Resumo: A ocupação do solo e a demanda de água doce tem sido crescente, de maneira que pesquisas voltadas à avaliação da qualidade das águas em áreas estratégicas são consideradas fundamentais. Neste contexto, a área de estudos foi escolhida pela disponibilidade de água, distribuição demográfica e pela sua importância industrial. Com o propósito de melhor compreender o impacto causado pelo efluente do pólo petroquímico de Paulínia, SP, na qualidade das águas do rio Atibaia, os parâmetros potencial hidrogeniônico (pH), temperatura da água, sólidos totais, turbidez, oxigênio dissolvido (OD), demanda bioquímica de oxigênio (DBO), nitrogênio total (NT), íons fósforo (íons P), pluviosidade, estações seca e chuvosa, condutividade elétrica da água e concentração de cloretos foram analisados. Verificou-se, ainda, a influência dos parâmetros mencionados sobre a micobiota transiente de amostras coletadas no período entre agosto de 2007 a março de 2009. O método de plaqueamento para contagem dos fungos e as análises físicas e químicas seguiram Clesceri et al. (1998). Correlação de Pearson, análise de variância multivariada, correlação canônica para dados multivariados e análise dos componentes principais foram as análises estatísticas realizadas. Estas revelaram diferentes influências dos parâmetros independentes sobre as contagens fúngicas. A micobiota transiente detectada no período estudado foi sensível aos parâmetros cloretos, sólidos totais, condutividade elétrica da água e OD, pois estes fatores abióticos influenciaram negativamente nas contagens. Entretanto, o número de colônias de fungos foi estimulada positivamente pela pluviosidade (estação chuvosa), DBO, turbidez e NT. Das análises estatísticas, apenas a correlação de Pearson pareceu não ser eficiente para estudos ambientais sujeitos a variações diversas / Abstract: The use of the soil and fresh-water has increased, so that investigations on the water quality in strategic areas are considered of fundamental importance. In this context, the study area was chosen for its water availability, demographic distribution and industrial relevance. With an eye on the water quality of the influence of an industrial effluent discharged in the Atibaia river, in the surroundings of a petrochemical refinery in Paulínia, SP, the following parameters were analyzed: pH, water temperature; total dissolved solids; turbidity; dissolved oxygen (DO); biochemical oxygen demand (BOD), total nitrogen (TN), phosphorous; rain; dry and rain seasons; water conductivity and chlorides. Also, the influence of these parameters on transient mycota between August 2007 and March 2009 was investigated. The method for counting the forming colony units of fungi was according to Clesceri et al. (1998). Pearson correlation coefficient, multivariate analysis of variance, canonical correlation to multivariate data and principal component analysis were the statistical methods employed. The results revealed differences in the influence of the independent parameters on the counting of fungal colony forming units (CFU). The fungi present in the samples were negatively affected by chloride concentration, total dissolved solids, water conductivity and DO. However, the CFU was increased by the rain, BOD, turbidity and TN. Among the statistical tests used, only Pearson correlation was not satisfactory for our studies / Orientador: Derlene Attili de Angelis / Coorientador: Fernando Carls Pagnocca / Banca: Iracema Helena Schoenlein-Crusius / Banca: Sandra Regina Ceccato Antonini / Mestre

Orientadores: José Roberto Guimarães, Carlos Gomes da Nave Mendes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-18T03:12:06Z (GMT). No. of bitstreams: 1 Gasparini_MirthysCozzett_M.pdf: 1574617 bytes, checksum: 879f212f74e005fca5974d6f943a790e (MD5) Previous issue date: 2011 / Resumo: No presente trabalho foi realizada a caracterização de várias correntes de águas de processo da REPLAN (Refinaria de Paulínia), bem como a avaliação dos processos de fotólise (UV), peroxidação (H2O2), peroxidação assistida por radiação ultravioleta (H2O2/UV), reagente de Fenton (H2O2/Fe2+) e foto-Fenton (H2O2/Fe2+/UV) no tratamento de um dos efluentes, principalmente na degradação dos compostos orgânicos. Analisando-se os dados de caracterização dos diferentes efluentes foi possível sugerir alternativas de reuso no processo de refino, como também selecionar a corrente de água ácida retificada para aplicação dos processos físico-químicos de tratamento. A eficiência dos ensaios de tratabilidade foi baseada na redução da concentração do carbono orgânico dissolvido (COD). Dentre os processos estudados, os processos oxidativos avançados (POA) H2O2/UV e foto-Fenton apresentaram 95 % de eficiência após 150 minutos de ensaio. As condições ótimas foram obtidas na relação mássica COD: H2O2 de 1:7 para o processo peroxidação assistida por radiação UV, e de 1:5 e concentração de Fe2+ de 31 mg/L para o processo foto-Fenton. O efluente tratado pelo processo H2O2/UV poderia ser reutilizado como água de reposição no sistema de resfriamento, já que esta é responsável por 49 % do total de água utilizada na refinaria / Abstract: In the present study was performed the characterization of various process water from REPLAN (Paulínia Refinery) as well as an assessment of 5 processes to treat one of the effluents: photolysis (UV), peroxidation (H2O2), peroxidation assisted by ultraviolet radiation (H2O2/UV), Fenton reagent (H2O2/Fe2+) and photo-Fenton (H2O2/Fe2+/UV), in order to degrade the organic compounds. Effluents characterization results provided reuse possibilities in the process refining and also selected the stripped sour water stream for application of physical-chemical treatments. The processes efficiency was evaluated by the dissolved organic carbon (DOC) reduction. Among the processes studied, the advanced oxidation processes (AOPs) H2O2/UV and photo-Fenton reached 95 % efficiency after 150 minutes of reaction. The optimum conditions were obtained in a mass ratio COD: H2O2 of 1:7 for peroxidation assisted by UV radiation, and of 1:5 with 31 mg/L of Fe2+ for photo-Fenton. The effluent treated by AOP H2O2/UV could be reused as make-up water in cooling systems, since it is responsible for 49 % of the total water used in the refinery / Mestrado / Saneamento e Ambiente / Mestre em Engenharia Civil

