Fundação de Apoio a Pesquisa e à Inovação Tecnológica do Estado de Sergipe - FAPITEC/SE / The presence of high concentrations of toxic metals in water bodies requires a constant search for new and more effective methods to treat industrial waste. The present work proposes a technique for the removal of chromium present in leather tannery effluent, using a hybrid magnetic adsorbent, CoFe2O4/NOM, synthesized using an environmentally friendly procedure. Salts of the metals (Co and Fe) were used as precursors and natural organic matter (NOM) was used as the gelification agent, replacing the traditional reagents that are toxic and expensive. Comparisons were made of CoFe2O4/NOM produced at ambient temperature (FeAMB) and the materials produced after calcination at 200 (Fe200), 400 (Fe400), and 800 °C (Fe800). The materials were analyzed by X-ray diffractometry and infrared spectroscopy, which revealed the presence of NOM in the structure of the material, together with the formation of cobalt ferrite, hence confirming the suitability of the new synthesis route. Adsorption tests, performed as a function of pH and time, showed the effectiveness of FeAMB at the natural pH of the effluent (pH 4.2), while at pH 6.0 the removal percentages were approximately 94, 100, 98, and 89% for FeAMB, Fe200, Fe400, and Fe800, respectively, with corresponding equilibration times of 60, 120, 120, and 60 minutes, respectively. Kinetics assays showed that high adsorption of 70-87% was achieved after only 20 minutes. The adsorption kinetics could be fitted using a pseudo-second order model, and the likely removal mechanism was electrostatic attraction between carboxylate groups and the cationic chromium species CrOH2+ and Cr(OH)2 +. Amongst the adsorbents studied, the FeAMB/NOM hybrid material was especially attractive because it did not require heat treatment and showed high removal capacities during five reuse cycles, ranging from 96% in the first cycle to 82% in the fifth cycle. The residues remaining after the reuse cycles, comprising the FeAMB hybrid saturated with chromium (FeAMB_Sat) and the desorbed chromium solution (dried and calcined at 500 °C, denoted CrD), showed excellent catalytic activity in the reduction of 4-nitrophenol to 4-aminophenol, the latter being an important compound used in the synthesis of pharmaceuticals and corrosion inhibitors. The conversion rates and times were 99.9% and 55 seconds for vi FeAMB_Sat, and 99.9% and 3 seconds for CrD. A magnetic hybrid material (denoted FeSF) was also synthesized replacing the analytical grade iron salt precursor by a ferric sulfate solution derived from the treatment of iron ore mining waste. This hybrid was highly efficient as an adsorbent, with 98% removal of chromium present in an industrial effluent in only 20 minutes. The technique described here contributes to the development of industrial symbiosis since it uses materials prepared using natural substances and enables the reuse of waste in the production cycle. The procedure is a technologically viable alternative for the remediation of metal-contaminated effluents. / O aumento da concentração de metais tóxicos nos corpos hídricos impulsiona uma busca constante por tratamentos eficientes para remediar resíduos industriais. Portanto, neste trabalho é proposto a remediação do cromo existente em efluente industrial de curtimento de couro utilizando um adsorvente híbrido magnético, CoFe2O4/MON, sintetizado por uma rota modificada, eco-amigável. Utiliza-se como precursores sais dos metais de interesse e a matéria orgânica natural (MON) como substância gelificante, em substituição aos reagentes tradicionais que são tóxicos e de alto custo. Para fins comparativos, a CoFe2O4/MON obtida à temperatura ambiente (FeAMB) foi calcinada a 200 (Fe200), 400 (Fe400) e 800°C (Fe800) e a formação do material foi confirmada por difratometria de raios x, que indicou também, simultaneamente, com o infravermelho, a presença da MON na estrutura do material, a formação da ferrita de cobalto e assim, a eficácia da rota de síntese proposta. Os ensaios de adsorção em função do pH e do tempo, evidenciaram a eficiência da FeAMB, no pH natural do efluente (4,2), enquanto que para os demais, no pH 6,0; com percentuais de remoção de aproximadamente 94, 100, 98 e 89% para FeAMB, Fe200, Fe400, Fe800, respectivamente, e tempos de equilíbrio de 60, 120, 120 e 60 minutos. Entretanto, com apenas 20 minutos de ensaios cinéticos houve uma alta resposta de adsorção, entre 70-87%. A cinética de adsorção ajustou-se melhor ao modelo de pseudo-segunda ordem e o possível mecanismo de remoção ocorre por atração eletrostática entre os grupos carboxilatos e as espécies catiônicas do cromo, CrOH2+, Cr(OH)2 +. O material híbrido FeAMB/MON destaca-se entre os demais adsorventes em estudo por não ter sido submetido a tratamento térmico e porque apresentou uma elevada capacidade de remoção após ser submetido a cinco ciclos de reutilização, variando de 96% no primeiro ciclo para 82% no quinto ciclo. Os resíduos decorrentes dos ciclos de reutilização, o híbrido FeAMB saturado com cromo (FeAMB_Sat) e a solução de cromo dessorvido, seca e calcinada a 500°C (CrD), apresentaram excelentes potenciais catalíticos na redução do 4- nitrofenol a 4-aminofenol, o qual é um importante insumo para a síntese de produtos farmacêuticos e inibidores de corrosão. A taxa e o tempo de conversão da redução, foram de 99,9% e 55 segundos para FeAMB_Sat e 99,9% e 3 segundos para CrD. De modo eminente, também foi sintetizado um material híbrido magnético substituindo o precursor sal de ferro em grau analítico por solução de sulfato férrico oriunda de um resíduo tratado da mineração de ferro, denominado FeSF. Este híbrido revelou uma eficiência notável como adsorvente, pois o percentual de remoção de cromo presente em efluente industrial foi de 98% em apenas 20 minutos. Diante disso, o presente estudo contribuiu para a prática da simbiose industrial ao propor o emprego de substâncias naturais na elaboração de materiais, bem como a reutilização dos resíduos, e sua reinserção no ciclo produtivo desenvolvendo uma alternativa tecnologicamente viável para remediação de metais.

