Made available in DSpace on 2015-09-25T12:18:51Z (GMT). No. of bitstreams: 1 Marielle Ferreira de Oliveira.pdf: 1255416 bytes, checksum: 2938d36ef06506a40bbe2b05c9695f98 (MD5) Previous issue date: 2012-03-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The research aimed to treat sewage through combined anaerobic/aerobic system, using primary sludge and lysed excess sludge as an endogenous carbon source for removal of nutrients, aiming to produce effluent with low concentrations of organic material and nutrients and lower production excess sludge. The experiment was conducted in three phases. In the first, were performed respirometric tests as tool to assess the biodegradability of lysed biological sludge, through by techniques of cellular lysis induced: mechanical action, thermal and acid-base reaction. In the second phase, was monitored a Sequential Batch Reactor (SBR) together with Fermentation and Hydrolysis Reactor (FHR), which received excess sludge of SBR, tritured by mechanical action and primary sludge. SBR and FHR were operated with TRC of 3.36 and 10 days respectively. The third phase consisted of an anaerobic reactor followed by Immobilized Submerged with support Medium (polyurethane synthetic sponge) Aerated Reactor (ISMAR) operated in recirculation batch system. The results obtained from the respirometric tests found that the thermal sludge showed concentration biodegradable readily material greater than the tritured sludge and treated sludge by acid-base reaction. Values of the percentages of COD solubilized varied from 1.6% to 4.2%, with an average of 2.6%. The system presented promising results for the removal of nutrients, with removal efficiency of 85%, 93% and 98% for phosphorus soluble, nitrate and nitrite, respectively. However, the final effluent was maintained with concentration average of ammonia of 27 mgN-NH , considered out of the discharge standards. The combined system, anaerobic reactor and Immobilized Submerged with support Medium Aerobic Reactor (ISMAR), removed efficiently carbonaceous material (88%), TSS (86%), SSV (90%), TKN (94%) and N-NH4 - (96%). Producing effluent with average concentrations of nitrite and nitrate, respectively of 0.19 mgN-NO2-.L-1 and 2.52 mgN-NO3-.L. After addition of primary sludge the system, this presented a better performance with efficiency of COD removal gross and filtered 95%. However, the process of phosphorus removal was considered unsatisfactory since there was sludge disposal in the ISMAR reactor. Introducing an efficiency of removing just 20% for total phosphorus and 22% for the orthophosphate. / A pesquisa teve como objetivo principal tratar esgotos sanitários através de sistema combinado anaeróbio/aeróbio, utilizando lodo primário e lodo de excesso lisado como fonte endógena de carbono para remoção de nutrientes, buscando produzir efluente com baixas concentrações de material carbonáceo e de nutrientes e menor produção de lodo de excesso. O experimento foi realizado em três fases. Na primeira, foram realizados testes respirométricos como ferramenta para avaliar a biodegradabilidade de lodo biológico lisado, por meio de técnicas de lise celular induzida: ação mecânica, térmica e reação ácido-base. Na segunda fase, foi monitorado um Reator em Batelada Seqüencial (RBS) conjuntamente com Reator de Hidrólise e Fermentação (RHF), o qual recebia lodo de excesso do RBS, triturado por ação mecânica e lodo primário. O RBS e o RHF foram operados com TRC de 3,36 e 10 dias, respectivamente. A terceira fase foi constituída de reator anaeróbio seguido de reator aerado com meio suporte (esponja sintética de poliuretano) submerso imobilizado (RAMSI) operado em regime de bateladas com recirculação. Os resultados obtidos através dos testes respirométricos constataram que o lodo térmico apresentou concentração de material rapidamente biodegradável superior ao lodo triturado e ao lodo lisado por reação ácido-base. Os valores dos percentuais da DQO solubilizada variaram de 1,6% a 4,2%, com uma média de 2,6%. O sistema apresentou resultados promissores para a remoção de nutrientes, com eficiência de remoção de 85%, 93% e 98% para fósforo solúvel, nitrato e nitrito, respectivamente. Entretanto, o efluente final manteve-se com concentração média de nitrogênio amoniacal de 27 mgN-NH4.L-1, considerada fora dos padrões de lançamento. O sistema combinado, reator anaeróbio e reator aeróbio com meio suporte submerso imobilizado (RAMSI), removeram de forma eficiente material carbonáceo (88%), SST (86%), SSV (90%), NTK (94%) e N-NH4 -(96%). Produzindo efluente com concentrações médias de nitrito e nitrato, respectivamente de 0,19 mgN-NO e 2,52 mgN-NO3 -.L-1. Após a adição do lodo primário no sistema, este apresentou um melhor desempenho, com eficiência de remoção de DQO bruta e filtrada de 95%. No entanto, o processo de remoção de fósforo foi considerado insatisfatório, visto que não havia descarte de lodo no reator RAMSI. Apresentando uma eficiência de remoção de apenas 20% para o fósforo total e 22% para o ortofosfato.

