The rising use of mineral-based fertilizer and water for agricultural operations to feed a growing population has polluted water bodies and depleted resources. In addition, nutrient contamination has caused eutrophication and wastewater concerns that conventional wastewater treatment cannot solve. Thus, meeting new water treatment regulations and procuring more value-added products from these procedures is crucial. Conductive ultrafiltration membranes precipitate and extract struvite, an ecologically good fertilizer, from synthetic livestock effluent. This technique produces solid fertilizer and irrigation-quality water. Since the recovery process relies on electrochemical hydrolysis and local pH modulation along the membrane surface, pH correction does not need chemical additions. The system was tested using cow effluent with up to 1,000 mg/L of nitrogen and phosphorus. Analytical tests showed that the precipitates were struvite and that up to 65% of the phosphorus and nitrogen were removed in the first 30 minutes of electrochemical filtration. Low membrane fouling and flux drop made the recovery technique successful. A mathematical model of N, P, and Mg ions in an external electric field explained the fouling and precipitation tests. Thus, precipitation happens near the membrane but not on it. This reduces surface fouling. Forward osmosis was used to make struvite with less energy. A voltage near the FO membrane enabled magnesium to migrate opposite into the feed chamber, where it reacted with ammonium and phosphate in the feed solution to form struvite. Electrical charging increased struvite recovery by 77% and water recovery by 39%. Ion migration may have reduced dilutive and concentrative polarization on the draw and feed sides of the FO membrane, causing the rise. High external voltage, draw concentration, and draw pH made water recovery and struvite precipitation simpler. This study suggests that reverse salt flow might improve FO systems' nutrition and water recovery. These devices were combined with microbial electrolytic cells to generate electricity and prevent biofouling. FO treatment was investigated using vacuum membrane distillation for sustainability and zero discharge. Constant draw solution reconcentration yields more steady flux values than the typical lowering flux. The research will increase knowledge of treatment system synergy in water reclamation and nutrient recovery. It also identifies possible obstacles to development. / Environmental Engineering

Addition of iron to sewer lines for chemical phosphorus removal is widely practiced around the world. However, high dosage of iron may prove detrimental to the anaerobic digestion process and also lead to higher organic sulfur odors and deteriorating biosolids quality. The following research focuses on finding an alternative to the use of iron in wastewater systems by comparing the roles of iron and magnesium on mesophilic anaerobic digestion, the digested effluent characteristics and odors in biosolids. Three anaerobic digesters were operated, one serving as a control with no additives, and the other two having known doses of iron and magnesium added. Comparison of the effluent characteristics revealed an improvement in the overall performance of the magnesium amended digester (in terms of pH, solids and COD reduction, alkalinity and gas production) over the other two reactors, suggesting the benefits of magnesium addition. Both iron and magnesium were found to be effective in achieving high levels of phosphate removals and reducing nuisance odors in dewatered sludge cakes. / Master of Science

Lixiviados de aterros sanitários apresentam altas concentrações de nitrogênio amoniacal e matéria orgânica, além de outros poluentes, que não permitem seu descarte no meio ambiente, sem um prévio tratamento. Lixiviados de aterros sanitários mais antigos, com matéria orgânica mais estabilizada, apresentam grande potencial poluidor, principalmente devido à presença de substâncias recalcitrantes que, usualmente, não são removidas através de tratamento biológico, necessitando, portanto, da aplicação de um pós-tratamento. A presente pesquisa objetivou aplicar o tratamento físico-químico a dois efluentes de sistemas biológicos de tratamento. O primeiro sistema era constituído de um reator de lodo ativado operado em bateladas seqüenciais (70 Litros) cujo efluente era submetido à processo de coagulaçãofloculação usando sais de ferro e alumínio, para remoção da matéria orgânica recalcitrante. Operou-se, em paralelo, uma lagoa aerada, em escala de bancada, dimensionada para remoção da matéria orgânica biodegradável cujo efluente era submetido a processo de precipitação química para remoção de amônia, através da formação do mineral estruvita (MgNH4PO4.6H2O). Os resultados obtidos demonstraram que o cloreto férrico (FeCl3) foi o coagulante mais apropriado sob o ponto de vista econômico, embora, dosagens elevadas (1.160 mg FeCl3/L), frente a 2.465 mg Al2(SO4)3.6H2O/L tenham sido requeridas para o alcance