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)

O impacto de um lançamento de efluente na qualidade da água do corpo hídrico depende de características do lançamento e do corpo hídrico, a exemplo de suas condições hidrodinâmicas. O conhecimento das relações entre os fatores envolvidos permite avaliar os riscos envolvidos, alterar a forma de lançamento de efluentes de modo a reduzir seu impacto e reduzir os custos com as formas de controle da poluição, entre outras ações. Nesse contexto, o objetivo deste trabalho é compreender as relações entre os fatores dominantes das condições hidrodinâmicas e a dispersão de poluentes na região nordeste da Laguna dos Patos, buscando identificar formas de utilizar a modelagem hidrodinâmica para melhorar a gestão do corpo hídrico e de lançamento de efluentes. A área de estudo consiste na região nordeste da Laguna dos Patos, no Rio Grande do Sul, onde o vento e a vazão afluente são os fatores determinantes de circulação de água. O modelo utilizado (IPH-A) apresentou boa representação da variação de nível, exceto pelo posto mais próximo da região estuarina, e da circulação de água. O coeficiente de dispersão foi definido a partir da comparação visual da simulação da dispersão dos sedimentos em suspensão afluentes ao Lago Guaíba e a pluma do Guaíba observada em imagens de satélite. Cenários de vento e vazão foram determinados a partir da análise da série histórica de dados de vento na estação de Rio Grande e da vazão afluente ao Lago Guaíba.Os resultados dos ventos sudoeste e nordeste foram semelhantes ao verificado na literatura com uso de modelo bidimensional para o corpo lagunar. Na região nordeste, uma célula de circulação entre o Banco das Desertas e o Banco dos Abreus é observada no sentido horário (anti-horário) para os cenários com vento sudoeste (nordeste). O vento sudeste provoca o aumento do nível na margem oeste e redução na margem leste É observada uma maior renovação de água na região ao norte do Banco das Desertas e menor troca de água com a Lagoa do Casamento do que nos cenários anteriores. Nos cenários de vento nulo, as velocidades da água na região nordeste da laguna são bastante baixas. A vazão necessária para manutenção do nível na laguna dependeu do vento predominante. Os diferentes cenários de vento produziram diferentes plumas de dispersão do lançamento de efluente simulado, seguindo os padrões da circulação de água no local. As maiores concentrações foram observadas no local de lançamento do efluente para o cenário de vento nulo e a maior área de influência foi observada para os cenários de vento nordeste (maior velocidade de vento simulada). Para os cinco dias de simulação, foi observada pouca influência da vazão afluente no nível e na circulação de água do corpo lagunar e, consequentemente, na dispersão de poluentes. Os resultados evidenciam a necessidade de as concentrações de lançamento permitidas serem estabelecidas com base em estudo da dispersão física do efluente no corpo hídrico receptor, conforme determinado pela legislação nacional para corpos d’água onde não se aplica a vazão de referência. A consideração de uma zona de mistura onde as concentrações dos parâmetros podem estar em desacorpo com o enquadramento do corpo hídrico é debatida nas discussões. As simulações permitiram ainda identificar locais prioritários para monitoramento dos efeitos do efluente lançado na qualidade da água, cenários críticos para conflitos de uso da água considerando outros usos na região e verificar possíveis consequências do encurtamento ou alongamento do emissário. / The aim of this study is to understand the relationship between hydrodynamic and the pollutants dispersion in the northeast region of the Patos Lagoon, looking for identify ways of using hydrodynamic modeling to improve water resources and effluent discharge management. The study area is the northeastern region of Patos Lagoon, a chocked lagoon in the brazilian state of Rio Grande do Sul, where winds and freshwater runoff drive water circulation. The model IPH-A performed well, except for the estuarine region. The dispersion coefficient was defined from the visual comparison between the dispersion of suspended sediments on Guaíba Lake simulated and observed in satellite images. The wind and freshwater runoff scenarios were determined by analyzing the historical wind data series at the Rio Grande station and the freshwater discharge of the main tributaries of Guaíba Lake. The results for the scenarios of the southwest and northeast winds were similar to those observed in the literature using a two-dimensional hydrodynamic model. In the northeast region, a circulation cell between the Banco das Desertas and Banco dos Abreus is observed clockwise (counter-clockwise) for the southwest (northeast) wind scenarios. The southeast wind increases water level in the west margin and reduces in the east margin. It is observed a more intense water exchange in the region to the north of the Banco das Desertas and less water exchange with the Casamento Lagoon than in the previous scenarios In null wind speed scenarios, the water velocities in the northeast region of the lagoon are quite low. The water inflow necessary to maintain the water level in the lagoon depends on the wind condition. Different wind scenarios produced different effluent plumes, following the local water circulation patterns. The highest concentrations were observed at the effluent discharge site for the scenario with null wind speed and the largest area of influence was observed for the northeast wind scenario (highest simulated wind speed). Due to the only 5-days period of simulation, little influence was observed of the freshwater runoff on the water level and on the lagoon circulation, and, consequently, on the dispersion of pollutants. This evidences the need for the maximum permitted concentrations of pollutants to be established based on a study of the physical dispersion of the effluent in the receiving water body, as determined by national legislation for water bodies where the reference flow does not apply. The simulations also allowed to identify priority sites for monitoring the effects of effluent discharge on water quality, critical scenarios for water use conflicts considering other uses, and to verify possible consequences of changes in emissary length.

