O tingimento de tecidos começou há milhares de anos e a disponibilidade comercial de corantes é enorme e crescente. A indústria têxtil brasileira desempenha um papel de inquestionável importância, destacando-se entre as principais atividades econômicas do país. O processo de tingimento é um dos fatores fundamentais no sucesso comercial dos produtos têxteis, uma vez que o consumidor exige cores resistentes à exposição ao calor, à luz, à transpiração e às lavagens. Segundo a literatura, condições de transpiração intensa contribuem para uma alta taxa de migração e subseqüente penetração de corantes têxteis para a pele humana. Além disso, 2 a 50% desses compostos permanecem no banho de tingimento e são descartados nos efluentes industriais, contaminando o ambiente e colocando em risco a saúde humana, uma vez que os métodos convencionais de tratamento de efluentes são ineficientes na remoção da coloração e da mutagenicidade de alguns corantes. Dentro deste contexto, este trabalho teve como objetivo avaliar os efeitos toxicogenéticos do corante Direct Black (DB38) original e após extração por lixiviação com suor sintético, utilizando o teste do cometa com fibroblastos e queratinócitos de pele humana, o teste Anexina V com fibroblastos e o ensaio de mutagenicidade com Salmonella typhimurium. Adicionalmente, foi investigada a ecotoxicidade dos corantes têxteis Direct Black 38 e Reactive Blue 15 (RB15) originais por meio de ensaios com sementes, dapnhias, minhocas e zebrafish realizados na UTOX, em Barcelona. O corante DB38 original e lixiviado não induziram genotoxicidade em fibroblastos e queratinócitos de pele humana. O corante DB38 original foi mutagênico para as linhagens TA98 e TA100 de S. typhimurium na presença de S9. Entretanto, o corante lixiviado não induziu mutagenicidade para essas linhagens testadas, considerando que a maior taxa de migração do corante para a solução de suor foi de ~1% nas seguintes condições: tingimento sem ensaboamento, pH 8,0 e 8 horas de incubação à 42°C. O corante original é citotóxico para fibroblastos após 48 horas de exposição. No entanto, essa citotoxicidade não foi mais observada após a lixiviação no suor. Os corantes DB38 e RB15 originais não foram tóxicos para as sementes de pepino, alface e tomate, e nem para as minhocas Eisenia foetida. Ambos os corantes foram fracamente tóxicos para Daphnia magna, porém o RB15 apresenta maior potencial tóxico em relação ao DB38. Os corantes DB38 e RB15 induziram malformações em larvas de zebrafish Danio rerio, caracterizadas por falha na inflação da bexiga natatória e alteração na cauda. Portanto, nossos resultados mostram a importância de se fazer não só a análise individual de corantes têxteis, mas também dos tecidos que os contêm. Além da necessidade de se desenvolver técnicas de tingimento mais seguras em relação à solidez da cor sob condições úmidas e as perdas de corante para o ambiente durante a etapa de fixação, indicando maior atenção ao estudo de efeitos sub-letais na avaliação do impacto desses compostos no ecossistema aquático. / The fabrics dyeing began thousands of years ago and the commercial availability of dyes is increasingly. The Brazilian textile industry plays a role of high importance, highlighting among the main economic activities in the country. The dyeing process is one of the key factors in the commercial success of textile products, since consumers are demanding colors more resistant to heat, light exposure, perspiration and washing. According to the literature, conditions of intense perspiration contribute to the migration and subsequent penetration of textile dyes to human skin. Furthermore, 2 to 50% of the initial dye load is present in the dye bath effluent and these compounds are discharged in industrial effluents, contaminating the environment and endangering human health, since the wastewater treatment systems are ineffective in removing the color and mutagenicity of some dyes. In this context, this study aimed to evaluate the toxicogenetic effects of the Direct Black 38 (DB38) dye original and extracted by leaching with artificial sweat using Comet assay with fibroblasts and keratinocytes from human skin, Anexin V assay with fibroblasts and Salmonella mutagenicity test. Additionally, we investigated the ecotoxicity of textile dye Direct Black 38 and Reactive Blue 15 (RB15) using assays with seeds, dapnhias, worms and zebrafish performed in UTOX in Barcelona. The original and leached DB38 dye did not induce genotoxicity in fibroblasts and keratinocytes from human skin. The original DB38 was mutagenic for TA98 and TA100 of S. typhimurium with S9. However, the solution with the leached dye did not induce mutagenicity for these tested strains, since the highest migration rate of the dye to the solution of artificial sweat was ~ 1% in the following conditions: type of dyeing without rinsing, pH 8.0 and 8-hour incubation at 42°C. The original dye was cytotoxic for fibroblasts after 48 hours of exposure. However, this cytotoxicity was no longer observed after leaching in sweat. The original DB38 and RB15 dyes showed no toxicity for cucumber, lettuce and tomato seeds and for earthworms Eisenia foetida. Both dyes were weakly toxic for Daphnia magna, but the RB15 has a higher toxic potential compared to DB38. The dyes DB38 and RB15 induced malformations in larvae of zebrafish Danio rerio by failure of the swim bladder inflation and changes in the tail. Therefore, our results show the importance of making the individual analysis of textile dyes, but also of fabrics containing them. Furthermore, it is necessary to develop safer techniques of dyeing in relation to the color fastness under humid conditions and the loss of dyes into the environment during the fixation step, indicating more attention to the study of sub-lethal effects in the evaluation of the impact of these compounds in the aquatic ecosystem.

