Orientador: Nelson Eduardo Duran Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-05T10:31:57Z (GMT). No. of bitstreams: 1 Assalin_MarciaRegina_D.pdf: 6063801 bytes, checksum: 275c581d4250a4932181e1314febc995 (MD5) Previous issue date: 2005 / Resumo: Neste trabalho foram estudados diversos aspectos de aplicação dos processos químicos (ozônio) e biológico (lodo ativado), aplicados de maneira isolada e combinada no tratamento do efluente papeleiro Kraft E1. A caracterização do efluente Kraft E1 foi realizada frente a vários parâmetros físico-químicos: fenóis totais, cor, carbono orgânico total (COT), demanda química de oxigênio (DQO), além da toxicidade frente a alga Selenastrum capricornutum. A eficiência dos processos estudados foi avaliada frente a redução de valores dos parâmetros de caracterização. As melhores condições de ozonização para o tratamento do efluente Kraft E1 foram pH 10 e 14 mg L de O3, por até 60 minutos de tratamento. Observou-se que a ozonização aplicada em meio fortemente alcalino (pH > 10) resulta num menor consumo de ozônio, o que pode ser relacionado com uma cinética de degradação mais lenta. O tratamento com ozônio mostrou maior eficiência para a remoção de cor, fenóis totais e toxicidade do efluente papeleiro. O processo biológico realizado num tempo de retenção hidraúlica (TRH) igual a 12 h, foi bastante eficiente na degradação da matéria orgânica do efluente. A remoção da cor e fenóis totais por este processo foi bastante afetada pelo TRH aplicado, o que não ocorreu com a remoção de carga orgânica. O processo combinado Iodo ativado (12 h) - ozônio (30 minutos) foi o que apresentou os melhores resultados para o tratamento do efluente papeleiro (DQO 75 %; COT 73 %, COR 80,7 % e fenóis totais 66,9 %). / Abstract: The efficiency of combined chemical (ozone) and biological (activated sludge) process in the treatment of Kraft E1 mill effluent was studied. The reduction of total phenols, color, total organic carbon (TOC), chemical oxygen demand (COD) and the toxicity (Selenastrum capricornutum) was evaluated. Different doses of ozone and pH of the effluent were studied. Treatment using pH 10 and concentration of 14 mg L of O3 in 60 min were the most efficient in the total phenols and color removal, but the results indicated negligible TOC reduction by application of the ozonation processes. The increase of pH as the reduction of ozone concentration influenced the kinetics properties of the process. The activated sludge process, (hydraulic retention time -HRT 12 h) was the most efficient for the TOC removal. Degradation of total phenolic compounds and decoloration were seriously affected by HRT variation. The combined process activated sludge (12 h) - ozonation (30 minutes) showed good results for the treatment of the Kraft E1 effluent (COD 75 %; TOC 73 %, Decoloration 80,7 % and Total Phenols 66,9 %). / Doutorado / Físico-Química / Doutor em Ciências

The hypothesis tested in this study is that the application of ozone to reuse aquaculture water provides more favorable conditions for hybrid striped bass at production levels. Evaluation of water quality in fish culture systems being treated with ozone was made during a production trial (1200 fish/14,OOO 1). Originally, a control and four ozonated systems with doses of 3, 13, 25, and 45 g O3/kg feed/day supported fish for experimentation but, due to mechanical failure, only the control, the 13 and 25 g O3/kg feed/day treatments completed the full 35 week study. On an equal feeding basis, concentrations of dissolved organic carbon (DOC), carbonaceous biochemical oxygen demand (CBODs), and chemical oxygen demand (COD) were lowest in the most heavily ozonated systems. Ozone increased the biodegradation of DOC. Total suspended solids, particle size and distributions were impacted by ozone's flocculating properties. The percentages of particles in the smallest size range, 5-20 microns, were greater in the control system than the ozonated systems during weeks of equal feeding rates. When feeding rates differed, the control system maintained a larger number total particles per kilogram of feed administered. The pH of the ozonated systems was lower than the control which favored the ionized (less toxic) form