Made available in DSpace on 2017-07-10T19:24:02Z (GMT). No. of bitstreams: 1 Shaiane__Lucas.pdf: 2393290 bytes, checksum: 9e5c684ef130e9552f01b3191e3e8e1d (MD5) Previous issue date: 2015-02-20 / This study evaluated the hydrogen and methane production from cassava starch wastewater in reactors in series. The acidogenic and methanogenic reactors were operated in a continuous flow and trials were divided into three stages. In Stage 1, three essays for hydrogen production evaluated the effect of initial pH (6.0 and 4.5), substrate concentration (1.4, 1.1 and 2.2 g total carbohydrates.L-1) and strategies to control biomass (by disposal or change in the structure of such support material with low density polyethylene) in anaerobic reactors of fixed bed and upflow at 36 °C. The best operating condition among the evaluated ones was pH 6.0 and concentration of 1.4 g total carbohydrates.L-1, which resulted in Hydrogen Volumetric Productions (HVP) of 229 mL.L-1.d-1 and yield of 29.4 mL.g-1total carbohydrate. The best strategy to control biomass was the sort of bed with polyethylene cylinders, which provided the least changes in flow regime and excessive growth of biomass. In Stage 2, the effect of inoculum source was evaluated in two packed-bed reactors operating according to the following conditions: pH 6.0; 2 g.L-1concentration of substrate, 20 g.L-1.d-1organic loading rate (OLR) and hydraulic retention time (HRT) of 2-hour. In the inoculated reactor with autofermented effluent, the answers were: 550 mL.L-1.d-1and hydrogen yield of 38mL.g-1total carbohydrates. These values were higher than those observed for the reactor inoculated with anaerobic heat-treated sludge, which indicated that the use of simple inoculums is a viable strategy for hydrogen production under the tested conditions. In addition to these essays, the influence of ORL and HRT were also evaluated. The increase of ORL (10 to 20 g-total carbohydrates.L-1.d-1) and decrease of HRT (4 to 2 hour) resulted in a higherhydrogen production (467 mL.L-1.d-1), hydrogen percentage in the studied biogas (40%) and molar flow rate (2.16 mmol.h-1). Therefore, the average yield of 30 mL H2.g-1 total carbohydrate was the same for both conditions tested. In general, butyric acid was associated with higherhydrogen production, followed by acetic and propionic acids, besides ethanol, in the five analyzed essays. In Stage 3, methane production from the acidified effluent was evaluated in a horizontal anaerobic reactor of fixed bed and continuous flow, operated at mesophilic temperature. The operating conditions were divided into four stages, whose variations were: initial pH (5.0 and 7.0), OLR (1.54; 3.54 and 6 g-COD.L-1.d-1) and HRT (5; 1.5 and 1.1 d). The results of effluent pH greater than 7.0, volatile acidity/total alkalinity of 0.2 and 98% removal of organic matter showed that the reactor performance was not impaired by the separation of acidogenic and methanogenic stages. The highest production of methane was observed in Phase IV, with pH 5.0, 6 g.L-1.d-1 OLR and 1.1 d HRT, resulting in average values of 0.82 L.L-1.d-1 for volumetric methane production, 0.85 L.g-1CODremoved yield and 80% methane in biogas composition. The energy efficiency in the combined system was 17% higher than the one observed in the single system for the treatment of cassava starch wastewater. / Este trabalho avaliou a produção de hidrogênio e metano a partir de efluente de fecularia de mandioca em sistema combinado. Os reatores acidogênico e metanogênico foram operados em fluxo contínuo, e os ensaios divididos em três etapas. Na Etapa 1, três ensaios para produção de hidrogênio avaliaram o efeito do pH inicial (6,0 e 4,5), concentração de substrato (1,4, 1,1 e 2,2 g carboidratos totais.L-1) e estratégias de controle da biomassa (por descarte ou mudança na estruturação do material suporte de polietileno de baixa densidade) em reatores anaeróbios de leito fixo e fluxo ascendente, à temperatura de 36 C. A melhor condição operacional dentre as avaliadas foi pH 6,0 e concentração de 1,4 g carboidratos totais.L-1, que resultou em Produções Volumétricas de Hidrogênio (PVH) de 229 mL.L-1.d-1 e rendimento de 29,4 mL.g-1 carboidrato total. A melhor estratégia de controle de biomassa foi a ordenação do leito com cilindros de polietileno, a qual proporcionou menores alterações no regime de escoamento e crescimento excessivo da biomassa. Na Etapa 2, o efeito da fonte de inóculo foi avaliado em dois reatores de leito empacotado nas condições operacionais pH 6,0; concentração de substrato de 2 g.L-1, Carga Orgânica Volumétrica aplicada (COV) de 20 g.L-1.d-1 e Tempo de Detenção Hidráulica (TDH) de 2 horas. No reator inoculado com efluente autofermentado verificou-se PVH de 550 mL.L-1.d-1 e rendimento de hidrogênio de 38 mL.g-1 carboidratos totais. Esses valores foram maiores que os observados para o reator inoculado com lodo anaeróbio tratado termicamente, os quais indicaram que a utilização de inóculos simples representa uma estratégia viável para produção de hidrogênio nas condições testadas. Além desses ensaios, a influência da COV e do TDH também foi avaliada. O aumento COV (de 10 para 20 g.L-1.d-1) e a redução do TDH (de 4 para 2 h) resultaram em maior produção de hidrogênio (467 mL.L-1.d-1), percentual de hidrogênio no biogás (40%) e vazão molar (2,16 mmol.h-1). Entretanto, o rendimento médio de 30 mL H2.g-1 carboidrato total foi igual para as duas condições testadas. De modo geral, o ácido butírico foi associado à maior produção de gás hidrogênio, seguido dos ácidos acético e propiônico, além de etanol, nos cinco ensaios realizados. Na Etapa 3, a produção de metano a partir do efluente acidificado foi avaliada em reator anaeróbio horizontal de leito fixo e fluxo contínuo, operado em condição mesofílica de temperatura. As condições operacionais foram divididas em quatro fases, com variação do pH inicial (5,0 e 7,0), da COV (1,54; 3,54 e 6 g DQO.L-1.d-1) e do TDH (5; 1,5 e 1,1 d). Os resultados de pH efluente superior a 7,0, relação acidez volátil/alcalinidade total de 0,2 e remoção de 98% da matéria orgânica evidenciam que o desempenho do reator não foi prejudicado pela separação das fases acidogênica e metanogênica. A maior produção de metano foi observada na Fase IV, com pH 5,0, COV de 6 g.L-1.d-1e TDH de 1,1 d, que resultou em valores médios de produção volumétrica de metano de 0,82 L.L-1.d-1, rendimento de 0,85 L.g-1DQOremovida e 80% de metano na composição do biogás. O rendimento energético no sistema combinado foi 17% superior ao observado em sistema único no tratamento de efluente de fecularia.