Modelling and evaluating the aquatic fate of detergents - Abstract Within this thesis an environmental assessment and evaluation method for analysing aquatic ecotoxicological impacts of household laundry is developed. The methodology allows comparative assessments of different product alternatives, washing habits, and wastewater treatment techniques in order to identify their relevance with respect to waterborne discharges. Elements from both analytical tools Life Cycle Assessment (LCA) and Environmental Risk Assessment of chemicals (ERA) are combined in this methodology. The core consists of the Geography-referenced Regional Exposure Assessment Tool for European Rivers (GREAT-ER), which calculates concentrations of `down-the-drain' chemicals in surface waters due to point releases. In order to simulate the aquatic fate of detergents, a new GREAT-ER emission model is developed, called GREAT-ER product mode, which calculates calculates concentration increases of detergent ingredients in surface waters based on product formulations and assumptions concerning washing habits. Two evaluation methods, the Critical Length (CL) and the Product Risk Ratio (PRRx), are defined for evaluating the results. CL is the sum of mean concentration increases, divided by substance-specific no effect concentrations (NECs), over all river stretches and all ingredients weighted by the lengths of the stretches. PRRx is the (percentual) number of river stretches in a region, in which the x-percentiles of the predicted concentration increases of at least one ingredient exceed a substance-specific NEC. The emission model requires input data that can be derived from the functional unit of an LCA, which allows an assessment of other impact categories by using any existing LCA method. The methodology is applied to a case study which is based on scenarios given in the comprehensive product assessment `Washing and washing agents' (`Produktlinienanalyse', PLA). In order to apply the GREAT-ER product mode, the Rur river basin in Western North-Rhine Westphalia is chosen as study area. The catchment integration includes the development of a simple hydrological model that combines a nonlinear regression analysis with a local refinement procedure. The quality of the integration of the Rur catchment data is analysed by a comparison of monitoring data and predicted concentrations of detergent and cleaning agent ingredients using actual consumption data of the two years 1993 and 2000. The product mode results show that use habits have a larger influence on the results than product formulations. However, the largest influence is caused by varying wastewater treatment techniques. Boron and the surfactants are the most relevant detergent ingredients. Furthermore, using different detergents for white and coloured laundry lowers the predicted emissions significantly. Based on this methodology, sustainable development indicators (SDIs) for describing the aquatic aspects of household laundry are defined. CL is proposed as pressure indicator and PRRx as state indicator for describing aquatic aspects of the sustainability of household laundry in a region. Different regions can be compared by normalising the CL by the region's population and expressing the PRRx as a percentage of stretches in a region. Annually evaluating regional CLs and PRRxs allows the assessment whether a region is moving towards a more sustainable state. Concluding, the new method analyses and evaluates the environmental fate of detergents discharged after use via the wastewater pathway. It provides information not obtainable by other existing methods, which has been made possible due to the focussing on a specific application, for which the method is developed. Its application in the context of sustainable development offers a means to evaluate environmental implications of this important human activity.