of ammonia. Enhanced biodegradation of organics in the ozonated systems may have increased carbon dioxide production and caused a decline in pH. Greater nitrification in the ozonated systems may have also decreased the pH. Higher total ammonia nitrogen (TAN) levels were produced in the control on an equal feeding basis. Average weekly TAN t unionized ammonia (NH3), nitrite and nitrate concentrations remained at acceptable levels across treatments and throughout the production trial. Overall, the major indication of improved system conditions due to ozone treatment was that fish raised in the ozonated systems fed steadily throughout the growth trial while the control system's culture experienced periods of reduced feeding. / Master of Science

The decolorization of reactive dye-containing waste streams using oxidizing chemicals and the determination of the effect of the oxidizing agents on the subsequent biotreatment of the streams was investigated. Three oxidizing schemes were chosen for study: molecular ozone, base-promoted ozonation, and Fenton’s reagent (Fe²⁺ and H₂O₂). The ADMI color value of the solutions was used as the primary parameter for color comparison and dissolved organic carbon (DOC) removal was the measure of the effect of biodegradation. Three different waste streams from a textile dyeing facility were chosen: a Navy slack washer effluent from a pad-dyeing operation, a Navy dyebath effluent from a dyejet, and a Brilliant Blue dyejet effluent. Pure dye solutions were oxidized as well to determine the effect of interfering species in the waste streams. The results demonstrated that base-promoted ozonation was more effective than molecular ozone for the decolorization of the Navy slack washer effluent. In both cases the ADMI color value could be decreased by 82% but almost half as much ozone was necessary for the high pH trials. The high pH ozonation proved more effective for the Navy jet-dye effluent, as well, achieving a much lower color value with less ozone. Greater decolorization (96%) of the Navy jet-dye effluent was achieved by Fenton’s reagent than for either of the ozonation schemes. Ozonation of the Brilliant Blue jet-dye bath showed no dependence on pH and the color value of the solution was reduced could be 63%. The results indicate that the dyes were selectively oxidized by ozonation and the amount of ozone required for decolorization depended mainly the initial color of the dye waste stream. The amount of hydrogen peroxide required for Fenton’s reagent oxidation depended on the initial DOC of the dye waste stream. Oxidation of the wastewater streams proved to neither enhance nor hinder the operation of the biological reactors. The color removals by biological activity were minimal for both control and experimental reactors. Dissolved carbon removal was not enhanced by oxidative pretreatment. / Master of Science / incomplete_metadata

Os efluentes de lavanderia hospitalar representam uma mistura complexa de produtos químicos, matéria orgânica, medicamentos e seus metabólitos e microrganismos patogênicos. Para tanto, a inadequação no tratamento ou a falta de tratamento deste efluente acarreta risco potencial à saúde humana e ao meio ambiente. Neste contexto, surgem os chamados Processos Oxidativos Avançados (POAs), que são métodos eficientes para a degradação de compostos orgânicos. Nesse sentido, o presente trabalho de pesquisa teve como objetivo avaliar a potencialidade da combinação dos processos de ozonização catalítica e Fenton na degradação de poluentes do efluente de lavanderia hospitalar proveniente da indústria Lavebras Higienização de Têxteis S/A. A caracterização do efluente de lavanderia hospitalar in natura foi realizada empregando-se métodos consolidados como DQO, COT, DBO5, surfactantes aniônicos, fenol, peróxido de hidrogênio, Sólidos (ST, STV e STF), entre outros. Para a otimização das variáveis e dos respectivos níveis dos processos oxidativos foi realizado o planejamento estatístico completo do tipo 23, sendo determinado as melhores condições entre as concentrações catalíticas de Fe+2 e do agente oxidante de H2O2, além das condições de pH do meio reacional, tendo como variáveis resposta os percentuais de redução de DQO e COT. Os