Excessive nitrates in drinking water pose a human health threat, especially to infants. Methemoglobinemia, or blue-baby syndrome, is a potentially fatal condition that inhibits the ability of red blood cells to bind and transport oxygen. Nitrates/nitrites have also been linked to such conditions as cancer, birth defects, and behavioral and developmental abnormalities. Nitrates are frequently found in wells in rural farming areas because synthetic fertilizers (containing nitrates) leach from the soil into the groundwater. The Lower Umatilla Basin (LUB) in Morrow and Umatilla counties of Oregon represents an intensively farmed and irrigated area in which relatively high amounts of nitrates are present in the groundwater and domestic well water. This study investigated population demographics for the rural Lower Umatilla Basin, comparing these data to identified well-water nitrate levels for the purpose of estimating nitrate exposures and potential risk of adverse health effects in the survey area. Results of the investigation revealed that 25 percent of the domestic-use wells in the survey area had nitrate levels that were in excess of the 10 ppm nN MCL for drinking water, as established by the U.S. Environmental Protection Agency. From access to these wells, 23 percent of the surveyed population was exposed to nitrate concentrations in excess of the MCL standard. However, resident infants were neither exposed to well-water nitrates in excess of the standard, nor were they exposed to illness that could have increased the risk of methemoglobinemia. The LUB survey population was generally older than the populations from cities in the LUB or the combined populations of rural areas of Morrow and Umatilla counties. The population included few women of childbearing age, and it was not subject to an appreciable increase in the proportion of younger to older families. These factors reduced the likelihood of a significant increase in the infant population, which also minimized the risk of methemoglobinemia to this population. Even though the risk of methemoglobinemia to infants was low in the LUB area, it is recommended that exposures to well-water nitrates be prevented, if possible even for adults, to reduce the potential for chronic, adverse health effects from excess nitrate ingestion. Continued monitoring of private wells by state agencies is recommended, with attention directed at domesticuse wells with nitrate levels in excess of 10 ppm nN. This information should be shared with local health departments for follow-up, investigation, and educational efforts as needed. Future studies by the Oregon DEQ, or other agencies which seek to document the sources of well-water nitrate contamination in the LUB, should include an investigation of the influence of local sources of nitrate contamination. / Graduation date: 1993

Thesis (M. Tech. (Environmental Health)) -- Central University of technology, Free State, 2013 / Introduction: Drinking water of poor quality can cause a variety of diseases and may even result in death. The impact of poor drinking water is a course for concern even in South Africa. Therefore, the physical, chemical and microbiological drinking water quality was investigated in the peri-urban area of Bainsvlei and the Woodlands Hills Estate in Bloemfontein, Free State. Materials and Methods: The water quality was assessed in 20 identified sampling sites for three series with ten weeks apart. These sites use treated municipal and untreated borehole water for drinking. The determinants analysed for were pH, electrical conductivity (EC), turbidity, temperature, Ca, Mg, Na, F, Cl, N, SO₄,N, Free chlorine, Al, As, CN, Fe, Mn, Pb, Hg, total coliforms and E. coli. The water samples were collected and analysed on site and in the laboratory. Both the physical and chemical determinants were measured using standard methods whereas the microbiological determinants were measured using the Defined Substrate Technology (DST) method. The measurements were first compared to the SANS 241 (2011) for compliance. The ANOVA tests were used to investigate if any seasonal variations existed in the water quality as well as to compare the levels of the determinants between borehole and municipal water. In the assessment of the overall drinking water quality of different water sampling sites the water quality index (WQI) was used. Results and Discussions: Significant effects were believed to exist if the p-values of the ANOVA and Scheffe tests were at a significance level of 5% (p < 0.05). The study results revealed that of the four physical determinants that were measured turbidity exceeded the standard in many sampling sites in the three series. Of all the chemical determinants, nitrates exceeded the standard. In the same way coliforms exceeded the standard in a number of sampling sites while E. coli was found in a few sampling sites in the first series. ANOVA tests revealed that seasonal variations existed between pH, EC, temperature, cyanide and iron at a significant level of 5% (p < 0.05) while the Post-hoc Scheffe test further revealed the series in which the effect existed. Similarly, the ANOVA tests revealed that the levels of the determinants between municipal versus borehole varied in pH, EC, Ca, Mg, Na, F, Cl, N, and SO₄ at a significant level of 5% (p < 0.05). The WQI showed that in all the series when combining the good and excellent category season 2 had the highest percentage of 80%, followed by season 3 with 79% and season 1 with 70%. Only borehole sampling sites were found in the poor, very poor and unsuitable categories. Similarly all the highest WQI values were found in borehole sampling sites. Conclusion: This study revealed that the water quality is of good quality in the Bainsvlei and Woodlands Hills Estate of the Mangaung metropolitan municipality in Bloemfontein, in the Free State, South Africa. The presence of E. coli, though found in a few sampling sites and the high levels of turbidity, nitrates and coliforms are of concern to public health.