L’utilisation de plus en plus fréquente des agents de contraste à base de Gd (AC-Gd) au cours des examens d’Imagerie par Résonnance Magnétique (IRM), engendre le rejet de ces produits pharmaceutiques dans les eaux usées retraitées en STation d’EPuration (STEP). En l’absence de retraitement spécifique de ces AC-Gd en STEP, ils sont rejetés dans le milieu aquatique, où de nombreuses études ont relevé leur présence aussi bien dans les eaux de surface que dans les eaux souterraines et jusqu’à l’eau du robinet. Le manque de connaissances concernant les effets des AC-Gd suite à leur rejet a mis en évidence la nécessité d’étudier leurs impacts environnementaux sur les organismes vivants dans les milieux aquatiques. Dans ce contexte, nous avons choisi de déterminer les concentrations en Gd d’origine anthropique à proximité de rejets de STEP et de zones de captage en eau potable situés en région Lorraine. Nos mesures ont permis de montrer la présence Gd d’origine anthropique sur l’ensemble des échantillons prélevés, avec des concentrations mesurées comprises de quelques ng(Gd)/L à quelques dizaines de µg(Gd)/L. Ces concentrations de Gd anthropique seraient dues à la présence d’AC-Gd. Nous nous sommes plus particulièrement intéressés aux effets de l’AC-Gd le plus stable et l’un des plus fréquemment commercialisé : le Gd-DOTA (Dotarem®). Pour cela, nous avons choisis plusieurs espèces représentatives des taxons rencontrés dans les cours d’eau Lorrains. Des essais ont été menés en conditions contrôlées de laboratoire afin de mesurer l’accumulation du Gd-DOTA dans les tissus et les effets de l’AC-Gd ont été appréhendés au travers de mesures de croissance, de reproduction et de mortalité au niveau individuel chez les microalgues vertes unicellulaires (Chlorella vulgaris et Pseudokirchneriella subcapitata), chez un microcrustacé (Daphnia magna) et chez un vertébré aquatique (Danio rerio) exposés à des concentrations en Gd-DOTA réalistes d’un point de vue environnemental. L’accumulation du Gd-DOTA a aussi été mesurée chez les bivalves (Corbicula fluminea et Dresseina rostriformis bugensis) et comparée à des mesures d’accumulation du Gd in situ. Les réponses physiologiques des bivalves ont été évaluées à l’aide d’une batterie de 11 biomarqueurs dans leurs branchies et leur glande digestive. Les effets de l’AC-Gd ont également été étudiés in vitro sur des fibroblastes de D. rerio (cellules ZF4 - ATCC-2050). Nos travaux ont montré que les AC-Gd et le Gd-DOTA en particulier étaient responsables d’effets écotoxiques indirects à différents niveaux d’organisation biologiques. Seuls les bivalves accumulent le Gd-DOTA mais tous les individus semblent mettre en place des mécanismes de dépuration pour parer à la toxicité de l’AC-Gd. Les résultats obtenus au cours de cette recherche ont confirmé la nécessité d’un suivi des concentrations en AC-Gd dans le milieu aquatique et la nécessité d’approfondir les études de l’écotoxicité de ces produits pharmaceutiques. Ceci pourra aboutir à une évaluation pertinente de leur risque environnemental et de proposer des solutions pour la gestion environnementale de ces composés / The increasing use of Gadolinium-based Contrast Agents (Gd-CA) for Magnetic Resonance Imaging (MRI) results in their rejection in Waste Water Treatment Plants (WWTPs). Due to the lack of specific recycling process in European WWTPs, these pharmaceutical produces enter the aquatic environment from river to tap water. The effects of Gd-CA in aquatic media have been not studied yet. The lack of knowledge about these effects highlighted the need to study their environmental impacts on aquatic organisms. In this context, we decided to measure anthropogenic concentrations of Gd in the aquatic environment in the Lorraine region (France) closed to WWTPs outputs and catchment areas used for drinking water. Our measurements underlined the presence of anthropogenic Gd on all the collected samples at concentrations ranging from few ng/L to several dozen of µg/L. In this research we focused on the effects of the most frequently used Gd-CA, the gadoteric acid (Gd-DOTA - Dotarem®) which is also the most stable one. Several representative species of aquatic environment were selected for ecotoxicological assays: i.e. unicellular green microalgae (Chlorella vulgaris and Pseudokirchneriella subcapitata), microcrustacean (Daphnia magna) and aquatic vertebrate (Danio rerio). Assays were conducted in laboratory under controlled conditions as well as in situ. Gd-DOTA accumulation was measured in the tissues of the different organisms. Environmental realistic concentrations of Gd-CA were used to assess their effects at the individual level by means of growth, reproduction and mortality measurements. The Gd-DOTA accumulation was also measured in bivalves’ tissues (Corbicula fluminea and Dresseina rostriformis bugensis) and compared to Gd ones in situ in these organisms. Physiological responses were assessed based on a battery of 11 complementary biomarkers measured in the digestive gland and in the gills of both bivalve species. At cellular level, the effects of Gd-DOTA were studied in vitro on D. rerio fibroblasts (ZF4 – ATCC-2050). Indirect ecotoxicological effects of Gd-CA and of Gd-DOTA especially have been highlighted at all biological levels. Accumulation of Gd-DOTA was observed in bivalves only, but defense systems were mobilized in all organisms to limit toxicity. Our results demonstrated that following both research on ecotoxicological effects of the Gd-CA and evolution of their concentrations in aquatic ecosystem are necessary to assess more precisely their environmental risk and to propose solutions for their environmental management