resultados obtidos mostraram-se promissores, sendo que a redução média de COT com 95,24 % e de DQO com 95,00 % para os ensaios com as variáveis da reação otimizada, com o custo no valor de R$ 0,09 / L de efluente. Após o processo de ozonização e Fenton, a amostra do melhor experimento: concentração de Fe2+ 2,0 g L-1, concentração de H2O2 5,0 g L-1 e pH 4,0; foi tratado por um processo biológico - Sistema Lodo Ativado (SLA), a fim de verificar a eficiência de degradação da matéria orgânica do efluente estudado através do sistema conjugado (POA - SLA). Neste teste combinado POA - SLA foi possível atender às características de águas para fins de reuso. / Hospital laundry wastewater represent a complex mixture of chemicals, organic matter, drugs and their metabolites and pathogenic microorganisms. To this end, inadequate treatment or lack of treatment of this effluent carries potential risk to human health and the environment. In this context, the so called advanced oxidation processes (AOPs) arise, which are extremely effective methods for degrading organic compounds. In this sense, this research was to evaluate the potential of the combination of catalytic ozonization processes and Fenton in pollutant degradation of hospital laundry effluent from the Lavebras Hygiene industry Textiles S/A. The characterization of the hospital laundry efluente in natura was performed by using optimized methods such as COD, TOC, BOD5, anionic surfactants, oils and grease, phenol, hydrogen peroxide, Solid (TS, FTS and VTS), among others. For the optimization of the variables and respective levels of the oxidative processes was performed complete statistical design of the type 23, it is determined the best conditions of the catalytic concentration of Fe+2 and of the oxidizing agente H2O2, in addition to the pH condictions of the reaction medium, with a response factor of COD and COT reduction. The results obtained were promising, with the average reduction of 95.24% COT and COD with 95.00% for the tests with the optimized reaction variables, with a cost of R $ 0.09 / L of effluent. After the ozone and Fenton processes, the best experiment sample: concentration of Fe2+ 2.0 g L-1, concentration of H2O2 5.0 g L-1 and pH 4.0; was treated by a biological process - Activated Sludge System (ASS), in order to verify the degradation efficiency of the organic matter of the studied effluent through the conjugated system (APO - ASS). In this combined APO - ASS test it was possible to meet the water characteristics for reuse purposes.

Os efluentes de lavanderia hospitalar representam uma mistura complexa de produtos químicos, matéria orgânica, medicamentos e seus metabólitos e microrganismos patogênicos. Para tanto, a inadequação no tratamento ou a falta de tratamento deste efluente acarreta risco potencial à saúde humana e ao meio ambiente. Neste contexto, surgem os chamados Processos Oxidativos Avançados (POAs), que são métodos eficientes para a degradação de compostos orgânicos. Nesse sentido, o presente trabalho de pesquisa teve como objetivo avaliar a potencialidade da combinação dos processos de ozonização catalítica e Fenton na degradação de poluentes do efluente de lavanderia hospitalar proveniente da indústria Lavebras Higienização de Têxteis S/A. A caracterização do efluente de lavanderia hospitalar in natura foi realizada empregando-se métodos consolidados como DQO, COT, DBO5, surfactantes aniônicos, fenol, peróxido de hidrogênio, Sólidos (ST, STV e STF), entre outros. Para a otimização das variáveis e dos respectivos níveis dos processos oxidativos foi realizado o planejamento estatístico completo do tipo 23, sendo determinado as melhores condições entre as concentrações catalíticas de Fe+2 e do agente oxidante de H2O2, além das condições de pH do meio reacional, tendo como variáveis resposta os percentuais de redução de DQO e COT. Os resultados obtidos mostraram-se promissores, sendo que a redução média de COT com 95,24 % e de DQO com 95,00 % para os ensaios com as variáveis da reação otimizada, com o custo no valor de R$ 0,09 / L de efluente. Após o processo de ozonização e Fenton, a amostra do melhor experimento: concentração de Fe2+ 2,0 g L-1, concentração de H2O2 5,0 g L-1 e pH 4,0; foi tratado