O impacto da oxidação com ozônio na transformação de compostos orgânicos de elevada massa molar (HMW) para o aumento da biodegradabilidade dos efluentes da indústria de celulose e papel foi investigado sob diferentes doses de ozônio. Os experimentos foram realizados utilizando-se os efluentes primário e de extração alcalina de duas indústrias de celulose sob dois valores iniciais de pH (12 e 7). Utilizou-se um reator em escala de laboratório equipado com um difusor de bolhas finas para a aplicação do ozônio. Os resultados revelaram o potencial da aplicação de ozônio como uma etapa de tratamento anterior ao processo biológico convencional. Para o efluente primário, a aplicação de 0,70 mg\'O IND.3\'/mL efluente elevou a razão DBO5/DQO de 0,18 para 0,35 e foi alcançada uma remoção de cor na ordem de 87%. Para o efluente de extração alcalina da indústria Howe Sound, a razão DBO5/DQO foi elevada de 0,07 para 0,15 (pH inicial 12) e para 0,20 (pH inicial 7) e obteve-se uma remoção de cor por volta de 44% com a aplicação de 0,80 mg\'O IND.3\'/mL efluente. Para o efluente de extração alcalina da indústria Catalyst Paper, obteve-se uma remoção de cor por volta de 78% e a razão DBO5/DQO foi elevada de 0,07 para 0,16 após a aplicação de uma dose de ozônio de 0,80 mg\'O IND.3\'/mL efluente. Essas modificações foram alcançadas por uma redução nas frações de elevada massa molar durante a aplicação de ozônio. Para o efluente primário, observou-se uma elevada redução da faixa de maior massa molecular ( > 2kDa) após a aplicação de 0,72 mg\'O IND.3\'/mL efluente. Alcançaram-se 85% e 61% de remoção da faixa superior a 5 kDa para os efluentes de extração alcalina da indústria Howe Sound sob pH inicial 7 e 12, respectivamente, com a aplicação de cerca de 0,72 mg\'O IND.3\'/mL efluente. A faixa de maior massa molar ( > 10 kDa) dos efluentes de extração alcalina da indústria Catalyst Paper foi removida com a aplicação de aproximadamente 0,80 mg \'O IND.3\'/mL efluente. O papel do ozônio molecular disponível sob pH neutro parece ser de fundamental importância quando o objetivo é a redução dos compostos de elevada massa molecular. / The impact of ozone oxidation in transforming high molecular weight (HMW) organic compounds in order to improve the biodegradability of pulp and paper effluents was investigated under different ozone doses. The experiments were conducted uppon a primary treated effluent and an alkaline bleach plant effluent taken from two pulp mills. The effluents were investigated under different initial pH (7 and 12). Ozone was applied using a semi-batch reactor equipped with fine bubble diffuser. The results showed the potential for using ozone as a pre-treatment to the conventional biological process. Applying 0.70 mg\'O IND.3\'/mLww to the primary treated effluent enhanced the ratio of BOD5/COD was from 0.18 to 0.35 and decreased the colour by 87%. The ratio of BOD5/COD was increased from 0.07 to 0.15 (initial pH 12) and to 0.20 (initial pH 7) and colour was reduced by 44% after applying 0.80 mg\'O IND.3\'/mLww to the alkaline bleach effluent from Howe Sound\'s mill. A similar behavior was observed after 0.80 mg\'O IND.3\'/mLww was applied to the alkaline bleach effluent from Catalyst\'s mill. The ratio of BOD5/COD was increased from 0.07 to 0.16 and the effluent colour decreased by 78%. These changes were primarily driven by reductions of the HMW fractions of the effluent during ozonation. Organics with molecular range higher than 2 kDa were completely removed from the primary treated effluent. Aproximately 85% and 61% of the organics higher than 5 kDa were removed from the Howe Sound\'s alkaline bleach effluent under initial pH 7 and 12, respectively, after applying 0.72 mg\'O IND.3\'/mLww. Organic compounds with molecular weight higher than 10 kDa were completely removed from the Catalyst\'s alkaline bleach effluent after applying 0.80 mg\'O IND.3\'/mLww. Molecular ozone available under neutral conditions seems to play an important role when the removal of the high molecular weight organic compounds is the main objective.

Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-04-26T23:32:00Z No. of bitstreams: 1 Aline_Pauli_2018.pdf: 5534766 bytes, checksum: 389503e1e5a4307c462f405e73451ed5 (MD5) / Made available in DSpace on 2018-04-26T23:32:00Z (GMT). No. of bitstreams: 1 Aline_Pauli_2018.pdf: 5534766 bytes, checksum: 389503e1e5a4307c462f405e73451ed5 (MD5) Previous issue date: 2018-02-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work aims to remove efficiently organic and inorganic pollutants from a municipal sanitary landfill leachate effluent (SLLE) through of the integrated purification treatment application, composed by the electrocoagulation (ECP) and biological oxidation processes (BOP), looking for the drastic drop on the toxicity. In the first treatment phase, an ECP-based reactor was constructed consisting in a series of 6 aluminum electrode, providing an effective area of 350 cm2 and a useful volume of 1,0 L. In the framework of the response surface methodology (RSM), a 3³ complete factorial experimental design (CFED) at three levels of the three ECP important parameters: initial pH, electric current density (ECD) and electrolysis time (ET) was regarded. A set of responses related to the ECP treatment, such as, the reduction of color, turbidity, COD and iron concentration, was interpreted within the RSM. Additionally, the Analysis of Variance (ANOVA was applied to assess the quality of the second-order polynomial mathematical models that were adjusted to the CFED data. Keeping fixed the best ECP condition (pH and ECD) for the pollutant removals, a set of kinetic tests was carried out regarding a wide range of ET values. The toxicity of ECP treated samples was assessed by the application of bioassays based on the mortality level of the brine shrimp (Artemia salina) and the germination of Lactuca sativa seeds. The toxicity level was assessed by a statistical estimation of the median lethal concentration (LC50) through the application of bioassays with Artemia salina and Lactuca sativa. The biodegradability index by applying the Zahn Wellens test was also assessed. Keeping fixed the ECP condition for which was obtained the lowest toxicity and the highest biodegradability index, the second phase of treatment by BOP was performed. In this regard, a biological reactor with a useful volume of 3.5 L was adjusted to operate keeping fixed the condition of pH 7, temperature of 33 oC and dissolved oxygen of 50%. A relation food/microorganism of one was considered. After that, the residual ammonia in samples was completely removed applying the stripping method (air injection of 50 Lh-1). From the CFED data related to the first treatment phase, the best ECP condition was found by setting the pH at 5, ET at 120 min and ECD at 128.57 Am-2 for which was obtained the maximum removal of 99, 98, 68 e 99% for color, turbidity, COD and iron concentration, respectively. From the kinetic tests, it was possible to verify that the application of the ECP has actually reduced the SLLE toxicity being an ET of 5 min enough to achieve the minimum time required to obtain the lowest toxicity index (LC50 of 43%) that was found in both biotests. The highest biodegradability index was found when an ET value of 45 min. was regarded. The second POB treatment has showed a significant performance on removals of the organic parameters, with values of 95% and 89% for COD and DOC, respectively. Because of achieving an almost 100% removal of the ammoniacal nitrogen, the main result was the substantial improvement on the LC50 value about of 95%, as suggested by the A. salina biotest. Thus, although there were small amounts of pollutants after both treatments (PEC and POB), an almost total toxicity depletion. / Este trabalho, tem como objetivo remover eficientemente os poluentes orgânicos e inorgânicos de efluente de lixiviado proveniente de aterro sanitário municipal mediante a aplicação do tratamento de purificação integrado composto pelos Processos de Eletrocoagulação (PEC) e Oxidação Biológica (POB), visando especificamente a queda da toxicidade e o cumprimento da condição ambientalmente segura para o descarte final em corpos hídricos. Para o PEC, construiu-se um reator com 6 eletrodos de alumínio, tendo uma área efetiva de 350 cm2 e um volume efetivo de efluente de 1,0 L. No contexto da Metodologia de Superfícies de Resposta (MSR), foi proposto um planejamento experimental 3³, variando-se três parâmetros importante do PEC: pH inicial, Densidade de Corrente Elétrica (DCE) e Tempo de Eletrólise (TE). As respostas ao tratamento por PEC (cor, turbidez, DQO e concentração de ferro) foram interpretadas dentro da MSR, verificando pela Análise de variância (ANOVA) a qualidade da representatividade dos modelos matemáticos, polinomiais de segunda ordem, ajustados aos dados. Mantendo fixa a melhor condição de remoção de poluentes pelo PEC quanto ao pH e DCE, experimentos cinéticos foram realizados considerando um amplo intervalo de TE. O nível de toxicidade foi inferido a partir da estimativa