Industrial effluents with high concentrations of heavy metals are widespread pollutants of great concerns as they are known to be persistent and non-degradable. Continuous monitoring and treatment of the effluents become pertinent because of their impacts on wastewater treatment plants. The aim of this study is to determine the correlation between heavy metal pollution in water and the location of industries in order to ascertain the effectiveness of the municipal waste water treatment plant. Heavy metal identification and physico-chemical analysis were done using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and multi-parameter probe respectively. Correlation coefficients of the measured values were done to investigate the effect of the industrial effluents on the treatment plants. Heavy metal resistant bacteria were identified and characterised by polymerase chain reaction and sequencing. Leeuwkuil wastewater treatment plants were effective in maintaining temperature, pH, and chemical oxygen demand within South Africa green drop and SAGG Standards whereas the purification plant was effective in maintaining the values of Cu, Zn, Al, temperature, BOD, COD, and TDS within the SANS and WHO standard for potable water. This findings indicated the need for the treatment plants to be reviewed.The industrial wastewater were identified as a point source of heavy metal pollution that influenced Leeuwkuil wastewater treatment plants and the purification plants in Vaal, Vereenining South Africa. Pseudomonas aeruginosa, Serratia marcescens, Bacillus sp. strain and Bacillus toyonensis that showed 100% similarity were found to be resistant to Al, Cu, Pb and Zn. These identified bacteria can be considered for further study in bioremediation. / Environmental Sciences / M. Sc. (Environmental Science)

O impacto de um lançamento de efluente na qualidade da água do corpo hídrico depende de características do lançamento e do corpo hídrico, a exemplo de suas condições hidrodinâmicas. O conhecimento das relações entre os fatores envolvidos permite avaliar os riscos envolvidos, alterar a forma de lançamento de efluentes de modo a reduzir seu impacto e reduzir os custos com as formas de controle da poluição, entre outras ações. Nesse contexto, o objetivo deste trabalho é compreender as relações entre os fatores dominantes das condições hidrodinâmicas e a dispersão de poluentes na região nordeste da Laguna dos Patos, buscando identificar formas de utilizar a modelagem hidrodinâmica para melhorar a gestão do corpo hídrico e de lançamento de efluentes. A área de estudo consiste na região nordeste da Laguna dos Patos, no Rio Grande do Sul, onde o vento e a vazão afluente são os fatores determinantes de circulação de água. O modelo utilizado (IPH-A) apresentou boa representação da variação de nível, exceto pelo posto mais próximo da região estuarina, e da circulação de água. O coeficiente de dispersão foi definido a partir da comparação visual da simulação da dispersão dos sedimentos em suspensão afluentes ao Lago Guaíba e a pluma do Guaíba observada em imagens de satélite. Cenários de vento e vazão foram determinados a partir da análise da série histórica de dados de vento na estação de Rio Grande e da vazão afluente ao Lago Guaíba.Os resultados dos ventos sudoeste e nordeste foram semelhantes ao verificado na literatura com uso de modelo bidimensional para o corpo lagunar. Na região nordeste, uma célula de circulação entre o Banco das Desertas e o Banco dos Abreus é observada no sentido horário (anti-horário) para os cenários com vento sudoeste (nordeste). O vento sudeste provoca o aumento do nível na margem oeste e redução na margem leste É observada uma maior renovação de água na região ao norte do Banco das Desertas e menor troca de água com a Lagoa do Casamento do que nos cenários anteriores. Nos cenários de vento nulo, as velocidades da água na região nordeste da laguna são bastante baixas. A vazão necessária para manutenção do nível na laguna dependeu do vento predominante. Os diferentes cenários de vento produziram diferentes plumas de dispersão do lançamento de efluente simulado, seguindo os padrões da circulação de água no local. As maiores concentrações foram observadas no local de lançamento do efluente para o cenário de vento nulo e a maior área de influência foi observada para os cenários de vento nordeste (maior velocidade de vento simulada). Para os cinco dias de simulação, foi observada pouca influência da vazão afluente no nível e na circulação de água do corpo lagunar e, consequentemente, na dispersão de poluentes. Os resultados evidenciam a necessidade de as concentrações de lançamento permitidas serem estabelecidas com base em estudo da dispersão física do efluente no corpo hídrico receptor, conforme determinado pela legislação nacional para corpos d’água onde não se aplica a vazão de referência. A consideração de uma zona de mistura onde as concentrações dos parâmetros podem estar em desacorpo com o enquadramento do corpo hídrico é debatida nas discussões. As simulações permitiram ainda identificar locais prioritários para monitoramento dos efeitos do efluente lançado na qualidade da água, cenários críticos para conflitos de uso da água considerando outros usos na região e verificar possíveis consequências do encurtamento ou alongamento do emissário. / The aim of this study is to understand the relationship between hydrodynamic and the pollutants dispersion in the northeast region of the Patos Lagoon, looking for identify ways of using hydrodynamic modeling to improve water resources and effluent discharge management. The study area is the northeastern region of Patos Lagoon, a chocked lagoon in the brazilian state of Rio Grande do Sul, where winds and freshwater runoff drive water circulation. The model IPH-A performed well, except for the estuarine region. The dispersion coefficient was defined from the visual comparison between