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.

[ES] En los últimos años, se ha incrementado la sensibilidad en torno a las cuestiones ambientales derivadas del uso de los materiales poliméricos basados en el petróleo y el impacto de éstos en el medio ambiente. La concienciación social y ambiental adquirida por parte de los consumidores hace que industrias tradicionales, como la del juguete, donde el uso del plástico está ampliamente extendido, desee adaptarse voluntariamente a la demanda del mercado y las empresas quieran desarrollar nuevas líneas de producto empleando materiales más ecológicos y sostenibles. El principal objetivo de esta tesis doctoral es el desarrollo y caracterización de biocomposites (biocompuestos) obtenidos a partir de una matriz polimérica procedente de fuentes renovables y biodegradable, concretamente almidón termoplástico (TPS), y como relleno, cáscara de almendra en polvo (ASP), aptos para ser procesados por inyección cuyas propiedades mecánicas, térmicas y estéticas permitan su uso en el sector del juguete. En un primer bloque, esta investigación estudia la influencia de la variedad de cáscara de almendra en las propiedades finales del biocomposite TPS/ASP desarrollado. Para ello, se seleccionan cinco variedades de almendra: Desmayo Rojo, Largueta, Marcona, Mollar y una mezcla comercial de variedades desconocidas, ya suministrada en formato polvo. También se estudia la influencia del tamaño de partícula de dicha carga (menor a 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm y 0.125<p<0.250 mm) considerando una cantidad fija de ASP (30 % en peso). Finalmente, se analiza el efecto del contenido de ASP (5-30 % en peso). Para ello, los diferentes biocomposites son fabricados mediante técnicas convencionales de extrusión e inyección. Se emplea una metodología basada en diferentes técnicas experimentales para la determinación de las propiedades mecánicas (ensayos de tracción, flexión, impacto Charpy y dureza Shore D), propiedades térmicas (análisis calorimétrico (DSC) y termogravimétrico (TGA)), medidas colorimétricas (CIELab) y análisis morfológico (SEM). En general, de este primer bloque se concluye que, la adición de ASP al TPS aumenta la rigidez del material y disminuye su deformación a rotura, la resistencia al impacto y la resistencia térmica con respecto a la matriz polimérica TPS. La incorporación de ASP proporciona un acabado similar a la madera. Una vez seleccionada la variedad, el tamaño de partícula y el contenido de ASP más adecuado, se considera mejorar la interacción carga/matriz con objeto de incrementar las propiedades mecánicas que se han visto afectadas por la adición de la carga. Los métodos de compatibilización que se han llevado a cabo para ello han sido mediante la incorporación de sustancias de origen renovable. En concreto, los compatibilizantes de origen renovable empleados en esta tesis doctoral son tres aceites vegetales epoxidados (EVOs): el aceite de linaza epoxidado (ELO), el aceite de soja epoxidado (ESBO) y el aceite de maíz epoxidado (ECO). Los diferentes EVOs se han incorporado entre 5-20 phr. La caracterización de las propiedades de los bicomposites desarrollados se realiza de forma análoga a los obtenidos en el primer bloque. Los resultados obtenidos muestran una notable mejora de las propiedades mecánicas con el empleo de estos compatibilizantes derivados de aceites vegetales. Además, la adición de estas sustancias tiene un efecto estabilizante en la desintegración del material. Finalmente, se estudia si es posible reprocesar el TPS y el biocomposite TPS/ASP y cómo afecta el reprocesado de estos biomateriales a sus propiedades finales (estéticas, mecánicas y térmicas). A pesar de la progresiva degradación del material, en ambos casos, es técnicamente factible volver a procesar el material al menos tres veces sin necesidad de incorporar material virgen. / [CA] En els últims anys, s'ha incrementat la sensibilitat entorn a les qüestions ambientals derivades de l'ús dels materials polimèrics basats en el petroli i l'impacte d'aquests en el medi ambient. La conscienciació social i ambiental adquirida per part dels consumidors fa que indústries tradicionals, com la del joguet, on l'ús del plàstic està àmpliament estés, desitge adaptar-se voluntàriament a la demanda