estatística da concentração letal mediana (CL50) mediante a aplicação de biotestes utilizando o microcrustáceo Artemia salina e sementes de Lactuca sativa. Avaliou-se o índice de biodegradabilidade, segundo o teste de Zahn Wellens. Na menor toxicidade e o maior índice de biodegradabilidade do lixiviado tratado pelo PEC foi realizada a aplicação da segunda fase de tratamento por POB. Para tanto, foi ajustado o reator biológico, com volume útil de 3,5 L a operar, de forma controlada, na condição de pH 7, temperatura de 33 oC e oxigênio dissolvido de 50%. Utilizou-se uma relação alimento/microrganismo igual a um. Após a realização da integração dos processos, foi feita a remoção de amônia residual do efluente pelo método de arraste (injeção de ar a 50 Lh-1). Da análise do planejamento da primeira fase de tratamento, encontrou-se a melhor condição do PEC no valor de pH igual a 5; TE em 120 min e DCE em 128,57 Am-2 cujo efeito foi a obtenção da máxima remoção de 99, 98, 68 e 99% na cor, turbidez, DQO e concentração de ferro, respectivamente. A partir dos testes cinéticos, foi possível verificar que o PEC reduziu consideravelmente a toxicidade, sendo o TE de 5 minutos a condição de menor toxicidade (CL50 de 43%) que foi encontrada por ambos os biotestes. O índice de biodegradabilidade do efluente de lixiviado tratado teve um aumento de aproximadamente 20% em relação ao efluente bruto para todos os tempos de tratamento por PEC; porém, o maior índice de biodegradabilidade foi encontrado quando houve um TE de 45 minutos. O segundo tratamento por POB apresentou expressiva remoção dos parâmetros orgânicos, sendo obtidas remoções de 95% e 89% para a DQO e o COD, respectivamente. Após a aplicação do processo de arraste de amônia, uma remoção de quase 100% do nitrogênio amoniacal foi alcançada, obtendo uma a CL50 da ordem de 95%, como revelada pelo bioteste com A. salina. Portanto, embora houvesse quantidades pequenas de poluentes após ambos os tratamentos (PEC e POB), atingiu-se a quase total depleção da toxicidade.

O controle das águas residuárias nas indústrias e nos terminais de armazenagem de produtos químicos líquidos a granel é uma difícil tarefa, por conta da alta rotatividade e grande variedade de produtos químicos orgânicos armazenados e movimentados em suas atividades. Oito terminais e duas indústrias químicas localizadas no Porto de Santos foram avaliados por 10 anos. Foram realizadas mais de 2.500 análises químicas e ecotoxicológicas em 200 amostras de efluentes brutos e tratados. Nosso principal objetivo foi verificar se o teste de toxicidade aguda usando Vibrio fischeri poderia ser utilizado na gestão de águas residuais nas diferentes instalações dos terminais químicos e mostrar o seu papel como instrumento de prevenção a poluição, reduzindo a descarga de substâncias tóxicas persistentes nos ambientes aquáticos. Os índices de biodegradabilidade obtidos pela relação de Demanda Bioquímica de Oxigênio (DBO5) / Demanda Química de Oxigênio (DQO) dos efluentes brutos indicaram que 44% das amostras apresentaram matéria orgânica recalcitrante. Das 86 amostras do efluente final analisadas, 45 (52%) apresentaram resultados tóxicos para o teste com V. fischeri. Não houve correlação de DQO e ecotoxicidade, mostrando que efluentes com DQO baixa podem conter substâncias tóxicas com baixa capacidade de degradação. Foi possível recomendar a aplicação das melhores práticas operacionais, incluindo a segregação dos efluentes brutos ou um pré-tratamento com base nos resultados de ecotoxicidade e índice de biodegradabilidade. O reúso de água também foi abordado, indicando fontes e oportunidades de reutilização. Testes de ozonização também foram conduzidos nas águas pluviais dos terminais químicos e nos efluentes tratados das indústrias com resultados promissores. A integração da análise química e ecotoxicológica se mostraram uma excelente ferramenta para gestão de águas residuais nos terminais químicos, permitindo a tomada de decisão rápida para o controle da poluição e a adoção de medidas de prevenção / Wastewater control at industries and storage terminals of liquid chemical products in bulk is very difficult task due to the high turnover and great variety of organic chemicals handled and stored in their activities. Eight terminals and two chemical plants located in Santos Port, SP, Brazil had been evaluated for 10 years. More than 2,500 chemical and ecotoxicological analysis were performed in 200 samples of raw and treated effluents. Our main objective was to verify if the acute toxicity test using Vibrio fischeri could be used in the wastewater management of those facilities and show its role as a tool for pollution prevention by reducing the discharge of persistent toxic substances in estuarine systems. The indexes of biodegradability obtained by the ratio of Biochemical Oxygen Demand (BOD5) / Chemical Oxygen Demand (COD) of raw effluents indicated that 44% of the samples presented recalcitrant organic matter. Out of 86 final effluent samples analyzed, 45 (52%) presented