por um processo biológico - Sistema Lodo Ativado (SLA), a fim de verificar a eficiência de degradação da matéria orgânica do efluente estudado através do sistema conjugado (POA - SLA). Neste teste combinado POA - SLA foi possível atender às características de águas para fins de reuso. / Hospital laundry wastewater represent a complex mixture of chemicals, organic matter, drugs and their metabolites and pathogenic microorganisms. To this end, inadequate treatment or lack of treatment of this effluent carries potential risk to human health and the environment. In this context, the so called advanced oxidation processes (AOPs) arise, which are extremely effective methods for degrading organic compounds. In this sense, this research was to evaluate the potential of the combination of catalytic ozonization processes and Fenton in pollutant degradation of hospital laundry effluent from the Lavebras Hygiene industry Textiles S/A. The characterization of the hospital laundry efluente in natura was performed by using optimized methods such as COD, TOC, BOD5, anionic surfactants, oils and grease, phenol, hydrogen peroxide, Solid (TS, FTS and VTS), among others. For the optimization of the variables and respective levels of the oxidative processes was performed complete statistical design of the type 23, it is determined the best conditions of the catalytic concentration of Fe+2 and of the oxidizing agente H2O2, in addition to the pH condictions of the reaction medium, with a response factor of COD and COT reduction. The results obtained were promising, with the average reduction of 95.24% COT and COD with 95.00% for the tests with the optimized reaction variables, with a cost of R $ 0.09 / L of effluent. After the ozone and Fenton processes, the best experiment sample: concentration of Fe2+ 2.0 g L-1, concentration of H2O2 5.0 g L-1 and pH 4.0; was treated by a biological process - Activated Sludge System (ASS), in order to verify the degradation efficiency of the organic matter of the studied effluent through the conjugated system (APO - ASS). In this combined APO - ASS test it was possible to meet the water characteristics for reuse 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.

The objectives of this project were to evaluate the efficacies of electrolyzed oxidizing (EO) and ozonated waters as antimicrobial agents for enhancing the microbiological safety of fresh strawberries (Fragaria x ananassa). The influence of sodium chloride (NaCl) concentrations used for preparing EO water was evaluated on their bactericidal activities against naturally occurring aerobic mesophiles on strawberries with a contact time of 5, 10, or 15 min. EO water and ozonated water containing about 1.90 ppm ozone were evaluated and compared with sodium hypochlorite (NaOCl) solution on their capabilities to inactivate and control the growth of Listeria monocytogenes and Escherichia coli O157:H7 inoculated onto strawberries stored at 4 ± 1 °C for up to 15 d, respectively. Post-treatment neutralization of fruit surfaces by washing was also investigated. More than 2 log₁₀ CFU/g reduction of mesophilic aerobic bacteria was achieved in samples washed for 10 or 15 min in EO water prepared from 0.10% (w/v) NaCl solution. Bactericidal activity of treatment solutions against L. monocytogenes and E. coli O157:H7 was not affected by post-treatment neutralization, and their effectiveness against both pathogens in whole fruit tissues did not significantly increase with increasing exposure time. The EO water had an equivalent antibacterial effect as compare with NaOCl in eliminating L. monocytogenes and E. coli O157:H7 on whole strawberry tissues. Fruit surfaces washing with distilled water resulted in 1.90 and 1.27 log₁₀ CFU/ml of rinse fluid reduction of L. monocytogenes and E. coli O157:H7, respectively, whereas ≥ 2.60 log₁₀ CFU/ml of rinse fluid reduction of L. monocytogenes and up to 2.35 and 3.12 log reduction of E. coli O157:H7 were observed on fruit surfaces washed with EO water and NaOCl solution, respectively. However, EO water and NaOCl solution treatments did not exhibit a higher microbicidal activity than water treatment during refrigeration storage. The ozone treatment on inoculated strawberries was not remarkably effective in removing and eliminating pathogens on the whole fruit tissues, but the populations of L. monocytogenes and E. coli O157:H7 were significantly decreased after ozone treatment regardless of the exposure time. The number of L. monocytogenes and E. coli O157:H7 on fruit surfaces was decreased by 2.17 and 2.02 log₁₀ CFU/ml of rinse fluid, respectively, after washing with ozonated water for 10 min. / Graduation date: 2008