O estuário de Santos abriga o maior porto da América Latina e um dos maiores complexos industriais do Brasil. Na década de 1970 foi considerado um dos maiores exemplos de degradação ambiental em ambientes costeiros, e apesar da melhora na qualidade ambiental observada nos últimos anos algumas áreas deste estuário apresentam sedimentos ainda altamente contaminados com compostos tóxicos e genotóxicos, especialmente os Hidrocarbonetos Policíclicos Aromáticos (HPA). Operações de dragagem para manutenção das atividades portuárias são necessárias e consequentemente durante este processo pode ocorrer a ressuspensão de contaminantes presentes nesses sedimentos, tornando-os disponíveis novamente na coluna d\'água. Desta forma é interessante ter uma estratégia eficiente e aplicável no monitoramento da qualidade dessas águas. O Blue rayon (BR) é um adsorvente seletivo para compostos policíclicos com três ou mais anéis fundidos em sua molécula e tem sido utilizado com sucesso no monitoramento de HPA e atividade mutagênica em ambientes aquáticos. Este trabalho teve como objetivo padronizar o uso da técnica de Blue rayon in situ ancorado, onde as fibras são fixas a uma distância padronizada dos sedimentos, associada ao teste de Salmonella/microssoma em microssuspensão a ser aplicada no monitoramento das águas desse estuário. Foram selecionados três pontos de amostragem com diferentes características e sedimentos com variados níveis de contaminação. As duas campanhas iniciais foram realizadas com o objetivo de avaliar a eficiência do BR e de escolher a linhagem de Salmonella mais sensível aos compostos mutagênicos possivelmente presentes nos extratos obtidos bem como verificar a presença de HPA. As cinco campanhas posteriores foram realizadas para verificar o comportamento e a eficiência da estratégia previamente definida no monitoramento das águas desse estuário utilizando experimentos de dose resposta. Os resultados obtidos nas duas primeiras campanhas mostraram que as águas do ponto 1, que contém os sedimentos mais contaminados e recebe os efluentes da COSIPA, apresentam maior contaminação por HPA e atividade genotóxica mais elevada que o ponto 2. Também foi possível determinar que a linhagem de Salmonella YG1041 foi a mais sensível para detectar atividade mutagênica tanto no ponto 1 quanto no ponto 2. Nas cinco campanhas subsequentes as maiores potências mutagênicas foram também observadas no ponto 1 com valores máximos de 5.100 e 36.000 revertentes/g de BR para a linhagem YG1041 na ausência e na presença de ativação metabólica (S9) respectivamente. Nos pontos 2 e 3 as potências observadas foram similares entre si, com valores em torno de 1.000 revertentes/g de BR. Com base nos resultados obtidos nas duas etapas deste trabalho pode-se concluir que a o Blue rayon utilizado in situ a uma distância padronizada dos sedimento associado ao teste de Salmonella/microssoma em microssuspensão com a linhagem YG1041 na presença e na ausência de ativação metabólica (S9) é uma ferramenta que pode ser aplicada no monitoramento da qualidade do estuário de Santos. / Santos estuary is the major Latin American harbor and one of the largest industrial complex of Brazil. In the 1970s, it was considered one of the major examples of coastal degradation. Due to enforcement actions the quality of the environment has improved in the last years in relation to the chemical parameters and toxicity but unfortunately the sediment is still contaminated with toxic and genotoxic compounds especially Polycyclic Aromatic Hydrocarbons (PAHs). For the maintenance of the port activities sediment dredging is needed and during this process contaminants resuspension can occur, leading to the contamination of the water column. Therefore it is interesting to have an efficient strategy that can be used for the water quality monitoring of this area. The Blue rayon is a selective adsorbent to polycyclic compounds containing three or more fused rings and has been successfully used in the monitoring of PAHs and mutagenic activity in aquatic environments. The objective of this work was to evaluate a modified blue rayon hanging technique, denominated in this work \"Blue rayon anchored technique\", where the fibers are placed at a fixed distance from the sediment, associated with the Salmonella/microsome microsuspension assay in order to monitor the water quality of Santos estuary. Three sites with different sources and sediment contamination levels were selected in this study. Two initial samplings were performed in order to evaluate the efficiency of the BR modified technique and find the most sensitive strain of Salmonella typhimurium to the mutagens possibly present in the those waters as well as verify the presence of PAHs. Five subsequent samplings were performed to verify the performance and efficiency of the defined strategy in the estuary water quality monitoring using dose response experiments. In the two initial samplings, the water from the site containing the most contaminated sediment and under influence of COSIPA (site 1) presented higher mutagenic activity and higher levels of PAHs. It was also possible to verify the highest sensitivity of the YG1041 strain in the detection of the mutagenic activity in both sites analyzed. In the subsequent five samplings, higher mutagenic potencies were again observed for site 1, reaching 5,100 and 36,000 revertants per gram of BR for the YG1 041 strain in the absence and presence of S9 respectively. Sites 2 and: presented similar potencies, around 1000 revertants per gram of BR. Based on the obtained results we can conclude that the Blue rayon anchored technique associated with the Salmonella/microsome microsuspension assay with the YG1041 strain in the presence and absence of S9 is an suitable tool to monito Santos estuarine waters.

Indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) are investigated for thin-film transistor (TFT) applications. Negative bias illumination stress (NBIS) is employed for electrical stability assessment. Unpassivated IGZO and ZTO TFTs suffer from severe NBIS instabilities. Zinc-tin-silicon oxide is found to be an effective passivation layer for IGZO and ZTO TFTs, significantly improving the NBIS stability. NBIS instabilities in unpassivated TFTs are attributed to an NBIS-induced desorption of chemisorbed oxygen from the channel layer top surface, exposing surface oxygen vacancies. A ZTSO layer protects the channel layer top surface from adsorbed gas interactions and also appears to reduce the density of oxygen vacancies. The best device architectures investigated with respect to TFT electrical performance are found to be staggered with aluminum electrodes for unpassivated TFTs and coplanar with ITO electrodes for ZTSO-passivated TFTs. Annealing in wet-O₂ is not found to be effective for improving the performance of IGZO or ZTO TFTs or for reducing the post-deposition annealing temperature. / Graduation date: 2012

Submitted by Guacira de Figueiredo Eufrasio Pauly null (guafe@yahoo.com.br) on 2018-03-22T19:42:28Z No. of bitstreams: 1 Avaliação da toxicidade de misturas Irgarol e contaminantes ambientais comumente observados em áreas costeiras.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) / Approved for entry into archive by Disleide Silvia Valerio Gounella null (disleide@clp.unesp.br) on 2018-03-23T18:54:19Z (GMT) No. of bitstreams: 1 pauly_gfe_me_svic.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) / Made available in DSpace on 2018-03-23T18:54:19Z (GMT). No. of bitstreams: 1 pauly_gfe_me_svic.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) Previous issue date: 2018-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Alguns contaminantes encontrados no ambiente costeiro incluem os princípios ativos de tintas anti-incrustantes, entre os quais se destaca o Irgarol. O Irgarol pode interagir com outros contaminantes comuns em áreas litorâneas antropizadas, tais como a amônia e os surfactantes, sendo que os efeitos dessas combinações são desconhecidos. O objetivo do presente trabalho foi avaliar a toxicidade de misturas binárias do biocida Irgarol com amônia e surfactante Alquil. Benzeno Sulfonado Linear - LAS, além das toxicidades dessas substâncias isoladas. Essa avaliação foi realizada em duas etapas. Na primeira etapa, náuplios de Artemia sp., copépodo Nitocra sp. e embriões de ouriço do mar Echinometra lucunter, foram expostos às concentrações isoladas de Irgarol, amônia e LAS, para definição dos níveis tóxicos dessas substâncias às espécies testadas. Na segunda etapa, náuplios de Artemia sp. foram expostos a uma mistura binária de contaminantes (i.é. Irgarol + amônia; ou Irgarol + LAS) a fim de se avaliar se as toxicidades das misturas seguem o padrão aditivo, sinérgico ou antagônico. Os dados obtidos da primeira etapa dos testes realizados com náuplios de Artemia sp. expostos à amônia, LAS e Irgarol apresentaram CL50-48h 122,85 mg/L, 21,21 mg/L, e 1,81 mg/L, respectivamente, e CEO de 100 mg/L, 81 mg/L e 10 mg/L, respectivamente. Para os testes realizados com os copépodos Nitocra sp., as respectivas CI50-7d foram estimadas em 27,89 mg/L, 4,61 mg/L, e 0,13 mg/L, enquanto as CEO foram 100 mg/L, 8,1 mg/L, e 10 mg/L. A CE50-42h obtida nos testes com embriões de Echinometra lucunter expostos à amônia foi de 0,32 mg/L, enquanto a CEO foi de 0,1 mg/L. Todas as concentrações de exposição ao LAS foram tóxicas para os embriões de Echinometra lucunter, e não foi observada toxicidade do Irgarol. Ambas as misturas binárias de Irgarol e amônia e Irgarol e LAS apresentaram melhor ajuste para o modelo IA (ação independente), com efeitos antagônicos e sinérgicos, respectivamente. As ferramentas utilizadas foram úteis para prever o padrão de respostas das misturas químicas sobre as espécies. / Contaminants found in the coastal environment include antifouling biocides, such as the Irgarol, ammonia and surfactants, among others. Since they can occur together in the environment, they can interact with each other and the resulting toxicities of their combinations are unknown. The aim this work was to evaluate the toxicity of binary mixtures of Irgarol with ammonia and the surfactant Linear Alkyl-Benzene Sulfonate - LAS, as well as the toxicity these single substances. This investigation was made in two steps. In the first step, nauplii of Artemia sp., the marine organisms Nitocra sp. (Copepoda), and embryos of the sea urchin Echinometra lucunter, were exposed to concentrations of Irgarol, ammonia and LAS, in order to define the toxic levels of each chemical to marine species. In the second step, nauplii of Artemia sp. were exposed to binary mixtures of the contaminants (Irgarol + ammonia; or Irgarol + LAS) in order to evaluate if the toxicities of the mixtures follow addictive, synergistic or antagonistic patterns. To nauplii Artemia sp. exposed to ammonia, LAS and Irgarol, the LC50-48h values were 122.85 mg/L, 21.21 mg/L, and 1.81 mg/L, respectively, and the LOECs were 100 mg/L, 81 mg/L and 10 mgl/L, respectively. The respective IC50-7d obtained in the tests with the copepod Nitocra sp., were 27.89 mg/L, 4.61 mg/L and 0.13 mg/L, while the LOECs were 100 mg/L, 8.1 mg/L and 10 mg/L. For the E. lucunter embryos, the EC50-42h of ammonia was 0.32 mg/L, while the LOEC was 0.1 mg/L. All the tested concentrations of LAS were toxic to the embryos of E. lucunter, where Irgarol did not caused toxicity to these organisms. Both binary mixtures of Irgarol and ammonia and Irgarol and LAS showed better fit to the model IA (Independent Action), with antagonistic and synergistic effects, respectively. The used tools were useful to predict the toxicities of chemical mixtures to marine tropical species. / 4693520