del mercat i les empreses vullguen desenvolupar noves línies de producte emprant materials més ecològics i sostenibles. El principal objectiu d'aquesta tesi doctoral és el desenvolupament i caracterització de biocomposites obtinguts a partir d'una matriu polimèrica procedent de fonts renovables i biodegradable, concretament almidó termoplàstic (TPS), i com a càrrega, pols de corfa d'ametla (ASP), aptes per a ser processats per injecció, les propietats mecàniques, tèrmiques i estètiques de les quals, permeten el seu ús en el sector del joguet. En un primer bloc, aquesta investigació estudia la influència de la varietat de corfa d'ametla, en les propietats finals del biocomposite de TPS/ASP desenvolupat. Per a això, se seleccionen cinc varietats d'ametla: Desmai Roig, Largueta, Marcona, Mollar i una mescla comercial de varietats desconegudes, ja subministrada en format de pols. També s'estudia la influència del tamany de partícula (menor a 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm i 0.125<p<0.250 mm) considerant una quantitat fixa d'ASP (30 % en pes). Finalment, s'analitza l'efecte del contingut d'ASP (5-30 % en pes). Per a això, els diferents biocomposites són fabricats mitjançant tècniques convencionals d'extrusió i injecció. S'empra una metodologia basada en diferents tècniques experimentals per a la determinació de les propietats mecàniques (assajos de tracció, flexió, impacte Charpy, duresa Shore D), propietats tèrmiques (anàlisis calorimètric (DSC) i termogravimètric (TGA), mesures colorimètriques (CIELab) i anàlisi morfològic (SEM). D'aquest primer bloc es conclou que, l'addició d'ASP al TPS augmenta la rigidesa del material, disminuïx la seua deformació a ruptura, la resistència a l'impacte i la resistència tèrmica respecte a la matriu polimèrica TPS. La incorporació d'ASP, proporciona un acabat similar a la fusta. Una vegada seleccionada, la varietat, el tamany de partícula i el contingut d'ASP més adequat, es considera millorar la interacció càrrega/matriu a fi d'incrementar les propietats mecàniques que s'han vist afectades per l'addició de la càrrega. Les tècniques de compatibilització que s'han dut a terme en aquest treball ha sigut mitjançant la incorporació de substàncies d'origen renovable. En concret, els compatibilitzants d'origen renovable utilitzats en aquesta tesi doctoral són tres olis vegetals epoxidats (EVOs): l'oli de llinosa epoxidat (ELO), l'oli de soja epoxidat (ESBO) i l'oli de panís epoxidat (ECO). Els diferents EVOs s'han incorporat entre 5-20 phr. La caracterització de les propietats dels bicomposites desenvolupats es realitza de forma anàloga als obtinguts en el primer bloc. Els resultats obtinguts mostren una notable millora de les propietats mecàniques amb l'ús d'estos compatibilitzants derivats d'olis vegetals. A més, l'addició de EVOs té un efecte estabilitzant en la desintegració del material. Finalment, si és possible reprocessar el TPS i el biocomposite TPS/ASP i com afecta el reprocessat d'estos biomaterials a les seues propietats finals (estètiques, mecàniques i tèrmiques). Malgrat la progressiva degradació del material, en ambdós casos, és tècnicament factible tornar a processar el material almenys tres vegades sense necessitat d'incorporar material verge. / [EN] In recent years, there has been a growing awareness of the environmental issues arising from the use of petroleum-based polymeric materials and their impact on the environment. The social and environmental awareness consumers now have makes traditional industries, such as the toy industry, where the use of plastic is widespread, want to voluntarily adapt to market demand and develop new product lines using more ecological and sustainable materials. The main objective of this doctoral thesis is the development and characterisation of biocomposites developed from a polymeric matrix of renewable and biodegradable sources, specifically thermoplastic starch (TPS), and as a filler, almond shell powder (ASP), suitable for processing by injection moulding whose thermal-mechanical and aesthetic properties allow their use in the toy sector. In the first block, the influence of the variety of almond shells on the final properties of the polymeric matrix is studied. For this purpose, five varieties are selected: Desmayo