Currently at the Savannah River Site (SRS), there are fifteen single-shell, 3.6-million liter tanks containing High Level Waste. To close the tanks, the sludge must be removed. Mechanical methods have had limited success. Oxalic acid cleaning is now being considered as a new technology. This research uses sample results and chemical equilibrium software to develop a preferred flowsheet and evaluate the acceptability of the system impacts. Based on modeling and testing, between 246,000 to 511,000 l of 8 wt% oxalic acid were required to dissolve a 9,000 liter Purex sludge heel. For SRS H-Area modified sludge, 322,000 to 511,000 l were required. To restore the pH of the treatment tank slurries, approximately 140,000 to 190,000 l of 50 wt% NaOH or 260,000 to 340,000 l of supernate were required. When developing the flowsheet, there were two primary goals to minimize downstream impacts. The first was to ensure that the Resultant oxalate solids were transferred to DWPF, without being washed. The second was to transfer the remaining soluble sodium oxalates to the evaporator drop tank, so they do not transfer through or precipitate in the evaporator pot. Adiabatic modeling determined the maximum possible temperature to be 73.5°C and the maximum expected temperature to be 64.6°C. At one atmosphere and at 73.5°C, a maximum of 770 l of water vapor was generated, while at 64.6°C a maximum 254 l of carbon dioxide were generated. Although tank wall corrosion was not a concern, because of the large cooling coil surface area, the corrosion induced hydrogen generation rate was calculated to be as high as 10,250 l/hr. Since the minimum tank purge exhaust was assumed to be 5,600 l/hr, the corrosion induced hydrogen generation rate was identified as a potential concern. Excluding corrosion induced hydrogen, trending the behavior of the spiked constituents of concern, and considering conditions necessary for ignition, energetic compounds were shown not to represent an increased risk Based on modeling, about 56,800 l of Resultant oxalates could be added to a washed sludge batch with minimal impact on the number of additional glass canisters produced. For each sludge batch, with 1 to 3 heel dissolutions, about 60,000 kg of sodium oxalate entered the evaporator system, with most collecting in the drop tank, where they will remain until eventual salt heel removal. For each 6,000 kg of sodium oxalate in the drop tank, about 189,000 l of Saltstone feed would eventually be produced. Overall, except for corrosion-induced hydrogen, there were no significant process impacts that would forbid the use of oxalic acid in cleaning High Level Waste tanks. / MATHEMATICAL SCIENCES / M. Tech. (Chemical Engineering)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A primeira etapa do presente trabalho consistiu em caracterizar um efluente lácteo industrial (soro de queijo) em termos microbiológicos e físico-químicos visando à obtenção de um consórcio de microrganismos para a sua biodegradação. Foram determinadas a contagem padrão de bactérias heterotróficas e a contagem de fungos filamentosos e leveduras de acordo com as metodologias oficiais, e a caracterização físico-química foi realizada em termos do teor de proteínas, cinzas, lipídios, carboidratos, pH e demanda química de oxigênio (DQO). O consórcio microbiano foi obtido em biorreator operando em batelada e contendo 1,5L do efluente, a 200rpm, aeração de 1vvm e temperatura de 28 - 30oC. Os cultivos foram realizados em duplicata durante onze dias, sendo realizado um pulso de 150mL do efluente (10% do volume útil do biorreator) no sétimo dia do cultivo. Foram obtidas concentrações iniciais de 3x109UFC/mL e 8x104UFC/mL para contagem total de bactérias e de fungos e leveduras, respectivamente. O efluente apresentou uma DQO inicial de 64.000mgO2/L, pH 5,0, e concentrações correspondentes a 5g/100mL de carboidratos, 0,8g/100 mL de proteínas e 0,6g/100 mL de lipídios. Os cultivos do efluente no biorreator demonstraram um aumento da concentração de bactérias ao longo do tempo, atingindo 1x1013UFC/mL após oito dias, enquanto que as concentrações de fungos filamentosos e de leveduras foram inibidas. Foi observada uma redução da DQO de 47 a 63,5% após 11 dias de cultivo, demonstrando a potencialidade da utilização do consórcio microbiano no tratamento do efluente. Ensaios qualitativos demonstraram a presença das enzimas: lipase, amilase, protease e celulase no extrato metabólito do consórcio microbiano. No entanto, foram obtidos baixos valores de atividade lipolítica quando comparados com a atividade da enzima comercial, sendo observado ainda que a atividade decresce ao longo do tempo. Na segunda etapa do trabalho foi avaliada a hidrólise enzimática de material flotado, obtido a partir do processo de flotação em coluna do efluente, utilizando a técnica de planejamento de experimentos. Inicialmente, foi avaliado o desempenho de uma lipase comercial (lipolase), sendo investigados os efeitos da agitação e da concentração de enzima sobre a hidrólise. Foi realizada a análise estatística considerando os efeitos significativos para um nível de confiança de 95%. Concentrações maiores de enzima dentro da faixa investigada (1 a 7%) maximizam a hidrólise de óleos e gorduras do material flotado, bem como para níveis de agitação entre 100 e 150rpm. Em todos os experimentos houve a liberação de ácidos graxos no meio em percentuais próximos a 100% apenas após 4 horas de reação. Vale salientar ainda que percentuais de liberação de ácidos graxos superiores a 92% foram obtidos para toda a faixa de concentração testada. Uma agitação de 150rpm foi utilizada em um segundo planejamento experimental, avaliando-se a concentração da enzima comercial associada a um consórcio microbiano, sendo verificado que a adição do consórcio não influenciou de maneira positiva o aumento do teor de ácidos graxos livres no meio. / The first step of the present work was characterizing a dairy effluent in terms microbiological and physical-chemical used to obtain a microbial consortium for its biodegradation. Microbiological characterization was performed by total heterotrophic bacteria, filamentous fungi and yeasts count according to the official methodologies. Physical-chemical characterization was accomplished by content of protein, ash, lipids, carbohydrates, pH and chemical oxygen demand (COD). Microbial consortium was obtained in batch using a bioreactor containing 1,5L of dairy effluent, at 200 rpm, 1vvm, at 28 - 30oC. Cultivations were performed in duplicate for eleven days, being applied a pulse of 10% (v/v) of effluent on the seventh day of the experiment. Cellular growth kinetics, chemical oxygen demand