de remoções da matéria orgânica recalcitrante. Com a aplicação de FeCl3 o pH ótimo de coagulação foi próximo de 4,0 e para o Al2(SO4)3; por volta de 5,0. Ao longo dos testes, avaliouse a influência das condições de mistura sobre os fenômenos físico-químicos. Os resultados demonstram que, para o despejo estudado, o gradiente de velocidades e o tempo de mistura não exercem influência sobre os fenômenos de coagulaçãofloculação. Quanto à precipitação química da amônia na forma do mineral estruvita, as melhores remoções (~ 90%) foram alcançadas quando o limite de solubilidade do mineral estruvita foi excedido, para tanto se faz necessária aplicar uma razão molar igual a 1,5:1:1,4 entre os íons envolvidos (Mg+2:NH4 +:PO4 -3). Entretanto, o efluente final desse sistema apresentou uma concentração residual de fósforo solúvel superior a 12 mg P-PO4 -3/L, o que o torna pouco recomendável para fins práticos. / Landfill leachates present high ammonia and organic matter concentrations, besides other pollutants, which do not allow its discharge to the environment without a previous treatment. Older landfill leachates, with more stabilized organic matter, present great pollutant potential, mainly due to the presence of recalcitrant substances that not often are removed by biological treatment and need the application of a post-treatment. The present research aimed to apply the physicochemical treatment for two biological wastewater treatment plant effluents. The first one was constituted by an activated sludge (sequence batch reactor - 70 liters), which effluent was submitted to a coagulation-flocculation process, using iron and aluminum salts, for recalcitrant organic matter removal. A lab scale aerated lagoon was operated in parallel. The lagoon was dimensioned for biodegradable organic matter removal, which effluent was submitted to a chemical precipitation process for ammonia removal (formation of the mineral struvite (MgNH4PO4.6H2O).The results showed that the ferric chloride (FeCl3) was the more appropriated coagulant considering the economic point of view, however high dosages (1,160 mg FeCl3/L) comparing with 2.465 mg Al2(SO4)3.6H2O/L had been required to achieve recalcitrant organic matter removal. Applying FeCl3, the optimum pH was of the order of 4.0 and for Al2(SO4)3, approximately 5.0. During the tests, the influence of the mixture conditions on the physicochemical phenomena was evaluated. The results demonstrated that the velocities gradient and the mixture time do not influenced the coagulation-flocculation phenomena. Regarding to the chemical precipitation of ammonia in struvite form, the better removals (~ 90%) were achieved when the solubility limit of the mineral was exceeded. Due to this fact, it was necessary to apply a molar rate of 1.5:1:1.4 between the ions (Mg+2:NH4 +:PO4 -3). Nevertheless, the final effluent of this system presented a residual soluble phosphorus concentration higher than 12 mg P-PO4 -3/L, hence it is not recommended for practical purposes.

A recuperação de nitrogênio e fósforo presente no esgoto tem se tornado uma alternativa bastante promissora para fornecer uma fonte renovável e ecologicamente sustentável de nutrientes para a agricultura e, consequentemente, melhorar a qualidade do efluente final do sistema de tratamento. Os compostos de fósforo, durante o tratamento de esgoto, numa primeira etapa são removidos por processos biológicos, sendo incorporados no lodo pelos organismos heterotróficos ordinários e organismos acumuladores de fósforo (PAOs). Seguidamente, em condições anaeróbias, o fósforo armazenado no lodo pode ser liberado para a fase líquida e em seguida recuperado como estruvita (MgNH4PO4 .6H2O) num processo de cristalização sob condições controladas. No Brasil, ainda não existem documentados estudos em escala piloto, que simulem condições reais, utilizando sistemas EBPR e reatores de precipitação. Por tal motivo, esta pesquisa foi desenvolvida com o intuito de contribuir com uma melhor compreensão do fenômeno de recuperação de fósforo como cristais de estruvita. A pesquisa foi dividia em três etapas: 1) Operação da configuração UCT modificado e digestor anaeróbio de lodo misto e testes preliminares no reator de precipitação de estruvita; 2) Delineamento e realização de experimentos de precipitação e 3) caracterização dos sólidos obtidos nos experimentos de precipitação. A primeira etapa consistiu em dar partida ao sistema biológico de remoção de fósforo (UCT modificado) e digestor anaeróbio de lodo, e consequentemente a produção do sobrenadante. Paralelamente, foram realizados testes no reator de precipitação. A partir do filtrado e o planejamento fatorial 33, foram definidos o pH, dosagem de magnésio e tempo de detenção hidráulico como fatores que exercem influência na precipitação de estruvita. Definiram-se as remoções de nitrogênio e fósforo como as variáveis respostas ao delineamento experimental. Os resultados mostraram remoções de nitrogênio entre 30 e 40% para pH 8,50 e 9,50, enquanto que remoções de