toxic result for V. fischeri test. No correlation was observed of COD and ecotoxicity, showing that with low COD effluent may contain toxic substances with low degradation capacity. It was possible to recommend the use of best operational practices including segregation of influents or a pre-treatment based on toxicity results and index biodegradability. Water reuse was also discussed indicating sources and opportunities for reuse in these facilities. Ozonisation tests were also conducted on the rain waters collected at the terminals facilities and on the treated effluents of the industries, showing promising results. The integration of chemical and ecotoxicity analysis turned out to be an excellent tool for wastewater management in chemical terminals, allowing rapid decision making for pollution control and prevention measures

A proposta desta pesquisa foi avaliar a aplicação do processo oxidativo avançado (POA), peróxido de hidrogênio (\'H IND.2\'O IND.2\') e radiação ultravioleta (UV), como pós-tratamento de um reator anaeróbio utilizado para tratar efluentes de branqueamento de indústrias de celulose kraft. O principal objetivo do pós-tratamento químico foi aumentar a biodegradabilidade e a remoção de compostos recalcitrantes nos efluentes. O tratamento biológico foi realizado por meio de reator anaeróbio horizontal de leito fixo (RAHLF), em escala de bancada, seguido pelo tratamento \'H IND.2\'O IND.2\'/UV dos efluentes. As doses do agente oxidante variaram de 50 a 500 mg \'H IND.2\'O IND.2\'/L e as aplicações de energia pela lâmpada de radiação ultravioleta foram variadas, principalmente, de 3,8 a 15,0 kWh por \'M POT.3\' de efluente tratado. Desta forma, amostras de efluentes foram coletadas de duas indústrias brasileiras de celulose kraft branqueada, originando respectivamente duas fases experimentais. Na primeira fase, o RAHLF apresentou boa estabilidade de operação, obtendo adequadas eficiências de remoção de DQO (61 ± 3%), COT (69 ± 9%), \'DBO IND.5\' (90 ± 5%) e AOX (55 ± 14%). Todavia, não ocorreu boa remoção dos compostos de absorbância na \'UV IND.254\'. Além disso, houve aumento de constituintes da lignina do afluente para o efluente do RAHLF. Por sua vez, o pós-tratamento com \'H IND.2\'O IND.2\'/UV no efluente anaeróbio proporcionou eficiência de remoção variada nos parâmetros DQO (0 a 11%), \'UV IND.254\' (16 a 35%), lignina (0 a 29%) e AOX (23 a 54%). Em relação a melhoria da biodegradabilidade, todas as dosagens de \'H IND.2\'O IND.2\' estudadas promoveram aumento na relação \'DBO IND.5\'/DQO. Para uma relação \'DBO IND.5\'/DQO média inicial igual a 0,09, correspondente ao efluente do RAHLF, o maior aumento obtido foi de 131% aplicando 500 mg \'H IND.2\'O IND.2\'/L e 7,5 kWh/\'M POT.3\'. O tratamento conjugado biológico e químico foi necessário para atingir ao padrão europeu de emissão de AOX (< 0,4 kg AOX por tonelada de polpa de celulose seca produzida). Na segunda fase, o RAHLF apresentou alguns problemas operacionais, tais como entupimento nas conexões e quebras do reator de vidro, pelo possível aumento da carga orgânica volumétrica aplicada presente nos efluentes coletados na segunda indústria de celulose. O pós-tratamento com \'H IND.2\'O IND.2\'/UV mostrou menor desempenho nessa fase experimental, o que pode ser explicado também pelo maior teor de matéria orgânica residual, lignina, alcalinidade e íons cloretos ainda remanescentes nos efluentes tratados biologicamente. Visando complementar os estudos, testes em reatores aeróbios nos efluentes do RAHLF, tratados e não tratados pelos processos \'H IND.2\'O IND.2\'/UV, foram avaliados. Os resultados demonstraram que os melhores resultados (menor tempo de aeração necessário para atingir a mesma concentração dos parâmetros avaliados) foram alcançados pelos reatores que receberam efluentes previamente tratados pelo POA. Uma avaliação simplificada do custo operacional associado com a aplicação do tratamento \'H IND.2\'O IND.2\'/UV, em escala plena, indicou um custo de R$ 1,87 por \'M POT.3\' de efluente tratado. / The purpose of this research was to assess the application of the advanced oxidation processes (AOP), hydrogen peroxide (\'H IND.2\'O IND.2\') and ultraviolet radiation (UV), as post-treatment for an anaerobic reactor used to treat bleaching effluents from kraft pulp mills. The main objective of the chemical post-treatment was to increase the biodegradability and remove recalcitrant compounds from the wastewater. The biological treatment was performed in a fixed bed anaerobic horizontal reactor (FBAHR), in bench scale, followed by \'H IND.2\'O IND.2\'/UV treatment of the effluents. The oxidizer dosage varied from 50 to 500 mg \'H IND.2\'O IND.2\'/L while the energy applied by the UV lamp ranged, mainly, from 3.8 to 15.0 kWh per \'M POT.3\' of treated effluent. This way, wastewater samples were collected from two brazilian bleached kraft pulp mills thus the results were reported as two different experimental phases. In the first phase the FBAHR showed good operational