concentration and lipolytic activity were determined. Initial concentrations of bacteria and fungi and yeasts were equal to 3x109CFU/mL and 8x104CFU/mL, respectively. Effluent presented a COD of 64.000mgO2/L, pH 5,0 and concentrations of 5g/100mL of carbohydrates, 0,8g/100mL of protein and 0,6g/100mL of lipids. Cultivations showed an increase on the bacteria concentration, reaching 1x1013CFU/mL after eight days, while filamentous fungi and yeast concentrations were inhibited. An reduction of COD concentration in the range of 47 to 63,5% was observed after eleven days of cultivation, demonstrating the potentiality of use of microbial consortium for effluent treatment. Qualitative assays showed the presence of the enzymes lipase, amylase, protease and cellulase in the metabolic extract of the microbial consortium. However, low values of lipolytic activity were obtained as compared to the commercial enzyme, being observed that activity decreases along time. In the second step of this study, was evaluated the enzymatic hydrolysis of floated material, obtained from the column flotation of a dairy industry, using the technique of experimental design. Initially, performance was evaluated by a commercial lipase (lipolase), being investigated the effects of agitation and enzyme concentration on hydrolysis. A statistical analysis was performed considering the significance of effects to a confidence level of 95%. Higher enzyme concentrations in the range investigated (1 to 7%) maximize the hydrolysis of oils and fats in the floated material, and to agitation levels between 100 and 150rpm. In all experiments, fatty acids were released in rates near to 100% only after 4 hours of reaction. Moreover, rates of released fatty acids were greater than 92% in all the concentration range tested. An agitation of 150rpm was used in a second experimental design, evaluating the concentration of commercial enzyme associated with a microbial consortium. The kinetic monitoring of the process showed that the addition of the consortium did not influence in a positive manner the increase the content of free fatty acids.

Os curtumes são indústrias que causam importante impacto ambiental, pois utilizam grande volume de água na produção do couro e o volume total de efluentes gerados normalmente é similar ao total de água captada. Além disso, há a utilização de vários compostos químicos no beneficiamento do couro, gerando, consequentemente, efluentes que possuem alta carga poluidora, com elevada DQO, matéria orgânica, sólidos em suspensão, sais dissolvidos e metais. Portanto, é indispensável o tratamento eficiente deste tipo de efluente, visando minimizar seus impactos ambientais e atender à legislação vigente. A clarificação química coagulação/floculação/decantação) é uma das etapas mais utilizadas no tratamento de efluente de curtume, ainda é utilizado coagulantes à base de sais de alumínio e ferro, porém estes são, comprovadamente, tóxicos ao ambiente. Com intuito de substituir os coagulantes inorgânicos, muitas pesquisas com polímeros naturais vêm sendo desenvolvidas. O PGα21Ca foi desenvolvido com esse propósito, sendo composto principalmente por sulfato de cálcio e ácido--poliglutâmico, possui alta biodegradabilidade e baixa toxicidade. O presente trabalho teve como objetivo o estudo do tratamento de efluente de curtume, por meio do processo de clarificação química com o coagulante PGα21Ca e degradação fotocatalítica utilizando o catalisador TiO2. As condições ideais de tratamento foram determinadas aplicando a metodologia de planejamento fatorial e pelo delineamento composto central rotacional (DCCR). Em condições otimizadas, a clarificação química apresentou remoção de 75% da cor real, 61% da DQO, 77% da turbidez, 94 % do cromo total, 95% de cromo trivalente e 92% do cromo hexavalente. Constatando assim, que o PGα21Ca foi eficiente, principalmente na remoção de cromo. O processo de tratamento completo com clarificação química e fotocatálise heterogênea resultou em remoção de 87% da cor real, 92% da DQO, 91% da turbidez, 97 % do cromo total, 98% de cromo trivalente e 94% do cromo hexavalente. O processo de fotocatálise heterogênea contribuiu principalmente com as remoções de turbidez. Por meio desta pesquisa, comprovou-se a viabilidade da utilização do coagulante PGα21Ca para tratamento de efluente de curtume, considerando-o uma boa opção de coagulante devido ao alto rendimento e capacidade para remoção de compostos orgânicos e inorgânicos. / Tanneries are industries that cause significant environmental impact, because they use a large volume of water in leather production and the total wastewater volume generated is normally similar to the total water caught. In addition, there is the use of several chemical compounds in leather processing, generating highly polluted wastewater with high COD, organic matter, suspended solids, dissolved salts and metals. Therefore, the efficient treatment of this type of wastewater is indispensable, in order to minimize its environmental impacts and to comply with the current legislation. Chemical clarification (coagulation / flocculation / decantation) is one of the most used steps in the treatment of tannery wastewater, it is still used coagulants based on aluminum and iron salts, but they have been proven to be toxic to the environment. In order to replace the inorganic coagullants, many researches with natural polymers have being developed. PGα21Ca was developed for this purpose. It is mainly composed of calcium sulphate and γ-polyglutamic acid, presenting high biodegradability and low toxicity. The present work had the objective of studying the treatment of tannery wastewater by chemical clarification with coagullant PGα21Ca and photocatalytic degradation using the TiO2. The ideal treatment conditions were determined using experimental design methodology and central rotational compound design (CCD). Under optimized conditions, chemical clarification presented removal of 75% of color, 61% of COD, 77% of turbidity, 94% of total chromium, 95% of trivalent chromium and 92% of hexavalent chromium. Thus, PGα21Ca was mainly efficient for chromium removal. Complete treatment process with chemical clarification and heterogeneous photocatalysis resulted in removal of 87% of color, 92% of COD, 91% of turbidity, 97% of total chromium, 98% of trivalent chromium and 94% of hexavalent chromium. Heterogeneous photocatalysis process contributed mainly to turbidity removal. This research proved the feasibility of usage of PGα21Ca for the treatment of tannery wastewater, considering it a good coagulant option due to the high yield and capacity for removal of organic and inorganic compounds.