La présence des antibiotiques à usage humain et vétérinaire dans l’écosystème aquatique, est devenue un problème écologique sérieux. En effet, ces substances résistent aux traitements des stations d’épuration, ce qui engendre leur introduction et accumulation dans l’environnement. Par conséquent, le développement de méthodes efficaces pour le traitement de ces polluants est nécessaire. La première partie de ce travail de thèse s’inscrit dans le cadre de la dégradation des antibiotiques par procédé électro-Fenton. Ce procédé consiste à produire in situ des espèces fortement oxydantes, les radicaux hydroxyle, permettant la dégradation totale des composés organiques persistants. La sulfaméthazine (SMT) et le triméthoprime (TMP) ont été choisis comme composés modèles, en raison de leur détection régulière dans les effluents des stations d’épuration, les eaux de surface et les eaux souterraines. Dans cette première partie, nous avons examiné l’influence de différents paramètres expérimentaux, sur l’efficacité du procédé électro-Fenton. Les conditions opératoires optimales nécessaires pour la dégradation totale des deux antibiotiques étudiés, ont été également déterminées. En outre, les produits intermédiaires aromatiques générés lors de la dégradation des deux antibiotiques, ont été identifiés. Leur évolution durant l’électrolyse a été également suivie. La deuxième partie est consacrée à l’étude de la minéralisation de la SMT et du TMP par procédé électro-Fenton. Les résultats obtenus indiquent que les taux de minéralisation de la SMT et du TMP sont respectivement de 91 et 85% après dix-huit heures de traitement. Les acides carboxyliques formés, ainsi que les ions inorganiques libérés ont été identifiés, leur évolution a été suivie au cours du traitement. De plus, en se basant sur les différents sous-produits générés, nous avons proposé des mécanismes réactionnels pour la minéralisation de la SMT et du TMP par procédé électro-Fenton. La troisième partie de ce travail porte sur l’étude de la minéralisation des deux antibiotiques considérés par couplage du procédé électro-Fenton et d’un traitement biologique. La SMT et le TMP, ont été prétraités par procédé électro-Fenton, ce qui a conduit à leur dégradation totale, avec des taux de minéralisation faibles. Par la suite, un traitement biologique a été effectué durant 20 jours, les taux globaux de minéralisation ont alors augmenté pour atteindre 81 et 68% pour respectivement la SMT et le TMP. Dans une dernière partie, nous avons procédé à la minéralisation de deux effluents industriels, contenant les antibiotiques étudiés, par couplage du procédé électro-Fenton et d’un traitement biologique. Les taux de minéralisation globaux obtenus sont de 81 et 89% pour respectivement l’effluent SMT et l’effluent TMP. Ce qui prouve la pertinence du procédé combiné, pour le traitement des effluents industriels. / The occurrence of human and veterinary antibiotics in the aquatic ecosystem becomes a serious environmental problem. These compounds cannot be treated by wastewater treatment plants, resulting in their entry and accumulation to measurable levels in the environment. Over the last decade, the conventional biological processes were used for wastewater treatment, but did not appear to be enough effective when dealing with wastes containing antibiotics, owing to the important recalcitrance of these compounds. Therefore, the development of efficient methods to treat antibiotics is needed. The first part of this thesis is focused on the degradation of antibiotics by electro-Fenton process. This process consists in producing in situ strongly oxidizing species, hydroxyl radicals, allowing the total degradation of persistent and toxic organic compounds. Sulfamethazine (SMT) and trimethoprim (TMP) were selected as model compounds, because of their regular detection in the effluents of sewage plants, surface water and groundwater. In this first part, we examined the influence of various operating parameters, on the efficiency of electro-Fenton process. The optimal operating conditions necessary for the removal of the studied antibiotics, were also determined. Moreover, the aromatic intermediate products, generated during antibiotics degradation, were identified. Their evolution during electrolysis was also followed. The second part is devoted to the study of mineralization, of SMT and TMP, by the electro-Fenton process. The obtained results indicate that the yields of SMT and TMP mineralization were 91 and 85%, respectively after eighteen hours of treatment. The identification and monitoring of short chain carboxylic acids and released inorganic ions during the treatment, were carried out. Furthermore, based on the identified by-products, we proposed a plausible mineralization reaction pathway for SMT and TMP. The third part of this work concerns the study of the mineralization of considered antibiotics by a combined process coupling an electro-Fenton pretreatment and a biological degradation. SMT and TMP were pretreated by the electro-Fenton process, which led to their total degradation, with low levels of mineralization, ensuring significant residual organic content for a subsequent biological treatment. Afterwards, biological treatment was performed during 20 days and showed that the level of overall mineralization increased to reach 81 and 68% for SMT and TMP, respectively. In a last part, we carried out the mineralization of two industrial effluents containing SMT and TMP, by combining electro-Fenton and activated sludge treatment. Overall mineralization yields of the combined process of 81 and 89% were obtained for SMT effluent and TMP effluent, respectively. This result confirms the relevance of combined process, even for the treatment of industrial effluents.

