en température similaires à celles du pot catalytique au démarrage à froid. À des vitesses de montée en température de l’ordre de 5-10°C/s, les pics de thermodésorption des hydrocarbures ont été translatés vers des températures plus élevées qui sont aux à l’entour de 240°C pour l’éthylène et de 245°C pour le toluène. Il a été conclu que la Ag-ZSM-12 a une meilleure capacité d’adsorption des hydrocarbures et une meilleure stabilité thermique. Une étude numérique a été développée pour étudier la diffusion du mélange binaire toluène-éthylène dans le réseau poreux zéolithique de la zéolithe ZSM-12. Les simulations numériques montrent qu’en tenant compte de l’effet de la température sur le coefficient de diffusion d’une seule molécule dans la loi d’Arrhénius a permis d’avoir des résultats comparables aux résultats expérimentaux, permettant d’expliquer plusieurs caractéristiques des profils de désorption obtenus expérimentalement. Deux étapes ont été envisagées; le saut d’une cage à une autre (ED) puis le saut de la cage frontalière à la phase gazeuse (EΓ). Ces deux étapes ont différentes énergies d’activation avec . Pour chaque gaz, les deux énergies d’activation dépendent fortement du rapport atomique Si/Al et du rayon du contre ion (Na⁺, H⁺ et Ag⁺). / As regulations for emissions from gasoline engines become stricter, attention has been focused on the start-up phase (cold-start), when about 70-80% of total hydrocarbon (HC) emissions of an engine are released. This phase is a short period of 1-2 min prior to reaching the minimum catalyst operating temperature, around 200°C. In this thesis, the concept of single-file diffusion (in 1-D zeolites) was employed as a feasible approach to control automotive HC emissions during cold-start. This mechanism was investigated over a variety of zeolites with MTW structures for studying their trapping ability for lighter HC molecules, which are often desorbed before the three-way catalyst reaches its light-off temperature. In this thesis, a serie of ZSM-12 zeolites which different conterions (Na⁺, H⁺, Ag⁺) and with different Si/Al molar ratios (52, 64, 80) were synthesized. Temperature-programmed desorption (TPD) of ethylene and toluene, as models of light and heavy hydrocarbon molecules, was employed to screen these synthesized zeolites as potential HC traps. High heating rate desorption experiments were performed using the Phytronix Laser Diode Thermal Desorption system (S-960 LDTD) after desorption of toluene-ethylene mixture. Three heating rates which reflect the actual heating rate of the catalytic muffler have been used for the desorption process: 3, 5 and 9°C/s. For all solids considered in this study, the two HCs desorbed above 240°C. Ag-ZSM-12 was found the most appropriate HCs trapping adsorbent. Numerically, using a transient diffusion boundary value problem coupled with Fick’s law, it was possible to explain all qualitative features of the temperature dependent desorption profiles observed experimentally. Two steps must be considered, a cage to cage jumping followed by an escape from cage to gas phase. The two steps have different activation energies with EΓ> ED. For each component, both activation energies are strongly dependent on Si/Al ratio and radius of counterions. Moreover the effect of thermal vibration of the host lattice on diffusivities was also depicted.

Made available in DSpace on 2014-12-17T14:02:01Z (GMT). No. of bitstreams: 1 SinaraCTSN_DISSERT.pdf: 2908664 bytes, checksum: ab5d0fd4fae3407675ed29d3bfa6ed5f (MD5) Previous issue date: 2010-05-21 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Untreated effluents that reach surface water affect the aquatic life and humans. This study aimed to evaluate the wastewater s toxicity (municipal, industrial and shrimp pond effluents) released in the Estuarine Complex of Jundia?- Potengi, Natal/RN, through chronic quantitative e qualitative toxicity tests using the test organism Mysidopsis Juniae, CRUSTACEA, MYSIDACEA (Silva, 1979). For this, a new methodology for viewing chronic effects on organisms of M. juniae was used (only renewal), based on another existing methodology to another testorganism very similar to M. Juniae, the M. Bahia (daily renewal).Toxicity tests 7 days duration were used for detecting effects on the survival and fecundity in M. juniae. Lethal Concentration 50% (LC50%) was determined by the Trimmed Spearman-Karber; Inhibition Concentration 50% (IC50%) in fecundity was determined by Linear Interpolation. ANOVA (One Way) tests (p = 0.05) were used to determinate the No Observed Effect Concentration (NOEC) and Low Observed Effect Concentration (LOEC). Effluents flows were measured