O tratamento de esgoto por meio de reatores anaeróbios, entre eles o tipo “Up-flow Anaerobic Slugde Blanket” – UASB é realizado há vários anos em alguns estados do Brasil. Para o dimensionamento e o controle destes reatores é considerada uma série de fatores como temperatura, pH do meio, carga hidráulica e, o objeto deste estudo, relação de nutrientes do afluente. As Estações de Tratamento de Esgoto recebem afluentes com variadas relações de nutrientes e não há na literatura consenso acerca de quais seriam os valores ótimos para funcionamento dos reatores. A fim de buscar maior entendimento sobre o assunto e assessorar o projeto, dimensionamento, e controle dos reatores anaeróbios, foi avaliada a influência da relação dos principais nutrientes (carbono, nitrogênio e fósforo) no desempenho de reatores tipo UASB tratando afluente sintético. Neste trabalho foram utilizados quatro reatores tipo UASB com as mesmas características, além disso, condições como TDH, carga orgânica e temperatura também eram constantes entre os reatores, sendo a única variável entre eles a relação C:N:P do afluente. O afluente sintético produzido tinha DQO esperada de 500 mg/L, valor próximo ao de esgotos domésticos. As análises se dividiram em duas partes, o monitoramento que durou 362 dias e os três perfis com 10 horas cada. No monitoramento foram realizadas análises de DQO, alcalinidade, ácidos voláteis, produção de gás metano, além da medição de temperatura e ph. Nos perfis foram feitas análises de DQO, fosfatos e nitrogênio amoniacal. Para discussão dos resultados foram realizados testes estatísticos a fim de indicar a existência de correlação entre as relações C:N:P dos afluentes e alguns dos resultados encontrados como: remoção de DQO, produção e consumo de alcalinidade e ácidos voláteis e produção de metano. Foi encontrada correlação apenas entre a produção de metano e as relações C:N:P testadas, sendo que para as outras análises esta correlação não foi confirmada. Todos os reatores obtiveram altas taxas quanto à remoção de DQO, estando estas acima de 75%, isto provavelmente se deve a fonte de carbono do afluente sintético ser a glicose; com relação a alcalinidade e ácidos voláteis, os resultados entre os reatores foram próximos e indicaram o bom funcionamentos destes; e quanto a geração de metano, o reator que operou sob a relação prevista de 300:5:1 obteve um rendimento 40% maior que os demais, alcançando a média diária de 162,05 mLCH4/gDQO. / Wastewater treatment using Anaerobic reactors, such as Up-flow Anaerobic Sludge Blanket – known as UASB, has been utilized for several years in some regions of Brazil. For design criteria and process control, it is considered several parameters as temperature, substrate pH, hydraulic load and nutrient ratio. Wastewater treatment plants process effluents with a variety of nutrient ratios and there is no consensus about what would be the optimal ranges for operating those reactors. Aiming to understand and assist the design, dimensioning and control of these reactors, this work evaluated the influence of the ratios of major nutrients (carbon, nitrogen and phosphorus) in the performance of a UASB reactor treating synthetic effluent. This work has used four UASB reactors with same characteristics, besides that, conditions such as HRT, organic load and temperature were the same among reactors, the only condition varying was C:N:P affluent ratios. The synthetic affluent produced had a COD expected of 500 mg/L, value similar to domestic wastewater. The analyses were divided in two parts: monitoring lasting 362 days and three profiles of 10 hours each. During monitoring were realized analyses of COD, alkalinity, volatile fatty acids, methane production, besides temperature and pH. Profiles analysed COD, phosphate and ammoniacal nitrogen. For the results discussion were realized statistical tests in order to find a correlation between affluents C:N:P ratios and results of COD removal, production and consumption of alkalinity and volatile fatty acids, and methane production rates. It was only found correlation between methane production and C:N:P ratios tested; for the other analyses no correlation was confirmed. All reactors obtained high COD removal rates - above 75 percent, this probably happened because synthetic affluent source of carbon was glycose; production of alkalinity and consume of volatile fatty acids among the reactors were similar, indicating an effective functioning. Regarding methane production, the reactor that operated with expected ratio of 300:5:1 obtained a performance 40% higher than the others, reaching a daily average of 162,05 mLCH4/gDQO.