Thesis (MSc Food Sc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: The wine industry significantly contributes to South Africa's water demand and subsequent pollution of the limited resource. Wastewater is produced throughout the year with an increase in volume and organic load during the vintage season. Anaerobic digestion (AD), specifically the upflow anaerobic sludge bed (UASB) technology has been shown to be feasible in the treatment of cellar wastewater. However, the legal standard for chemical oxygen demand (COD) for disposal in a natural water resource (75 rnq.L") is often not met. The aim of the study was to conduct a laboratory-scale investigation into the feasibility of combining pre- and post-ozonation processes with AD in order to achieve a final COD closer to the legal disposal limit. While acclimatising an UASB bioreactor containing mixed anaerobic granules to a cellar wastewater with a pH set at 8.0, stable-state conditions were not reached. Sucrose additions to the substrate, increased substrate loads, heattreatment of the substrate and an addition of isolated cellar effluent bacteria to facilitate degradation prior to AD, were all unsuccessful in maintaining stable-state in terms of COD removal efficiency. Once the substrate pH was re-set to 7.5, the reactor stabilised. The lowest efficient operational pH was found to be 5.73 resulting in a COD removal of 88% at a substrate COD < 5 000 rnq.L". At a substrate pH of 6.0, the lowest efficient operational hydraulic retention time (HRT) and corresponding organic loading rate (OLR) were 19.7 hand 9.75 kg COD.m-3d-1 , respectively, with the COD removal being maintained around 84%. The reactor effluent still had a final COD of 1280 rnq.L", which was well above the legal South African limit. Dominant bacteria were isolated from raw cellar wastewater and identified as Acinetobacter haemolyticus, Burkholderia cepacia and Cryseomonas luteola. In order to investigate the possibility that ozonation improved biodegradability, the growth of the isolates at 35°C was monitored over 24 h in sterile ozonated and non-ozonated substrates from the vintage and non-vintage seasons. All the isolates increased by at least 1.5 log cycles in the control substrates from both seasons. Ozonation of the wastewater batches for 10 min at a rate of 73 rnq.L" led to slightly increased growth of the inoculants in the substrate batch from the vintage season. For the substrates from the non-vintage season, ozonation had an inhibitory effect on the bacterial growth. A 5 min ozonation treatment at a concentration of 73 rnq.L" was found to be optimal for both a pre- and post-treatment to UASB-treatment of cellar wastewater. Both UASB treatment and ozonation were effective in reducing the COD by 85% and 20%, respectively. The COD reduction was improved to 88% when UASB treatment was combined with post-ozonation. The total reduction in total suspended solids (TSS) for the combined process was 97%, compared to 80% for UASB and 73% for an ozone treatment alone. The reduction for volatile suspended solids (VSS) was 98% compared to 81% for UASB and 73% for the ozone treatment alone. The total reduction when using a pre-ozonation UASB treatment combination was an average of 86% for COD. The TSS and VSS were both reduced by 95%. Biogas production increased from 1.4 L.d-1 to 3.8 L.d-1 when an ozonated wastewater was used as substrate. When the UASB treatment was combined with both a pre- and post-ozonation treatment process, the COD was reduced by 89% while TSS and VSS were both reduced by 99%. This study showed that pre- and post-ozonation treatment processes could successfully be utilised to improve UASB treatment of cellar wastewater. Although the legal limits for discarding into a natural resource were not