stability and reached the expected removal efficiencies for COD (61 ± 3%), TOC (69 ± 9%), \'BOD IND.5\' (90 ± 5%) and AOX (55 ± 14%). However, the anaerobic treatment did not provide good removal of compounds indicated by \'UV IND.254\' absorbency. Furthermore, there was an increase of lignin from the affluent to effluent of the FBAHR. In its turn the \'H IND.2\'O IND.2\'/UV post-treatment provided a wide range of removal depending upon the dosage: COD (0 to 11%), \'UV IND.254\' (16 to 35%), lignin (0 to 29%) and AOX (23 to 54%). Regarding to the improvement in biodegradability, all dosages of \'H IND.2\'O IND.2\' applied in this work promoted an increase in the \'BOD IND.5\'/COD ratio. For an average initial \'BOD IND.5\'/COD ratio equal to 0.09, which corresponds to the FBAHR effluent, the greatest increase was 131% with 500 mg \'H IND.2\'O IND.2\'/L and 7.5 kWh/\'M POT.3\'. It was necessary to couple the anaerobic and the oxidative treatment to reach the current European allowable AOX emission load (< 0.4 kg AOX per ton of produced dried cellulose pulp). During the second phase of the experiments, the FBAHR had operational problems as plugging of the tubes and cracking of the reactor wall that may be partially attributed to the higher organic load applied, as the effluents from the second mill were stronger. The AOP post-treatment also had lower performance during this experimental phase, which may be explained by the higher concentration of the organic matter, lignin, alkalinity and chloride ions, still present in the biologically treated effluents. To complete the experiments samples from effluents of the FBAHR and AOP process were submitted to aerobic assays. By tests done in aerobic reactors in the FBAHR effluents, treated and non-treated by the processes \'H IND.2\'O IND.2\'/UV, it was verified that the best results, shorter aeration time requirement to reach the same concentration of the evaluated parameters, were obtained from reactors that received previously treated by AOP effluents. A simplified evaluation of the operational cost associated with the use of the tested AOP, in full scale, indicated a cost of R$ 1.87 per \'M POT.3\' of treated effluent.

Le secteur de la méthanisation à la ferme ou territoriale connait un fort développement, entrainant la production de grandes quantités de digestats. Si la fraction solide de ces digestats est généralement utilisée en tant qu’amendement organique, la fraction liquide peut être valorisée par la récupération des éléments minéraux bien que la présence de composés organiques pose des problèmes de traitement et d’élimination. Les objectifs de cette thèse sont i) de caractériser la fraction liquide des digestats et donner des premiers éléments pour leur futur traitement et ii) d’expliquer la variabilité des composés résiduels présents dans cette fraction liquide en relation avec l’origine des substrats, les paramètres du procédé de méthanisation et le type de séparation solide/liquide. Dans une première partie, nous avons caractérisé de manière détaillée onze digestats issus d’installations industrielles de co-digestion. Le fractionnement par neuf filtrations successives de la fraction liquide des digestats a permis de quantifier la contribution des matières en suspension, des colloïdes grossiers et fins et des matières dissoutes aux différents paramètres physico-chimiques et biologiques. Il a été montré la faible biodégradabilité aérobie des composés organiques dont la majeure partie se trouve dans la matière en suspension (> 1,2 µm). Pour élargir la base de données, nous avons caractérisé dix-huit digestats supplémentaires et un digestat de boues de station d’épuration dont les fractions liquides ont été fractionnées par deux filtrations successives (1,2 μm et 1 kDa). L’analyse en composantes principales, la classification hiérarchique et la matrice de corrélation réalisées sur l’ensemble des 30 digestats ont mis en avant l’impact majeur des techniques de séparation solide/liquide sur la composition de la fraction liquide des digestats. Dans le groupe des techniques de séparation hautement performantes, des sous-groupes ont permis de distinguer les digestats à base de boues d’épuration, ceux à base de lisiers porcins et ceux issus de procédés piston thermophiles. Dans le groupe des procédés de séparation à faible performance, les teneurs en DCO et matières sèches de la fraction liquide des digestats ont été corrélées aux teneurs en cultures énergétiques et fumiers bovins dans l’alimentation. Finalement, pour l’ensemble des digestats, le paramètre SUVA, lié à la teneur en matière aromatique et à la stabilisation des composés, a été corrélé au temps de séjour des digesteurs. Pour comprendre l’origine des composés résiduels observés dans la fraction liquide des digestats issus de la co-digestion avec de fortes proportions de fumier bovin, quatre réacteurs CSTR alimentés avec respectivement de la paille de blé, de la bouse de vache et du fumier ont été conduits pendant 48 semaines. Les performances