CAPES; CNPq / O presente trabalho teve como objetivo caracterizar o efluente da Indústria de Compensado e avaliar a utilização do fungo filamentoso Pleurotus ostreatus no tratamento deste resíduo em reator air lift, além de verificar a potencialidade da complementação do tratamento do efluente utilizando um POA do tipo Fenton, a fim de ajustar valores em concordância com os padrões legais estabelecidos pelos órgãos regulamentadores. O efluente bruto apresentou 12.192 ± 100 mgO2L-1 de DQO, 8.849 ± 60 mgO2L-1 de DBO5,20(Demanda Bioquímica de Oxigênio), 8.333 ± 30 unidades de cor, 1.220 ± 5 mgL-1 de fenóis totais e pH 4,63. O teor de sólidos totais no efluente foi de 18,45 ± 0,15 gL-1, sendo que desse total 2,73 ± 0,04 gL-1 correspondia a cinzas, 1,36 ± 0,03 gL-1 a lignina klason solúvel, 49 ± 3 mgL-1 de lignina klason insolúvel e aproximadamente 71% de toxicidade aguda expressa em inibição de E. coli. A espectrometria por FTIR dos sólidos do efluente indicou bandas em 3430–3440 cm-1, 2938 cm-1, 1603 cm-1, que puderam ser atribuídas aos grupos O-H, C-H e C=C, respectivamente. O tratamento biológico utilizando o fungo Pleurotus ostreatus inicialmente foi otimizado em incubadora orbital (shaker) por meio de delineamento fatorial(23) obtendo-se as melhores condições reacionais para a redução da DQO (pH 5,7, concentração de sacarose 7,5 gL-1 e concentração de nitrato de amônio igual a 4,0 gL-1). O tratamento biológico após 40 dias em reator air lift foi capaz de remover 87 % da DQO, 92 % da DBO5, 73 % de fenóis totais, 36 % de cor e ainda 99 % da toxicidade aguda. A análise espectrométrica por FTIR confirmou a degradação por meio da redução de picos característicos. Apesar dos resultados do tratamento fúngico terem se apresentados bastante significativos, houve necessidade de complementação com processo Fenton, o que resultou numa redução de 99 % da DQO, 92 % do teor de fenóis e 96 % da cor do efluente. Desta forma, a biorremediação utilizando o fungo Pleurotus ostreatus e a combinação com o processo Fenton, apresentou resultados promissores, para enquadramento dentro da maioria dos parâmetros exigidos pela legislação. / The present work had the objective of characterizing the effluent from the Plywood Industry and evaluate the use of filamentous fungus Pleurotus ostreatus in the treatment in an air lift reactor, besides verifying the potentiality of the complementation of effluent treatment using a POA, Fenton type, in order to adjust it to the legal parameters to release it into water bodies in accord to the regulatory authorities. The brute effluent present 12.192 ± 100 mgO2L-1 of COD (Chemical Oxygen Demand), 8.849 ± 60 mgO2L-1 of BOD5,20 (Biochemical Oxygen Demand), 8.333 ± 30 color units, 1.220 ± 5 mgL-1 of total phenols and pH 4,63. The total solids content in the effluent was 18, 45 ± 0, 15 gL-1, in this total 2,73 ± 0,04 gL-1 corresponds to ashes, 1,36 ± 0,03 gL-1 soluble klason lignin and 49 ± 3 mgL-1 of insoluble klason lignin and approximately 71% toxicity expressed as inhibition to E.coli. The FTIR spectrometry of the solids of the effluent, indicated bands in 3430-3440 cm-1, 2938 cm-1, 1603 cm-1, that could be attributed to groups O-H, C-H, C=C. The biological treatment using the fungus Pleurotus ostreatus was initially optimized in an orbital incubator (shaker) by factorial design (2³) that getting the best reactional conditions to COD reduction (pH 5,7 and sucrose concentration of 7,5 gL-1 and nitrate concentration of 4,0 gL-1), being estimated a reduction of 64% of COD of effluent in 10 days. The biological treatment after 40 days in optimized conditions in air lift was capable of remove 87 % of COD of the effluent, 92 % of the BOD5,20, 72 % of reduction of total phenols, 36 % of color removal and acute toxicity reduced. The spectrometric analysis by FTIR confirmed the biological degradation by the correspondent peak reduction in relation to the characteristic peaks. Despite the results of fungal treatment being quite significant, there was a need of a complementation of treatment using AOP Fenton type, showing a reduction of 99 % of COD, 92 % of phenols content and 96 % effluents color. In this way, the bioremediation using the Pleurotus ostreatus combined with the Fenton process, presented promising results, in order to fit the majority of the parameters required by the legislation.

Thesis submitted in fulfilment of the requirements for the degree Master of Technology: Chemical Engineering in the Faculty of Engineering at the Cape Peninsula University of Technology 2014 / Environmental legislation focusing on wastewater disposal in industries that utilise cyanide and/or cyanide-related compounds has become increasingly stringent worldwide, with many companies that utilise cyanide products required to abide by the Cyanide International Code associated with the approval of process certifications and management of industries which utilise cyanide. This code enforces the treatment or recycling of cyanide-contaminated wastewater. Industries such as those involved in mineral processing, photo finishing, metal plating, coal processing, synthetic fibre production, and extraction of precious metals, that is, gold and silver, contribute significantly to cyanide contamination in the environment through wastewater. As fresh water reserves throughout the world are low, cyanide contamination in water reserves threatens not only the economy, but also endangers the lives of living organisms that feed from these sources, including humans. In the mining industry, dilute cyanide solutions are utilised for the recovery of base (e.g. Cu, Zn, Ni, etc.) and precious metals (e.g. Au, Ag, etc.). However, for technical reasons, the water utilised for these processes cannot be recycled upstream of the