A presente pesquisa objetivou estudar a remoção dos poluentes presentes em uma água residuária de coqueria, através do processo biológico de nitritação/desnitritação operando um reator de lodo ativado em bateladas seqüenciais em duas etapas sucessivas. Durante a primeira, o reator foi alimentado com um efluente sintético composto por dois poluentes abundantes em despejos de coqueria: nitrogênio amoniacal (500 mg N/L) e fenol (1.000 mg C6H5OH/L). Na segunda, o reator foi alimentado com o despejo gerado na unidade de coqueria de uma indústria siderúrgica integrada. Ao longo da primeira etapa, ao final da fase aeróbia dos 28 ciclos de tratamento, foi possível alcançar eficiências de remoção de N-NH3 superiores a 90% com predominância do N-NO2 - na massa líquida do reator evidenciado pelas relações N-NO2 -/ (N-NO2 - + N-NO3 -) superiores a 86%. O principal mecanismo de inibição das bactérias oxidantes de nitrito (BON) foram concentrações de amônia livre no conteúdo do reator entre 3,2 e 19,5 mg NH3/L. As taxas específicas de nitritação variaram entre 0,03 e 0,11 kg N-NH3/ kg SSV.dia, para temperaturas no conteúdo do reator entre 15 e 34°C. Durante a fase anóxica, o fenol mostrou-se adequado como fonte de carbono para a biomassa desnitritante, desde que as taxas de aplicação volumétricas fossem inferiores a 0,02 kg fenol/m³.hora. Respeitando essa condição, foi possível alcançar: eficiências de remoção de fenol entre 45 e 56%; taxas específicas de remoção de fenol entre 0,03 e 0,09 kg C6H5OH / kg SSV.dia; taxas específicas de desnitritação entre 0,03 e 0,06 kg N-NO2 -/ kg SSV.dia e eficiências de remoção de (N-NO2 - + N-NO3 -) superiores a 95%. Ao longo da fase anóxica foram retiradas amostras do conteúdo do reator para a realização de análises de nitrofenóis (NF). Os resultados acusaram a presença de 2 nitrofenol e 4 nitrofenol em concentrações proporcionais à taxa de aplicação volumétrica do fenol na massa líquida do reator. A presença desses compostos em concentrações inferiores a 0,5 mg/L não causou impacto sobre a desnitritação biológica. As análises realizadas em amostras coletadas ao final da reação anóxica, não acusaram a presença de 2 e 4 NF, demonstrando que esses compostos podem ser biodegradados por uma biomassa bem adaptada ao fenol. A concepção do sistema para tratamento da água residuária de coqueria via nitritação/desnitritação envolveu a operação de dois reatores (principal e reator de polimento) operados em bateladas seqüenciais. As condições de operação do reator principal eram manipuladas para viabilizar o acúmulo de NNO2 - ao final da fase aeróbia e promover a desnitritação durante a fase anóxica, utilizando como fonte de carbono a própria matéria orgânica presente no despejo. Como o sobrenadante do reator principal apresentava concentrações elevadas de N-NO2 -, esse efluente era aplicado no reator de polimento, juntamente com etanol como fonte de carbono para redução do NNO2 -. Ao final da fase aeróbia dos ciclos de tratamento conduzidos no reator principal alcançaram-se: relações NO2 -/ (N-NO2 - + N-NO3 -) superiores a 88%; eficiências de remoções de nitrogênio total superiores a 60%; remoções de N-NH3 superiores a 90%, para valores de pH na massa líquida do reator entre 7,8 e 8,5 e, temperatura entre 23 e 31°C. Tal qual ocorrido durante a primeira etapa da investigação, o principal mecanismo de inibição da atividade das bactérias oxidantes de nitrito foi a toxicidade conferida pelas concentrações de amônia livre (3,7 a 15,7 mg NH3/L) no conteúdo do reator. Durante a fase anóxica, as eficiências de remoção de (N-NO2 - foram limitadas pela disponibilidade de matéria orgânica biodegradável no despejo da coqueria, razões DBO/DQOafluente superiores a 80% resultaram em remoções de N-NO2 - próximas de 100%. Quanto ao reator de polimento, pode-se afirmar que o etanol teve um efeito positivo sobre a remoção de matéria orgânica da água residuária da coqueria, considerando a configuração (dois lodos) utilizada. / The present research aimed to study the coke-oven wastewater treatment over nitritation/denitritation in an activated sludge sequencing batch reactor in two successive phases. During the first one, the reactor was fed with a synthetic effluent composed by two abundant pollutants present in coke-oven wastewaters: total ammonia nitrogen (500 mg TAN.l-1) and phenol (1,000 mg C6H5OH.l-1). During the second phase, the reactor was fed with the wastewater produced in an integrated steel industrys coke-plant. The results of the first phase (28 cycles) showed that was possible to achieve TAN removal efficiencies higher than 90% with NO2 --N predominance in the reactor content, evidenced by the rates NO2 --N/ (NO2 --N + NO3 --N) higher than 86%. The main mechanism of the nitrite oxidizer bacteria (NOB) inhibition was free ammonia concentrations between 3.2 and 19.5 mg NH3.l-1. The specific nitritation rates varied between 0.03 and 0.11 kg TAN. kg VSS-1.d-1, for temperatures between 15 and 34oC. Phenol showed to be suitable as carbon source for denitrifying biomass, once the volumetric application rates were lower than 0.02 kg phenol.m-3.h-1. Obeying this condition, it was possible to achieve: phenol removal efficiencies between 45 and 56%; specific phenol removal rates between 0.03 and 0.09 kg C6H5OH. kg VSS-1.d-1; specific denitritation rates between 0.03 and 0.06 kg NO2 --N . kg VSS-1.d-1 and removal efficiencies of (NO2 --N + NO3 --N) higher than 95%. During the anoxic phase, samples were collected from the reactor content for nitrophenols analyses. The results showed the presence of 2- nitrophenol (2-NP) and 4-nitrophenol (4-NP) in concentrations proportional to phenol volumetric application rate in the reactor liquid mass. The presence of those compounds in concentrations lower than 0.5 mg/L does not cause impact over the biological denitritation. The analyses accomplished in samples collected at the end of the anoxic reaction do not show the presence of 2 and 4-NP, demonstrating that these compounds can be biodegraded by a well-adapted biomass. The arrangement of the system for the treatment of coke-oven wastewater (Phase 02) over nitritation/denitritation involved the operation of two sequencing batch reactors (the main reactor and the polishing one). The operational conditions of the main reactor were manipulated to make feasible the NO2 --N accumulation at the end of the aerobic stage and promote the denitritation using the own organic matter present in the cokeoven wastewater as carbon source. As the supernatant of the main reactor presented high nitrite concentrations, this effluent was conducted to a biological denitrifying polishing reactor with ethanol as carbon source. At the end of the aerobic stage of the treatment cycles conducted in the main reactor, it was achieved: NO2 --N/ (NO2 --N + NO3 --N) higher than 88%; total nitrogen removal efficiencies higher than 60%; ammonia nitrogen removal higher than 90%. As occurred during the first phase of the investigation, the main NOB activity inhibition was the toxicity of the free ammonia concentrations (3.7 to 15.7 mg NH3.l-1) in the reactor content. At the end of anoxic stage, the NO2 --N removal efficiencies were limited by the availability of the biodegradable organic matter in the coke-oven wastewater but BOD/CODinfluent higher than 80% resulted in NO2 --N removals next to 100%. Regarding to the polishing reactor, it can be stated that the ethanol had a positive effect over the organic matter removal of the coke-oven wastewater.