de méthanisation ont mis en évidence le caractère âgé du fumier qui avait été partiellement dégradé pendant le stockage à la ferme. Ainsi la fraction liquide du digestat du fumier a présenté les plus fortes concentrations en composés organiques qui en outre présentaient une complexité, mesurée par fluorimétrie 3D, plus élevée que les autres substrats. La fraction liquide du digestat issue de la méthanisation de la paille a révélé les plus fortes proportions de DCO dans les fractions colloïdales et dissoutes. La faible biodégradabilité des composés organiques et leur forte proportion dans les matières en suspension suggèrent le développement de procédés physico-chimiques de séparation tels que la coagulation pour le traitement de la fraction liquide des digestats. / Agricultural and centralized biogas plants are facing a fast development, leading to the production of huge amounts of digestates. Whereas the solid fraction of digestates is used as fertilizer, the liquid fraction can be valorized by the recovery of mineral materials, although the presence of organic compounds may be problematic for the treatment and disposal of this effluent. The objectives of this thesis are: i) to characterize the liquid fraction of digestates and to provide guidelines for its further treatment, ii) to explain the variability of residual compounds in the liquid fraction of digestates in relation with substrate origin, process parameters and the type of solid-liquid separation. In a first part, eleven digestates from full scale codigestion plants were thoroughly characterized. Their liquid fractions were fractionated by nine successive filtrations, which allowed quantifying the contribution of suspended particles, coarse and fine colloids and dissolved matter on several physico-chemical and biological parameters. Organic compounds were mainly found in suspended particles (> 1.2 µm) and presented low aerobic biodegradability. To enlarge the data base, eighteen more digestates from codigestion and one digestate from waste activated sludge were characterized; their liquid fractions were fractionated by two successive filtrations (1.2 μm and 1 kDa). Principal component analysis, hierarchical clustering analysis and correlation matrix carried out on the 30 digestates set, highlighted the major impact of the solid-liquid separation process on the composition of the liquid fraction of digestates. In the high performance separation process group, subgroups allowed separating digestates from sewage sludge, digestates from pig manure and digestates from plug-flow thermophilic processes. In the low performance separation process group, COD and total solids concentration in the liquid fraction of digestates were correlated to the percentage of energy crops and cow manure in the feed. Finally, SUVA parameter which accounts for aromatic compounds content and the stabilization of organic matter, was correlated to the retention time in digester for the whole digestates set. To understand the origin of residual compounds in the liquid fraction of digestates from co-digestion of high proportions of cattle manure, four CSTR reactors fed with wheat straw, cow dung and cow manure were operated for 48 weeks. Anaerobic digestion performances showed that cow manure had undergone some aerobic degradation during its storage at the farm. Therefore, the liquid fraction of manure digestate had the highest concentrations in organic compounds. In addition, these organic compounds had the highest complexity measured by 3D fluorimetry. The low biodegradability of organic compounds and their high percentage in suspended particles suggest the development of physico-chemical separation process such as coagulation for the treatment of the liquid fraction of digestates

La co-digestion anaérobie (CoDA) des substrats agro-industriels s’inscrit pleinement dans les objectifs sociétaux d’une gestion optimisée des agroressources, d’une réduction des impacts anthropogéniques, ainsi que d’un développement des énergies renouvelables. Toutefois, en considérant les verrous industriels et scientifiques, il est apparu que la problématique méthodologique, relative à l’étude et à l’optimisation, était primordiale dans l’amélioration des performances méthanogènes en CoDA. En cela, il s’est avéré que le principal actionneur pour l’optimisation de la CoDA soit la formulation du mélange en substrats et co-substrats constituant l’intrant du digesteur. Ainsi, les travaux de thèse étaient inscrits dans un double objectif, industriel et scientifique, dont les résultats ont permis de (i) mettre en œuvre des méthodes simples, peu chronophages et surtout peu coûteuses, pour la caractérisation des intrants et le suivi de la CoDA, (ii) déterminer la relation fondamentale entre la formulation du mélange de substrats et son potentiel biométhanogène, (iii) développer des outils de prédiction du potentiel biométhanogène des mélanges de substrats, ainsi que des biodégradabilités globales et spécifiques de ces derniers, (iv) améliorer