El objetivo de esta tesis ha sido el tratamiento de un residuo (lodo de fundición) procedente del lavado húmedo de los gases del horno fusor. Para ello, se ha evaluado la peligrosidad del residuo y, posteriormente, se han estudiado diferentes tratamientos previos al vertido y se ha realizado su evaluación ambiental. El lodo de fundición es un residuo ecotóxico, debido principalmente a la alta concentración de cinc y a la carga orgánica (fenoles) del mismo, pudiéndose establecer relaciones matemáticas entre la ecotoxicidad y la concentración de cinc y fenoles, tanto en el residuo original como en los productos finales. Entre las diferentes tecnologías de tratamiento, destacan los procesos de estabilización/solidificación con cal o cemento como agente aglomerante, por su elevado interés en residuos de carácter tóxico mixto: orgánico e inorgánico. Se ha llevado a cabo un estudio exhaustivo de los diferentes aditivos utilizados en dichos procesos y se han desarrollado diferentes formulaciones cal o cemento y aditivos/residuo con el fin de cumplir los parámetros ambientales, concluyéndose con la relación existente entre formulación y evaluación ambiental y obteniendo una patente de invención. / The aim of this work has been the study of the treatment of foundry sludge coming from after wet cleaning of gases of the furnace in foundry activities. Previously, the hazardous of the waste material has been evaluated. Later, different treatments have been studied and the environmental evaluation have been conducted. Foundry sludge is an ecotoxical waste due to inorganic (basically zinc) and organic (phenols) pollutants, being able to establish mathematical relationships between the ecotoxicity and the concentration of zinc and phenols, both in waste and end-products. Among the different technologies for the treatment, stabilisation/solidification processes with lime or cement as binders are very interesting technologies for waste of mixed character (organic and inorganic). An exhaustive study of different additives used in these processes has been carried out and different formulations have been developed in order to inertise the waste materials, concluding with the relationships between formulation and environmental evaluation and obtaining a patent.

La intensificación de procesos consiste en el desarrollo de equipos y técnicas innovadoras que ofrecen mejoras sustanciales en el proceso, principalmente mediante la disminución del volumen del equipo, consumo de energía o generación de residuos, dando lugar a tecnologías más baratas, seguras y sostenibles. Esta tesis enfatiza la intensificación de procesos como estrategia en la recuperación de dióxido de azufre mediante el empleo de la tecnología de membranas y de líquidos iónicos como absorbente con objeto de eliminar las pérdidas de disolvente.La intensificación del proceso se lleva a cabo en dos etapas:i) Sustitución del equipo convencional (e.g. scrubbers) por un sistema de membranas para eliminar el arrastre de gotas y,ii) Sustitución del disolvente de absorción (N,N-dimetilanilina) por líquidos iónicos para eliminar pérdidas de disolvente por su volatilización en la corriente de gas debido a su presión de vapor despreciable. La selección de un líquido iónico adecuado se basa en su afinidad hacia dióxido de azufre, baja viscosidad, bajo coste y baja ecotoxicidad.En resumen, esta tesis es el primer trabajo que combina el empleo de un contactor de membranas de fibra hueca con líquidos iónicos, contribuyendo al desarrollo de procedimientos innovadores para intensificar el proceso de absorción de dióxido de azufre. / Process intensification consists of the development of innovative devices and techniques that offer significant improvements in chemical manufacturing and processing, decreasing substantially equipment volume, energy consumption, or wastes, and ultimately leading to cheaper, safer and sustainable technologies. This thesis emphasizes the process intensification as the strategy to the recovery of sulfur dioxide, according to the material efficiency and environmental protection, by means of technology based on membranes and ionic liquids as absorption solvents in order to avoid solvent losses.Process intensification is performed in two steps:i) Substitution of conventional equipment (e.g. scrubbers) for a membrane device to avoid drops dragging and,ii) Substitution of the absorption solvent (N,N-dimethylaniline) for ionic liquids to avoid solvent losses due to volatilization of solvent into the gas stream because of their negligible vapor pressure. Selection of a suitable ionic liquid is based on its affinity towards sulfur dioxide, low viscosity, low cost and low ecotoxicity.Thus, this thesis is the first work that combines a hollow fibre membrane contactor and ionic liquids, contributing to the development of innovative procedures to intensify the sulfur dioxide absorption process.