fósforo acima de 80% foram obtidas para uma dosagem de magnésio de 80 mg Mg2+/L e pH 8,50 e 9,50. A influência do tempo de detenção hidráulico não foi significativa tanto na remoção de nitrogênio quanto de fósforo. As imagens obtidas pelas análises de MEV constataram a presença de um sistema ortorrômbico, típica dos cristais de estruvita. No entanto, observou-se que os tamanhos dos cristais mudaram consideravelmente em função dos tempos A caracterização dos sólidos por difração de raios X mostrou que na maioria dos experimentos foi obtida estruvita (23 das 27 condições experimentais), seguida de bobbierrita e newberita, em alguns casos, phosphamita, biphosphamita e brucita. Para as condições de pH 8,50 e 9,50 foi obtida pureza da estruvita entre 80 e 97%. / The recovery of nitrogen and phosphorus present in sewage has become a very promising alternative to provide a renewable and ecologically sustainable source of nutrients for agriculture and a consequently improve of the final effluent quality of the treatment system. The phosphorus compounds are initially removed by biological processes, being incorporated in the sludge through phosphorus-accumulating organisms (PAOs). Later, the phosphorus stored under anaerobic conditions in the sludge, is released to the liquid phase and finally recovered as struvite (MgNH4PO4 .6H2O) following its crystallization process under a controlled setting. No pilot-scale studies, which simulate the real conditions using EBPR and precipitation reactors, have been documented in Brazil so far. Therefore, this research aimed to contribute to improve the understanding of the phosphorus recovering phenomenon as struvite crystals. This project was divided in three main stages: 1) Operation of the UCT-modified setting and the anaerobic digester of mixed sludge; 2) Design and performance of precipitation experiments and. 3) Characterization of the obtained solids during the precipitation experiments. At the first stage, the biological system for phosphorus removal (UCT-modified), and the anaerobic sludge digester were initiated, followed by the production of supernatant. Simultaneously, precipitation tests were carried out at the reactor. Following the factorial design, and using the recovered supernatant, the pH, addition of magnesium and hydraulic retention time, were identified as factors influencing the struvite precipitation. The phosphorus and nitrogen removal were defined as the dependent variables for the experimental design. The results showed a nitrogen removal between 30% and 40% for pH values of 8.50 and 9.50, independently of the used magnesium dose. On the otherhand, over 80% of phosphorus removal was attained with addition of magnesium of 80 mg Mg2+/L and pH values of 8.50 and 9.50. The hydraulic retention time have not influenced the total nitrogen and phosphorus removal, but the grain-size of the struvite crystals precipitated. The characterization of the recovered solids by X-ray diffraction showed that struvite was precipitated in most of the performed experiments (23 of 27 settings), although bobierrite, newberyite, phosphamite, biphosphamite and brucite, were formed as well. The maximum values for struvite pureness, between 80% and 97%, were obtained with pH values of 8.50 and 9.50. The MEV analyses supported the presence of a orthorhombic crystallographic system, which is a typical feature of struvite.

Lixiviados de aterros sanitários apresentam altas concentrações de nitrogênio amoniacal e matéria orgânica, além de outros poluentes, que não permitem seu descarte no meio ambiente, sem um prévio tratamento. Lixiviados de aterros sanitários mais antigos, com matéria orgânica mais estabilizada, apresentam grande potencial poluidor, principalmente devido à presença de substâncias recalcitrantes que, usualmente, não são removidas através de tratamento biológico, necessitando, portanto, da aplicação de um pós-tratamento. A presente pesquisa objetivou aplicar o tratamento físico-químico a dois efluentes de sistemas biológicos de tratamento. O primeiro sistema era constituído de um reator de lodo ativado operado em bateladas seqüenciais (70 Litros) cujo efluente era submetido à processo de coagulaçãofloculação usando sais de ferro e alumínio, para remoção da matéria orgânica recalcitrante. Operou-se, em paralelo, uma lagoa aerada, em escala de bancada, dimensionada para remoção da matéria orgânica biodegradável cujo efluente era submetido a processo de precipitação química para remoção de amônia, através da formação do mineral estruvita (MgNH4PO4.6H2O). Os resultados obtidos demonstraram que o cloreto férrico (FeCl3) foi o coagulante mais apropriado sob o ponto de vista econômico, embora, dosagens elevadas (1.160 mg FeCl3/L), frente a 2.465 mg Al2(SO4)3.6H2O/L tenham sido requeridas para o alcance de remoções da matéria orgânica recalcitrante. Com a aplicação de FeCl3 o pH ótimo de coagulação foi próximo de 4,0 e para o Al2(SO4)3; por volta de 5,0. Ao longo dos testes, avaliouse a influência das condições de mistura