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No. of bitstreams: 2 Dissertação - Lara Barroso Brito - 2016.pdf: 19284674 bytes, checksum: 73aa3e2fc34b886b960712220045839d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-03-23 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Pharmaceuticals can be introduced directly into the environmental by household disposal or pharmaceutical industry waste and indirectly through the excretion of humans and animals. Antibiotics are considered emerging contaminants because they are typically present at very low levels in the environmental and their human or ecological health effects are unclear. β-lactams represent more than 70% of antibiotics consumed in Brazil. Thus, in this context, this work evaluated the environmental impact of antibiotic amoxicillin (AMX) in different organisms, considering its presence in water. For that, we used the phytotoxicity test with seeds of tomato (Lycopersicon esculentum), cucumber (Cucumis sativus) and lettuce (Lactuca sativa), brine shrimp toxicity assay (Artemia salina), and embryo-larval toxicity test zebrafish (D. rerio), considering the lethal and sublethal effects and biomarkers determinations. AMX showed no toxicity to seeds of tomato, cucumber and lettuce in relation to seed germination and root elongation endpoints. For microcrustacean A. salina, AMX did not induce significant mortality after 24 h and 48 h exposure (LC50 > 100 mg/L) and it was classified as non-toxic (not categorized) according to the Globally Harmonized System (GHS). AMX also did not cause significant mortality in embryos and larvae zebrafish during 168 h of exposure. It had no significant effect on embryos hatching and larvae equilibrium. However, AMX significantly increased the larvae size at 6.25, 12.5 and 25 mg/L. Catalase (CAT), glutathione S-transferase (GST) and lactate dehydrogenase (LDH) activities in embryos and larvae of zebrafish were inhibited at 12.5 mg/L of AMX, 6.25, 12.5, 25, 50 and 100 mg/L of AMX and 1.5, 3.0, 6.25 and 12.5 mg/L of AMX, respectively. Therefore, AMX showed no significant acute toxicity to tested organisms, but it induced sublethal effects on larvae zebrafish in concentrations greater than those found in the aquatic environment, indicating that long-term chronic exposures must be investigated. / Os fármacos e insumos farmacêuticos podem ser introduzidos no ambiente de forma direta, ou seja, através do descarte doméstico ou por efluentes da indústria farmacêutica, e ainda indiretamente, por meio da excreção humana e animal. Os antibióticos são considerados contaminantes emergentes, uma vez que são detectados em concentrações muito baixas no ambiente e seus efeitos sobre o ambiente e saúde humana permanecem incertos. Os β- lactâmicos representam mais de 70% dos antibióticos consumidos no Brasil. Assim, dentro deste contexto, este trabalho propôs avaliar o impacto ambiental do antibiótico amoxicilina (AMX) em diferentes organismos, considerando a sua presença nos recursos hídricos. Para tanto foram utilizados os ensaios de fitotoxicidade com sementes de tomate (Lycopersicon esculentum), pepino (Cucumis sativus) e alface (Lactuca sativa) e de toxicidade aguda com Artemia salina, assim como o teste com o estágio embriolarval de zebrafish (Danio rerio), considerando os efeitos letais, subletais e atividade de biomarcadores enzimáticos. A AMX não foi tóxica para as sementes de tomate, pepino e alface, não apresentando diferenças estatísticas significativas para os parâmetros de germinação das sementes e do desenvolvimento das raízes. Para o microcrustáceo A. salina, a AMX não induziu mortalidade significativa com valores de CL50 maior que 100 mg/L para 24 h e 48 h de exposição, sendo classificada como não tóxica (não categorizada) de acordo com o Globally Harmonized System (GHS). A AMX não provocou mortalidade significante nos embriões e larvas de zebrafish durante as 168 h de exposição, assim como não alterou significativamente a eclosão dos embriões e o equilíbrio de larvas de zebrafish. Entretanto, o antibiótico aumentou significativamente o tamanho das larvas desse peixe nas concentrações de 6,25; 12,5 e 25 mg/L. As atividades da catalase (CAT), da glutationa Stransferase (GST) e da lactato desidrogenase (LDH) de embriões e larvas de peixezebra foram inibidas significativamente nas exposições à 12,5 mg/L de AMX, 6,25; 12,5; 25; 50 e 100 mg/L de AMX e 1,5; 3,0; 6,25 e 12,5 mg/L de AMX, respectivamente. Portanto, o antibiótico AMX não apresenta toxicidade aguda relevante para os organismos testados, mas causa alguns efeitos subletais em larvas de zebrafish em concentrações superiores às encontradas no ambiente aquático, o que indica a necessidade de se investigar exposições a esse composto a longo prazo.