met, significant progress was made in reducing COD levels. Cellar wastewaters do however, vary according to season and the wastewater composition could affect the efficiency of a pre-ozonation process. / AFRIKAANSE OPSOMMING: Die wynindustrie maak "n beduidende bydrae tot die eise wat aan Suid-Afrika se waterbronne gestel word en gevolglik die besoedeling van die beperkte hulpbron. Afloopwater, wat in volume en organiese lading gedurende die parstyd toeneem, word reg deur die jaar opgelewer. Anaërobiese vertering (AV), spesifiek die "Upflow anaerobic sludge blanket" (UASB) tegnologie, is alreeds suksesvol gebruik om kelderafloop te behandel. Die wetlike vereiste vir chemiese suurstof behoefte (CSB) vir storting in "n natuurlike hulpbron (75 rnq.L"), word egter dikwels nie bereik nie. Die doel van die studie was om in "n laboratorium-skaal ondersoek AV te kombineer met voor- en na-osoneringsprossesse, om sodoende te poog om "n CSB nader aan die wetlike standaard te verkry. Terwyl"n UASB bioreaktor wat gemengde anaerobiese granules bevat het, geakklimatiseer is tot kelderafloop met "n pH gestel tot 8.0, kon stabiele toestande nie bereik word nie. Die byvoeging van sukrose tot die substraat, verhoogde substraatladings, hitte-behandeling van die substraat en die byvoeging van geïsoleerde kelderafloop bakterië om substraatafbraak voor AV aan te help, was onsuksesvol om stabiliteit in terme van CSB-verwydering, te handhaaf. "n Verstelling van die substraat pH na 7.5, het gelei tot reaktorstabiliteit. By die laagste doeltreffende bedryfs-pH van 5.73 en substraat CSB < 5 000 rnq.L", was die CSB-verwydering 88%. By "n substraat pH van 6.0 was die laagste doeltreffende bedryfs-hidroliese retensie tyd en -organiese ladingstempo 19.7 h en 9.75 kg CSB.m-3d-1, onderskeidelik, terwyl die CSB verwydering rondom 84% gehandhaaf is. Die CSB van die reaktoruitvloesel van 1 280 rnq.L", was steeds ver bo die wetlike vereiste. Dominante bakterië is uit kelderafloop geïsoleer en as Acinetobacter haemolyticus, Burkholderia cepacia en Cryseomonas luteola, geïdentifiseer. Die moontlikheid dat osonering bioafbreekbaarheid bevorder, is ondersoek deur die groei van die isolate by 35°C oor 24 h in steriele geësoneerde en ongeësoneerde substrate te monitor. Die substrate is berei vanaf kelderafloop wat in die parsseisoen sowel as die nie-parsseisoen versamel is. AI die isolate het met ten minste 1.5 log siklusse in die kontrole substrate van beide seisoene, vermeerder. Vir die kelderafloop wat in die parsseisoen versamel is, het osonering vir 10 min teen 73 rnq.L" gelei tot effens verbeterde groei van die innokulante. Osonering het 'n onderdrukkende effek op die groei van bakterië in die afloopwater versamel in die nie-parsseisoen, gehad. Osonering vir 5 min teen 'n konsentrasie van 73 rnq.L" is as optimum vir beide voor- en na-osoneringsbehandeling tot UASB-behandeling van die kelderafloop, gevind. UASB-behandeling en osonering het die CSB met 85 en 20% onderskeidelik, verminder. Die vermindering kon tot 88% verhoog word wanneer UASB-behandeling met na-osonering gekombineer is. Die vermindering in totale gesuspendeerde vastestowwe (TGV) vir die gekombineerde proses was 97%, in vergelyking met 80% vir UASB- en 73% vir osoonbehandeling alleen. Die vermindering in vlugtige gesuspendeerde vastestowwe (VGV) was 98% in vergelyking met 81% vir UASB- en 73% vir osoonbehandeling alleen. Die totale CSB verwydering vir 'n voor-osonerings UASB kombinasie was gemiddeld 86%. Die TGV en VGV is beide met 95% verminder. Biogasproduksie het ook vermeerder vanaf 1.4 L.d-1 tot 3.8 L.d-1 toe geosoneerde afloopwater as substraat gebruik is. Die kombinasie van UASB-behandeling met voor-osonering, sowel as na-osonering het gelei tot 'n CSB-verwydering van 89% terwyl TGV en VGV beide met 99% verminder is. Hierdie studie het getoon dat voor- en na-osonering suksesvol gebruik kan word om UASB-behandeling van kelderafloop te verbeter. Hoewel wetlike vereistes vir storting in 'n natuurlike hulpbron nie bereik is nie, is beduidende vordering gemaak in die verlaging van CSB-vlakke. Die verskil in die samestelling van kelderafloop gedurende die onderskeie seisoene, kan egter die doeltreffendheid van die voor-osoneringsproses beïnvloed.