CAPES / Muitos estudos demonstram que ocupações irregulares, descartes inadequados de resíduo e ineficiência no tratamento de efluentes, têm reduzido a qualidade dos corpos hídricos. Além das altas concentrações de nutrientes, baixas concentrações de oxigênio e elevadas cargas de matéria orgânica, os rios da região de Curitiba também estão contaminados com diversos micro poluentes orgânicos. Os contaminantes emergentes começaram a ser detectados recentemente, em baixas concentrações, mas são comprovadamente tóxicos aos seres vivos, devido à exposição constante. A fim de conhecer a situação atual do rio Barigui foram realizadas duas coletas, uma sazonal e outra de 24 h. Na sazonal foram coletadas amostras de água em 3 pontos do rio, nos meses de março, junho e novembro de 2015 e foram analisados cafeína, fenofibrato, genfibrozila, paracetamol, ibuprofeno, diclofenaco, naproxeno, cetoprofeno, ácido acetilsalicílico, ácido salicílico, estrona, estradiol, etinilestradiol, metilparabeno, etilparabeno, propilparabeno, butilparabeno, benzilparabeno e triclosan. Na de 24 h foram monitorados dois pontos, um à montante e outro à jusante da Estação de Tratamento de Esgoto (ETE) Santa Quitéria, em junho de 2016. Nesta foram estudados, na água, diversos parâmetros físicos e químicos, matéria orgânica, nutrientes, todos as substâncias citadas acima, progesterona, octocrileno, etilhexil metoxicinamato e 4-metilbenzelideno cânfora. Entre as concentrações máximas obtidas, o ácido salicílico foi o que apresentou a maior concentração e maior variação entre a coleta sazonal (2,38 μg L-1 ) e a de 24 h (31,85 μg L-1 ). A cafeína apresentou detecção de 100 %, comprovando sua presença constante no ambiente. Ela também apresentou boa correlação com nitrogênio amoniacal (r = 0,87; p < 0,0001; n = 24) e os demais contaminantes apresentaram boas correlações entre si, como por exemplo paracetamol e o ácido salicílico (r = 0,9434; p < 0,0001; n = 24). Os estrogênios tiveram detecção baixa, e não foram quantificados na maioria dos pontos. O estudo dos parabenos e dos filtros UV foi interessante para avaliar os picos de maior produção de esgoto. As maiores concentrações foram detectadas à jusante da ETE às 15 h, que equivale às 7 h, considerando o tempo de detenção hidráulica da estação. As correlações obtidas e as maiores concentrações no ponto BA-J, sugerem que esses compostos têm uma fonte em comum, sendo provavelmente efluentes clandestinos e/ou provenientes das ETEs. Sendo assim, a melhoria nos tratamentos de efluentes é imprescindível, a fim de reduzir a concentração dessas substâncias no ambiente. É importante também um estudo de priorização de contaminantes, levando em consideração as concentrações de exposição e toxicidade, para inseri-los em legislações futuras com limites de lançamento nos corpos aquáticos. Além disso, há necessidade de estudar o comportamento dessas substâncias no meio ambiente e de aprimorar as técnicas analíticas, a fim de conseguir monitorar simultaneamente metabólitos e substâncias com concentrações ainda mais baixas, de maneira automatizada e rápida, com sensibilidade e seletividade. / Many studies have demonstrated that irregular occupations, inadequate waste disposal, inefficiency in the treatment of effluents, have reduced the quality of water bodies. In addition to the high concentrations of nutrients, low concentration of oxygen and high organic matter loads, the rivers in the Curitiba region are also contaminated with several organic micro pollutants. The emerging contaminants (EC) recently began to be detected in low concentrations, but they are proven toxic to living beings due to constant exposure. In order to know the current situation of the Barigui River, two samplings were made, a seasonal and another of 24 hours. In the seasonal sampling, water samples were collected at 3 points in the river, in the months of March, July and November of 2015. In addition, were analyzed caffeine, fenofibrate, gemfibrozil, acetaminophen, ibuprofen, diclofenac, naproxen, ketoprofen, acetylsalicylic acid, salicylic acid, estrone, estradiol, ethinylestradiol, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, benzyl paraben and triclosan. At the 24 h sampling, two points were monitored, one upstream and one downstream from the Santa Quitéria Wastewater Treatment Plant (WWTP), in June 2016. In this sampling, several physical and chemical parameters, organic matter, nutrients, all substances mentioned above, progesterone, octocrylene, ethylhexyl methoxycinnamate and 4-methylbenzelidene camphor were studied in the water. Among the maximum concentrations of EC in the water, salicylic acid presented the highest concentration and a greater variation between the seasonal sampling (2.38 μg L-1 ) and the 24 h sampling (31.85 μg L-1 ). Caffeine presented 100% of detection, confirming its constant presence in the environment. It also presented good correlation with ammoniacal nitrogen (r = 0.87, p <0.0001, n = 24) and the other contaminants showed good correlations with each other, such as paracetamol and salicylic acid (r = 0.9434; <0.0001; n = 24). Estrogens presented low detection, and were not quantified at most points. The study of parabens and UV filters was interesting to evaluate the peaks of higher sewage production. The highest concentrations were detected downstream from WWTP at the 15 h, which is equivalent to the 7 h, considering the hydraulic holding time of the treatment plant. The correlations obtained and the highest concentration values in the BA-J point suggest that these compounds have a common source, probably been clandestine effluents and/or derived from the WWTPs. Therefore, the improvement on effluent treatment is indispensable to reduce the concentration of these substances on the environment. A prioritization study of contaminants is also important, considering the exposure concentrations and toxicity, to incorporate them into future legislation and establish release limits on aquatic bodies. In addition, it is necessary to study the behavior of these substances in the environment and improve analytical techniques. In order to be able to simultaneously monitor metabolites and substances with even lower concentrations, in a fast, automated way, with sensitivity and selectivity.