Made available in DSpace on 2016-05-02T13:54:10Z (GMT). No. of bitstreams: 1 RosangelaZampero-dissertacaocompleta.pdf: 820803 bytes, checksum: ec31de7b8b2d172d25dda29c7917c9ef (MD5) Previous issue date: 2011-12-09 / The use of biopolymers extracted from plants in the clotting process has several advantages compared with chemical salts. Among the advantages: low cost and variation in the nature of the alkalinity of the water in the process, because the sludge generated after treatment has lower volume compared with the sludge generated with the use of chemical constituents. The specific study of wastewater generated in the industry of glass quenching calls attention to the high rate of waste sludge. The effluent is a major concern regarding the disposal or reuse. In this case, the hardening process studied uses 110,000 liters of water per month, which generates 40 tons / month of solid waste and consequently large volumes of wastewater. During the study the objective was to check the behavior of Moringa oleifera seeds as natural coagulant in the effluent liquid from the glass industry and water reuse in the process. / O uso de biopolímeros extraídos de vegetais no processo de coagulação tem várias vantagens em comparação com os sais químicos. Dentre as vantagens, destaca-se o baixo custo e o fato que não existe variação na natureza da alcalinidade da água no processo, pois o lodo gerado após tratamento apresenta menor volume quando comparado com o lodo gerado com uso de constituintes químicos. O estudo dos efluentes líquidos gerados na indústria de têmpera de vidros chamou a atenção pelo alto índice de lodos residuais. Este efluente é a grande preocupação quanto ao seu descarte ou reuso. Neste caso, o processo de têmpera estudado utiliza 110 mil litros de água por mês, que gera 40 ton./mês de efluentes sólidos e consequentemente grande volume de efluente líquido. No decorrer do estudo objetivou-se verificar o comportamento das sementes de Moringa oleifera como coagulante natural no efluente líquido da indústria de vidros e reuso da água no processo.

Tinta pode ser conceituada como uma película ou camada de polímero utilizada para proteger, sinalizar e iluminar ou mesmo para embelezar o substrato sobre o qual ela é aplicada. Basicamente, esta mistura polimérica é formada por elementos, tais como: resinas, pigmentos, cargas, solventes e aditivos. Os resíduos e o efluente líquido gerados na produção de tintas devem ser tratados de modo que não causem contaminação de rios e das nascentes de água. A reutilização do efluente tratado é uma das possibilidades que deve ser considerada a fim de minimizar os impactos ambientais e reduzir o uso de recursos naturais. Processos de oxidação química são promissores para a degradação de compostos orgânicos tóxicos. O caminho mais eficiente para a oxidação é o ataque pelo radical hidroxila (OH), por meio do processo de oxidação avançada, POA. Um dos exemplos de POA é o que faz uso de aceleradores de feixe de elétrons, adotado por vários países para a remoção de compostos orgânicos. O objetivo deste estudo é aplicar o POA por radiação ionizante para o tratamento do efluente da fabricação de tintas para repintura automotiva, industrial e automotivo. A metodologia utilizada foi um estudo de caso, desenvolvido por meio do processamento com feixe de elétrons aplicados a esses efluentes de indústria de tintas. O estudo foi realizado em três fases. Na primeira, aplicou-se 10 kGy, 30 kGy e 50 kGy de dose absorvida; na segunda, 50 kGy, 80 kGy e 100 kGy, e, na última fase, foi aplicada nas amostras uma dose de 50 kGy e dopadas com 0,005%, 0,05% e 0,5% de peróxido de hidrogénio em volume. Os principais resultados demonstraram uma redução média de cerca de 10% da Demanda Química de Oxigênio, DQO e cerca de 25% da Demanda Bioquímica de Oxigênio, DBO. Os padrões de efluentes finais definidos pelos requisitos legais, em especial pelo Decreto Estadual 8468/1976. para o descarte do corpo no rio ou reutilização em aplicações industriais, foram atendidos. / Paint can be conceptualized as a film or a layer of polymer, to protect, to signal and to illuminate or even to embellish the substrate on which it is applied. Basically, this polymeric compound is formed by elements such as: resin, pigments, fillers, solvents, and additives. Waste and wastewater generated in the production of paint, have to be treated so they do not cause the contamination of rivers and springs water. The reuse of the treated effluent is one of the possibilities that should be considered in order to minimize the environmental impacts and to reduce the use of natural resources. Chemical oxidation processes are promising for degradation of toxic organic compounds. The most efficient path for the oxidation is the attack by hydroxyl radical (OH), and the Advanced Oxidation Process, AOP, using electron beam accelerators have been adopted by several countries for the removal of organic compounds. The aim of this study is to apply the AOP by ionizing radiation to treat the effluent from the manufacture of automotive, automotive refinish and industrial paints. The methodology used was a case study, developed through the electron beam processing of these effluents. The study was developed in three phases: in the first one it was applied 10 kGy, 30 kGy and 50 kGy of absorbed dose, in the second one, 50 kGy, 80 kGy and 100 kGy, and in the last one it was applied 50 kGy in samples and doped with 0.005%, 0.05% and 0.5% of hydrogen peroxide. The main results have shown an average reduction of about 10% of Chemical Oxygen Demand, COD and about 25% of Biochemical Oxygen Demand, BOD. The final effluent standards set by legal requirements for disposal of the body in the river or reuse in industrial application.