mineral bioleaching circuit as the microorganisms employed in mineral bioleaching are sensitive to cyanide and its complexes, and thus the presence of such compounds would inhibit microbial activity, resulting in poor mineral oxidation. The inability to recycle the water has negative implications for water conservation and re-use, especially in arid regions. A number of treatment methods have been developed to remediate cyanide containing wastewaters. However, these chemical and physical methods are capital intensive and produce excess sludge which requires additional treatment. Furthermore, the by-products that are produced through these methods are hazardous. Therefore, there is a need for the development of alternative methods that are robust and economically viable for the bioremediation of cyanide-contaminated wastewater. Biological treatment of free cyanide in industrial wastewaters has been proved a viable and robust method for treatment of wastewaters containing cyanide. Several bacterial species, including Bacillus sp., can degrade cyanide to less toxic products, as these microorganisms are able to use the cyanide as a nitrogen source, producing ammonia and carbon dioxide. These bacterial species secrete enzymes that catalyse the degradation of cyanide into several end-products. The end-products of biodegradation can then be utilised by the microorganisms as nutrient sources. This study focused on the isolation and identification of bacterial species in wastewater containing elevated concentrations of cyanide, and the assessment of the cyanide biodegradation ability of the isolates. Thirteen bacterial isolates were isolated from electroplating wastewater by suppressing the growth of fungal organisms and these species were identified as species belonging to the Bacillus genus using the 16S rDNA gene. A mixed culture of the isolates was cultured in nutrient broth for 48 hours at 37°C, to which FCN as KCN was added to evaluate the species‟ ability to tolerate and biodegrade cyanide in batch bioreactors. Subsequently, cultures were supplemented solely with agro-waste extracts, that is, Ananas comosus extract (1% v/v), Beta vulgaris extract (1% v/v), Ipomea batatas extract (1% v/v), spent brewer‟s yeast (1% v/v) and whey (0.5% w/v), as the primary carbon sources. Owing to the formation of high ammonium concentration from the cyanide biodegradation process, the nitrification and aerobic denitrification ability of the isolates, classified as cyanide-degrading bacteria (CDB) was evaluated in a batch and pneumatic bioreactor in comparison with ammonia-oxidising bacteria (AOB). Furthermore, the effects of F-CN on the nitrification and aerobic denitrification was evaluated assess the impact of F-CN presence on nitrification. Additionally, optimisation of culture conditions with reference to temperature, pH and substrate concentration was evaluated using response surface methodology. Using the optimised data, a continuous biodegradation process was carried out in a dual-stage packed- bed reactor combined with a pneumatic bioreactor for the biodegradation of F-CN and subsequent nitrification and aerobic denitrification of the formed ammonium and nitrates. The isolated bacterial species were found to be gram positive and were able to produce endospores that were centrally located; using the 16S rDNA gene, the species were found to belong to the Bacillus genus. The species were able to degrade high cyanide concentration in nutrient broth with degradation efficiencies of 87.6%, 65.4%, 57.0% and 43.6% from 100 mg F-CN/L, 200 mg F-CN/L, 300 mg F-CN/L, 400 mg F-CN/L and 500 mg F-CN/L respectively over a period of 8 days. Additionally, the isolates were able to degrade cyanide in an agro-waste supported medium, especially in a medium that was supplemented with whey which achieved a degradation efficiency of 90% and 60% from 200 mg F-CN/L and 400 mg F-CN/L, respectively over a period of 5 days. The nitrification ability of the isolates was evaluated and the removal of NH4 +/NO3 - by the CDB and AOB in both shake flasks and pneumatic bioreactor was determined to be pH dependent. The maximum NH4 +/NO3 - removal evaluated over a period of 8 days for CDB and 15 days for AOB, observed at pH 7.7 in shake flasks, was 75% and 88%, respectively, in the absence of F-CN. Similarly, the removal of NH4 +/NO3 - in a pneumatic bioreactor was found to be 97.31% for CDB and 92% for AOB, thus demonstrating the importance of aeration in the designed process. The nitrification by CDB was not inhibited by cyanide loading up to a concentration of 8 mg FCN/ L, while the AOB were inhibited at cyanide loading concentration of 1 mg F-CN/L. The CDB removed the NH4 +/NO3 - in PBSs operated in a fed-batch mode, obtaining efficiencies >99% (NH4 +) and 76 to 98% (NO3 -) in repeated cycles (n = 3) under F-CN (≤8 mg F-CN/L). The input variables, that is, pH, temperature and whey-waste concentration, were optimised using a numerical optimisation technique where the optimum conditions were found to be: pH 9.88, temperature 33.60 °C and whey-waste concentration 14.27 g/L, under which 206.53 mg CN-/L in 96 h can be biodegraded by the microbial species from an initial cyanide concentration of 500 mg F-CN/L. Furthermore, using the optimised data, cyanide biodegradation in a continuous mode was evaluated in a dual-stage packed-bed bioreactor connected in series to a pneumatic bioreactor system used for simultaneous nitrification including aerobic denitrification. The whey-supported Bacillus sp. culture was not inhibited by the free cyanide concentration of up to 500 mg F-CN/L, with an overall degradation efficiency of ≥99% with subsequent nitrification and aerobic denitrification of the formed ammoniu and nitrates over a period of 80 days.