Um sistema de análises em fluxo com multicomutação foi desenvolvido para a mecanização do bioensaio de toxicidade aguda com a bactéria Vibrio fischeri, o qual é baseado na diminuição da luminescência bacteriana causada por espécies tóxicas.Microbombas solenoide foram utilizadas para melhorar as condições de mistura, permitindo também que diluições fossem realizadas em linha com a alteração do volume de amostra e a sobreposição parcial entre a zona da amostra e a suspensão bacteriana. Uma cela de fluxo em espiral, posicionada na janela de emissão de um espectrofluorímetro, foi empregada para as medidas de luminescência e um banho de água construído em laboratório, baseado no efeito Peltier, foi utilizado para manter a temperatura do bioensaio em (13,0±0,1) °C. Um pequeno volume da suspensão bacteriana (120 ?L) foi selecionado visando minimizar o consumo e, consequentemente, os custos do ensaio. O tempo de contato entre a suspensão bacteriana e a amostra foi reduzido para 5 min para aumentar a frequência de amostragem e evitar a atenuação da luminescência devido ao tempo de vida curto das bactérias. Os valores de CE50 para os controles positivos foram estimados em 2,5 ± 0,7, 2,0 ± 0,5 e 10 ± 4 mg L-1 para o Zn(II), Cu(II), e Cr(VI), respectivamente, sendo concordantes com os valores da literatura. Os valores de CE50 para alguns poluentes emergentes (parabenos, cafeína, acetaminofeno, diclofenaco e ácido salicílico) concordaram com os obtidos utilizando o kit comercial BioTox(TM), realizado em micro placa, a nível de confiança de 95 %. Os coeficientes de variação foram estimados em 2,4 e 2 % (n = 10), na ausência e na presença de 0,6 mg L-1 de Zn(II), respectivamente. O sistema de análises em fluxo proposto é, então, uma alternativa simples, rápida, robusta e precisa para a determinação da toxicidade aguda utilizando pequenos volumes de amostra e suspensão bacteriana. Além disso, o sistema apresenta vantagens em comparação com os bioensaios em batelada e em fluxo, tais como ajuste de salinidade e diluições das amostras em linha e a determinação da cinética de toxicidade das espécies químicas / A multicommuted flow system was developed for automation of the acute toxicity bioassay using Vibrio fischeri bacteria, which exploits the decrease of the bacterial luminescence caused by toxic species. Solenoid micro-pumps were employed to improve mixing conditions and to perform on-line dilutions of the tested compounds by changing the sample volume and exploiting the partial overlap between sample zone and the bacterial suspension. A spiral flow cell, placed at the emission window of a spectrofluorimeter, was employed for signal measurement and a lab-made water bath based on the Peltier effect was used for maintain the temperature of the bioassay at (13.0±0.1) oC. A low volume of the bacterial suspension (120 ?L) was selected in order to minimize its consumption and, consequently, the costs of the assay. The contact time between bacterial suspension and sample was reduced to 5 min to increase the sampling rate and to avoid luminescence fading due to the bacteria short lifetime. EC50 values for positive controls were estimated as 2.5 ± 0.7, 2.0 ± 0.5 and 10 ± 4 for Zn(II), Cu(II), and Cr(VI), respectively, being in agreement with literature values. The EC50 values for some emerging pollutants (parabens, caffeine, acetaminophen, diclofenac and salicylic acid) agreed with those obtained from commercial BioTox(TM) kit performed in micro plate at the 95% confidence level. The coefficients of variation were estimated as 2.4 and 2 % (n=10), in the absence and presence of 0.6 mg L-1 Zn(II), respectively. The proposed flow system is then a simple, fast, robust and accurate alternative for acute toxicity determination, using low sample and bacterial suspension volumes. Furthermore, the system presents advantages in comparison to batch and previous flow-based bioassays, such as the achievement of in-line salinity adjustment and sample dilutions, and the determination of toxicity kinetic for every assayed chemical species