sobre os fenômenos físico-químicos. Os resultados demonstram que, para o despejo estudado, o gradiente de velocidades e o tempo de mistura não exercem influência sobre os fenômenos de coagulaçãofloculação. Quanto à precipitação química da amônia na forma do mineral estruvita, as melhores remoções (~ 90%) foram alcançadas quando o limite de solubilidade do mineral estruvita foi excedido, para tanto se faz necessária aplicar uma razão molar igual a 1,5:1:1,4 entre os íons envolvidos (Mg+2:NH4 +:PO4 -3). Entretanto, o efluente final desse sistema apresentou uma concentração residual de fósforo solúvel superior a 12 mg P-PO4 -3/L, o que o torna pouco recomendável para fins práticos. / Landfill leachates present high ammonia and organic matter concentrations, besides other pollutants, which do not allow its discharge to the environment without a previous treatment. Older landfill leachates, with more stabilized organic matter, present great pollutant potential, mainly due to the presence of recalcitrant substances that not often are removed by biological treatment and need the application of a post-treatment. The present research aimed to apply the physicochemical treatment for two biological wastewater treatment plant effluents. The first one was constituted by an activated sludge (sequence batch reactor - 70 liters), which effluent was submitted to a coagulation-flocculation process, using iron and aluminum salts, for recalcitrant organic matter removal. A lab scale aerated lagoon was operated in parallel. The lagoon was dimensioned for biodegradable organic matter removal, which effluent was submitted to a chemical precipitation process for ammonia removal (formation of the mineral struvite (MgNH4PO4.6H2O).The results showed that the ferric chloride (FeCl3) was the more appropriated coagulant considering the economic point of view, however high dosages (1,160 mg FeCl3/L) comparing with 2.465 mg Al2(SO4)3.6H2O/L had been required to achieve recalcitrant organic matter removal. Applying FeCl3, the optimum pH was of the order of 4.0 and for Al2(SO4)3, approximately 5.0. During the tests, the influence of the mixture conditions on the physicochemical phenomena was evaluated. The results demonstrated that the velocities gradient and the mixture time do not influenced the coagulation-flocculation phenomena. Regarding to the chemical precipitation of ammonia in struvite form, the better removals (~ 90%) were achieved when the solubility limit of the mineral was exceeded. Due to this fact, it was necessary to apply a molar rate of 1.5:1:1.4 between the ions (Mg+2:NH4 +:PO4 -3). Nevertheless, the final effluent of this system presented a residual soluble phosphorus concentration higher than 12 mg P-PO4 -3/L, hence it is not recommended for practical purposes.

A decomposição dos resíduos sólidos dispostos em aterro sanitário produz um líquido denominado chorume, o qual apresenta altos teores de poluentes. A caracterização do chorume do aterro sanitário de Cachoeira Paulista-SP, conforme os parâmetros de descarte, comprovam a presença de contaminantes tais como DQO (3596 mg L-1), COT (1773 mg L-1), nitrogênio amoniacal (1496 mg L-1), nitrogênio orgânico (49 mg L-1) e fenol (162 mg L-1). Após aprovada a Política Nacional de Resíduos Sólidos, a legislação aumenta a fiscalização e o controle da disposição e destinação adequada de resíduos sólidos urbanos e, desta forma, a sociedade moderna passou a necessitar de processos capazes de tratar tal lixiviado. As indústrias metalúrgicas, ao executarem técnicas de proteção de superfícies metálicas, produzem um rejeito industrial denominado de borra de fosfato. Nesta perspectiva, este trabalho visou o reuso deste rejeito devido à presença de metais de transição (catalisador na ozonização catalítica) e de fosfato (reagente de precipitação de amônia) para o processo de degradação do chorume. O objetivo desse reagente residual é proporcionar uma redução no custo do processo de tratamento, aplicar uma destinação para tal rejeito e ainda, talvez, reduzir a toxicidade do chorume para o devido descarte ou pré-tratamento. O experimento com 60 minutos, pH 2,5, 90 g L-1 de borra in natura e 3 L de chorume obteve redução de 15,41% de DQO. O mesmo experimento, exceto o fosfato, usando reagentes de sulfato de ferro, zinco e manganês obteve 57,5% de DQO. Isso comprovou o efeito negativo do íon fosfato, pelo sequestro de radical hidroxila, na ozonização catalítica em média de 40% na redução de DQO. Uma metodologia foi desenvolvida para separar o fosfato dos demais íons metálicos, através de dois processos (ácido sulfúrico e ácido clorídrico) para obter dois produtos (borra em pó com a presença dos metais de interesse e solução alcalina concentrada de fosfato). A ozonização catalítica da borra em pó foi avaliada em planejamento fatorial 23 com ponto central, cuja maior degradação foi em 90 minutos e pH 4, quando realizada com borra em pó sulfúrica (4,2 g L-1) obteve uma redução média de 59,09% COT (R$ 0,101 por litro) e com borra em pó