and the toxic load of the effluents was estimated. Multivariate analysis - Principal Component Analysis (PCA) and Correspondence Analysis (CA) - identified the physic-chemical parameters better explain the patterns of toxicity found in survival and fecundity of M. juniae. We verified the feasibility of applying the only renewal system in chronic tests with M. Juniae. Most efluentes proved toxic on the survival and fecundity of M. Juniae, except for some shrimp pond effluents. The most toxic effluent was ETE Lagoa Aerada (LC50, 6.24%; IC50, 4.82%), ETE Quintas (LC50, 5.85%), Giselda Trigueiro Hospital (LC50, 2.05%), CLAN (LC50, 2.14%) and COTEMINAS (LC50, IC50 and 38.51%, 6.94%). The greatest toxic load was originated from ETE inefficient high flow effluents, textile effluents and CLAN. The organic load was related to the toxic effects of wastewater and hospital effluents in survival of M. Juniae, as well as heavy metals, total residual chlorine and phenols. In industrial effluents was found relationship between toxicity and organic load, phenols, oils and greases and benzene. The effects on fertility were related, in turn, with chlorine and heavy metals. Toxicity tests using other organisms of different trophic levels, as well as analysis of sediment toxicity are recommended to confirm the patterns found with M. Juniae. However, the results indicate the necessity for implementation and improvement of sewage treatment systems affluent to the Potengi s estuary / Efluentes sem tratamento pr?vio adequado, ao atingirem corpos d ?gua, afetam a biota aqu?tica e o ser humano. Este trabalho objetivou avaliar a toxicidade dos efluentes (sanit?rios, industriais e de despesca) que atingem o Complexo Estuarino do Jundia?/Potengi, Natal/RN, atrav?s de testes cr?nicos qualitativos e quantitativos utilizando o organismo-teste Mysidopsis juniae, CRUSTACEA, MISIDACEA (Silva, 1979). Para isso, uma nova metodologia para visualiza??o de efeitos cr?nicos em organismos de M. juniae foi usada (renova??o ?nica), baseada em outra metodologia existente para outro organismo-teste bastante similar ao M. juniae, o M. Bahia (renova??o di?ria). Testes de Toxicidade cr?nicos com dura??o de 7 dias foram aplicados para detectar efeitos dos efluentes na sobreviv?ncia e na fecundidade dos organismos testados. Para a determina??o da Concentra??o Letal (CL50), utilizou-se o m?todo Trimmed Spearman-Karber; para a determina??o da Concentra??o de Inibi??o (CI50) da fecundidade, utilizouse o m?todo de Interpola??o Linear. M?todos de An?lise de Vari?ncia ?nico Fator (p=0,05) foram usados para a determina??o da Concentra??o de Efeito N?o Observ?vel (CENO) e da Concentra??o de Efeito Observ?vel (CEO). As vaz?es de descarga dos efluentes foram medidas e estimou-se a carga t?xica dos efluentes. Foram realizadas an?lises multivariadas de ordena??o - An?lise de Componentes Principais (ACP) e An?lise de Correspond?ncia (AC) - para identificar quais os par?metros f?sico-qu?micos dos efluentes que melhor explicam os padr?es de toxicidade encontrados na sobreviv?ncia e na fecundidade de M. juniae. Com esse trabalho verificou-se a viabilidade da aplica??o do sistema de renova??o ?nica nos testes cr?nicos com M. juniae. A maioria dos efluentes se mostrou t?xicos quanto ? sobreviv?ncia e fecundidade de M. juniae, com exce??o de alguns efluentes de despesca, sendo os mais t?xicos o efluente da ETE Lagoa Aerada (CL50, 6,24% e CI50, 4,82%), ETE Quintas (CL50, 5,85%), Hospital Giselda Trigueiro (CL50, 2,05%), CLAN (CL50, 2,14%) e COTEMINAS (CL50, 38,51% e CI50, 6,94%). Nos efluentes de carcinicultura foi verificada maior toxicidade em efluentes coletados ao final do per?odo de despesca, o que denota que ela foi causada pela excessiva carga org?nica. Os efluentes sanit?rios de maior carga t?xica foram os efluentes originados das ETEs ineficientes de alta vaz?o, enquanto que os industriais de maior carga t?xica foram, em geral, os efluentes t?xteis e o da CLAN. A carga org?nica relacionou-se com os efeitos t?xicos dos efluentes sanit?rios e hospitalar na sobreviv?ncia de M. juniae, assim como metais pesados, cloro residual total e fen?is. Nos efluentes industriais verificou-se rela??o entre toxicidade e carga org?nica, fen?is, ?leos e graxas e benzeno. Os efeitos sobre a fecundidade relacionaram-se, por sua vez, com cloretos e metais pesados. Testes de toxicidade utilizando outros organismos, bem como an?lises da toxicidade do sedimento, s?o recomendados para confirmar os padr?es encontrados com o M. juniae. Os resultados dos testes indicam a necessidade de implementa??o e melhoria dos sistemas de tratamento de efluentes que s?o conduzidos ao estu?rio do Rio Potengi