A remoção da matéria orgânica biodegradável e não biodegradável presente em efluentes de branqueamento de polpa celulósica kraft foi investigado utilizando processos biológicos anaeróbios seguidos de processos de oxidação avançada (POA) baseados em ozônio. Os experimentos foram realizados utilizando-se efluentes da planta de branqueamento de polpa celulósica kraft de duas indústrias. O reator anaeróbio horizontal de leito fixo (RAHLF) em escala de bancada operou em regime contínuo durante 418 dias e o efluente biotratado era submetido à oxidação avançada aplicando ozônio e ozônio/UV em regime de batelada. Os resultados demonstraram que a sequência de tratamento Anaeróbio + POA baseados em ozônio, favoreceu satisfatoriamente a remoção da matéria orgânica (biodegradável e não biodegradável) presente no efluente de branqueamento de polpa celulósica Kraft, medida como DQO, COd, AOX, lignina solúvel em ácido (LSA), e valores da absorbância em comprimentos de onda na região UV-VIS do espectro (UV215, UV254, UV280, VIS346).Verificou-se com testes de ecotoxicologia aquática utilizando Daphnia similis e Ceriodaphnia sp, que os efluentes de branqueamento são tóxicos aos organismos aquáticos. Do mesmo modo, ensaios de genotoxicidade utilizando células da região meristemática da raiz do Allium cepa L (cebola comum), revelaram que esses efluentes apresentam atividade mutagênica, genotoxica e citotóxica. No entanto, observou-se que tantos os efeitos tóxicos bem como os genotóxicos e mutagênicos, estão estreitamente relacionados com o conteúdo da matéria orgânica biodegradável, uma vez que, após o processo anaeróbio apresentaram-se remoções estatisticamente significativas para todos os efeitos já mencionados (até 100%) com concomitante remoção da demanda química de oxigênio (até 55 \'+ OU -\' 9%) e do carbono orgânico dissolvido (até 57 \'+ OU -\' 7%). Ainda, verificou-se que após a aplicação do ozônio/UV, embora, o teste de biodegradabilidade aeróbia pelo método de Zahn Wellens revelasse que esse efluente era o mais biodegradável, tanto a toxicidade crônica como a genotoxicidade e a citotoxicidade resultaram estatisticamente significativas em relação ao controle negativo. Este resultado indica que, efetivamente a matéria orgânica biodegradável deset tipo de efluentes pode se relacionar com a presença de efeitos tóxicos e genotóxicos. Tal fato não foi verificado no caso do tratamento apenas com ozônio. / Removal of biodegradable and non biodegradable organic matter present in kraft pulp mill effluent was investigated integrating an anaerobic biological process and advanced oxidation processes based on ozone. The experiments were carried out using two different Brazilian pulp mill. The bench scale Horizontal Anaerobic Immobilized Sludge Bioreactor (HAIS) was operated during 418 days; subsequently the biotreated effluent was oxidized applying ozone and ozone/UV in batch regime. The results show that the treatment sequence, anaerobic process + advanced oxidation processes based on ozone, results in removal of both organic matter biodegradable and non-biodegradable measured as chemical oxidation demand (COD), dissolved organic carbon (COd), adsorbable organic halides (AOX), acid soluble lignin (ASL) and absorbance values in the UV-VIS spectrum (i.e. UV215, UV205, UV280, VIS346). Ecotoxicological tests using Daphnia similis and Ceriodaphnia sp. confirmed that bleached kraft pulp mill is toxic to aquatic organisms. Moreover, genotoxicity tests with meristematic cells of Allium cepa (i.e. common onion) roots show that this type of effluent results in mutagenic, genotoxicological and citotoxicological activities. It is to be highlighted however that both toxicological and genotoxicological effects are closely related to the biodegradable organic matter, thus, after the anaerobic processes the removal of these effects occur, concomitant to reductions is chemical oxygen demand (55 \'+ OU -\' 9%) and dissolved organic carbon (57 \'+ OU -\' 7%). It was also observed that after ozone/UV application, both the chronic toxicity and genotoxicity activity were statically significant if compared with the negative control, although the Zahn Wellens test revealed that this effluent had the highest biodegradability. These results confirmed that biodegradable organic matter could be related with toxic and genotoxic effects. In the case of ozone application alone this behavior was not observed.