clorídrica (4,75 g L-1) de 65,52% COT (R$ 0,100 por litro). Nestes tratados, um fatorial 22 com ponto central, foi usado na avaliação de precipitação da estruvita, o qual comprovou-se que a remoção de amônia é melhor em pH 12, diferente da literatura (pH 9,5), e quando executadas com prévio tratamento físico-químico (remoção dos catalisadores da ozonização), devido a menor interação no meio reacional. Nestas condições, com solução alcalina de fosfato (sulfúrica) em 20 minutos obteve redução de 96,74% de N-NH3 (R$ 0,365 por litro) e com solução alcalina de fosfato (clorídrica) em 10 minutos uma redução de 94,71% de N-NH3 (R$ 0,305 por litro). Isso demonstra o uso potencial desse rejeito no tratamento de chorume, ao tratar dois passivos ambientais e minimizar impactos ambientais antropogênicos, além da possível aplicação produção de fertilizante. / The decomposition of solid waste present in landfill produces the landfill leachate, which has high levels of pollutants. The characterization of the landfill leachate from Cachoeira Paulista - SP, according the discard parameters, proves the presence of contaminants due to high level of COD (3596 mg L-1), TOC (1773 mg L-1), ammonia nitrogen (1496 mg L-1), organic nitrogen (49 mg L-1) and phenol (162 mg L-1). After National Solid Waste Policy approval, the legislation increases the supervision and control of the proper disposal of solid waste, so the modern society began to require processes able to treat such leachate. Metallurgical industries do the metal surfaces protection techniques and produce an industrial waste of phosphate sludge. In this perspective, the aim of this study comprehends the reuse of metallurgical waste due to the presence of transition metals (catalyzer in ozonation) and phosphate (ammonia precipitation reagent) for the degradation process. The objective of this residual reagent is induce a reduction in the cost of the treatment process, apply a proper disposal for metallurgical waste and, perhaps, reduce the toxicity of landfill leachate to discard or pre-treatment. The experiment with 60 minutes, pH 2.5, 90 g L-1 sludge waste in natura and 3 L of landfill leachate obtained 15.41% reduction in COD. The same experiment, except the phosphate, using iron, zinc and manganese sulfate reagents reached 57.5% of the COD. This proved the negative effect of phosphate ion, the scavenger of hydroxyl radical in the catalytic ozonation around 40% reduction of COD. A method had been developed to separate phosphate from other metal ions, through two processes (hydrochloric acid and sulfuric acid) to obtain two products (phosphate sludge powder with metals of interest and phosphate concentrated alkaline solution). The catalytic ozonation of sludge powder was evaluated in 23 factorial design with central point, and the better degradation was obtained in 90 minutes and pH 4, when performed with sludge powder sulfuric (4.2 g L-1) had an average reduction of 59.09% TOC (R$ 0,101 per liter) and with sludge powder hydrochloric (4.75 g L-1) 65.52% TOC (R$ 0,100 per liter). In landfill leachate treated, a 22 factorial design with center point was used in the precipitation evaluation of struvite, which proved that the ammonia removal is better at pH 12, different from the literature (pH 9.5), and when performed after to physico-chemical treatment (removal of catalyzer of ozonation) due to the less interaction in the reaction. In these adjust conditions, with phosphate alkaline solution (sulfuric) was obtained in 20 minutes 96.74% of reduction of N-NH3 (R$ 0,365 per liter) and phosphate alkaline solution (hydrochloric) in 10 minutes a decrease of 94.71% N-NH3 (R$ 0,305 per liter). This result demonstrates the potential use of this waste in the treatment of landfill leachate, treat two contaminants and minimize anthropogenic environmental impacts, as well as possible application of struvite on fertilizer production.

A decomposição dos resíduos sólidos dispostos em aterro sanitário produz um líquido denominado chorume, o qual apresenta altos teores de poluentes. A caracterização do chorume do aterro sanitário de Cachoeira Paulista-SP, conforme os parâmetros de descarte, comprovam a presença de contaminantes tais como DQO (3596 mg L-1), COT (1773 mg L-1), nitrogênio amoniacal (1496 mg L-1), nitrogênio orgânico (49 mg L-1) e fenol (162 mg L-1). Após aprovada a Política Nacional de Resíduos Sólidos, a legislação aumenta a fiscalização e o controle da disposição e destinação adequada de resíduos sólidos urbanos e, desta forma, a sociedade moderna passou a necessitar de processos capazes de tratar tal lixiviado. As indústrias metalúrgicas, ao executarem técnicas de proteção de superfícies metálicas, produzem um rejeito industrial denominado de borra de fosfato. Nesta perspectiva, este trabalho visou o reuso deste rejeito devido à presença de metais de transição (catalisador na ozonização catalítica) e de fosfato (reagente de precipitação de amônia) para o processo de degradação do chorume. O objetivo desse reagente residual