Tinta pode ser conceituada como uma película ou camada de polímero utilizada para proteger, sinalizar e iluminar ou mesmo para embelezar o substrato sobre o qual ela é aplicada. Basicamente, esta mistura polimérica é formada por elementos, tais como: resinas, pigmentos, cargas, solventes e aditivos. Os resíduos e o efluente líquido gerados na produção de tintas devem ser tratados de modo que não causem contaminação de rios e das nascentes de água. A reutilização do efluente tratado é uma das possibilidades que deve ser considerada a fim de minimizar os impactos ambientais e reduzir o uso de recursos naturais. Processos de oxidação química são promissores para a degradação de compostos orgânicos tóxicos. O caminho mais eficiente para a oxidação é o ataque pelo radical hidroxila (OH), por meio do processo de oxidação avançada, POA. Um dos exemplos de POA é o que faz uso de aceleradores de feixe de elétrons, adotado por vários países para a remoção de compostos orgânicos. O objetivo deste estudo é aplicar o POA por radiação ionizante para o tratamento do efluente da fabricação de tintas para repintura automotiva, industrial e automotivo. A metodologia utilizada foi um estudo de caso, desenvolvido por meio do processamento com feixe de elétrons aplicados a esses efluentes de indústria de tintas. O estudo foi realizado em três fases. Na primeira, aplicou-se 10 kGy, 30 kGy e 50 kGy de dose absorvida; na segunda, 50 kGy, 80 kGy e 100 kGy, e, na última fase, foi aplicada nas amostras uma dose de 50 kGy e dopadas com 0,005%, 0,05% e 0,5% de peróxido de hidrogénio em volume. Os principais resultados demonstraram uma redução média de cerca de 10% da Demanda Química de Oxigênio, DQO e cerca de 25% da Demanda Bioquímica de Oxigênio, DBO. Os padrões de efluentes finais definidos pelos requisitos legais, em especial pelo Decreto Estadual 8468/1976. para o descarte do corpo no rio ou reutilização em aplicações industriais, foram atendidos. / Paint can be conceptualized as a film or a layer of polymer, to protect, to signal and to illuminate or even to embellish the substrate on which it is applied. Basically, this polymeric compound is formed by elements such as: resin, pigments, fillers, solvents, and additives. Waste and wastewater generated in the production of paint, have to be treated so they do not cause the contamination of rivers and springs water. The reuse of the treated effluent is one of the possibilities that should be considered in order to minimize the environmental impacts and to reduce the use of natural resources. Chemical oxidation processes are promising for degradation of toxic organic compounds. The most efficient path for the oxidation is the attack by hydroxyl radical (OH), and the Advanced Oxidation Process, AOP, using electron beam accelerators have been adopted by several countries for the removal of organic compounds. The aim of this study is to apply the AOP by ionizing radiation to treat the effluent from the manufacture of automotive, automotive refinish and industrial paints. The methodology used was a case study, developed through the electron beam processing of these effluents. The study was developed in three phases: in the first one it was applied 10 kGy, 30 kGy and 50 kGy of absorbed dose, in the second one, 50 kGy, 80 kGy and 100 kGy, and in the last one it was applied 50 kGy in samples and doped with 0.005%, 0.05% and 0.5% of hydrogen peroxide. The main results have shown an average reduction of about 10% of Chemical Oxygen Demand, COD and about 25% of Biochemical Oxygen Demand, BOD. The final effluent standards set by legal requirements for disposal of the body in the river or reuse in industrial application.