In 2014, the global pesticide industry's projected worth is $52 billion and by 2020, the developing world will make up one-third of the world's chemical production and consumption. Pesticides can have unintended negative consequences for human health and the environment, especially in the developing world where regulations are loose or nonexistent. One country with unrestricted use of pesticides is Panam[aacute], especially in Santa Rosa de Cucunatí. In this indigenous village, small-scale farmers and ranchers spray paraquat, glyphosate, picloram, and 2,4-D at higher elevations than the spring water source of a gravity-fed water system, the river, and the village. The objective of this study was to estimate the concentration of these pesticides in the water system and the river and to perform a human health and ecological risk assessment. Pesticide fate and transport models in the graphical user interface EXAMS-PRZMS Exposure Simulation Shell (EXPRESS), which was developed by the United States Environmental Protection Agency, were used to predict concentrations of the four mentioned pesticides in drinking water and the river using chemical properties, data from Food and Agriculture Organization and Smithsonian Tropical Research Institute, and the author's experience as a Peace Corps Volunteer. The results from Tier I model FQPA Index Reservoir Screening Tool (FIRST) were used to compare immediate and delayed rain events, noting minimal difference. The Tier II PRZM-EXAMS shell provided estimated drinking water concentration (EDWC) profiles. The paraquat profile was much lower than picloram, glyphosate, and 2,4-D, which had almost identical profiles with peak concentrations around 12 ppm and the average annual concentration 100 ppb. Average Daily Dose (ADD) via drinking water was calculated for men, women, and children using model results and compared to the oral reference dose (RfD). ADDs only exceeded the RfD with maximum peak EDWCs, implying low risk. However, RfD was used to calculate a breakpoint concentration, the concentration at which each pesticide presents a risk to the consumer. This was then compared to the maximum peak (highest, i.e. worst-case scenario) and annual (lowest, i.e. best-case scenario) EDWC profiles. In the best-case scenario, glyphosate and picloram did not pose a threat, paraquat posed a moderate threat and 2,4-D posed a high threat, with the concentration exceeding the breakpoint for 90 percent of the years. With respect to the worst-case scenario, all four chemicals posed high threats to the consumer. Individual exposure via consumption of fish from the river was calculated using a calculated bioconcentration (BCF) factor and calculated breakpoint concentrations. For the best case scenario, picloram presented a low risk and 2,4-D presented a high risk but for the worst case, both of these chemicals presented a very high risk. An additive exposure of these two human health pathways found that for the best case scenario, exposure from most of the four chemicals did not approach the RfD. However, for the worst-case scenario the exposures were significantly higher than the oral RfD--therefore, between the lowest and the highest concentrations, the general population is at risk. For the ecological risk assessment, the 96-hour peak profile was compared to the 96-hour lethal dose (LD50); glyphosate posed a high risk to fathead minnows and low risk to bluegills and 2,4-D presented a high risk to fathead minnows, low risk to channel catfish, and very high risk to bluegills. A more general risk assessment compared maximum peak and annual concentrations to the US EPA's aquatic life benchmarks. Glyphosate presented no threat and 2,4-D only presented a threat to plants. For picloram, fish were at very high risk at the chronic level and low risk at the acute level, and plants were at moderate risk. Paraquat presented the most significant threat to aquatic life, exceeding benchmarks for all plants and invertebrates at the chronic level 100 percent of the time. It presented no threat to fish in the best-case scenario, but a high risk for fish at the chronic level in the worst case scenario, as well as very high risk for all invertebrates and plants. Improvements in application and watershed protection as part of a multi-disciplinary approach are proposed in place of technological mitigation strategies. Recommendations for future studies include the development of a developing-world context model and experimental studies in the developing world to compare to model results, where possible.