é proporcionar uma redução no custo do processo de tratamento, aplicar uma destinação para tal rejeito e ainda, talvez, reduzir a toxicidade do chorume para o devido descarte ou pré-tratamento. O experimento com 60 minutos, pH 2,5, 90 g L-1 de borra in natura e 3 L de chorume obteve redução de 15,41% de DQO. O mesmo experimento, exceto o fosfato, usando reagentes de sulfato de ferro, zinco e manganês obteve 57,5% de DQO. Isso comprovou o efeito negativo do íon fosfato, pelo sequestro de radical hidroxila, na ozonização catalítica em média de 40% na redução de DQO. Uma metodologia foi desenvolvida para separar o fosfato dos demais íons metálicos, através de dois processos (ácido sulfúrico e ácido clorídrico) para obter dois produtos (borra em pó com a presença dos metais de interesse e solução alcalina concentrada de fosfato). A ozonização catalítica da borra em pó foi avaliada em planejamento fatorial 23 com ponto central, cuja maior degradação foi em 90 minutos e pH 4, quando realizada com borra em pó sulfúrica (4,2 g L-1) obteve uma redução média de 59,09% COT (R$ 0,101 por litro) e com borra em pó clorídrica (4,75 g L-1) de 65,52% COT (R$ 0,100 por litro). Nestes tratados, um fatorial 22 com ponto central, foi usado na avaliação de precipitação da estruvita, o qual comprovou-se que a remoção de amônia é melhor em pH 12, diferente da literatura (pH 9,5), e quando executadas com prévio tratamento físico-químico (remoção dos catalisadores da ozonização), devido a menor interação no meio reacional. Nestas condições, com solução alcalina de fosfato (sulfúrica) em 20 minutos obteve redução de 96,74% de N-NH3 (R$ 0,365 por litro) e com solução alcalina de fosfato (clorídrica) em 10 minutos uma redução de 94,71% de N-NH3 (R$ 0,305 por litro). Isso demonstra o uso potencial desse rejeito no tratamento de chorume, ao tratar dois passivos ambientais e minimizar impactos ambientais antropogênicos, além da possível aplicação produção de fertilizante. / The decomposition of solid waste present in landfill produces the landfill leachate, which has high levels of pollutants. The characterization of the landfill leachate from Cachoeira Paulista - SP, according the discard parameters, proves the presence of contaminants due to high level of COD (3596 mg L-1), TOC (1773 mg L-1), ammonia nitrogen (1496 mg L-1), organic nitrogen (49 mg L-1) and phenol (162 mg L-1). After National Solid Waste Policy approval, the legislation increases the supervision and control of the proper disposal of solid waste, so the modern society began to require processes able to treat such leachate. Metallurgical industries do the metal surfaces protection techniques and produce an industrial waste of phosphate sludge. In this perspective, the aim of this study comprehends the reuse of metallurgical waste due to the presence of transition metals (catalyzer in ozonation) and phosphate (ammonia precipitation reagent) for the degradation process. The objective of this residual reagent is induce a reduction in the cost of the treatment process, apply a proper disposal for metallurgical waste and, perhaps, reduce the toxicity of landfill leachate to discard or pre-treatment. The experiment with 60 minutes, pH 2.5, 90 g L-1 sludge waste in natura and 3 L of landfill leachate obtained 15.41% reduction in COD. The same experiment, except the phosphate, using iron, zinc and manganese sulfate reagents reached 57.5% of the COD. This proved the negative effect of phosphate ion, the scavenger of hydroxyl radical in the catalytic ozonation around 40% reduction of COD. A method had been developed to separate phosphate from other metal ions, through two processes (hydrochloric acid and sulfuric acid) to obtain two products (phosphate sludge powder with metals of interest and phosphate concentrated alkaline solution). The catalytic ozonation of sludge powder was evaluated in 23 factorial design with central point, and the better degradation was obtained in 90 minutes and pH 4, when performed with sludge powder sulfuric (4.2 g L-1) had an average reduction of 59.09% TOC (R$ 0,101 per liter) and with sludge powder hydrochloric (4.75 g L-1) 65.52% TOC (R$ 0,100 per liter). In landfill leachate treated, a 22 factorial design with center point was used in the precipitation evaluation of struvite, which proved that the ammonia removal is better at pH 12, different from the literature (pH 9.5), and when performed after to physico-chemical treatment (removal of catalyzer of ozonation) due to the less interaction in the reaction. In these adjust conditions, with phosphate alkaline solution (sulfuric) was obtained in 20 minutes 96.74% of reduction of N-NH3 (R$ 0,365 per liter) and phosphate alkaline solution (hydrochloric) in 10 minutes a decrease of 94.71% N-NH3 (R$ 0,305 per liter). This result demonstrates the potential use of this waste in the treatment of landfill leachate, treat two contaminants and minimize anthropogenic environmental impacts, as well as possible application of struvite on fertilizer production.