As atividades humanas vêm aumentando dramaticamente a quantidade de nitrogênio inorgânico liberado nos ecossistemas, seja através da aplicação de fertilizantes na agricultura, da descarga de dejetos humanos e de seus rebanhos, ou da queima de combustíveis fósseis. Os excessos de nitrogênio são eventualmente transportados para corpos d´água, onde podem, na forma de nitrato, nitrito e amônio, atingir concentrações tóxicas para organismos aquáticos. Nesta pesquisa tive dois objetivos principais. O primeiro foi testar em laboratório a toxicidade relativa dos íons nitrato, nitrito e amônio, e a variação interespecífica na sensibilidade a esses íons, em larvas de cinco espécies de anuros (Rhinella ornata, Hypsiboas faber, Hypsiboas pardalis, Physalaemus cuvieri e Physalaemus olfersii ). Para isso utilizei bioensaios seguindo protocolos internacionalmente padronizados para testes de ecotoxicidade com organismos aquáticos, e que portanto permitem máximas reprodutibilidade e comparabilidade de resultados entre compostos, espécies, e laboratórios. No entanto, estes bioensaios carecem de realismo uma vez que simulam um cenário de exposição aguda a altas concentrações de contaminantes quando na natureza o cenário de exposição tende a ser crônico e prolongado a baixas concentrações. Além disso, bioensaios usam mortalidade como principal variável de resposta, quando também efeitos subletais podem influenciar a persistência de populações ao modular o sucesso dos indivíduos. Por isso, meu segundo objetivo foi testar em laboratório se concentrações relativamente baixas e ecologicamente relevantes de nitrato, nitrito e amônio podem afetar a sobrevivência, o crescimento, o desenvolvimento e o comportamento das larvas de R. ornata, P. cuvieri e H. faber. Demonstrei através dos bioensaios de exposição aguda que nitrato, a forma mais abundante na natureza, é de baixa toxicidade quando comparada a nitrito e amônio. Demonstrei também que há significativa variação interespecífica na sensibilidade ao nitrogênio inorgânico, e que o ranqueamento de sensibilidade das espécies ao nitrato e ao nitrito foram similares, possivelmente por conta de mecanismos comuns de ação tóxica. Através de experimentos de exposição crônica demonstrei que concentrações relativamente baixas de nitrogênio inorgânico podem causar efeitos letais e subletais às larvas de anuros se houver exposição prolongada. O nitrato causou redução no desenvolvimento larval de P. cuvieri e o amônio na sobrevivência e nas taxas de atividade nos girinos de H. faber. A exposição crônica ao nitrito também reduziu significativamente a sobrevivência das três espécies testadas, o crescimento de H. faber e as taxas de atividade de R. ornata. Contudo, é improvável que as concentrações de nitrito que manipulei em laboratório sejam comuns na natureza, especialmente em condições aeróbicas. Esta pesquisa, além de fornecer importantes informações sobre os possíveis efeitos da poluição por nitrogênio em larvas de anuros, contribui para o avanço da ecotoxicologia no Brasil ao estabelecer as bases para o emprego de espécies nativas de anfíbios como sistema-modelo experimental. Estudos futuros que almejem avaliar o risco ambiental da contaminação por nitrogênio deverão por um lado monitorar concentrações em hábitats naturais e por outro avaliar as consequências das interações sinérgicas entre nitrogênio inorgânico e outros estressores físicos, químicos ou biológicos para larvas de anfíbios. / Human activities dramatically increased the amount of inorganic nitrogen released in ecosystems through the application of fertilizers in agriculture, the generation of human and livestock waste, and the combustion of fossil fuels. This nitrogen eventually reaches water bodies where it can, in the form of nitrate, nitrite and ammonium, be toxic to aquatic organisms. In this study I had two main objectives. The first was to test the relative toxicity of nitrate, nitrite and ammonium, and the interspecific variation in sensitivity to these ions, in tadpoles of five anuran species (Rhinella ornata, Hypsiboas faber, Hypsiboas pardalis, Physalaemus cuvieri and Physalaemus olfersii ). This objective was accomplished by laboratory bioassays following internationally standardized protocols for