Rojo, Largueta, Marcona, Mollar, and a commercial mixture of unknown varieties, already supplied in powder form. The influence of particle size (smaller than 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm and 0.125<p<0.250 mm) is also studied considering a fixed amount of ASP (30 %). Finally, the effect of ASP content (5-30 %) is analysed. For this purpose, the different biocomposites are manufactured by conventional extrusion and injection techniques. A methodology based on different experimental techniques is used to determine the mechanical properties (tensile, flexural, Charpy impact, Shore D hardness), thermal properties (calorimetric analysis (DSC), and thermogravimetric analysis (TGA), colorimetric measurements (CIELab), and morphological analysis (SEM). In general, it is concluded from this first block that the addition of ASP to the TPS increases the stiffness of the material, but then decreases its deformation at break, impact resistance and thermal resistance in respect to the TPS polymeric matrix. The addition of ASP provides a wood-like finish. Once the most suitable variety, particle size, and ASP content have been selected, consideration is given to improving the particle/matrix interaction. The compatibilisation techniques carried out in this work have been through the incorporation of substances of renewable origin. The compatibilisers of renewable origin used in this doctoral thesis are three epoxidised vegetable oils (EVOs): epoxidised linseed oil (ELO), epoxidised soybean oil (ESBO) and epoxidised corn oil (ECO). The different EVOs have been incorporated between 5-20 phr. The results obtained show a remarkable improvement of the mechanical properties with the use of vegetable oil-derived compatibilisers. Moreover, the addition of EVOs has a stabilising effect on the disintegration of the material. Finally, it is studied how the reprocessing of TPS and TPS/ASP biocomposite affects their final characteristics. Despite the progressive degradation of the material, in both cases, it is technically feasible to reprocess the material at least three times without the need to incorporate virgin material. / Ibáñez García, A. (2021). Desarrollo y caracterización de biocomposites con cáscara de almendra para el sector juguetero [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/172341 / TESIS

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.

Tesis por compendio / [ES] El sistema musculoesquelético tiene una capacidad de regeneración limitada. Las pérdidas importantes de tejido no se pueden regenerar, lo que provoca necrosis y deterioro funcional. Los tratamientos tradicionales basados en implantes o trasplantes no han demostrado ser del todo exitosos, con múltiples efectos secundarios como inmunogenicidad o rechazos. Por ello, es muy importante desarrollar nuevas alternativas para tratar la degeneración muscular. La ingeniería tisular combina biomateriales, células y agentes bioactivos para desarrollar constructos biológicos biocompatibles donde las células encuentran un entorno que imita sus condiciones in vivo para crecer, proliferar y diferenciarse en tejido muscular y restaurar su funcionalidad. Los biomateriales conductores son de particular interés en tejidos electro-sensibles como es el caso del sistema musculoesquelético. Se ha demostrado que los polímeros conductores (polipirrol, polianilina, etc.), los materiales de carbono (grafeno, óxido de grafeno reducido, etc.) y los nanomateriales metálicos mejoran la diferenciación muscular, incluso sin estimulación eléctrica externa. Además, diferentes moléculas bioactivas como factores de crecimiento (FGF-2, IGF-1, etc.) o iones inorgánicos "terapéuticos" (zinc, magnesio, etc.) son alternativas para potenciar la diferenciación celular en diferentes tejidos. Por lo tanto, la combinación de biomateriales conductores y moléculas bioactivas para mejorar la regeneración muscular representa una gran oportunidad en la ingeniería de tejidos musculares. El objetivo de este proyecto de tesis es desarrollar y caracterizar nuevos biomateriales electroactivos con diferentes composiciones, estructuras y propiedades y evaluar su potencial para tratar la regeneración musculoesquelética, así como la combinación de estos biomateriales electroactivos con iones inorgánicos buscando