Swine production represents approximately 40% of the world's meat production, and swine wastes contain high concentrations of organic matter, nitrogen (N) and phosphorus (P). Swine production is intensifying as meat demand increases and concentrated animal feeding operations (CAFOs) are becoming increasingly common, making it difficult to treat the waste generated. A system for holistic treatment of swine waste produced in CAFOs was investigated in this study that sustainably generates energy and recovers N and P as saleable fertilizers. The system uses anaerobic digestion (AD) for methane production and solids stabilization, followed by precipitation of struvite (MgNH4PO4*6H2O) and recovery of N by ion exchange onto natural zeolites. This process is expected to mitigate both eutrophication of receiving waters and greenhouse-gas emissions while generating products that meet agronomic nutrient demands; however, the economic and environmental sustainability remains unknown. The objectives of this study were to: (1) evaluate water quality and the fate of nutrients and ions in each step in the proposed system through pilot and bench scale experiments, (2) evaluate content/quality of struvite precipitates formed in wastewater treatment processes, (3) assess basic composition of zeolite materials that are being considered for use as IX materials, (4) quantify the environmental impact of the proposed system, and (5) estimate the economic benefits and costs of the proposed system. The results of a bench scale evaluation of the system show that although water quality greatly improves throughout the treatment process, the effluent water quality has high concentrations of COD (2,803 mg O2/L) and E. coli (106.3 CFU/100ml). This limits reuse options for the reclaimed water, however a variety of on-farm applications may be suitable. During struvite precipitation, the recovery efficiency of SRP was 87% (60 mg/L recovered); however, although measurements that take into account P in suspended solids show a lower recovery efficiency, they also show higher mass recovery (77% efficiency, 66 mg/L recovered). N recovery during struvite precipitation showed a similar trend, with 49% of TN and 7% of NH4-N being recovered. Struvite recovery can only occur from NH4-N and soluble reactive P. The additional recovery observed is likely due to adsorption of the nutrients onto the precipitate. Therefore, to accurately measure and report recovery, measurements of N and P that take into account suspended solids should be used. In most wastes, magnesium is the limiting constituent for struvite formation, but for swine AD effluents, P is the limiting constituent. Therefore, a higher soluble P concentration would increase recovery potential. The majority of the remaining N and P as well as a significant amount of potassium (K) were recovered during IX. Six struvites from commercial processes as well as our bench-scale experiments were assessed and compared by X-ray diffraction, SEM imaging, and SEM-EDX scans. All samples were confirmed as struvite by XRD, however they varied widely in crystal size and shape. The elemental composition of the samples was similar; however, struvite formed from phosphate mining waste had higher amounts Mg and P, indicating more pure struvite formation. The presence of impurities in some samples was likely due to the reactor design and solids separation methods. XRD was also used to confirm the identity of zeolites. Three clinoptilolites had similar crystal size and elemental composition except for Zeosand [reg] which showed a surface roughness, which likely contributes to higher cation exchange capacity. Chabazite has smaller crystal size and larger pores than clinoptilolite, which also likely contributes to its higher capacity. Life cycle assessment (LCA) was used to evaluate the environmental sustainability of the system and the results suggested that environmental benefits were provided across almost all impact categories. Two alternatives for raising the pH in struvite precipitation (NaOH addition vs. aeration) and two alternatives for zeolite IX materials (chabazite vs. clinoptilolite) were assessed, but there were negligible differences between alternatives. The system was also assessed at a medium and large scale, and the large scale was more environmentally friendly across all categories. Operational impacts were significantly greater than construction impacts; therefore, the environmental impact of the system can be accurately assessed by only including operation. A life cycle cost assessment (LCCA) was also performed on the system and showed a payback period of 39 years for a medium sized system and 15 years for a large size. This, however, is when compared to a "business-as-usual" scenario and does not consider renewable energy credits or government grants. Furthermore, although a larger system is more economically beneficial, this must be balanced with quality of animal care. From a cost standpoint, IX recovery using chabazite is not recommended and struvite precipitation using aeration is more economically beneficial than NaOH addition.