A complex process like risk assessment and the subsequent risk management decision makingshould be regularly evaluated, in order to assess the need to improve its workings. In this thesisthree related matters are addressed: evaluation of environmental risk management strategies,evaluation of environmental risk assessments, and how ecotoxicity data from the open scientificliterature can be used in a systematic way in regulatory risk assessments. It has resulted in thefollowing: a publically available database with ecotoxicity data for pharmaceuticals (Paper I); anevaluation and review of the Swedish Environmental Classification and Information System forpharmaceuticals (Papers II and III); a comparison of current reliability evaluation methods and areliability evaluation of ecotoxicity data (Paper IV); and an improved reliability and relevancereporting and evaluation scheme (Paper V).There are three overall conclusions from this thesis:(1) Ecotoxicity data from the open scientific literature is not used to the extent it could be inregulatory risk assessment of chemicals. Major reasons for this are that regulators prefer standarddata and that research studies in the open scientific literature can be reported in a way that affectstheir reliability and the user-friendliness. To enable the use of available data more efficiently actionsmust be taken by researchers, editors, and regulators. A more structured reliability and relevanceevaluation is needed to reach the goal of transparent, robust and predictable risk assessments.(2) A risk assessment is the result of the selected data and the selected methods used in theprocess. Therefore a transparent procedure, with clear justifications of choices made, is necessaryto enable external review. The risk assessments conducted within the Swedish EnvironmentalClassification and Information System for pharmaceuticals vary in their transparency and choice ofmethod. This could come to affect the credibility of the system since risk assessments are notalways consistent and guidelines are not always followed.(3) The Swedish Environmental Classification and Information System for pharmaceuticalscontribute, in its current form, to data availability and transparency but not to risk reduction. Thesystem has contributed to the general discussion about pharmaceuticals’ effect on the environmentand made data publicly available. However, to be an effective risk reduction tool this is not sufficient. / <p>QC 20121119</p> / MistraPharma / Formas - Evaluation of the Swedish Environmental Classification and Information System for Pharmaceutcals.

Neste trabalho foi avaliada a qualidade das águas da Bacia do Rio Morto, localizado na Baixada de Jacarepaguá Rio de Janeiro, com base em análise físicoquímicas e ensaios ecotoxicológicos agudos com Danio rerio, Daphnia similis e Aliivibrio fischeri e ensaios ecotoxicológicos crônicos referentes à reprodução com Daphnia similis. Foram comparadas as sensibilidades dos organismos-teste, que pertencem a níveis tróficos diferentes, nos quatro pontos selecionados para coleta de amostras de água no Rio Morto e seus principais tributários: Rio Branco, Rio Sacarrão e canal do Morro do Bruno. Além disso, foi implementado no laboratório o método de ensaio crônico com o microcrustáceo Daphnia similis. As amostras, em sua maioria, apresentaram parâmetros físico-químicos dentro dos limites permitidos pela legislação nacional para a classe de águas doces em que a Bacia estudada está inserida. Não foram observados efeitos agudos nos organismos-teste, não sendo possível o cálculo da CE50 ou CL50, por conseqüência, o FT ficou fixado em 1. No teste agudo para Aliivibrio fischeri, para algumas amostras, foi constatado efeito Hormesis. O mesmo foi verificado em algumas amostras submetidas aos testes crônicos com Daphnia similis. / The quality of Rio Morto watershed, located in Jacarepagua district, Rio de Janeiro city, was investigated performing physicochemical determinations of water samples, as well as, acute ecotoxicity assays with three organisms (Danio rerio, Daphnia similes, Aliivibrio fischeri) and chronic ecotoxicity assays with Daphnia similis. The responses of the three organisms, belonging to different trophic levels, were compared for samples collected from four selected places in River Morto and its tributaries: River Branco, River Sacarrao and Morro do Bruno channel. In addition, the method of determination of chronic ecotoxicity using Daphnia similis was successfully implanted in the laboratory. Most samples presented physicochemical parameters that fulfill the requirements of the national standards for the River Morto watershed. Acute ecotoxicity was not observed for the tested organisms, not allowing the determination of the parameters EC50 and LC50 and imposing a FT value equal to one. Acute toxicity assays with Aliivibrio fischeri revealed, for some samples, the Hormesis effect. The same was observed for some samples submitted to chronic ecotoxicity determination with Daphnia similis.