la compréhension des interactions entre les substrats codigérés et le consortium microbien de digestion, ainsi que la capacité de ce dernier à s’adapter aux diverses charges organiques qui lui sont appliquées (capacité homéostasique). / The co-digestion of agro-industrial substrates in anaerobic conditions falls within the objectives of an optimized management of agricultural resources along with reduction of anthropogenic impacts and development of renewable energies. Considering scientific and industrial bottlenecks from literature review, it could be identified that a methodological approach was the key to an enhanced understanding of anaerobic co-digestion. Ultimately, formulation of the substrate and co-substrates (digestor’s inputs) appeared to be the main actuator to optimize anaerobic co-digestion. Conciliating both scientific and industrial issues, this thesis led to the following findings : (i) an implementation of simple and cost-saving methods to characterize the inputs of digestor and biogas production, (ii) a determination of fundamental relationship between substrate blend and his biomethane potential, (iii) a development of predictive tools for biomethane potential of substrate blends as well as global and specific biodegradability of substrates, (iv) an enhanced comprehension of first, interactions between codigested substrates and the microbial consortium and second, the adaptation capacity of the microbial consortium to various organic loading (homeostatic capacity).

This work deals with a current topic, which are biodegradable bone implants. These implants seem to be a suitable candidate for temporary fixations, with their gradual decomposition. An important parameter is not only the mechanical properties so that the material can withstand the load, but above all the corrosion properties and the degradation process. This work introduces the physiology of bone, trace elements and also describes current trends in the field of implants. The last part is a theoretical introduction to cross-stage processes. The practical part is focused on the preparation of iron-based samples with various dopants, subsequent annealing and analysis.

Synthetic polymer materials have been a part of human life since the 20th century. A variety of their use had resulted in a growing demand for their mass production, which then led to their increasing accumulation at waste dumps. After their deposition, these materials are exposed to many environmental factors causing their decomposition and subsequent release of the degradation products into the environment. This thesis is focused on the analysis of the photodegradation products from synthetic polymer materials and particularly polyurethane foams modified with the biodegradable fillers. One dimensional GC/MS and two dimensional comprehensive gas chromatography with time-of-flight mass spectrometry (GCxGC/TOF-MS ) were used for the measurements. The most of photodegradation products of polyurethane foams are injurious to health and environment.

Nowadays, exceptional advantages of silk fibroin over synthetic and natural polymers have impelled the scientists to application of this biomaterial for tissue engineering purposes. Recently, we showed that embedding natural degummed silk fibers in regenerated Bombyx mori silk-based scaffold significantly increases the mechanical stiffness, while the porosity of the scaffolds remains the same. In the present study, we evaluated degradation rate, biocompatibility and regenerative properties of the regenerated 2% and 4% wt silk-based composite scaffolds with or without embedded natural degummed silk fibers within 90 days in both athymic nude and wild-type C57BL/6 mice through subcutaneous implantation. In all scaffolds, a suitable interconnected porous structure for cell penetration was seen under scanning electron microscopy. Compressive tests revealed a functional relationship between fiber reinforcement and compressive modulus. In addition, the fiber/fibroin composite scaffolds support cell attachment and proliferation. On days 30 to 90 after subcutaneous implantation, the retrieved tissues were examined via gross morphology, histopathology, immunofluorescence staining and reverse transcription-polymerase chain reaction as shown in Figure 1. Results showed that embedding the silk fibers within the matrix enhances the biodegradability of the matrix resulting in replacement of the composite scaffolds with the fresh connective tissue. Fortification of the composites with degummed fibers not only regulates the degradation profile but also increases the mechanical performance of the scaffolds. This report also confirmed that pore size and structure play an important role in the degradation rate. In conclusion, the findings of the present study narrate key role of additional surface area in improving in vitro and in vivo biological properties of the scaffolds and suggest the potential ability of these fabricated composite scaffolds for connective tissue regeneration.