descubrir nuevas sinergias biomateriales conductores-iones terapéuticos en términos de diferenciación muscular. ¿ / [CA] El sistema musculoesquelètic té una capacitat de regeneració limitada. Les pèrdues importants de teixit no es poden regenerar, cosa que provoca necrosi i deteriorament de la funcionalitat. Els tractaments tradicionals basats en implants o trasplantaments no han demostrat ser del tot exitosos, amb múltiples efectes secundaris com ara immunogenicitat o rebutjos. Per això, és molt important desenvolupar noves alternatives per tractar la degeneració muscular. L'enginyeria tissular combina biomaterials, cèl·lules i agents bioactius per desenvolupar constructes biològics biocompatibles on les cèl·lules troben un entorn que imita les seves condicions in vivo per créixer, proliferar i diferenciar-se en teixit muscular i restaurar-ne la funcionalitat. Els biomaterials conductors són de particular interès en teixits electrosensibles com és el cas del sistema musculoesquelètic. S'ha demostrat que els polímers conductors (polipirrol, polianilina, etc.), els materials de carboni (grafè, òxid de grafè reduït, etc.) i els nanomaterials metàl·lics milloren la diferenciació muscular, fins i tot sense estimulació elèctrica externa. A més, diferents molècules bioactives com a factors de creixement (FGF-2, IGF-1, etc.) o ions inorgànics "terapèutics" (zinc, magnesi, etc.) són alternatives per potenciar la diferenciació cel·lular en diferents teixits. Per tant, la combinació de biomaterials conductors i molècules bioactives per millorar la regeneració muscular representa una gran oportunitat a l'enginyeria de teixits musculars. L'objectiu d'aquest projecte de tesi és desenvolupar i caracteritzar nous biomaterials electroactius amb diferents composicions, estructures i propietats i avaluar-ne el potencial per tractar la regeneració musculoesquelètica, així com la combinació d'aquests biomaterials electroactius amb ions inorgànics buscant descobrir noves sinergies biomaterials conductors-ions terapèutics en termes de diferenciació muscular. / [EN] The musculoskeletal system can self-regenerate in a limited way. Major tissue losses cannot be regenerated, resulting in necrosis and functional impairment. Traditional treatments based on implants or transplants have not proven to be completely successful, with multiple side effects such as immunogenicity or rejections. Therefore, it is very important to develop new alternatives to treat muscle degeneration. Tissue engineering combines biomaterials, cells and bioactive agents to develop biological and biocompatible constructs where cells find an in vivo likely environment to grow, proliferate and differentiate into muscle tissue and restore its functionality. Conductive biomaterials are of particular interest in electrosensitive tissues such as the musculoskeletal system. Conductive polymers (polypyrrole, polyaniline, etc.), carbon materials (graphene, reduced graphene oxide, etc.) and metal nanomaterials have proved to enhance cell differentiation, even without external electrical stimulation. Moreover, different bioactive molecules such as growth factors (FGF-2, IGF-1, etc.) or inorganic "therapeutic" ions (zinc, magnesium, etc.) are alternatives to enhance cell differentiation into different tissues. Therefore, the combination of conductive biomaterials and bioactive molecules to enhance muscle regeneration represents an exciting opportunity in muscle tissue engineering. This thesis project aims to develop and characterize novel electroactive biomaterials with different compositions, structures and properties and evaluate their potential to treat musculoskeletal regeneration, as well as its combination with inorganic ions looking forward to discovering new conductive biomaterial-therapeutic ions synergies in terms of muscle differentiation. / Gracias a la financiación del Ministerio de Ciencia e Innovación, a la Agencia Estatal de Investigación y a los fondos FEDER por la financiación del proyecto RTI2018- 097862-B-C21 que ha permitido llevar a cabo esta tesis doctoral. / Aparicio Collado, JL. (2023). Development of Novel Biomimetic Electroactive Environments with Bioactive Molecules for Musculoskeletal Regeneration [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/195233 / Compendio