Made available in DSpace on 2014-06-11T19:27:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-07-12Bitstream added on 2014-06-13T19:35:29Z : No. of bitstreams: 1 cruz_as_me_rcla.pdf: 2096941 bytes, checksum: e034fe58bade607f70d6be667b1b3079 (MD5) / A ocupação do solo e a demanda de água doce tem sido crescente, de maneira que pesquisas voltadas à avaliação da qualidade das águas em áreas estratégicas são consideradas fundamentais. Neste contexto, a área de estudos foi escolhida pela disponibilidade de água, distribuição demográfica e pela sua importância industrial. Com o propósito de melhor compreender o impacto causado pelo efluente do pólo petroquímico de Paulínia, SP, na qualidade das águas do rio Atibaia, os parâmetros potencial hidrogeniônico (pH), temperatura da água, sólidos totais, turbidez, oxigênio dissolvido (OD), demanda bioquímica de oxigênio (DBO), nitrogênio total (NT), íons fósforo (íons P), pluviosidade, estações seca e chuvosa, condutividade elétrica da água e concentração de cloretos foram analisados. Verificou-se, ainda, a influência dos parâmetros mencionados sobre a micobiota transiente de amostras coletadas no período entre agosto de 2007 a março de 2009. O método de plaqueamento para contagem dos fungos e as análises físicas e químicas seguiram Clesceri et al. (1998). Correlação de Pearson, análise de variância multivariada, correlação canônica para dados multivariados e análise dos componentes principais foram as análises estatísticas realizadas. Estas revelaram diferentes influências dos parâmetros independentes sobre as contagens fúngicas. A micobiota transiente detectada no período estudado foi sensível aos parâmetros cloretos, sólidos totais, condutividade elétrica da água e OD, pois estes fatores abióticos influenciaram negativamente nas contagens. Entretanto, o número de colônias de fungos foi estimulada positivamente pela pluviosidade (estação chuvosa), DBO, turbidez e NT. Das análises estatísticas, apenas a correlação de Pearson pareceu não ser eficiente para estudos ambientais sujeitos a variações diversas / The use of the soil and fresh-water has increased, so that investigations on the water quality in strategic areas are considered of fundamental importance. In this context, the study area was chosen for its water availability, demographic distribution and industrial relevance. With an eye on the water quality of the influence of an industrial effluent discharged in the Atibaia river, in the surroundings of a petrochemical refinery in Paulínia, SP, the following parameters were analyzed: pH, water temperature; total dissolved solids; turbidity; dissolved oxygen (DO); biochemical oxygen demand (BOD), total nitrogen (TN), phosphorous; rain; dry and rain seasons; water conductivity and chlorides. Also, the influence of these parameters on transient mycota between August 2007 and March 2009 was investigated. The method for counting the forming colony units of fungi was according to Clesceri et al. (1998). Pearson correlation coefficient, multivariate analysis of variance, canonical correlation to multivariate data and principal component analysis were the statistical methods employed. The results revealed differences in the influence of the independent parameters on the counting of fungal colony forming units (CFU). The fungi present in the samples were negatively affected by chloride concentration, total dissolved solids, water conductivity and DO. However, the CFU was increased by the rain, BOD, turbidity and TN. Among the statistical tests used, only Pearson correlation was not satisfactory for our studies

The study was done in Adaa district which is one of the 12 districts in East Shoa zone in Oromia regional state of Ethiopia. It is located southeast of Addis Ababa at 38o51’ 43.63’’ to 39o04’ 58.59’’ E and 8o46’ 16.20’’ to 8o59’ 16.38’’ N, on the western margin of the Great East African Rift Valley. The altitude ranges from 1 500 to ≥ 2 000 meters above sea level. The district has a high potential for mixed livestock and crop production systems. The purpose of this study was to make up for the paucity of information on livestock and environment interaction by assessing the relationship of livestock, soil, water, land, climate and crops under mixed crop-livestock production systems in central Ethiopian highlands. The objectives of the study were: (a) to assess the effect of change in land management on carbon storage and the contribution of livestock to carbon storage; (b) to examine the impact of livestock on natural resources and the environment; (c) to assess the effects of the change in traditional agricultural practices, expansion of factories, slaughter houses, greenhouses and flower farms on water and soil quality; (d) to evaluate the effect of climate change on livestock production under small-scale agriculture; and (e) to recommend options for mitigation and adaptation to environmental changes. The research design was non-experimental and did not involve the manipulation of the situation, circumstances or experiences of the interviewees. The design was comparative research that compared two or more groups on one or more variables, such as the effect of agricultural land use management, tillage type etc. on carbon storage in the soil. This research also applied a longitudinal design that examined variables such as the performance exhibited by groups over time. Purposive sampling was often used to measure the effect of agricultural, industrial effluent and human interferences on the environment by measuring nutrient contents at sources in the soil, water and manure. Biological data were complemented by key socio-economic survey by interviewing individual farmers and focus groups from sampling sites. Secondary data were also reviewed to measure soil degradation and run-off attributed to livestock. Results showed that animal waste and farmyard manure had the highest contribution in the addition of carbon in the soil. This implied that for most of carbon inputs livestock products and by-products had a greater place in the carbon sink. Therefore, livestock production could be considered as one of the major agricultural production systems in soil carbon storage. Similarly, livestock production systems also play an important role in maintaining the eco-system balance through nutrient recycling. On the average, the number of livestock per household for most species increased during the Derge regime in the 1990s compared to the Haile Sellassie regime in the 1970s when people did not own land; and then the number declined in the 2000s except for equines, crossbreeds and oxen. The change to crop intensification led to the change in the purpose for livestock keeping. Farmers started keeping certain types of animals for specific purposes unlike before when livestock was kept for prestige and economic security. The major drive for the change of attitude towards the purpose of keeping livestock was scarcity of resources, mainly feed and water. Equine ownership has significantly increased due to their low off-take rate and their feeding habits which allowed them to survive in harsh