Dentre as tecnologias para tratamento de efluentes, este trabalho abordou processos de oxidação avançada fundamentados no uso de catalisadores heterogêneos, sendo este processo também conhecido por fotocatálise heterogênea. A eficiência desse tipo de processo já é bastante conhecida e reportada na literatura, no entanto, sua aplicação conta com gastos de energia artificial para ativação do catalisador responsável pela degradação de contaminantes. Neste sentido, novos materiais têm sido desenvolvidos para promoverem a fotossensibilização de catalisadores como TiO2, o que viabiliza ativação pela luz visível e aplicações com energia renovável solar. No desenvolvimento de novos catalisadores, os materiais nanoestruturados compósitos, formados por duas ou mais substâncias em contato íntimo, destacam-se pelo sinergismo que confere propriedades singulares ao material. Este trabalho teve como objetivo a síntese, caracterização e aplicação de nanocompósitos formados por polianilina (PANI), TiO2-P25 e NTCs como catalisadores na degradação do fármaco sulfametoxazol sob luz solar simulada. A síntese do catalisador consistiu na polimerização interfacial (água/tolueno) da anilina, contento fase orgânica com NTCs e anilina, e dióxido de titânio na fase aquosa. Diferentes associações dos materiais e concentrações de TiO2 foram testadas e resultaram nos seguintes catalisadores PANI:TiO2, PANI:TiO2-conc, NTC:PANI:TiO2 e NTC:PANI:TiO2-conc. Os materiais foram caracterizados por espectroscopia Raman, difração de raios X, microscopias eletrônicas de varredura e transmissão e análise termogravimétrica. O potencial desses materiais em fotocatálise de sulfametoxazol foi avaliado por um sistema de luz solar simulada. A síntese interfacial resultou em compósitos verdes, cor característica da polianilina. As técnicas de caracterização indicaram a formação de polianilina como uma massa polimérica contendo NTCs e/ou TiO2. O polímero nos compósitos mostrou, por espectroscopia Raman, ser mais polariônico, planar e menos reticulado. Análises termogravimétricas revelaram que os compósitos foram constituídos por cerca de ~ 85 % de TiO2 nas amostras com NTCs e ~ 95 % de óxido nas amostras formadas apenas por polianilina e óxido de titânio. Foi discutido condições fundamentais sobre a determinação da fotossensibilização do TiO 2-P25 por polianilina e NTCs, através de um sistema solar simulado. O catalisador PANI:TiO2-conc mostrou maior capacidade de fotodegradação de sulfametoxazol sob luz solar simulada em relação ao TiO2-P25. Diante disso, o compósito formado por polianilina e TiO2 com baixo percentual de polímero, resultou em um material com maior potencial para aplicações em sistemas solares. / Among the technologies for wastewater treatment, this work addressed advanced oxidation processes based on the use of heterogeneous catalysts, this process is also known as heterogeneous photocatalysis. The efficiency of this type of process is already well known and reported in the literature, however, its application has artificial energy costs for activation of the catalyst responsible for the degradation of contaminants. In this sense, new materials have been developed to promote the photosensitizing catalysts such as TiO2, which enables activation by visible light and solar renewable energy applications. In the development of new catalysts the nanostructured composite materials formed of two or more substances in close contact, stand out due to synergism which confers unique properties to the material. This study aimed to the synthesis, characterization and application of nanocomposites formed by polyaniline (PANI), TiO2-P25 and CNTs as catalysts in the degradation of the drug sulfamethoxazole under simulated sunlight. The catalyst synthesis was the interfacial polymerization (water / toluene) of aniline, containing organic phase with CNTs and aniline, and titanium dioxide in the aqueous phase. Different associations of materials and TiO2 concentrations were tested and resulted in the following catalysts PANI:TiO2, PANI:TiO2-conc, NTC:PANI:TiO2 and NTC:PANI:TiO2-conc. The materials were characterized by Raman spectroscopy, X- ray diffraction, electronic microscopy of scanning and transmission, and thermogravimetric. The potential for these materials in photocatalysis of sulfamethoxazole was evaluated by a simulated solar light system. The interfacial synthesis resulted in a green composite color, characteristic of polyaniline. The characterization techniques indicated the formation of polyaniline as a polymeric mass containing CNTs and / or TiO2. The polymer in the composite showed by Raman spectroscopy, to be more polaronic form, planar, an less reticulation. Thermogravimetric analysis showed that the composite consisted of approximately ~ 85 % TiO2 on samples with CNTs and ~ 95 % oxide in the samples formed only polyaniline and titanium oxide. Was discussed fundamental conditions on determining the photosensitivity of TiO2-P25 by polyaniline and CNTs, through a simulated solar system. The catalyst PANI:TiO2-conc showed higher photodegradation ability to sulfamethoxazole under simulated sunlight compared to TiO2-P25. Thus, the composite formed by polyaniline and TiO 2 with low percentage of polymer, resulted in a material with the greatest potential for applications in solar systems.

CNPq / No meio da ampla biodiversidade da flora brasileira, a ora-pro-nobis (Pereskia aculeata Miller) desperta especial interesse, pela alta quantidade de mucilagem em suas folhas. Plantas mucilaginosas são estudadas há algum tempo no processo de floculação/coagulação em tratamentos de água, com a intenção de, reduzir ou até mesmo suceder a utilização do sulfato de alumínio. A mucilagem é um biopolímero com grande capacidade de formar gel, soluções viscosas e estabilizar sistemas de emulsão. O presente trabalho teve como finalidade, avaliar o rendimento da mucilagem em processos de extração, caracterizar a mucilagem não clarificada, e clarificada e aplicar o biopolímero clarificado da P. aculeata, no processo de coagulação/floculação. Para tal as folhas foram secas em estufa até peso constante, foi feita a extração da mucilagem em solução aquosa por duas metodologias diferentes avaliando assim o rendimento, caracterização da morfologia por microscopia eletrônica de varredura (MEV) e difratometria de raio X (DRX), composição estrutural por infravermelho com transformada de Fourier (FT-IR), determinação do pH potencial de carga zero e do comportamento térmico por análise termogravimétrica (TG/DSC). Para a avaliação de coagulação e floculação, o biopolímero foi avaliado em água do Rio Pato Branco por ensaios em Jar Test avaliando a eficiência da remoção de turbidez, remoção de substâncias húmicas, e aromáticas. A extração da mucilagem foi avaliada no rendimento da produção, em que a extração a 95 ºC (30 min) apresentou rendimento três vezes maior que a extração a 60 ºC (6 horas). A caracterização morfológica exibiu uma estrutura amorfa, esponjosa e com adesão de partículas menores à superfície das partículas maiores, indicando um material higroscópico que pode ser usado como coagulante, sendo semelhante a outras mucilagens pesquisadas, em aspectos de grupos funcionais e de comportamento térmico. A P. aculeata se confirmou como auxiliar no processo de coagulação/floculação em relação aos parâmetros e faixas estudadas, sendo mais eficaz em conjunto com o sulfato de alumínio. Como é uma planta de fácil cultivo, atóxica e com custo relativamente baixo para a extração do seu biopolímero é uma alternativa promissora no tratamento de água e efluentes diminuindo a utilização do sulfato de alumínio no processo de floculação/coagulação. / In the midst of the wide biodiversity of Brazilian flora, the ora-pro-nobis (Pereskia aculeata Miller) arouses special interest because of the high amount of mucilage in its leaves. Mucilage plants have been studied for some time in the flocculation / coagulation process in water treatments, with the intention of reducing or even succeeding the use of aluminum sulphate. Mucilage is a biopolymer with great gelforming, viscous solutions and stabilizing emulsion systems. The purpose of this study was to evaluate the yield of the mucilage in extraction processes, to characterize the clarified and clarified mucilage and to apply the clarified biopolymer of P. aculeata in the coagulation / flocculation process. For this, the leaves were oven dried to constant weight, the mucilage was extracted in aqueous solution by two different methodologies, evaluating the yield, characterization of the morphology by scanning electron microscopy (SEM) and X-ray diffractometry (XRD) (FT-IR), determination of potential zero charge pH and thermal behavior by thermogravimetric analysis (TG / DSC). For the evaluation of coagulation and flocculation, the biopolymer was evaluated in water of the Pato Branco River by tests in Jar Test evaluating the efficiency of the removal of turbidity, removal of humic and aromatic substances. The extraction of the mucilage was evaluated in the yield of the production, in which the extraction at 95 ºC (30 min) yielded a three times higher yield than the extraction at 60 ºC (6 hours). The morphological characterization showed an amorphous structure, spongy and with adhesion of smaller particles to the surface of larger particles, indicating a hygroscopic material that can be used as a coagulant, being similar to other mucilages studied, in aspects of functional groups and thermal behavior. P. aculeata was confirmed as an aid in the coagulation / flocculation process in relation to the parameters and ranges studied, being more effective in conjunction with aluminum sulphate. As it is an easy-to-grow, non-toxic plant with relatively low cost for the extraction of its biopolymer, it is a promising alternative in the treatment of water and effluents by reducing the use of aluminum sulphate in the flocculation / coagulation process.