the dispersion of suspended sediments on Guaíba Lake simulated and observed in satellite images. The wind and freshwater runoff scenarios were determined by analyzing the historical wind data series at the Rio Grande station and the freshwater discharge of the main tributaries of Guaíba Lake. The results for the scenarios of the southwest and northeast winds were similar to those observed in the literature using a two-dimensional hydrodynamic model. In the northeast region, a circulation cell between the Banco das Desertas and Banco dos Abreus is observed clockwise (counter-clockwise) for the southwest (northeast) wind scenarios. The southeast wind increases water level in the west margin and reduces in the east margin. It is observed a more intense water exchange in the region to the north of the Banco das Desertas and less water exchange with the Casamento Lagoon than in the previous scenarios In null wind speed scenarios, the water velocities in the northeast region of the lagoon are quite low. The water inflow necessary to maintain the water level in the lagoon depends on the wind condition. Different wind scenarios produced different effluent plumes, following the local water circulation patterns. The highest concentrations were observed at the effluent discharge site for the scenario with null wind speed and the largest area of influence was observed for the northeast wind scenario (highest simulated wind speed). Due to the only 5-days period of simulation, little influence was observed of the freshwater runoff on the water level and on the lagoon circulation, and, consequently, on the dispersion of pollutants. This evidences the need for the maximum permitted concentrations of pollutants to be established based on a study of the physical dispersion of the effluent in the receiving water body, as determined by national legislation for water bodies where the reference flow does not apply. The simulations also allowed to identify priority sites for monitoring the effects of effluent discharge on water quality, critical scenarios for water use conflicts considering other uses, and to verify possible consequences of changes in emissary length.

O impacto de um lançamento de efluente na qualidade da água do corpo hídrico depende de características do lançamento e do corpo hídrico, a exemplo de suas condições hidrodinâmicas. O conhecimento das relações entre os fatores envolvidos permite avaliar os riscos envolvidos, alterar a forma de lançamento de efluentes de modo a reduzir seu impacto e reduzir os custos com as formas de controle da poluição, entre outras ações. Nesse contexto, o objetivo deste trabalho é compreender as relações entre os fatores dominantes das condições hidrodinâmicas e a dispersão de poluentes na região nordeste da Laguna dos Patos, buscando identificar formas de utilizar a modelagem hidrodinâmica para melhorar a gestão do corpo hídrico e de lançamento de efluentes. A área de estudo consiste na região nordeste da Laguna dos Patos, no Rio Grande do Sul, onde o vento e a vazão afluente são os fatores determinantes de circulação de água. O modelo utilizado (IPH-A) apresentou boa representação da variação de nível, exceto pelo posto mais próximo da região estuarina, e da circulação de água. O coeficiente de dispersão foi definido a partir da comparação visual da simulação da dispersão dos sedimentos em suspensão afluentes ao Lago Guaíba e a pluma do Guaíba observada em imagens de satélite. Cenários de vento e vazão foram determinados a partir da análise da série histórica de dados de vento na estação de Rio Grande e da vazão afluente ao Lago Guaíba.Os resultados dos ventos sudoeste e nordeste foram semelhantes ao verificado na literatura com uso de modelo bidimensional para o corpo lagunar. Na região nordeste, uma célula de circulação entre o Banco das Desertas e o Banco dos Abreus é observada no sentido horário (anti-horário) para os cenários com vento sudoeste (nordeste). O vento sudeste provoca o aumento do nível na margem oeste e redução na margem leste É observada uma maior renovação de água na região ao norte do Banco das Desertas e menor troca de água com a Lagoa do Casamento do que nos cenários anteriores. Nos cenários de vento nulo, as velocidades da água na região nordeste da laguna são bastante baixas. A vazão necessária para manutenção do nível na laguna dependeu do vento predominante. Os diferentes cenários de vento produziram diferentes plumas de dispersão do lançamento de efluente simulado, seguindo os padrões da circulação de água no local. As maiores concentrações foram observadas no local de lançamento do efluente para o cenário de vento nulo e a maior área de influência foi observada para os cenários de vento nordeste (maior velocidade de vento simulada). Para os cinco dias de simulação, foi observada pouca influência da vazão afluente no nível e na circulação de água do corpo lagunar e, consequentemente, na dispersão de poluentes. Os resultados evidenciam a necessidade de as concentrações de lançamento permitidas serem estabelecidas com base em estudo da dispersão física do efluente no corpo hídrico receptor, conforme determinado pela legislação nacional para corpos d’água onde não se aplica a vazão de referência. A consideração de uma zona de mistura onde as concentrações dos parâmetros podem estar em desacorpo com o enquadramento do corpo hídrico é debatida nas discussões. As simulações permitiram ainda identificar locais prioritários para monitoramento dos efeitos do efluente lançado na qualidade da água, cenários críticos para conflitos de uso da água considerando outros usos na região e verificar possíveis consequências do encurtamento ou alongamento do emissário. / The aim of this study is to understand the relationship between hydrodynamic and the pollutants dispersion in the northeast region of the Patos Lagoon, looking for identify ways of using hydrodynamic modeling to improve water