A recuperação de nitrogênio e fósforo presente no esgoto tem se tornado uma alternativa bastante promissora para fornecer uma fonte renovável e ecologicamente sustentável de nutrientes para a agricultura e, consequentemente, melhorar a qualidade do efluente final do sistema de tratamento. Os compostos de fósforo, durante o tratamento de esgoto, numa primeira etapa são removidos por processos biológicos, sendo incorporados no lodo pelos organismos heterotróficos ordinários e organismos acumuladores de fósforo (PAOs). Seguidamente, em condições anaeróbias, o fósforo armazenado no lodo pode ser liberado para a fase líquida e em seguida recuperado como estruvita (MgNH4PO4 .6H2O) num processo de cristalização sob condições controladas. No Brasil, ainda não existem documentados estudos em escala piloto, que simulem condições reais, utilizando sistemas EBPR e reatores de precipitação. Por tal motivo, esta pesquisa foi desenvolvida com o intuito de contribuir com uma melhor compreensão do fenômeno de recuperação de fósforo como cristais de estruvita. A pesquisa foi dividia em três etapas: 1) Operação da configuração UCT modificado e digestor anaeróbio de lodo misto e testes preliminares no reator de precipitação de estruvita; 2) Delineamento e realização de experimentos de precipitação e 3) caracterização dos sólidos obtidos nos experimentos de precipitação. A primeira etapa consistiu em dar partida ao sistema biológico de remoção de fósforo (UCT modificado) e digestor anaeróbio de lodo, e consequentemente a produção do sobrenadante. Paralelamente, foram realizados testes no reator de precipitação. A partir do filtrado e o planejamento fatorial 33, foram definidos o pH, dosagem de magnésio e tempo de detenção hidráulico como fatores que exercem influência na precipitação de estruvita. Definiram-se as remoções de nitrogênio e fósforo como as variáveis respostas ao delineamento experimental. Os resultados mostraram remoções de nitrogênio entre 30 e 40% para pH 8,50 e 9,50, enquanto que remoções de fósforo acima de 80% foram obtidas para uma dosagem de magnésio de 80 mg Mg2+/L e pH 8,50 e 9,50. A influência do tempo de detenção hidráulico não foi significativa tanto na remoção de nitrogênio quanto de fósforo. As imagens obtidas pelas análises de MEV constataram a presença de um sistema ortorrômbico, típica dos cristais de estruvita. No entanto, observou-se que os tamanhos dos cristais mudaram consideravelmente em função dos tempos A caracterização dos sólidos por difração de raios X mostrou que na maioria dos experimentos foi obtida estruvita (23 das 27 condições experimentais), seguida de bobbierrita e newberita, em alguns casos, phosphamita, biphosphamita e brucita. Para as condições de pH 8,50 e 9,50 foi obtida pureza da estruvita entre 80 e 97%. / The recovery of nitrogen and phosphorus present in sewage has become a very promising alternative to provide a renewable and ecologically sustainable source of nutrients for agriculture and a consequently improve of the final effluent quality of the treatment system. The phosphorus compounds are initially removed by biological processes, being incorporated in the sludge through phosphorus-accumulating organisms (PAOs). Later, the phosphorus stored under anaerobic conditions in the sludge, is released to the liquid phase and finally recovered as struvite (MgNH4PO4 .6H2O) following its crystallization process under a controlled setting. No pilot-scale studies, which simulate the real conditions using EBPR and precipitation reactors, have been documented in Brazil so far. Therefore, this research aimed to contribute to improve the understanding of the phosphorus recovering phenomenon as struvite crystals. This project was divided in three main stages: 1) Operation of the UCT-modified setting and the anaerobic digester of mixed sludge; 2) Design and performance of precipitation experiments and. 3) Characterization of the obtained solids during the precipitation experiments. At the first stage, the biological system for phosphorus removal (UCT-modified), and the anaerobic sludge digester were initiated, followed by the production of supernatant. Simultaneously, precipitation tests were carried out at the reactor. Following the factorial design, and using the recovered supernatant, the pH, addition of magnesium and hydraulic retention time, were identified as factors influencing the struvite precipitation. The phosphorus and nitrogen removal were defined as the dependent variables for the experimental design. The results showed a nitrogen removal between 30% and 40% for pH values of 8.50 and 9.50, independently of the used magnesium dose. On the otherhand, over 80% of phosphorus removal was attained with addition of magnesium of 80 mg Mg2+/L and pH values of 8.50 and 9.50. The hydraulic retention time have not influenced the total nitrogen and phosphorus removal, but the grain-size of the struvite crystals precipitated. The characterization of the recovered solids by X-ray diffraction showed that struvite was precipitated in most of the performed experiments (23 of 27 settings), although bobierrite, newberyite, phosphamite, biphosphamite and brucite, were formed as well. The maximum values for struvite pureness, between 80% and 97%, were obtained with pH values of 8.50 and 9.50. The MEV analyses supported the presence of a orthorhombic crystallographic system, which is a typical feature of struvite.

The focus of this thesis is the posibility of obtaining phosphorus from liquid digestate. The theoretical part of the thesis is focused on summarizing the current situation regarding phosphorus recovery. The research summarizes the essential information about the method of struvite precipitation, by which phoshphorus is obtained in the form of struvite, which can be further used as a fertilizer. Based on the process information, an experimental device was designed to obtain phosphorus in the form of struvite, corresponding to industry standards. It is a cylindrical vessel with a conical bottom, in which the liquid digestate with the chemicals is mixed with a stirrer. The functionality of the device was tested experimentally on the created device. The results of the experiment were analyzed by XPS method, which confirmed the formation of struvite. For future operation, modifications of the device and pre-treatment of the liquid digestate were proposed, which could improve the whole process and its results.