Neste trabalho foi avaliada a qualidade das águas da Bacia do Rio Morto, localizado na Baixada de Jacarepaguá Rio de Janeiro, com base em análise físicoquímicas e ensaios ecotoxicológicos agudos com Danio rerio, Daphnia similis e Aliivibrio fischeri e ensaios ecotoxicológicos crônicos referentes à reprodução com Daphnia similis. Foram comparadas as sensibilidades dos organismos-teste, que pertencem a níveis tróficos diferentes, nos quatro pontos selecionados para coleta de amostras de água no Rio Morto e seus principais tributários: Rio Branco, Rio Sacarrão e canal do Morro do Bruno. Além disso, foi implementado no laboratório o método de ensaio crônico com o microcrustáceo Daphnia similis. As amostras, em sua maioria, apresentaram parâmetros físico-químicos dentro dos limites permitidos pela legislação nacional para a classe de águas doces em que a Bacia estudada está inserida. Não foram observados efeitos agudos nos organismos-teste, não sendo possível o cálculo da CE50 ou CL50, por conseqüência, o FT ficou fixado em 1. No teste agudo para Aliivibrio fischeri, para algumas amostras, foi constatado efeito Hormesis. O mesmo foi verificado em algumas amostras submetidas aos testes crônicos com Daphnia similis. / The quality of Rio Morto watershed, located in Jacarepagua district, Rio de Janeiro city, was investigated performing physicochemical determinations of water samples, as well as, acute ecotoxicity assays with three organisms (Danio rerio, Daphnia similes, Aliivibrio fischeri) and chronic ecotoxicity assays with Daphnia similis. The responses of the three organisms, belonging to different trophic levels, were compared for samples collected from four selected places in River Morto and its tributaries: River Branco, River Sacarrao and Morro do Bruno channel. In addition, the method of determination of chronic ecotoxicity using Daphnia similis was successfully implanted in the laboratory. Most samples presented physicochemical parameters that fulfill the requirements of the national standards for the River Morto watershed. Acute ecotoxicity was not observed for the tested organisms, not allowing the determination of the parameters EC50 and LC50 and imposing a FT value equal to one. Acute toxicity assays with Aliivibrio fischeri revealed, for some samples, the Hormesis effect. The same was observed for some samples submitted to chronic ecotoxicity determination with Daphnia similis.

Neste trabalho, objetivou-se o avaliar ecotoxicidade potencial do sedimento do Reservatório Guarapiranga da cidade de São Paulo (Brasil) frente a contaminação por metais, a fim de discutir sua qualidade e sua atual política de gerenciamento ambiental. Os metais analisados foram: Al, Cd, Cr, Cu, Fe, Mn, Pb e Zn. Utilizou-se das ferramentas de sistema de informação geográfica, geoprocessamento de imagens e da geoestatística para avaliação da dispersão espacial dos metais ao longo do sedimento do Reservatório, considerado por este trabalho como aquela região de maior implicação ecotoxicológica para contaminantes metálicos. Analisaram-se também as variáveis granulometria, matéria orgânica, nitrogênio total, fósforo total e umidade do sedimento, a fim de se estudar quimiometria do sedimento, a fim de melhor compreender as distribuições dos contaminantes ao longo do sedimento. Denominou-se esta classe de variáveis quimiométricas de parâmetros estruturais do sedimento. Observou-se grande variabilidade quantitativa e espacial entre os metais analisados, denotando que o Reservatório Guarapiranga sofre contaminação por diferentes vias no sistema. Observou-se falta de correlação quimiométrica entre os parâmetros estruturais do sedimento com os contaminantes metálicos, denotando grande variabilidade interna desse sistema. Referente a política de manejo do Reservatório, especialmente relativa ao controle algal e cianofítico, observou-se um gerenciamento de grande impacto ecossistêmico, focado mais no custo imediato do que em planejamentos de longo prazo. Tal gerenciamento, hoje, traz risco ecotoxicológico ao reservatório, mas também toxicidade potencial à própria população abastecida pelo reservatório quanto àquela sob exposição direta a este reservatório por meio de recreação, esportes náuticos, ou alimentação / In this work, the metal ecotoxicological potential of an urban reservoir\'s sediment has been assessed, in order to discuss its management policies and its implications to the society and to the ecosystem. The Reservoir Guarapiranga has been selected as the model environment for this study, once it possess a long history since its damming, several studies regarding its water and sediment conditions and an easy accessibility. The metals of greater implication to the Guarapiranga\'s cause were the Al, Cd, Cr, Cu, Fe, Mn, Pb and Zn, being selected as the main parameters for this study. Several scientific areas have been applied in this work. Among them, it is cited the Geographical Information System, geostatistical analysis, imagem geoprocessing, geochemical and chemometric analysis and, finally, the ecotoxicology. In order to better understand the relationship between the sediment and its contaminants, this study also assessed the granulometry, organic matter, total nitrogen, total phosphorous and the umidity of the sediment as explainable variables, translated as chemometric variables. My results showed great variability among the metals analized, denoting that each metal