CAPES / A indústria têxtil brasileira ocupa um importante papel na economia e se posiciona entre as 10 maiores produtoras mundiais. Seus efluentes, gerados no processo de tingimento dos tecidos, contém cargas de 15 a 50% de corantes, além de outros contaminantes. Com vistas à remediação ambiental destes efluentes, o resíduo do processamento dos fios de algodão (RA), que é coletado na própria unidade fabril, revelou-se um material atraente para a remoção de corantes após sua derivatização química com ácido monocloroacético (AMCA) ou cloreto dietilaminoetil.cloridrato (DEAE+reagente), obtendo matrizes iônicas do tipo carboximetil-RA (CM--RA) e dietilaminoetil-RA (DEAE+-RA), respectivamente. Estas matrizes foram obtidas através de delineamentos experimentais, sendo que para a CM--RA foram avaliados os fatores: a) concentração de NaOH; b) volume de isopropanol e c) quantidade de AMCA, enquanto que para a DEAE+-RA, os fatores foram: a) concentração de NaOH e b) quantidade de DEAE-reagente. Tais matrizes foram ensaiadas, respectivamente, quanto à eficiência na retenção de corantes: catiônico, C.I. Basic Blue 41 (BB 41) e aniônico, C.I. Reactive Red 239 (RR 239), em experimentos em coluna e batelada. Também foi avaliada a biodegradabilidade desses materiais utilizando enzimas celulolíticas. Para as melhores matrizes obtidas foram realizados experimentos adicionais quanto à eficiência de retenção dos corantes (concentração inicial, tempo de contato e adição de sais), a biodegradabilidade após a retenção dos corantes e o ensaio de regeneração das matrizes. Para a CM--RA, a eficiência de captação de corante catiônico foi predominantemente determinada pela concentração de álcali. A inclusão do maior volume de isopropanol resultou em incremento da eficiência, entretanto, com custo adicional não justificável. A melhor matriz obtida na ausência de isopropanol apresentou valores de retenção para os testes em coluna e batelada maior que um produto comercial do tipo carboximetilcelulose. Para o teste de biodegradabilidade, as amostras derivatizadas tiveram hidrólises próximas aos controles com adição de NaOH. Para o DEAE+-RA, a principal variável responsável pela eficiência da retenção de corantes foi a quantidade do derivatizante, sendo que nos ensaios em coluna e batelada a resposta foi semelhante ao obtido com um produto comercial DEAE-Celulose. Através do teste de biodegradabilidade observou-se que a derivatização reduziu a porcentagem de hidrólise quando comparada aos seus controles com NaOH. Para as melhores matrizes, o ensaio de concentração inicial de corantes indicou que a retenção é maior com o aumento da concentração. Quanto à adição de NaCl, houve redução da retenção de corante na matriz carboximetilada enquanto para a dietilaminoetilada a influência foi positiva acima de 50 mM. A presença de corante reduziu em 4,10 e 37,36 % a hidrólise das matrizes carboximetilada e dietilaminoetilada, respectivamente. No presente trabalho, os derivados CM--RA e DEAE+-RA se revelaram eficientes para a remoção dos corantes BB 41 e RR 239, respectivamente, podendo assim se apresentar como uma alternativa no tratamento de efluentes têxteis. / The Brazilian textile industry occupies an important role in the economy and ranks among the 10 largest world producers The effluents generated in the process of fabrics dyeing contain 15 to 50% of dyes and others contaminants. With a view to environmental remediation of these effluents, the processing of cotton yarn waste (cotton dust waste - CDW) that is collected in the plant itself, proved to be an attractive material for the removal of the residual dyes effluents after the chemical derivatization with monochloroacetic acid (MCAA) or diethylaminoethyl chloride.hydrochloride (DEAE+reagent), thus originating matrices carboxymethyl- CDW (CM--CDW) and diethylaminoethyl-CDW (DEAE+-CDW), respectively. These matrices were obtained using experimental designs, when for CM--CDW three factors were evaluated: a) concentration of NaOH; b) volume of isopropanol and c) amount of MCAA, while for DEAE+-CDW, the factors were: a) concentration of NaOH and b) amount of DEAE+reagent. These matrices were tested for their effectiveness in the retention of dyes: the cationic, C. I. Basic Blue 41 (BB 41) and the anionic, C. I. Reactive Red 239 (RR 239), both in column and batch experiments. Also, the biodegradability of these materials was tested. For the best matrices obtained, additional experiments regarding the retention efficiency of the dyes (initial concentration, contact time and addition of salts) and matrices biodegradability after the dye retention were also carried out. For the CM--CDW, the efficiency of uptake of the cationic dye was predominantly determined by the concentration of alkali. The inclusion of the higher volume of isopropanol in the pretreatment step resulted in improved efficiency, but with an additional cost not justifiable. The best matrix obtained in the absence of isopropanol showed retention values for column and batch experiments with respective efficiencies of 3.9 and 2 times higher than a commercial CM-cellulose. For the biodegradability test, the samples of experimental design showed close enzymatic hydrolysis compared with the controls with alkali. For the DEAE+-CDW, the main variable for the efficiency of dye retention is