Thesis (MScFoodSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Large volumes of high strength wastewater are generated annually by distilleries. Treatment of this wastewater is essential to increase its reuse potential. Anaerobic digestion (AD) has been widely applied as high strength wastewater treatment. Additionally, grain distillery wastewater (GDWW) is high in fats, oils and grease (FOG) which can cause problems during AD. Pre-treatment is therefore often required to make the AD process more efficient. The overall objective of this study was to investigate the operational efficiency of upflow anaerobic sludge blanket (UASB) reactors while treating GDWW as substrate. The first aim was to investigate the pre-treatment of the GDWW specifically for the removal of FOG by evaluating the effect of pH adaption, coagulant concentration and ozone (O3) dosages on the FOG reduction efficiency. Secondly, the effect of two different pre-treatments (only coagulant and coagulant and ozone) on the subsequent UASB treatment step was investigated. The pH of raw GDWW (pH 3.4) was adapted to three different pH values (5.0, 6.0, and 7.0) and the coagulant, aluminium chlorohydrate (ACH) (140 mg.L-1), was added. To make the process more economically viable, the lowering the coagulant concentration (to 100 mgACH.L-1) was also investigated. Optimal reductions for chemical oxygen demand (COD) (33.2% ± 4.93), total suspended solids (TSS) (91.9% ± 1.73) and FOG (84.1% ± 1.98) were, however, achieved at a higher coagulant concentration of 140 mgACH.L-1, and at a wastewater pH of 7.0. The effect of additional ozone treatment was also investigated. Maximum reductions for the ozone treatment were obtained at 100 mgO3.L-1 for COD (3.6% ± 4.08), and at 900 mgO3.L-1 for TSS (27.7% ± 5.58) and FOG (23.9% ± 1.83). The ozone treatment was most efficient for FOG reduction (in terms of mg FOG reduced per mg ozone) at 100 mgO3.L-1. An ozone dosage of 300 mgO3.L-1, was decided on based on economic feasibility, findings in literature on toxicity of ozone and the potential degradation of recalcitrant compounds at this dosage. The final pre-treatment thus included pH adaption to 7.0, coagulant dosage of 140 mgACH.L-1, and an ozone dosage of 300 mgO3.L-1. The second part of this study involved the operation of two 2 L laboratory scale UASB reactors for 277 days. The substrate of the first reactor contained GDWW that had only undergone coagulant pre-treatment (Rcontrol), while the substrate of the second UASB reactor consisted of GDWW that had undergone coagulant and ozone pre-treatment (Rozone). Both reactors treated the pre-treated GDWW successfully at ca. 9 kgCOD.m-3d-1. COD reductions of 96% for Rcontrol and 93% for Rozone, were achieved. FOG reductions (%) showed variations throughout the study and maximum reductions of 88% and 92% were achieved for Rcontrol and Rozone, respectively. The Rozone produced more biogas, but the methane content was similar for both reactors. The additional ozone pre-treatment did not show any added benefits to the reactor performance results. UASB granule washout in Rcontrol did, however, suggest possible toxicity of unsaturated fatty acids present in the non-ozonated substrate. The feasibility of FOG removal was shown as both reactors successfully treated pre-treated GDWW. Ozonation, after a coagulant dosage, which resulted in further reduction in the FOG content of the GDWW, is thus not essential to ensure the success of an anaerobic digestion step. Ozonation of the pre-treated GDWW could, however, be beneficial to gas production and the efficiency of a tertiary biological process. / AFRIKAANSE OPSOMMING: Groot volumes hoë-sterkte afloopwater word jaarliks deur distilleerderye opgelewer. Die behandeling van hierdie afloopwater is