environments where feed resources were extremely scarce. There was a significant difference in crop response to manure application. Vegetables produced higher yields with manure than chemical fertilizers. Cereals on the other hand responded more to chemical fertilizers than to manure. Therefore, combining manure and chemical fertilizers was the best option for the sustainability of crop production in the study area. Some of the limitations to the use of manure as an organic fertilizer were inadequate manure production, high labour cost, bulkiness and high cost of transport to the fields and weed infestation. Manure management systems in the study area were affected by livestock husbandry practices. Only crossbred cattle (5%) were zero-grazed and used; and manure was stored in pits as slurry. Indigenous cattle were grazed outdoors in the fields during the day and at night they were kept in kraals near homesteads. There was a substantial loss of nutrients during the day when animals were grazing in the fields through leaching and trampling of dung and urine patches. Indoor or zero grazing of livestock could reduce nutrient losses. The use of manure as fuel in the study area had no significant effect on CO2 emissions at household or local level, but had a negative impact on soil organic carbon storage and soil fertility. Therefore, for improved yield and balanced eco-systems manure burning has to be replaced by other alternative energy sources such as bio-gas and kerosene. The largest carbon equivalent emissions were from CH4 (72.6%), N2O (24%) and CO2 (3.4%) which indicated the need to improve livestock and manure management systems under smallholder agriculture. Overall, there was an indication of a decline in water resources on per capita basis. The major contributing factors were combined pressure of human and animal population on natural resources that led to excessive deforestation, loss of biological diversity, overgrazing, soil degradation and various forms of pollution and contamination. The global climate change also played a role in the decline in water resources due to the decrease in annual precipitation and increasing temperatures. Urbanization and economic growth increased the demand for milk and meat, which required additional water use for each unit of increased animal protein. The demand for milk and meat is expected to double in the next 20 years with an annual growth rate of between 2.5 to 4%. From the sixty-year meteorological data (1951-2009) there was an established increase in rainfall by 2% per annum; and maximum and minimum temperature by 0.08oC per decade, which amounted to a cumulative temperature increase of 0.5oC in the last decade. The increase in precipitation and temperature favoured the adaption of lowland crops like maize and sorghum to highland agro-ecology. Climate prediction models forecasted that most of the highlands in Ethiopia will remain suitable for cereals like wheat and Teff for the next 50 to100 years. However, the perception of farmers indicated that they felt more heat and warm weather than they have experienced before. They reported that rainfall is now more erratic or comes late and stops earlier before plants completed their vegetative growth. / Environmental Sciences / D. Litt. et Phil. (Environmental Science)

Em um cenário global de indisponibilidade hídrica, até regiões sem histórico de escassez de recursos hídricos vêm sendo impactadas pela ausência de chuvas e circunstâncias de adversidade climática. Com perspectivas cada vez menos favoráveis quanto ao abastecimento hídrico, têm-se difundido progressivamente, no Brasil e no mundo, alternativas de tratamento de efluentes aquosos industriais visando seu reúso na própria indústria, diminuindo a necessidade de captação de água em corpos hídricos. Os processos de separação com membrana (PSM\'s) têm tido destaque, sobretudo para reúso em caldeiras e torres de resfriamento. Em um PSM, no entanto, os íons removidos da corrente de alimentação durante o processo de dessalinização concentram-se no compartimento de rejeito das membranas (concentrado). Consequentemente, os sais de baixa solubilidade comumente ultrapassam sua saturação e excedem seus limites metaestáveis, passando a oferecer risco de deposição sobre as membranas. As deposições salinas, chamadas incrustações (ou scaling) prejudicam o processo de dessalinização: reduzem a taxa de recuperação de água, aumentam o consumo energético e danificam membranas e tubulações. Uma vez que o sulfato de bário (BaSO4) é um dos sais com maior potencial incrustante em efluentes industriais, e cujas incrustações apresentam maiores resistências às práticas convencionais de limpeza, estudou-se métodos preventivos de incrustação de BaSO4 por remoção de íons bário de fase líquida a montante de um PSM. A depleção de bário de solução foi analisada mediante: (i) precipitação de BaSO4 por meio de dessupersaturação (com adição de sementes) e efeito do íon comum (excesso de sulfato) e (ii) precipitação de CaCO3 por abrandamento com incorporação do íon Ba2+ no precipitado. Desenvolveu-se, inicialmente, um estudo conceitual da precipitação de BaSO4 por modelagem termodinâmica, aplicada ao tratamento de um efluente padrão de refinaria de petróleo supersaturado em BaSO4. As simulações termodinâmicas apontam que o pre-tratamento de efluentes por dessupersaturação, com opção de adicionar sulfato (via adição externa ou reciclo) são promissores para aumentar o rendimento de PSM\'s. Em estudos experimentais com efluente sintético de refinaria de petróleo, foi obtida a cinética de precipitação do BaSO4 para o ajuste de um modelo de precipitação de BaSO4. Observou-se que o tempo de indução do BaSO4 foi reduzido à medida que se aumentou o excesso de sulfato (em relação ao bário presente) ou à medida que se adicionou sementes de BaSO4. Após um período curto de precipitação (alguns minutos), a solução permanecia supersaturada por longos períodos (horas), com razões de supersaturação residuais dentro da faixa de 1,1 a 3,0. Esses valores foram associados com uma dependência de quarta ordem da taxa de crescimento do cristal com a taxa de supersaturação. Verificou-se que a carga de sementes de BaSO4 é diretamente proporcional à depleção de supersaturação, que sementes heterogêneas (CaCO3, CaSO4.2H2O) são ineficazes para a precipitação do BaSO4 e que os íons cálcio inibem a precipitação de BaSO4. A precipitação de CaCO3 (em mix de vaterita e calcita) por abrandamento em efluente sintético foi eficaz para remover bário da solução. O mecanismo que controla o processo foi identificado como sendo a substituição isomórfica do íon cálcio pelo íon bário no retículo cristalino do carbonato de cálcio. Consequentemente, a remoção de bário da solução é favorecida quando se aumenta a quantidade de carbonato de cálcio precipitado e quando o coeficiente de distribuição aparente em vateita e calcita (DBa, que indica a quantidade de bário incorporada ao sólido) é elevado. Valores altos de pH e de concentração de cálcio elevam a precipitação de CaCO3 e, portanto, maximizam a remoção de bário. O coeficiente de distribuição aparente do