CAPES / Muitos estudos demonstram que ocupações irregulares, descartes inadequados de resíduo e ineficiência no tratamento de efluentes, têm reduzido a qualidade dos corpos hídricos. Além das altas concentrações de nutrientes, baixas concentrações de oxigênio e elevadas cargas de matéria orgânica, os rios da região de Curitiba também estão contaminados com diversos micro poluentes orgânicos. Os contaminantes emergentes começaram a ser detectados recentemente, em baixas concentrações, mas são comprovadamente tóxicos aos seres vivos, devido à exposição constante. A fim de conhecer a situação atual do rio Barigui foram realizadas duas coletas, uma sazonal e outra de 24 h. Na sazonal foram coletadas amostras de água em 3 pontos do rio, nos meses de março, junho e novembro de 2015 e foram analisados cafeína, fenofibrato, genfibrozila, paracetamol, ibuprofeno, diclofenaco, naproxeno, cetoprofeno, ácido acetilsalicílico, ácido salicílico, estrona, estradiol, etinilestradiol, metilparabeno, etilparabeno, propilparabeno, butilparabeno, benzilparabeno e triclosan. Na de 24 h foram monitorados dois pontos, um à montante e outro à jusante da Estação de Tratamento de Esgoto (ETE) Santa Quitéria, em junho de 2016. Nesta foram estudados, na água, diversos parâmetros físicos e químicos, matéria orgânica, nutrientes, todos as substâncias citadas acima, progesterona, octocrileno, etilhexil metoxicinamato e 4-metilbenzelideno cânfora. Entre as concentrações máximas obtidas, o ácido salicílico foi o que apresentou a maior concentração e maior variação entre a coleta sazonal (2,38 μg L-1 ) e a de 24 h (31,85 μg L-1 ). A cafeína apresentou detecção de 100 %, comprovando sua presença constante no ambiente. Ela também apresentou boa correlação com nitrogênio amoniacal (r = 0,87; p < 0,0001; n = 24) e os demais contaminantes apresentaram boas correlações entre si, como por exemplo paracetamol e o ácido salicílico (r = 0,9434; p < 0,0001; n = 24). Os estrogênios tiveram detecção baixa, e não foram quantificados na maioria dos pontos. O estudo dos parabenos e dos filtros UV foi interessante para avaliar os picos de maior produção de esgoto. As maiores concentrações foram detectadas à jusante da ETE às 15 h, que equivale às 7 h, considerando o tempo de detenção hidráulica da estação. As correlações obtidas e as maiores concentrações no ponto BA-J, sugerem que esses compostos têm uma fonte em comum, sendo provavelmente efluentes clandestinos e/ou provenientes das ETEs. Sendo assim, a melhoria nos tratamentos de efluentes é imprescindível, a fim de reduzir a concentração dessas substâncias no ambiente. É importante também um estudo de priorização de contaminantes, levando em consideração as concentrações de exposição e toxicidade, para inseri-los em legislações futuras com limites de lançamento nos corpos aquáticos. Além disso, há necessidade de estudar o comportamento dessas substâncias no meio ambiente e de aprimorar as técnicas analíticas, a fim de conseguir monitorar simultaneamente metabólitos e substâncias com concentrações ainda mais baixas, de maneira automatizada e rápida, com sensibilidade e seletividade. / Many studies have demonstrated that irregular occupations, inadequate waste disposal, inefficiency in the treatment of effluents, have reduced the quality of water bodies. In addition to the high concentrations of nutrients, low concentration of oxygen and high organic matter loads, the rivers in the Curitiba region are also contaminated with several organic micro pollutants. The emerging contaminants (EC) recently began to be detected in low concentrations, but they are proven toxic to living beings due to constant exposure. In order to know the current situation of the Barigui River, two samplings were made, a seasonal and another of 24 hours. In the seasonal sampling, water samples were collected at 3 points in the river, in the months of March, July and November of 2015. In addition, were analyzed caffeine, fenofibrate, gemfibrozil, acetaminophen, ibuprofen, diclofenac, naproxen, ketoprofen, acetylsalicylic acid, salicylic acid, estrone, estradiol, ethinylestradiol, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, benzyl paraben and triclosan. At the 24 h sampling, two points were monitored, one upstream and one downstream from the Santa Quitéria Wastewater Treatment Plant (WWTP), in June 2016. In this sampling, several physical and chemical parameters, organic matter, nutrients, all substances mentioned above, progesterone, octocrylene, ethylhexyl methoxycinnamate and 4-methylbenzelidene camphor were studied in the water. Among the maximum concentrations of EC in the water, salicylic acid presented the highest concentration and a greater variation between the seasonal sampling (2.38 μg L-1 ) and the 24 h sampling (31.85 μg L-1 ). Caffeine presented 100% of detection, confirming its constant presence in the environment. It also presented good correlation with ammoniacal nitrogen (r = 0.87, p <0.0001, n = 24) and the other contaminants showed good correlations with each other, such as paracetamol and salicylic acid (r = 0.9434; <0.0001; n = 24). Estrogens presented low detection, and were not quantified at most points. The study of parabens and UV filters was interesting to evaluate the peaks of higher sewage production. The highest concentrations were detected downstream from WWTP at the 15 h, which is equivalent to the 7 h, considering the hydraulic holding time of the treatment plant. The correlations obtained and the highest concentration values in the BA-J point suggest that these compounds have a common source, probably been clandestine effluents and/or derived from the WWTPs. Therefore, the improvement on effluent treatment is indispensable to reduce the concentration of these substances on the environment. A prioritization study of contaminants is also important, considering the exposure concentrations and toxicity, to incorporate them into future legislation and establish release limits on aquatic bodies. In addition, it is necessary to study the behavior of these substances in the environment and improve analytical techniques. In order to be able to simultaneously monitor metabolites and substances with even lower concentrations, in a fast, automated way, with sensitivity and selectivity.