noodsaaklik om die hergebruiksmoontlikheid daarvan te verhoog. Die toepassing van anaërobiese vertering (AV) is wydverspreid in hoë-sterkte afloopwaterbehandeling. Graandistillerings-afloopwater (GDAW) is boonop hoog in vette, olies en ghries (VOG), wat probleme kan veroorsaak tydens AV. Voorbehandeling word dus dikwels verlang om die AV meer doeltreffend te maak. Die oorhoofse doelstelling van hierdie studie was om die doeltreffendheid van opvloei-anaërobieseslykkombers- (OAS-) reaktore wat GDAW as substraat behandel, te ondersoek. Die eerste mikpunt was om die voorbehandeling van die GDAW, te ondersoek vir die verwydering van VOG. Dit is uitgevoer deur die uitwerking van pH aanpassing, koagulantkonsentrasie en osoon(O3)dosis op VOG vermindering te evalueer. Tweedens is die uitwerking van twee verskillende voorbehandelings (slegs koagulant asook koagulant en osoonbehandeling) op die opvolgende OAS-behandelingsstap ondersoek. Die pH van rou GDAW (pH 3.4) is aangepas tot drie verskillende pH waardes (5.0, 6.0 en 7.0) en die koagulant, aluminium-chlorohidraat (ACH), is bygevoeg (140 mg.L-1). Om die proses meer ekonomies uitvoerbaar te maak is ‘n verlaagde koagulantkonsentrasie (verlaag tot 100 mgACH.L-1) ook ondersoek. Die optimale afnames vir chemiese suurstofvereiste (CSV) (33.2% ± 4.93), totale oplosbare vastestowwe (TOV) (91.9% ± 1.73) en VOG (84.1% ± 1.98) is egter bereik teen ‘n hoër koagulant konsentrasie van 140 mgACH.L-1, en teen ‘n afloopwater-pH van 7.0. Die uitwerking van ‘n bykomende osoonbehandeling is ook ondersoek. Die hoogste afnames tydens die osoonbehandeling is bereik teen 100 mgO3.L-1 vir CSV (3.6% ± 4.08), en teen 900 mgO3.L-1 vir TOV (27.7% ± 5.58) en VOG (23.9% ± 1.83). Die osoonbehandeling was mees doeltreffend vir VOG (in terme van mg VOG verwyder per mg osoon) teen 100 mgO3.L-1. Daar is besluit op ‘n van 300 mgO3.L-1, as gevolg van die ekonomiese uitvoerbaarheid, bevindinge in literatuur vir die toksisiteit van osoon, en die moontlike afbraak van moeilik-afbreekbare komponente teen hierdie dosis. Die finale voorbehandeling het dus bestaan uit ‘n aanpassing van die afloopwater-pH na 7.0, ‘n koagulantdosis van 140 mgACH.L-1, en ‘n osoondosis van 300 mgO3.L-1. Tydens die tweede gedeelte van hierdie studie is twee 2 L laboratoriumskaal OAS reaktore bedryf vir 277 dae. Die substraat van die eerste reaktor het GDAW bevat wat slegs ‘n koagulant-voorbehandeling ondergaan het (Rkontrole), terwyl die substraat van die tweede OAS-reaktor GDAW bevat het wat koagulant- en osoon-voorbehandeling ondergaan het (Rosoon). Beide reaktore het die voorbehandelde-GDAW suksesvol behandel teen ‘n organieseladingstempo van ca. 9 kgCSV.m-3d-1. Afnames in CSV van 96% vir Rkontrole en 93% vir Rosoon, is bereik. Tydens die studie is deurlopende wisseling in VOG verwydering (%) waargeneem, en die hoogste verwyderings wat bereik is, is onderskeidelik 88% en 92% vir Rkontrole en Rosoon. Die Rosoon het meer biogas geproduseer, maar die metaanpersentasie was soortgelyk vir beide reaktore. Die osoon-voorbehandeling het nie enige toegevoegde voordele getoon in die reaktorprestasie resultate nie. Die uitwas van die OAS-granules vir die Rkontrole het egter moontlike toksisiteit van onversadigdevetsure aangedui, wat moontlik teenwoordig kon wees in die nie-geösoneerde substraat. Die uitvoerbaarheid van VOG verwydering is getoon aangesien beide reaktore voorbehandelde GDAW suksesvol behandel het. Osonering, wat verdere afname in die VOG inhoud van GDAW teweeggebring het (na ‘n koagulant dosis), is dus nie noodsaaklik vir die suksesvolle verloop van ‘n anaërobiese-verteringsstap nie. Osonering van die voorbehandelde GDAW kan egter voordelig wees vir gasvorming, en kan ook verder die doeltreffendheid van ‘n tersiêre biologiese behandeling verhoog.