resources and effluent discharge management. The study area is the northeastern region of Patos Lagoon, a chocked lagoon in the brazilian state of Rio Grande do Sul, where winds and freshwater runoff drive water circulation. The model IPH-A performed well, except for the estuarine region. The dispersion coefficient was defined from the visual comparison between the dispersion of suspended sediments on Guaíba Lake simulated and observed in satellite images. The wind and freshwater runoff scenarios were determined by analyzing the historical wind data series at the Rio Grande station and the freshwater discharge of the main tributaries of Guaíba Lake. The results for the scenarios of the southwest and northeast winds were similar to those observed in the literature using a two-dimensional hydrodynamic model. In the northeast region, a circulation cell between the Banco das Desertas and Banco dos Abreus is observed clockwise (counter-clockwise) for the southwest (northeast) wind scenarios. The southeast wind increases water level in the west margin and reduces in the east margin. It is observed a more intense water exchange in the region to the north of the Banco das Desertas and less water exchange with the Casamento Lagoon than in the previous scenarios In null wind speed scenarios, the water velocities in the northeast region of the lagoon are quite low. The water inflow necessary to maintain the water level in the lagoon depends on the wind condition. Different wind scenarios produced different effluent plumes, following the local water circulation patterns. The highest concentrations were observed at the effluent discharge site for the scenario with null wind speed and the largest area of influence was observed for the northeast wind scenario (highest simulated wind speed). Due to the only 5-days period of simulation, little influence was observed of the freshwater runoff on the water level and on the lagoon circulation, and, consequently, on the dispersion of pollutants. This evidences the need for the maximum permitted concentrations of pollutants to be established based on a study of the physical dispersion of the effluent in the receiving water body, as determined by national legislation for water bodies where the reference flow does not apply. The simulations also allowed to identify priority sites for monitoring the effects of effluent discharge on water quality, critical scenarios for water use conflicts considering other uses, and to verify possible consequences of changes in emissary length.

[ES] Esta Tesis Doctoral se centra en la recuperación mediante electrodeposición del Sb presente en un efluente residual proveniente de la metalurgia del cobre. El efluente en el que se basa este estudio se produce en el proceso de regeneración con HCl concentrado de las resinas de intercambio iónico de una de las subetapas del electro-refinado del cobre. Se trata de un electrolito ácido que contiene diversas impurezas, entre las que destacan, Sb y Bi, que son considerados materias primas críticas por la Unión Europea, debido al riesgo de suministro que presentan y a su importancia en la economía. El objetivo de esta Tesis es la recuperación del Sb y la reutilización del HCl. Para alcanzar ambos propósitos se ha estudiado el empleo de la electrodeposición como operación de separación para el tratamiento del efluente. Este proceso se ha investigado mediante técnicas electroquímicas, en particular, voltametría cíclica y de barrido lineal. En primer lugar, se ha realizado el estudio con disoluciones sintéticas que emulan el efluente generado en las metalurgias chilenas. La caracterización electroquímica de la disolución de Sb en medio HCl ha evidenciado que la reducción del Sb(III) a Sb metálico está limitada por la transferencia de materia y que una concentración elevada de HCl favorece la recuperación del Sb. Los ensayos de electrodeposición han destacado la relevancia de las reacciones secundarias, la reacción de evolución del hidrógeno (HER) y la generación de cloro, y su influencia negativa sobre la deposición de Sb. La HER tiene lugar en el cátodo y conlleva la generación de burbujas de hidrógeno a elevadas densidades de corriente, que reducen la superficie útil del electrodo de trabajo e incluso causan el desprendimiento del depósito de Sb. Por su parte, la generación de cloro gas en el ánodo provoca la redisolución de los depósitos de Sb desprendidos a causa de la HER. Tras la realización de estos ensayos se ha concluido que se puede aumentar la tasa de recuperación de Sb si se tienen mayores concentraciones del elemento en la disolución o si se mejoran las condiciones hidrodinámicas. Se ha analizado también cómo influye la presencia de Bi en la disolución sintética durante la electrodeposición del Sb. El potencial de reducción de ambos elementos es similar, lo que implica que la recuperación individual de Sb sea compleja. No obstante, si se trabaja bajo condiciones en las que no se supere la densidad de corriente límite del sistema, se logra una elevada selectividad hacia el Sb. Si la concentración de Bi en la disolución es superior a la de Sb, se electrodepositan ambos elementos, pero se logra un elevado valor de eficiencia de corriente debido a que la influencia de la HER sobre el Bi no es tan fuerte. A continuación, se ha estudiado la aplicación de las técnicas previamente analizadas con un efluente real, facilitado por una empresa española. Se ha verificado que las conclusiones obtenidas con las disoluciones sintéticas son aplicables al efluente real. En particular, se ha confirmado que, al aumentar la densidad de corriente aplicada, la deposición de Sb se ve mermada debido a la relevancia del resto de reacciones: la reducción de los demás elementos y la evolución del medio. Los depósitos obtenidos contienen algunos de los elementos presentes en el efluente real: Sb, Bi, As y Cu, siendo mayoritario el primero. Como