predominantly determined by the amount of DEAE+reagent. The maximum retention of the anionic dye was obtained in columns while the batch alternatve performance was close to that of a commercial DEAE-Cellulose. The biodegradability test revealed that the derivatization with DEAE+reagent reduced the percentage of hydrolysis by cellulases when compared to the controls with NaOH. The initial concentration test of dye indicated that the retention increases with increased dye concentration and contact time to reach equilibrium which was higher in the higher concentrations in both matrices. The addition of NaCl decreased the dye retention for the carboxymethylated matrix and for the diethylaminoethylizated matrix the influence was positive only after addition of 50 mM. The presence of dye in the matrices derivatized reduced the hydrolysis in 4.10 and 37.36 % for carboxymethylated and diethylaminoethylizated matrices, respectively. Therefore, the CM--CDW and DEAE+- CDW derivatives of CDW proved effective for the removal of the dyes BB 41 and RR 239, respectively, and thus both represent important alternatives in the treatment of colored textile effluents.

No Brasil a lei ambiental vigente estabelece que os efluentes não possam causar efeitos agudo ou crônico para a biota dos corpos hídricos. No presente estudo foram avaliados os efeitos toxicológicos de amostras de água superficial e sedimento integral, de três locais três locais próximos a uma estação de tratamento de esgotos domésticos, coletadas em um rio na região de Curitiba, Estado do Paraná. As amostras foram submetidas a testes de toxicidade aguda e crônica, com os invertebrados aquáticos D. magna e C. sancticaroli. Além dos testes ecotoxicológicos, foram mensurados DBO, DQO, Fósforo Total, Nitrogênio Amoniacal Total, e Coliformes termotolerantes, com as amostras de água superficial. A composição do sedimento integral foi avaliada com a Espectrometria de Fluorescência de Raios-X por Energia Dispersiva (EDXRF), para a determinação dos elementos químicos presentes nestas amostras. Os resultados das análises de DBO, DQO, Fósforo total, Nitrogênio amoniacal total, e Coliformes termotolerantes, demonstraram que possivelmente ocorreu a contaminação da água superficial por esgoto doméstico, para as amostras analisadas nas 3 campanhas. A composição dos sedimentos é compatível com os tipos de solos presentes nos respectivos locais, porém houve variação quantitativa de elementos como o silício, alumínio e ferro no decorrer das campanhas, parecendo não influenciar diretamente nos testes. Os resultados dos testes para toxicidade aguda com matriz água e sedimento não expressaram toxicidade para D. magna e C. sancticaroli. Para os testes de toxicidade crônica com água superficial, o efeito observado foi o acréscimo da reprodução em D. magna. Aspectos como letalidade e a ausência do desenvolvimento da maturidade sexual foram verificados em amostras puras, provenientes do ponto próximo da ETE em todas as campanhas, após 10 dias de teste para D. magna. As amostras de sedimento integral não promoveram letalidade nos Daphnideos, entretanto ocorreu o acréscimo da reprodução. Para C. sancticaroli, exposto ao sedimento integral, ocorreu o desenvolvimento anormal do comprimento dos organismos, emergindo em adultos até o 8o dia de teste crônico. / In Brazil the environmental law in force establishes that wastewaters can not cause acute or chronic effect to the water bodies’ biota. In the present study were evaluated the ecotoxicological effects of surface water and whole sediment samples, from three sites located nearby a wastewater treatment plant, that were collected from a river in the region of Curitiba, state of Paraná. The samples were submitted to acute and chronic toxicity tests, utilizing the aquatic invertebrates D. magna and C. sancticaroli. Besides the ecotoxicological tests, BOD, COD, Total Phosphorus, Total Nitrogen Ammonia and Thermotolerant coliforms were measured from the surface water samples. The whole sediment composition was evaluated by Energy-dispersive X- Ray Fluorescence Spectrometry (EDXRF) to determine chemical elements present in these samples. The BOD, COD, Total Phosphorus, Total Nitrogen ammonia, and Thermotolerant coliforms analysis’ results possibly demonstrated surface water contamination by domestic sewage, for the samples analyzed in 3 campaigns. The sediment composition is compatible with the kinds of soils present in the respective sites, however there were quantitative variation of chemical elements during the campaigns, such as silicon, aluminum and iron, not seeming to directly influence the tests. The test results for acute toxicity with water and sediment matrix have not expressed toxicity to D. magna and C. sancticaroli. For chronic toxicity tests with surface water, the observed effect was the reproduction increase in D. magna. Aspects such as lethality and the absence of sexual maturity development were observed in pure samples accruing from the nearest point of the WTP in all campaigns, after 10 test days for D. magna. The whole sediment samples have not promoted lethality in Daphnideos, although a reproduction increase occurred. For C. sancticaroli, exposed to the whole sediment, an abnormal length development of the organisms occurred, emerging in adults until the 8th chronic test day.