O estuário de Santos abriga o maior porto da América Latina e um dos maiores complexos industriais do Brasil. Na década de 1970 foi considerado um dos maiores exemplos de degradação ambiental em ambientes costeiros, e apesar da melhora na qualidade ambiental observada nos últimos anos algumas áreas deste estuário apresentam sedimentos ainda altamente contaminados com compostos tóxicos e genotóxicos, especialmente os Hidrocarbonetos Policíclicos Aromáticos (HPA). Operações de dragagem para manutenção das atividades portuárias são necessárias e consequentemente durante este processo pode ocorrer a ressuspensão de contaminantes presentes nesses sedimentos, tornando-os disponíveis novamente na coluna d\'água. Desta forma é interessante ter uma estratégia eficiente e aplicável no monitoramento da qualidade dessas águas. O Blue rayon (BR) é um adsorvente seletivo para compostos policíclicos com três ou mais anéis fundidos em sua molécula e tem sido utilizado com sucesso no monitoramento de HPA e atividade mutagênica em ambientes aquáticos. Este trabalho teve como objetivo padronizar o uso da técnica de Blue rayon in situ ancorado, onde as fibras são fixas a uma distância padronizada dos sedimentos, associada ao teste de Salmonella/microssoma em microssuspensão a ser aplicada no monitoramento das águas desse estuário. Foram selecionados três pontos de amostragem com diferentes características e sedimentos com variados níveis de contaminação. As duas campanhas iniciais foram realizadas com o objetivo de avaliar a eficiência do BR e de escolher a linhagem de Salmonella mais sensível aos compostos mutagênicos possivelmente presentes nos extratos obtidos bem como verificar a presença de HPA. As cinco campanhas posteriores foram realizadas para verificar o comportamento e a eficiência da estratégia previamente definida no monitoramento das águas desse estuário utilizando experimentos de dose resposta. Os resultados obtidos nas duas primeiras campanhas mostraram que as águas do ponto 1, que contém os sedimentos mais contaminados e recebe os efluentes da COSIPA, apresentam maior contaminação por HPA e atividade genotóxica mais elevada que o ponto 2. Também foi possível determinar que a linhagem de Salmonella YG1041 foi a mais sensível para detectar atividade mutagênica tanto no ponto 1 quanto no ponto 2. Nas cinco campanhas subsequentes as maiores potências mutagênicas foram também observadas no ponto 1 com valores máximos de 5.100 e 36.000 revertentes/g de BR para a linhagem YG1041 na ausência e na presença de ativação metabólica (S9) respectivamente. Nos pontos 2 e 3 as potências observadas foram similares entre si, com valores em torno de 1.000 revertentes/g de BR. Com base nos resultados obtidos nas duas etapas deste trabalho pode-se concluir que a o Blue rayon utilizado in situ a uma distância padronizada dos sedimento associado ao teste de Salmonella/microssoma em microssuspensão com a linhagem YG1041 na presença e na ausência de ativação metabólica (S9) é uma ferramenta que pode ser aplicada no monitoramento da qualidade do estuário de Santos. / Santos estuary is the major Latin American harbor and one of the largest industrial complex of Brazil. In the 1970s, it was considered one of the major examples of coastal degradation. Due to enforcement actions the quality of the environment has improved in the last years in relation to the chemical parameters and toxicity but unfortunately the sediment is still contaminated with toxic and genotoxic compounds especially Polycyclic Aromatic Hydrocarbons (PAHs). For the maintenance of the port activities sediment dredging is needed and during this process contaminants resuspension can occur, leading to the contamination of the water column. Therefore it is interesting to have an efficient strategy that can be used for the water quality monitoring of this area. The Blue rayon is a selective adsorbent to polycyclic compounds containing three or more fused rings and has been successfully used in the monitoring of PAHs and mutagenic activity in aquatic environments. The objective of this work was to evaluate a modified blue rayon hanging technique, denominated in this work \"Blue rayon anchored technique\", where the fibers are placed at a fixed distance from the sediment, associated with the Salmonella/microsome microsuspension assay in order to monitor the water quality of Santos estuary. Three sites with different sources and sediment contamination levels were selected in this study. Two initial samplings were performed in order to evaluate the efficiency of the BR modified technique and find the most sensitive strain of Salmonella typhimurium to the mutagens possibly present in the those waters as well as verify the presence of PAHs. Five subsequent samplings were performed to verify the performance and efficiency of the defined strategy in the estuary water quality monitoring using dose response experiments. In the two initial samplings, the water from the site containing the most contaminated sediment and under influence of COSIPA (site 1) presented higher mutagenic activity and higher levels of PAHs. It was also possible to verify the highest sensitivity of the YG1041 strain in the detection of the mutagenic activity in both sites analyzed. In the subsequent five samplings, higher mutagenic potencies were again observed for site 1, reaching 5,100 and 36,000 revertants per gram of BR for the YG1 041 strain in the absence and presence of S9 respectively. Sites 2 and: presented similar potencies, around 1000 revertants per gram of BR. Based on the obtained results we can conclude that the Blue rayon anchored technique associated with the Salmonella/microsome microsuspension assay with the YG1041 strain in the presence and absence of S9 is an suitable tool to monito Santos estuarine waters.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Atualmente, uma das maiores preocupações da humanidade é com a disponibilidade e qualidade da água. A exploração inadequada das fontes acarreta a contaminação das águas superficiais e subterrâneas que se tornam um risco para a saúde pública. Dentre as fontes biológicas de contaminação da água, incluem-se as bactérias, que são responsáveis por inúmeras doenças, sendo frequentemente tratadas com antimicrobianos. O amplo uso de antimicrobianos na medicina humana e na produção animal tem resultado no aumento do número de bactérias comensais e patogênicas resistentes a agentes antimicrobianos, fato que nos últimos anos vem se tornando um dos principais problemas de saúde pública. O presente trabalho resulta do interesse pelo estudo da qualidade da água consumida pelos alunos de 20 escolas estaduais da rede pública de Boa Vista RR, bem como obter o perfil de resistência a antimicrobianos de bactérias isoladas a partir de diferentes amostras de águas, coletadas nessas escolas. No período de outubro de 2010 a abril de 2011, foram coletas 40 amostras de águas de torneiras das copas e 40 amostras de águas de bebedouros, as quais foram submetidas à avaliação microbiológica. A determinação dos coliformes totais e termotolerantes foi realizada por meio da técnica dos tubos múltiplos com 3 diluições e série de 5 tubos. Para a detecção de bactérias heterotróficas uso-se o método pour plate, de acordo com as normas preconizadas no Standard Methods for the Examination of Water and Wastwater. O isolamento e a identificação dos isolados bacteriano foi realizada no LACEN-RR utilizando-se a série bioquímica. Para a avaliação da resistência aos antimicrobianos, utilizou-se a metodologia de difusão de disco, seguindo as normas estabelecidas pelo CLSI. Das amostras de águas que recebem tratamento completo, 10% apresentaram resultados positivos para coliformes totais e nas amostras de água clorada, 20% apresentaram resultados positivos para coliformes totais e 2,5% resultado positivo para coliformes termotolerantes, o que as tornam imprópria para o consumo humano. A contagem de