ecotoxicity tests with aquatic organisms, therefore allowing maximum reproducibility and comparability of results among compounds, species and laboratories. However, these bioassays lack realism for simulating a scenario of acute exposure to high concentrations of contaminants, while exposure in nature tends to be chronic and prolonged at low concentrations. Furthermore, bioassays use mortality as the main response variable, whereas sublethal effects may also influence the persistence of populations by modulating individual success. My second objective was therefore to test in the laboratory if low and environmentally relevant concentrations of nitrate, nitrite and ammonium affect survival, growth, development and behavior of R. ornata, P. cuvieri and H. faber larvae. Through acute exposure bioassays I demonstrated that nitrate, the most abundant N form in nature, has low toxicity when compared to nitrite and ammonium. I also demonstrated that there is significant interspecific variation in the sensitivity to inorganic nitrogen, and that the ranking of species sensitivity to nitrate and nitrite were similar, possibly due to common mechanisms of toxic action. Through chronic exposure I demonstrated that relatively low concentrations of inorganic nitrogen can cause lethal and sublethal effects on anuran larvae if there is extended exposure. Nitrate decreased developmental rate in P. cuvieri and ammonia decreased survival and activity rates in H. faber tadpoles. Chronic exposure to nitrite also significantly reduced survival of all three species tested, growth of H. faber and activity rates of R. ornata. However, it is unlikely that the concentrations of nitrite manipulated in the laboratory are common in nature, especially in aerobic conditions. This is the first study to document deleterious effects of nitrogen pollution to Brazilian amphibian species, and contributes to the development of ecotoxicology in Brazil by establishing the basis for the employment of native amphibians as model experimental system. Future studies that aim to assess the environmental risk of nitrogen contamination should monitor concentrations in natural habitats and evaluate the effects of synergistic interactions between inorganic nitrogen and other physical, chemical or biological stressors to amphibian larvae.

Orientador: José Eduardo Tanus dos Santos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciências Médicas / Made available in DSpace on 2018-08-18T18:14:31Z (GMT). No. of bitstreams: 1 Pinheiro_LucasCezar_M.pdf: 747256 bytes, checksum: f428f4ab7d72c88d9b72424fba5da404 (MD5) Previous issue date: 2011 / Resumo: O óxido nítrico (NO) regula diversos sistemas orgânicos. Disfunções na produção ou disponibilidade de NO podem comprometer sua atuação fisiológica. Além da produção de NO pelas óxido nítrico sintetases, outras vias de produção de NO são relatadas, entre elas a conversão de nitrito a NO. O nitrito é o produto inicial da oxidação do NO, sendo posteriormente oxidado a nitrato. Sabe-se que estas três moléculas formam um ciclo dentro do organismo. A conversão de nitrito a NO pode ocorrer de forma enzimática ou não enzimática. Como forma não enzimática, o nitrito é convertido a NO pela reação com H+. Esta reação ocorre principalmente no estômago, todavia não se sabe se este NO formado tem efeito na pressão arterial sistêmica ou atua apenas localmente. A fim de verificar a influência do pH gástrico no efeito hipotensor do nitrito de sódio, utilizamos animais tratados agudamente com LNAME e normotensos canulados acordados pré-tratados com omeprazol e, posteriormente, com nitrito de sódio 15mg/kg e 45mg/kg. Foi verificado que o nitrito de sódio reduz a pressão arterial média dos animais significativamente e de maneira dependente da dose. O pré-tratamento com omeprazol reduziu o efeito hipotensor do nitrito de sódio significativamente. Após, foram quantificados os níveis de nitrito e nitrato. Foi observado aumento em ambos após o tratamento com nitrito de sódio. A partir destes resultados podemos sugerir que o omeprazol atenua o efeito hipotensor do nitrito de sódio em ratos normotensos e hipertensos / Abstract: Many body systems are regulated by nitric oxide (NO). Dysfunctions in the production or availability