has its own path of contamination (contamination source point) in the reservoir, but a main direction (axis) of dispersion on the sediment. This later, mostly due to hydrological and eolic aspects of the ecosystem. Also, it\'s been observed lack of correlation between the chemometric and the metals parameters of the sediment, which also demonstrated the variation and stochasticity of the ecosystem. Lastly, the reservoir\'s environemntal management policies specially related to the algal and cyanophitic controlhave been analized through an ecotoxicological prisma, and it been denoted that it lacks long-term considerations, focusing only at punctual or short to middle-term solutions,resulting in the terrible ecotoxicological condition observed in the Guarapiranga\'s reservoir. Here, I punctuate the importance of new policy making, and its importance to the ecosystem and to the society, once hazardous condition of a reservoir is unberable not only through a ecosystemperspective, but as a sociological one

A remoção da matéria orgânica biodegradável e não biodegradável presente em efluentes de branqueamento de polpa celulósica kraft foi investigado utilizando processos biológicos anaeróbios seguidos de processos de oxidação avançada (POA) baseados em ozônio. Os experimentos foram realizados utilizando-se efluentes da planta de branqueamento de polpa celulósica kraft de duas indústrias. O reator anaeróbio horizontal de leito fixo (RAHLF) em escala de bancada operou em regime contínuo durante 418 dias e o efluente biotratado era submetido à oxidação avançada aplicando ozônio e ozônio/UV em regime de batelada. Os resultados demonstraram que a sequência de tratamento Anaeróbio + POA baseados em ozônio, favoreceu satisfatoriamente a remoção da matéria orgânica (biodegradável e não biodegradável) presente no efluente de branqueamento de polpa celulósica Kraft, medida como DQO, COd, AOX, lignina solúvel em ácido (LSA), e valores da absorbância em comprimentos de onda na região UV-VIS do espectro (UV215, UV254, UV280, VIS346).Verificou-se com testes de ecotoxicologia aquática utilizando Daphnia similis e Ceriodaphnia sp, que os efluentes de branqueamento são tóxicos aos organismos aquáticos. Do mesmo modo, ensaios de genotoxicidade utilizando células da região meristemática da raiz do Allium cepa L (cebola comum), revelaram que esses efluentes apresentam atividade mutagênica, genotoxica e citotóxica. No entanto, observou-se que tantos os efeitos tóxicos bem como os genotóxicos e mutagênicos, estão estreitamente relacionados com o conteúdo da matéria orgânica biodegradável, uma vez que, após o processo anaeróbio apresentaram-se remoções estatisticamente significativas para todos os efeitos já mencionados (até 100%) com concomitante remoção da demanda química de oxigênio (até 55 \'+ OU -\' 9%) e do carbono orgânico dissolvido (até 57 \'+ OU -\' 7%). Ainda, verificou-se que após a aplicação do ozônio/UV, embora, o teste de biodegradabilidade aeróbia pelo método de Zahn Wellens revelasse que esse efluente era o mais biodegradável, tanto a toxicidade crônica como a genotoxicidade e a citotoxicidade resultaram estatisticamente significativas em relação ao controle negativo. Este resultado indica que, efetivamente a matéria orgânica biodegradável deset tipo de efluentes pode se relacionar com a presença de efeitos tóxicos e genotóxicos. Tal fato não foi verificado no caso do tratamento apenas com ozônio. / Removal of biodegradable and non biodegradable organic matter present in kraft pulp mill effluent was investigated integrating an anaerobic biological process and advanced oxidation processes based on ozone. The experiments were carried out using two different Brazilian pulp mill. The bench scale Horizontal Anaerobic Immobilized Sludge Bioreactor (HAIS) was operated during 418 days; subsequently the biotreated effluent was oxidized applying ozone and ozone/UV in batch regime. The results show that the treatment sequence, anaerobic process + advanced oxidation processes based on ozone, results in removal of both organic matter biodegradable and non-biodegradable measured as chemical oxidation demand (COD), dissolved organic carbon (COd), adsorbable organic halides (AOX), acid soluble lignin (ASL) and absorbance values in the UV-VIS spectrum (i.e. UV215, UV205, UV280, VIS346). Ecotoxicological tests using Daphnia similis and Ceriodaphnia sp. confirmed that bleached kraft pulp mill is toxic to aquatic organisms. Moreover, genotoxicity tests with meristematic cells of Allium cepa (i.e. common onion) roots show that this type of effluent results in mutagenic, genotoxicological and citotoxicological activities. It is to be highlighted however that both toxicological and genotoxicological effects are closely related to the biodegradable organic matter, thus, after the anaerobic processes the removal of these effects occur, concomitant to reductions is chemical oxygen demand (55 \'+ OU -\' 9%) and dissolved organic carbon (57 \'+ OU -\' 7%). It was also observed that after ozone/UV application, both the chronic toxicity and genotoxicity activity were statically significant if compared with the negative control, although the Zahn Wellens test revealed that this effluent had the highest biodegradability. These results confirmed that biodegradable organic matter could be related with toxic and genotoxic effects. In the case of ozone application alone this behavior was not observed.