Made available in DSpace on 2017-07-10T18:13:14Z (GMT). No. of bitstreams: 1 Denise N de Bastos.pdf: 584150 bytes, checksum: 5ec6369c1a7266f038b37ea1a2b8ccdd (MD5) Previous issue date: 2013-06-26 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The objective of this study was to avaluate the toxicity to Daphnia magna cultivated on a large scale and post-larvae of jundia (Rhamdia quelen) to Glyphosate herbicide and the reference substances. Were used daphnia with age between 2 and 26 hours of life, from large scale cultured arrays. There were performed six sensitivity assays that were composed of seven treatments and three replica, at concentrations of 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1.2 mg.L-1 of potassium dichromate, with 24 hours duration. The acute toxicity assays, with copper sulfate at concentrations of 0; 0.01; 0.025; 0.05; 0.075 and 0.10 mg.L-1, and to the glyphosate concentrations of 0; 11; 21; 31; 41 and 51 µg.L-1, with three and two replica respectively, and 48 hours duration. However the post-larvae of jundia were exposed to concentrations of 0; 0.5; 1.0; 1.5; 2.0 and 2.5 mg.L-1 of glyphosate, per 96 hours. Each replica was composed of a bottle with 10 individuals. The chronic toxicity test, the daphnia were exposed to concentrations of 0, 2, 4, 6, 8 and 10 µg.L-1 of glyphosate, with 10 replica, being a daphnia per replica, evaluating the survival and fecundity in 21 days. For acute toxicity assays, was calculated mortality using the Median Effective Concentration (EC50) in each test. The mean EC50 for D. magna with potassium dichromate was 0.57 mg.L-1. The value of acute toxicity for copper sulphate was reached at a concentration of 0.034 mg.L-1. And for the glyphosate the EC50 of 32 µg.L-1 is toxic for the species. The chronic assay showed high rate of mortality, possibly the result of unfavourable conditions for the large scale cultivation of arrays, hurt his endurance. For the R. quelen the EC50 was achieved at 0.9 mg. L-1. The results showed that organisms of the species D. magna cultivated on a large scale can be used in acute toxicity tests, but not in chronic toxicity testing, for the assessment of water quality. / O objetivo deste trabalho foi avaliar a toxicidade de Daphnia magna cultivada em larga escala e pós-larvas do jundiá (Rhamdia quelen) ao herbicida Glifosato e a substâncias de referência. Foram utilizadas dáfnias com idade de 2 a 26 horas de vida, provenientes de matrizes cultivadas em larga escala. Foram realizados seis ensaios de sensibilidade que foram compostos por sete tratamentos e três réplicas, nas concentrações de 0; 0,1; 0,3; 0,5; 0,7; 0,9 e 1,2 mg.L-1 de dicromato de potássio, com duração de 24 horas. E os testes de toxicidade aguda, com sulfato de cobre nas concentrações de 0; 0,01; 0,025; 0,05; 0,075 e 0,10 mg.L-1, e para o glifosato as concentrações de 0; 11; 21; 31; 41 e 51 µg.L-1, com três e duas réplicas respectivamente, e duração de 48 horas. Já as pós-larvas de jundiá foram expostas às concentrações de 0; 0,5; 1,0; 1,5; 2,0 e 2,5 mg.L-1 de glifosato, por 96 horas. Cada réplica era composta de um frasco com 10 indivíduos. No teste de toxicidade crônica, as dáfnias foram expostas as concentrações de 0, 2, 4, 6, 8 e 10 µg.L-1 de glifosato, com 10 réplicas, sendo uma dáfnia por réplica, avaliando a sobrevivência e fecundidade em 21 dias. Para os experimentos de toxicidade aguda foi calculada mortalidade através da Concentração Efetiva Mediana (CE50) em cada teste. A média da CE50 para a D. magna com dicromato de potássio foi de 0,57 mg.L-1. O valor de toxicidade aguda para o sulfato de cobre foi alcançado na concentração de 0,034 mg.L-1. Já para o glifosato a CE50 de 32 µg.L-1 é toxica para a espécie. No teste crônico, a alta taxa de mortalidade possivelmente é resultado das condições desfavoráveis no cultivo das matrizes em larga escala, o que prejudicou sua resistência. Para o R. quelen a CE50 alcançada foi em 0,9 mg.L-1. Os resultados demostraram que organismos da espécie D. magna cultivadas em larga escala podem ser utilizados em testes de toxicidade aguda, mas não em testes de toxicidade crônica, para a avaliação da qualidade da água.

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