bactérias heterotróficas variou de 1,4 x 10 a 3,6 x 102 UFC/mL de água, não ultrapassando o estabelecido pela Portaria 518/2004/MS. Foram identificadas as seguintes bactérias Gram-negativas (66,7%): Acinetobacter spp., C. violacea, Cocobacilos spp., E. aerogenes, E. coli, K. ozaenae, Leptothrix ssp. e Bacilo Gram-negativo não fermentador de glicose, as bactérias Gram-positivas (33,3%), identificadas foram: B. subtilis, Micrococcus spp., S. aureus e Staphylococcus spp. Os resultados dos testes de sensibilidade aos antibióticos revelaram que a maioria das bactérias isoladas foi resistente a ampicilina (68,2%), 27,3% apresentaram resistência a oxacilina e 22,7% foram resistentes a eritromicina e meropenem. As cepas de S. aureus isoladas das amostras de águas apresentaram maior índice MAR (0,61) entre as bactérias Gram-positivas, enquanto que nas bactérias Gram-negativas, as cepas que apresentaram maior índice MAR foram as cepas de E. coli, com índice 0,61. Os resultados comprovam a ocorrência de instabilidade no padrão de qualidade da água fornecida a população de Boa Vista RR seja no tratamento, na distribuição ou no armazenamento da água. Além de constatar a presença de bactérias multirresistentes a antibióticos, o que representa risco à população. / One of the main concerns of humanity nowadays is water: its availability and its quality. An inadequate exploitation of the sources results in the contamination of both superficial and deep waters, which become a public health hazard. Bacteria are one of these biological sources of water contamination, responsible for countless diseases which are treated with antimicrobials. The widely spread use of antimicrobials in human medicine along with animal production had resulted in a steady increase in the number of pathogenic and commensal bacteria resistant to antimicrobial agents, which in recent years are becoming one of the main problems of public health. This paper is a result of an interest in studying the quality of water consumed by the students of 20 state schools of the public school system of Boa Vista RR, as well as trying to obtain a profile of antimicrobial resistance of the bacteria isolated in different water samples collected at these schools. Between October 2010 and April 2011, 40 water samples were collected from taps in lunchrooms, along with 40 samples from drinking wells, and all of them were submitted to microbiological examination. Using the multiple tubes technique, with 3 dilutions and a series of 5 tubes, we determined the total number of coliforms and thermotolerant coliforms. In agreement with the rules of the Standard Methods for the Examination of Water and Wastewater, the pour plate method was used at the CBio UFRR to detect heterotrophic bacteria. Isolation and identification of microorganisms was done at LACEN RR, using the biochemical series. In evaluating the resistance to antimicrobials, disk diffusion methods were used, in agreement with the established rules of the CLSI. In water samples that receive full treatment, 10% tested positive for total coliforms and, in chlorinated water samples, 20% tested positive for total coliforms and 2,5% for thermo-tolerant coliforms, which makes them inadequate for human consume. The counting of heterotrophic bacteria went from 1,4 x 10 to 3,6 x 10 CFU/mL of water, not surpassing what is established in the ordinance 518/2004/MS. The following Gram-negative bacteria (66,7%) were identified: Acinetobacter spp., C. violacea, Cocobacilos spp., E. aerogenes, E. coli, K. ozaenae, Leptothrix ssp. and Gram-negative glucose non fermenting bacillus. The Gram-positive bacteria identified were: B. subtilis, Micrococcus spp., S. aureus and Staphylococcus spp. The results of antibiotic sensibility tests revealed that most of the isolated bacteria were resistant to ampicilin (68,2%), 22,3% showed resistance to oxacilin and 22,7% were resistant to both eritromicin and meropenem. In Gram-positive bacteria, the growths of S. aureus isolated from water samples showed the greatest MAR index (0,61), while E. coli growths were the ones who showed the greatest MAR index in Gram-negative bacteria (also 6,1%). Results prove a great instability in the quality of water provided to the Boa Vista - RR population, being in its treatment, distribution or containment, as well as showing the presence of bacteria resistant to multiple antibiotics, which is a health hazard to the public.

Increasing nitrate concentration in ground water from improper disposal of sewage and excessive use of fertilizers is deleterious to human health as ingestion of nitrate contaminated water can cause methaemoglobinemia in infants and possibly cancer in adults. The permissible limit for nitrate in potable water is 45 mg/L. Unacceptable levels of nitrate in groundwater is an important environmental issue as nearly 80 % of Indian rural population depends on groundwater as source of drinking water. Though numerous technologies such as reverse osmosis, ion exchange, electro-dialysis, permeable reactive barriers using zero-valent iron exists, nitrate removal from water using affordable, sustainable technology, continues to be a challenging issue as nitrate ion is not amenable to precipitation or removable by mineral adsorbents. Tapping the denitrification potential of soil denitrifiers which are inherently available in the soil matrix is a possible sustainable approach to remove nitrate from contaminated drinking water. Insitu denitrification is a useful process to remove NO3–N from water and wastewater. In biological denitrification, nitrate ions function as terminal electron acceptor instead of oxygen; the carbon source serve as electron donor and the energy generated in the redox process is utilized for microbial cell growth and maintenance. In this process, microorganisms first reduce nitrate to nitrite and then produce nitric oxide, nitrous oxide, and nitrogen gas. The pathway for nitrate reduction can be written as: NO3-→ NO2-→ NO → N2O → N2. (i) Insitu denitrification process occurring in soil environments that utilizes indigenous soil microbes is the chosen technique for nitrate removal from drinking water in this thesis. As presence of clay in soil promotes bacterial activity, bentonite clay was mixed with natural sand and this mix, referred as bentonite enhanced sand (BES) acted as the habitat for the denitrifying bacteria. Nitrate reduction experiments were carried out in batch studies using laboratory prepared nitrate contaminated water spiked with ethanol; the batch studies examined the mechanisms, kinetics and parameters influencing the heterotrophic denitrification process. Optimum conditions for effective nitrate removal by sand and bentonite enhanced sand (BES) were evaluated. Heterotrophic denitrification reactors were constructed with sand and BES as porous media and the efficiency of these reactors in removing nitrate from contaminated water was studied. Batch experiments were performed at 40°C with sand and bentonite enhanced sand specimens that were wetted with nutrient solution containing 22.6 mg of nitrate-nitrogen and ethanol to give