resultado, se ha concluido que es posible purificar el HCl mediante la electrodeposición de los elementos contenidos en el electrolito. Finalmente, se ha planteado la posibilidad de sustituir el HCl empleado como regenerante por un disolvente eutéctico profundo, debido a la alta solubilidad de metales y su procedencia de fuentes renovables. En particular, la investigación se ha llevado a cabo con la oxalina, la cual presenta una elevada capacidad de disolución para el Sb y una amplia ventana de potencial que beneficiaría la aplicación de la técnica de electrodeposición para la recuperación del Sb. / [CA] Esta Tesi Doctoral se centra en la recuperació mitjançant electrodeposició del Sb present en un efluent residual provinent de la metal·lúrgia del coure. L'efluent en què es basa este estudi es produïx en el procés de regeneració amb HCl concentrat de les resines d'intercanvi iònic d'una de les subetapes de l'electro-refinat del coure. Es tracta d'un electròlit àcid que conté diverses impureses, entre les quals destaquen, Sb i Bi, que són considerats matèries primeres crítiques per la Unió Europea, a causa del risc de subministrament que presenten i a la seua importància en l'economia. L'objectiu d'esta Tesi és la recuperació del Sb i la reutilització de l'HCl. Per assolir aquests dos propòsits s'ha estudiat l'ús de l'electrodeposició com a operació de separació per al tractament de l'efluent. Este procés s'ha investigat mitjançant tècniques electroquímiques, en particular, voltametria cíclica i de rastreig lineal. En primer lloc, s'ha realitzat l'estudi amb dissolucions sintètiques que emulen l'efluent generat a les metal·lúrgies xilenes. La caracterització electroquímica de la dissolució de Sb en medi HCl ha evidenciat que la reducció del Sb(III) a Sb metàl·lic està limitada per la transferència de matèria i que una concentració elevada de HCl afavorix la recuperació del Sb. Els assajos d'electrodeposició han destacat la rellevància de les reaccions secundàries, la reacció d'evolució de l'hidrogen (HER) i la generació de clor, i la seua influència negativa sobre la deposició de Sb. La HER té lloc al càtode i comporta la generació de bambolles d'hidrogen a elevades densitats de corrent, la qual cosa reduïx la superfície útil de l'elèctrode de treball i fins i tot causa el despreniment del depòsit de Sb. Per la seua banda, la generació de clor gas a l'ànode provoca la redissolució dels depòsits de Sb despresos a causa de la HER. Després de la realització d'estos assajos s'ha conclòs que es pot augmentar la taxa de recuperació de Sb si es tenen majors concentracions de l'element en la dissolució o si es milloren les condicions hidrodinàmiques. S'ha analitzat també com influïx la presència de Bi en la dissolució sintètica durant l'electrodeposició del Sb. El potencial de reducció dels dos elements és similar, la qual cosa implica que la recuperació individual de Sb siga complexa. No obstant això, si es treballa sota condicions en què no se supere la densitat de corrent límit del sistema, s'aconseguix una elevada selectivitat cap al Sb. Si la concentració de Bi en la dissolució és superior a la de Sb, s'electrodepositen ambdós elements, però s'aconseguix un elevat valor d'eficiència de corrent pel fet que la influència de la HER sobre el Bi no és tan forta. A continuació, s'ha estudiat l'aplicació de les tècniques prèviament analitzades amb un efluent real, facilitat per una empresa espanyola. S'ha verificat que les conclusions obtingudes amb les dissolucions sintètiques són aplicables al efluent real. En particular, s'ha confirmat que, en augmentar la densitat de corrent aplicada, la deposició de Sb es veu minvada a causa de la rellevància de la resta de reaccions: la reducció dels altres elements i l'evolució del medi. Els depòsits obtinguts contenen alguns dels elements presents en el efluent real: Sb, Bi, As i Cu, sent majoritari el primer. Com a resultat, s'ha conclòs que és possible purificar l'HCl mitjançant l'electrodeposició dels elements continguts en l'electròlit. Finalment, s'ha plantejat la possibilitat de substituir l'HCl emprat com regenerant per un dissolvent eutèctic profund, a causa de l'alta solubilitat de metalls i la seua procedència de fonts renovables. En particular, la investigació s'ha dut a terme amb l'oxalina, la qual presenta una elevada capacitat de dissolució per al Sb i una àmplia finestra de potencial que beneficiaria l'aplicació de la tècnica d'electrodeposició per a la recuperació del Sb captat durant el procés de regeneració de les resines. / [EN] This Doctoral Thesis focuses on the recovery by electrodeposition of Sb present in an effluent from the copper metallurgy. The effluent on which this study is based is generated during the regeneration with concentrated hydrochloric acid of the ion exchange resins used in one of the sub-stages of copper electro-refining. It is an acid electrolyte containing several impurities, among them, Sb and Bi, which are considered critical raw materials by the European Union due to their supply risk and economic relevance. The aim of this Thesis is the recovery of Sb and reuse of HCl. To achieve both objectives, electrodeposition has been studied as a separation operation for the treatment of the effluent. This operation has been investigated through electrochemical techniques, primarily, cyclic and linear sweep voltammetry. First, the study has been conducted with synthetic solutions emulating the effluent generated in the Chilean metallurgy industries. The electrochemical characterization of the Sb solution in the HCl medium has shown that, mass-transfer limits the reduction of Sb(III) to metallic Sb and a high HCl concentration favors the recovery of Sb. From the electrodeposition tests the relevance and negative influence on Sb deposition of the secondary reactions, the hydrogen evolution reaction (HER) and the chlorine generation, has been proven. The HER occurs at