of NO may impair it physiological roles. However, other routes of NO production are reported in addition to NO production by nitric oxide synthases, including the conversion of nitrite to NO. Nitrite is the initial product of oxidation of NO and is further oxidized to nitrate. It is known that these three molecules form a cycle within the body. The conversion of nitrite to NO can occur enzymatic or nonenzymatic. Non-enzymatic nitrite is converted to NO by reacting with H+. This reaction occurs mainly in the stomach, however it is unclear whether this NO affects blood pressure or simply acts locally. To study the influence of gastric pH on the hypotensive effect of sodium nitrite, we used hypertensive or normotensive cannulated animals pretreated with omeprazole and with sodium nitrite 15 mg/kg and 45 mg/kg. We found that sodium nitrite reduces mean arterial pressure of animals in a dose-dependent manner. Pretreatment with omeprazole reduced the hypotensive effect of sodium nitrite significantly. Thereafter, we quantified the levels of nitrite and nitrate. We found increase in both species after treatment with sodium nitrite. These results suggest that omeprazole attenuates the hypotensive effect of sodium nitrite in normotensive and hypertensive rats / Mestrado / Farmacologia / Mestre em Farmacologia

Calcium nitrite as a corrosion inhibitor is mainly used to protect steel reinforcement in concrete by reducing its corrosion rate. Hence the effectiveness of calcium nitrite depends on its availability as a free nitrite in the pore solution. The present research work aims to determine the concrete mixture component mostly responsible for nitrite binding in concrete. Firstly, the experimental program included testing of nitrite binding in cement paste. Secondly, the effect of adding the fine aggregate (mortar mix) on nitrite binding was assessed. Finally, the mix with coarse aggregate (concrete mix) was evaluated. In-situ leaching method was used to obtain the pore solution that was needed. Measurement of pore solution with the In-situ leaching method and after an average of 48 days showed that concrete specimens have the most nitrite binding capacity. Then, the binding of nitrite was less in mortar and paste specimens respectively. Therefore, concrete specimens bind more nitrite compared to the paste and mortar specimens. The binding ratio increased whenever the nitrite addition level increased. Nevertheless, the free nitrite were similar in the case of the lowest nitrite addition for all types of mix. The pH levels for the mixes with nitrite present, were lower than those of the control mixes.

Metais são bastante usados como materiais implantáveis, principalmente para dispositivos feitos na área de ortopedia. Há uma constante relação dos processos de corrosão nesse biomateriais com a agressividade do meio fisiológico. Usando quatro tipo de metais e ligas metálicas – titânio puro, liga de titânio, aço inoxidável de baixo carbono e liga de cobalto – o processo de corrosão foi estudado. Além disso, o desempenho desses materiais revestidos com nitreto de titânio foi avaliado. Dois processos de revestimento por PVD – evaporação e magnetron sputtering – foram executados, verificando a eficiência desses materiais em meio fisiológico - O melhor comportamento se deu para o revestimento obtido por evaporação. O mecanismo de corrosão predominante para as amostras foi indicado. / Metals are very much used as implantable materials mainly for the construction of devices orthopaedic area. There is a constant concern about the corrosion process in those metallic biomaterials due to the aggressiveness of the physiological environment. By using four types of metals and metallic alloys – pure titanium, titanium alloy, low carbon stainless steel and cobalt-chromium alloy – the corrosion process in physiologic environment has been studied. Also, the performance of such materials coated with titanium nitrate was evaluated. Two PVD coating methods – evaporation and magnetron sputtering – were performed, and the efficiency of those materials in physiologic medium was verified. The best behaviour was found by the evaporation coating method. The predominant corrosion mechanism for coated samples was suggested.