Les nanoparticules métalliques manufacturées (NPs) sont des polluants émergents dont la concentration augmente dans les sols en raison de leur utilisation croissante dans de nombreux produits commerciaux de la vie courante (cosmétiques, aliments, peintures…). Des études in vitro ont montré la toxicité des NPs pour les microorganismes, mais il existe encore peu de données sur l'écotoxicité et le devenir de ces contaminants dans les sols. L'objectif de cette thèse est donc d'évaluer l'influence des paramètres abiotiques du sol sur (i) les caractéristiques physico-chimiques et le transfert des NPs, et (ii) sur la toxicité des NPs pour les communautés microbiennes du sol, en particulier pour des groupes fonctionnels microbiens impliqués dans le cycle du carbone et de l'azote. Nous avons mis en évidence que les propriétés du sol influençaient l'agrégation et la charge de surface des NPs de dioxyde de titane (TiO2) et d'oxyde de cuivre (CuO). Dans les six sols agricoles étudiés, nous avons observé un transport très faible des NPs testées lors d'une expérimentation en colonnes de sols. Nous avons mis en évidence une absence de toxicité des NPs de TiO2 sur les communautés microbiennes, sauf dans un sol limono-argileux à forte teneur en matière organique. Dans ce sol, des effets négatifs ont été observés après 90 jours d'exposition sur les activités microbiennes, sur l'abondance des microorganismes nitrifiants et la diversité des bactéries et des archées. Des études complémentaires en colonnes de sol, ont permis de mettre en évidence des effets délétères des NPs plus importants que la nitrification lors d'une contamination chronique au TiO2 que lors d'une contamination aigüe / Manufactured metallic nanoparticles (NPs) are emerging pollutants of soils due to their increasing utilization in numerous commercial products (cosmetics, food, paint…). In vitro studies have demonstrated NPs toxicity on microorganisms but data are still scarce on the fate and ecotoxicity of these contaminants in soils. The objective of this thesis was to assess the influence of soil properties on (i) the physicochemical characteristics and the transport of NPs, and (ii) on the NPs toxicity on soil microbial communities, especially on microbial functional groups involved in carbon and nitrogen cycles. This work highlighted that soil properties influenced the aggregation and the surface charges of titanium dioxide NPs (TiO2-NPs) and copper oxide NPs (CuO-NPs). In the six agricultural soils studied, we observed a very low transport of the two NPs in a soil column experiment. We observed a low toxicity of TiO2-NPs for soil microbial communities, except in a silty-clay soil with a high organic matter content. In this soil, microbial activities (soil respiration, nitrification and denitrification) and nitrifier abundances were strongly decreased and archaeal and bacterial community structure were altered after 90 days of exposure. Furthermore in this soil, we observed decreases of nitrification activity, even for very low TiO2-NPs concentrations (0.05 mg kg-1) which were explained by a high sensitivity of ammonia-oxidizing archaea (AOA) involved in this process. Additional studies in soil columns demonstrated that chronic contamination with TiO2-NPs caused more deleterious effects on nitrification than acute contamination