the cathode and involves the generation of hydrogen bubbles at high current densities, which decrease the effective surface area of the working electrode and even cause the detachment of the Sb deposits. The chlorine generation at the anode leads to the redissolution of the Sb deposits detached by the HER. After conducting these experiments, it has been concluded that it is possible to increase the Sb recovery rate, if higher concentrations of this element are present in the solution or the hydrodynamic conditions of the electrodeposition process are improved. The influence of the presence of Bi in the synthetic solution on the Sb electrodeposition has also been investigated. The reduction potential of both elements is similar, implying that the individual recovery of Sb by electrodeposition is challenging. However, if the operating conditions do not imply exceeding the limiting current density of the system, a high electrodeposition selectivity towards Sb is achieved. If the concentration of Bi in the solution is higher than that of Sb, the simultaneous electrodeposition of both elements takes place, but, on the contrary, a high value of current efficiency is obtained because the influence of the HER on Bi reduction is not as significant as that on Sb deposition. The application of the previously analyzed techniques has been studied with a real effluent, that was provided by a Spanish company. It has been proven that the conclusions obtained with the synthetic solutions can be applied to a real effluent. It has been confirmed that, as the applied current density increases, the Sb deposition worsens due to the relevance of the other reactions that take place during the process: the reduction of the other elements and the evolution of the medium. The deposits obtained contain some elements present in the real effluent: Sb, Bi, As and Cu, the most significant being the first. From this study, it has been concluded that purifying the HCl by removing the elements contained in the electrolyte via electrodeposition is possible. Finally, the possibility of replacing the HCl used as a regenerant with a deep eutectic solvent has been considered based on their properties, among which are a high solubility of metals and their synthesis from renewable sources. In particular, the research has been carried out with oxaline, which presents a high dissolution capacity for Sb and a wide potential window that would benefit the application of the electrodeposition technique to recover Sb captured during the resins regeneration process. / Me gustaría agradecer la financiación a la Agencia Estatal de Investigación (AEI/10.13039/501100011033) (España) bajo el proyecto PCI2019-103535, gracias al cual he podido desarrollar la presente Tesis Doctoral, y a FEDER Una manera de hacer Europa / Hernández Pérez, L. (2024). Estudio electroquímico para la recuperación de antimonio de efluentes del electro-refinado de cobre por electrodeposición [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203892

The goal of this project was to develop novel bacterial biomarkers for use in an industrial context. These biomarkers would be used to determine aluminium industry activity impact on a local ecosystem. Sediment bacterial communities of the Saguenay River are subjected to industrial effluent produced by industry in Jonquière, QC. In-situ responses of these communities to effluent exposure were measured and evaluated as potential biomarker candidates for exposure to past and present effluent discharge. Bacterial community structure and composition between control and affected sites were investigated. Differences observed between the communities were used as indicators of a response to industrial activity through exposure to effluent by-products. Diversity indices were not significantly different between sites with increased effluent exposure. However, differences were observed with the inclusion of algae and cyanobacteria. UniFrac analyses indicated that a control (NNB) and an affected site (Site 2) were more similar to one another with regard to community structure than either was to a medially affected site (Site 5) (Figure 2.4). We did not observe a signature of the microbial community structure that could be predicted with effluent exposure. Microbial community function in relation to bacterial mercury resistance (HgR) was also evaluated as a specific response to the mercury component present in sediments. Novel PCR primers and amplification conditions were developed to amplify merP, merT and merA genes belonging to the mer-operon which confers HgR (Table 5.6). To our knowledge, the roles of merP and merT have not been explored as possible tools to confirm the presence of the operon. HgR gene abundance in sediment microbial communities was significantly correlated (p < 0.05) to total mercury levels (Figure 3.4) but gene expression was not measurable. We could not solely attribute the release of Hg0 from sediments in bioreactor experiments to a biogenic origin. However, there was a 1000 fold difference in measured Hg0 release between control and affected sites suggesting that processes of natural remediation may be taking place at contaminated sites (Figure 3.7). Abundance measurements of HgR related genes represent a strong response target to the mercury immobilized in sediments. Biomarkers built on this response can be used by industry to measure long term effects of industrially derived mercury on local ecosystems. The abundance of mer-operon genes in affected sites indicates the presence of a thriving bacterial community harbouring HgR potential. These communities have the capacity to naturally remediate the sites they occupy. This remediation could be further investigated. Additional studies will be required to develop biomarkers that are more responsive to contemporary industrial activity such as those based on the integrative oxidative stress response.