C/N ratio of 3. The moist sand and BES specimens were incubated for periods ranging from 0 to 48 h. During nitrate reduction, nitrite ions were formed as intermediate by-product and were converted to gaseous nitrogen. There was little formation of ammonium ions in the soil–water extract during reduction of nitrate ions. Hence it was inferred that nitrate reduction occurred by denitrification than through dissimilatory nitrate reduction to ammonium (DNRA). The reduction in nitrate concentration with time was fitted into rate equations and was observed to follow first order kinetics with a rate constant of 0.118 h-1 at 40°C. Results of batch studies also showed that the first order rate constant for nitrate reduction decreased to 5.3x10-2 h-1 for sand and 4.3 x10-2 h-1 for bentonite-enhanced sand (BES) at 25°C. Changes in pH, redox potential and dissolved oxygen in the soil-solution extract served as indicators of nitrate reduction process. The nitrate reduction process was associated with increasing pH and decreasing redox potential. The oxygen depletion process followed first order kinetics with a rate constant of 0.26 h-1. From the first order rate equation of oxygen depletion process, the nitrate reduction lag time was computed to be 12.8 h for bentonite enhanced sand specimens. Ethanol added as an electron donor formed acetate ions as an intermediate by-product that converted to bicarbonate ions; one mole of nitrate reduction generated 1.93 moles of bicarbonate ions that increased the pH of the soil-solution extract. The alkaline pH of BES specimen (8.78) rendered it an ideal substrate for soil denitrification process. In addition, the ability of bentonite to stimulate respiration by maintaining adequate levels of pH for sustained bacterial growth and protected bacteria in its microsites against the effect of hypertonic osmotic pressures, promoting the rate of denitrification. Buffering capacity of bentonite was mainly due to high cation exchange capacity of the clay. The presence of small pores in BES specimens increased the water retention capacity that aided in quick onset of anaerobiosis within the soil microsites. The biochemical process of nitrate reduction was affected by physical parameters such as bentonite content, water content, and temperature and chemical parameters such as C/N ratio, initial nitrate concentration and presence of indigenous micro-organisms in contaminated water. The rate of nitrate reduction process progressively increased with bentonite content but the presence of bentonite retarded the conversion of nitrite ions to nitrogen gas, hence there was significant accumulation of nitrite ions with increase in bentonite content. The dependence of nitrate reduction process on water content was controlled by the degree of saturation of the soil specimens. The rate of nitrate reduction process increased with water content until the specimens were saturated. The threshold water content for nitrate reduction process for sand and bentonite enhanced sand specimens was observed to be 50 %. The rate of nitrate reduction linearly increased with C/N ratio till steady state was attained. The optimum C/N ratio was 3 for sand and bentonite enhanced sand specimens. The activation energy (Ea) for this biochemical reaction was 35.72 and 47.12 kJmol-1 for sand and BES specimen respectively. The temperature coefficient (Q10) is a measure of the rate of change of a biological or chemical system as a consequence of increasing the temperature by 10°C. The temperature coefficient of sand and BES specimen was 2.0 and 2.05 respectively in the 15–25°C range; the temperature coefficients of sand and BES specimens were 1.62 and 1.77 respectively in the 25–40°C range. The rate of nitrate reduction linearly decreased with increase in initial nitrate concentration. The biochemical process of nitrate reduction was unaffected by presence of co-ions and nutrients such as phosphorus but was influenced by presence of pathogenic bacteria. Since nitrate leaching from agricultural lands is the main source of nitrate contamination in ground water, batch experiments were performed to examine the role of vadose (unsaturated soil) zone in the nitrate mitigation by employing sand and BES specimens with varying degree of soil saturation and C/N ratio as controlling parameters. Batch studies with sand and BES specimens showed that the incubation period required to reduce nitrate concentrations below 45 mg/L (t45) strongly depends on degree of saturation when there is inadequate carbon source available to support denitrifying bacteria; once optimum C/N ratio is provided, the rate of denitrification becomes independent of degree of soil saturation. The theoretical lag time (lag time refers to the period that is required for denitrification to commence) for nitrate reduction for sand specimens at Sr= 81 and 90%, C/N ratio = 3 and temperature = 40ºC corresponded to 24.4 h and 23.1 h respectively. The lag time for BES specimens at Sr = 84 and 100%, C/N ratio = 3 and temperature = 40ºC corresponded to 13.9 h and 12.8 h respectively. Though the theoretically computed nitrate reduction lag time for BES specimens was nearly half of sand specimens, it was experimentally observed that nitrate reduction proceeds immediately without any lag phase in sand and BES specimens suggesting the simultaneous occurrence of anaerobic microsites in both. Denitrification soil columns (height = 5 cm and diameter = 8.2 cm) were constructed using sand and bentonite-enhanced sand as porous reactor media. The columns were permeated with nitrate spiked solutions (100 mg/L) and the outflow was monitored for various chemical parameters. The sand denitrification column (packing density of 1.3 Mg/m3) showed low nitrate removal efficiency because of low hydraulic residence time (1.32 h) and absence of carbon source. A modified sand denitrification column constructed with higher packing density (1.52 Mg/m3) and ethanol addition to the influent nitrate solution improved the reactor performance such that near complete nitrate removal was achieved after passage of 50 pore volumes. In comparison, the BES denitrification column achieved 87.3% nitrate removal after the passage of 28.9 pore volumes, corresponding to 86 h of operation of the BES reactor. This period represents the maturation period of bentonite enhanced sand bed containing 10 % bentonite content. Though nitrate reduction is favored by sand bed containing 10 % bentonite, the low flow rate (20-25 cm3/h) impedes its use for large scale removal of nitrate from drinking water. Hence new reactor was designed using lower bentonite content of 5 % that required maturation period of 9.6 h. The 5 and 10 % bentonite-enhanced sand reactors bed required shorter maturation period than sand reactor as presence of bentonite contributes to increase in hydraulic retention time of nitrate within the reactor. On continued operation of the BES reactors, reduction in flow rate from blocking of pores by microbial growth on soil particles and accumulation of gas molecules was observed that was resolved by backwashing the reactors.