bário mostra-se independente do pH inicial (na faixa de 9,5 a 11,7) e aumenta com a concentração de cálcio. Ele também aumenta com a quantidade de sementes de calcita, o que pode ser consequência de uma maior incorporação de bário em camadas que crescem sobre substratos puros de CaCO3 ou ainda, pode ser devido à manifestação de mecanismos de adsortivos com o aumento de lugares ativos disponíveis para incorporação de bário. Em experimentos com efluente real, ao contrário do observado com soluções sintéticas, a remoção de bário por dessupersaturação foi realizada com eficiência mesmo em presença do íon cálcio, devido provavelmente a sua complexação com aditivos orgânicos. Em precipitação de calcita, fatores que aumentam a supersaturação inicial, como adição de carbonato e aumento do pH, elevaram a precipitação de CaCO3, o que maximizou a remoção de bário. Tais fatores, no entanto, reduziram valores de DBa em calcita, possivelmente devido à diminuição na sorção de íons que estimulam a incorporação do bário. Dosagens de sulfato (insuficientes para precipitar BaSO4) reduziram a quantidade de calcita precipitada, diminuindo a remoção de bário e, inesperadamente, elevando DBa em calcita. Por fim uma análise de ecoeficiência foi feita em um estudo de reúso de água com zero de descarte líquido em refinaria de petróleo aplicando as técnicas de precipitação estudadas. A implantação de etapas de precipitação e de unidades maiores de osmose inversa (OI) acarretaram em reduções no consumo de energia no tratamento térmico do concentrado da OI, diminuindo proporcionalmente a emissão de gases de efeito estufa, consumo de água e degradação ecotoxicológica de água doce. Além disso, verificou-se redução de capital de investimento (dada à aquisição de equipamentos de evaporação menores) e redução nos custos energéticos operacionais. / In a global scenario of water unavailability, even regions with no records of water scarcity have been impacted by the absence of rainfall and climatic adversity. With increasingly unfavorable perspectives on water supply, alternatives to water treatment for industrial reuse have been progressively diffused in Brazil and around the world, reducing the need for water withdraw in water bodies. The membrane separation processes (PSM) have been emphasized in the tertiary treatment of industrial effluents, providing improvement in water quality for reuse in boilers or cooling towers. In a PSM, however, the salts removed from the feed stream during the desalination process are concentrated in the brine stream (concentrate). At this stage, the low solubility salts commonly exceed their saturation in the system, and surpasses their metastable limits, offering risk of deposition on the membranes. Salt deposits, called scaling, jeopardize the desalination process: they reduce the rate of water recovery, increase energy consumption and damage membranes and pipes. Since BaSO4 is one of the salts with the greatest scaling potential in the industry, and which the fouling presents the greatest resistance to conventional cleaning practices, preventive methods of BaSO4 scaling were studied by removal of barium ions from the liquid phase upstream a PSM. The barium depletion from solution was analyzed during the processes of: (i) precipitation of BaSO4 by means of desupersaturation (with addition of seeds) and common ion effect (excess of sulfate) and (ii) chemical precipitation of CaCO3 (softening) with incorporation of the Ba2+ ion in the precipitated crystal. A conceptual study of the BaSO4 precipitation was first developed by thermodynamic modeling, applied to the treatment of a standard oil refinery effluent supersaturated in BaSO4. The thermodynamic simulations show that effluents pretreatment by desupersaturation, with the option of adding sulfate (via external addition or recycle), are promising to increase the yield of PSM\'s. In experimental studies with synthetic oil refinery effluent, BaSO4 precipitation kinetics were obtained in order to adjust a BaSO4 precipitation model. The BaSO4 induction time was reduced as the excess sulfate (relative to the barium present) was increased and/or as BaSO4 seeds were added. After a short period of precipitation (a few minutes), the solution remained supersaturated for long periods (hours), with residual supersaturation ratios within the range of 1.1 to 3.0. These values were associated with a fourth order dependence of the crystal growth rate with the supersaturation rate. It was found that BaSO4 seed loading is directly proportional to the supersaturation depletion, heterogeneous seeds (CaCO3, CaSO4.2H2O) are ineffective for BaSO4 precipitation and that calcium ions inhibit BaSO4 precipitation. The precipitation of CaCO3 (as a mix of vaterite and calcite) by softening in synthetic effluent was effective to remove barium from solution. Isomorphic substitution of calcium by barium ion in the crystalline lattice of calcium carbonate was identified as the controlling mechanism of sorption process. Consequently, removal of barium from the solution is favored when the amount of precipitated calcium carbonate is increased and when the apparent distribution coefficient (DBa, which indicates the amount of barium incorporated into the solid) is raised. High values of pH and calcium concentration raise the precipitation of CaCO3 and, therefore, maximize the barium removal. The apparent barium distribution coefficient is independent of the initial pH (in the range of 9.5 to 11.7) and increases with calcium concentration. It also increases with the amount of calcite seeds, which may be consequence of higher barium incorporation in growing layers on CaCO3 pure substrates, or may be due to manifestation of adsorption mechanisms by the increase on available active places for barium incorporation. In experiments with real effluent, unlikely the synthetic solutions, the removal of barium by desupersaturation was performed efficiently even in the presence of calcium ion, probably due to its complexation with organic additives. In calcite precipitation, factors that increase initial supersaturation, such as carbonate addition and pH increase, elevates CaCO3 precipitation, which maximized the barium removal. These factors, however, reduced DBa in calcite, possibly due to a decrease on sorption process of ions which may stimulate barium incorporation. Sulphate dosages (insoluble to precipitate BaSO4) reduced the amount of precipitated calcite, decreasing barium removal and unespectly reducing the DBa in calcite. Finally, an eco-efficiency analysis was carried out in a water reuse study with zero liquid discharge in an oil refinery, applying the precipitation techniques studied. The implementation of precipitation stages and larger units of OI resulted in reductions in energy consumption in the thermal treatment of OI concentrate, reducing proportionally the emission of greenhouse gases, water consumption and ecotoxicological degradation of fresh water. In addition, there was reduction of investment costs (given the purchase of smaller evaporation equipment) and reduction in the operational energy costs.