The goal of this project was to develop novel bacterial biomarkers for use in an industrial context. These biomarkers would be used to determine aluminium industry activity impact on a local ecosystem. Sediment bacterial communities of the Saguenay River are subjected to industrial effluent produced by industry in Jonquière, QC. In-situ responses of these communities to effluent exposure were measured and evaluated as potential biomarker candidates for exposure to past and present effluent discharge. Bacterial community structure and composition between control and affected sites were investigated. Differences observed between the communities were used as indicators of a response to industrial activity through exposure to effluent by-products. Diversity indices were not significantly different between sites with increased effluent exposure. However, differences were observed with the inclusion of algae and cyanobacteria. UniFrac analyses indicated that a control (NNB) and an affected site (Site 2) were more similar to one another with regard to community structure than either was to a medially affected site (Site 5) (Figure 2.4). We did not observe a signature of the microbial community structure that could be predicted with effluent exposure. Microbial community function in relation to bacterial mercury resistance (HgR) was also evaluated as a specific response to the mercury component present in sediments. Novel PCR primers and amplification conditions were developed to amplify merP, merT and merA genes belonging to the mer-operon which confers HgR (Table 5.6). To our knowledge, the roles of merP and merT have not been explored as possible tools to confirm the presence of the operon. HgR gene abundance in sediment microbial communities was significantly correlated (p < 0.05) to total mercury levels (Figure 3.4) but gene expression was not measurable. We could not solely attribute the release of Hg0 from sediments in bioreactor experiments to a biogenic origin. However, there was a 1000 fold difference in measured Hg0 release between control and affected sites suggesting that processes of natural remediation may be taking place at contaminated sites (Figure 3.7). Abundance measurements of HgR related genes represent a strong response target to the mercury immobilized in sediments. Biomarkers built on this response can be used by industry to measure long term effects of industrially derived mercury on local ecosystems. The abundance of mer-operon genes in affected sites indicates the presence of a thriving bacterial community harbouring HgR potential. These communities have the capacity to naturally remediate the sites they occupy. This remediation could be further investigated. Additional studies will be required to develop biomarkers that are more responsive to contemporary industrial activity such as those based on the integrative oxidative stress response.

The goal of this project was to develop novel bacterial biomarkers for use in an industrial context. These biomarkers would be used to determine aluminium industry activity impact on a local ecosystem. Sediment bacterial communities of the Saguenay River are subjected to industrial effluent produced by industry in Jonquière, QC. In-situ responses of these communities to effluent exposure were measured and evaluated as potential biomarker candidates for exposure to past and present effluent discharge. Bacterial community structure and composition between control and affected sites were investigated. Differences observed between the communities were used as indicators of a response to industrial activity through exposure to effluent by-products. Diversity indices were not significantly different between sites with increased effluent exposure. However, differences were observed with the inclusion of algae and cyanobacteria. UniFrac analyses indicated that a control (NNB) and an affected site (Site 2) were more similar to one another with regard to community structure than either was to a medially affected site (Site 5) (Figure 2.4). We did not observe a signature of the microbial community structure that could be predicted with effluent exposure. Microbial community function in relation to bacterial mercury resistance (HgR) was also evaluated as a specific response to the mercury component present in sediments. Novel PCR primers and amplification conditions were developed to amplify merP, merT and merA genes belonging to the mer-operon which confers HgR (Table 5.6). To our knowledge, the roles of merP and merT have not been explored as possible tools to confirm the presence of the operon. HgR gene abundance in sediment microbial communities was significantly correlated (p < 0.05) to total mercury levels (Figure 3.4) but gene expression was not measurable. We could not solely attribute the release of Hg0 from sediments in bioreactor experiments to a biogenic origin. However, there was a 1000 fold difference in measured Hg0 release between control and affected sites suggesting that processes of natural remediation may be taking place at contaminated sites (Figure 3.7). Abundance measurements of HgR related genes represent a strong response target to the mercury immobilized in sediments. Biomarkers built on this response can be used by industry to measure long term effects of industrially derived mercury on local ecosystems. The abundance of mer-operon genes in affected sites indicates the presence of a thriving bacterial community harbouring HgR potential. These communities have the capacity to naturally remediate the sites they occupy. This remediation could be further investigated. Additional studies will be required to develop biomarkers that are more responsive to contemporary industrial activity such as those based on the integrative oxidative stress response.