Sporadic problems with pink color defect, or pinking, has occurred in cooked meat products for decades. Pink color can be due to the presence of undenatured myoglobin, denatured globin hemochromes, or nitrosylhemochrome. This research documented the level of added nitrite that produced nitrosylhemochrome in processed meat rolls from fabricated beef round, pork shoulder, turkey breast, and chicken breast. For each meat type, preliminary studies were conducted to narrow the range at which added nitrite caused pinking. Subsequently, the nitrite levels were increased incrementally by 1-ppm, and pink color was measured by trained panelists and by a Hunter color meter. Nitrosylhemochrome content was determined by acetone extraction. Panel and instrumental measurements identified pink color in beef samples formulated with 14-ppm nitrite; nitrosohemochrome extracts detected pigment at 12- ppm. Nitrite levels that caused pinking in pork shoulder were much lower than in beef. Panelists identified pink color at 4-ppm nitrite, and Hunter color meter values showed increased redness at 6-ppm. Pigment extraction detected nitrosylhemochrome at 4- ppm added nitrite. The trained panel and Hunter color meter detected pink color in turkey breast at 2-ppm added nitrite; nitrosohemochrome extraction detected pink pigment at 3-ppm added nitrite. In chicken breast, pink color was detected visually and instrumentally at 1-ppm added nitrite. Pigment extraction detected nitrosylhemochrome at 2-ppm added nitrite. Lower levels of nitrite (1-3-ppm) caused pinking in light-colored meats (turkey and chicken breast, meats with total pigment between 19-ppm and 27-ppm). Higher levels of nitrite (5-14-ppm) caused pink color defect in dark pigmented meat (beef round and pork shoulder, meats with total pigment levels between 56-ppm and 147-ppm). Regression analysis was used to relate total pigment and the minimum level of nitrite causing pinking. The minimum nitrite level causing pinking was the lowest level of nitrite at which the trained panel, acetone extraction, and instrumental results detected pink color or nitrosyl pigment. The formula obtained from the model was as follows: Y = 0.092X + 0.53, where "Y" is the minimum level of added nitrite to cause pinking and "X" is the total pigment of the meat. This formula can be used to estimate the level of nitrite that can be expected to cause pinking in a wide range of pigmented meats.

Iron and copper increased the decomposition of nitrite significantly during the first two hours of reaction when 150 parts per million (ppm) of nitrite and nitrogen was added to an acidic soil. Manganese was found to have a slight effect. There was no additional effect of the added metals after two hours reaction time. The higher concentration of metals was not effective in catalyzing the decomposition of the added nitrite in nitrogen. All the added nitrite nitrogen was not recovered and the deficit could be due to the formation of nitrogen gas.

The Pacific white leg shrimp, Litopenaeus vannamei, is a potential species for low salinity inland aquaculture. Due to several independent variables, such as species, age, size, salinity and pH, that must be taken into account, there are gaps in the literature pertaining to the toxicity of ammonia and nitrite to shrimp. This study was conducted to investigate the individual and combined effects of ammonia and nitrite on L. vannamei postlarvae (25-45 days old) at 10 ppt salinity, 28 C and a pH of 7.8. The independent variables were salinity, total ammonia as nitrogen (TAN) and nitrite-N (NO₂-N), separately and combined. The TAN experiments were conducted at 18 and 10 ppt salinity while the NO₂-N test was conducted at 10 ppt salinity. Combined TAN and NO2 tests were also conducted at 10 ppt salinity. The LC50 values for TAN at 18 ppt salinity, TAN at 10 ppt salinity, and NO2-N at 10 ppt were observed to be 42.92, 39.72 mg/L (2.26 and 2.09 mg/L unionized ammonia-N), and 153.75 mg/L, respectively. When NO₂- N was adjusted to the LOEC level and TAN concentrations were varied, synergistic effects were observed, with an LC50 calculated to be 28.2 mg/L TAN (1.49 mg/L unionized ammonia-N). However, when the ammonia level was adjusted to the LOEC and nitrite was varied, antagonistic effects were observed with an LC50 calculated to be 163.3 mg/L NO₂-N. The results suggest that further investigations into the combined effects of ammonia and nitrite at varying concentrations and lower salinities will be important in developing "standard operating procedures" for the shrimp industry. / Master of Science

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