Este trabalho buscou verificar a viabilidade do uso de fermentado de glicerol como fonte externa de carbono para a remoção biológica de nutrientes em um reator de leito estruturado, submetido à aeração intermitente (LEAI). O LEAI foi alimentado com efluente de reator UASB de bancada, usado no tratamento de esgoto sanitário. O reator LEAI possuía volume total de 12,3L e, devido às hastes cilíndricas verticais de espuma de poliuretano usadas como suporte para a biomassa, o volume útil foi de 8,6 L. Inicialmente, o reator foi operado sob aeração contínua com tempo de detenção hidráulica (TDH) de 24 horas e razão de recirculação de efluente igual a 3 para desenvolvimento de biomassa nitrificante no reator. Após a eficiência de nitrificação atingir 80%, o reator passou a ser operado com TDH de 12 horas e sob aeração intermitente, mantendo-se a razão de recirculação igual a 3. Foram então realizadas 4 fases em modo contínuo sob aeração intermitente (tempo de aeração/tempo sem aeração) de 2h/1h sem glicerol, 3h/1h sem glicerol, 2h/1h com glicerol, 3h/1h com glicerol. A adição de glicerol fermentado ocorreu somente durante os períodos não aerados. Em todas as fases, a DQO média efluente ao sistema variou entre 26±8 e 59±14 mg.L-1. Em relação à remoção de nitrogênio total (como NTK), verificou-se a baixa eficiência de remoção nas fases em que não houve a adição do fermentado, atingindo 49,6±13,5% (2h/1h) e 29,2±10,1% (3h/1h). Entretanto, nas fases em que houve a inserção do glicerol, as eficiências de remoção de N-total foram superiores, obtendo-se 64,9±21,6% (2h/1h) e 69,5±11,7% (3h/1h). Não foi observada remoção de fósforo em nenhuma das fases em que o reator foi operado com alimentação contínua. A fim de verificar a eficácia do fermentado de glicerol na remoção de N e P, o sistema foi modificado para que o reator LEAI operasse em bateladas sequenciais (RSB). Nessa etapa da pesquisa, observou-se o estabelecimento da comunidade acumuladora de fósforo no sistema, obtendo-se eficiência de remoção de fósforo de 56,1±8,5%. A eficiência de remoção de nitrogênio total também aumentou, atingindo 86,2±6,2%. Concluiu-se que o fermentado do glicerol apresenta potencial significativo para uso como fonte exógena de carbono no processo de remoção de fósforo e N-total. Concluiu-se também que, embora o glicerol fermentado contenha compostos favoráveis à remoção de fósforo em reatores de leito estruturado, a alimentação contínua do reator com aeração intermitente, não promove as condições ideais para o estabelecimento de processo estável de remoção de fósforo. No entanto, a elevada eficiência de oxidação de NTK, de remoção de matéria orgânica e de desnitrificação, aliadas à baixa produção sólida, mostram que o LEAI é uma alternativa interessante em comparação às tecnologias praticadas atualmente para pós-tratamento de efluentes de reatores anaeróbios. Contudo, quando a remoção de fósforo é necessária, a operação do reator em bateladas sequenciais é a alternativa viável. / This work aimed to verify the viability of the use of fermented glycerol as an external carbon source for the nutrient biological removal in structured-bed reactor subjected to recirculation and intermittent aeration (SBRRIA). The SBRRIA was fed effluent from UASB reactor bench scale, used in the treatment of domestic sewage. The SBTTIA reactor had a total volume of 12.3L and, due to the vertical cylindrical strips of polyurethane foam used as biomass support, the useful volume was 8.6 L. Initially, the reactor was operated under continuous aeration with hydraulic retention time (HRT) of 24 hours and effluent recirculation ratio of 3 for the development of nitrifying biomass in the reactor. After the nitrification efficiency reach 80%, the reactor started to be operated at the HRT of 12 h under intermittent aeration, maintaining the recirculation ratio equal to 3. Four phases were then carried out continuously under intermittent aeration (aeration / time without aeration) of 2h/1h without glycerol, 3h/1h without glycerol, 2h/1h with glycerol, 3h/1h with glycerol. The addition of fermented glycerol occurred only during time without aeration. In all phases, the average COD effluent of the system ranged between 26±8 and 59±14 mg.L-1. Low removal efficiency of total nitrogen (as TKN) was verified in the phases without addition of the fermented glycerol, reaching 49.6±13.5% (2h/1h) and 29.2±10.1% (3h/1h). However, the efficiency of total nitrogen removal efficiency was higher when fermented glycerol was added during the non-aerated period, attaining 64.9±21.6% (2h/1h) and 69.5±11.7% (3h/1h). No phosphorus removal was observed in any of the previous phases in which the reactor was operated under continuous feeding. In order to verify the feasibility of fermented glycerol in the removal of N and P, the system was modified so that the LEAI reactor operated in sequential batch mode (SRB). At this stage of the research, the establishment of the phosphorus accumulating community in the system was observed and phosphorus removal efficiency attained 56.1±8.5%. The efficiency of total nitrogen removal also increased up to 86.2±6.2%. It was concluded that the fermented glycerol presents significant potential for use as an exogenous carbon source in the process of phosphorus and nitrogen removal. It can be also concluded that fixed bed reactors can remove phosphorus from wastewaters using fermented glycerol presenting compounds favorable to the development of phosphorus accumulating microorganisms (PAO). However, reactors subjected to continuous feeding and intermittent aeration do not promote good conditions for the establishment of stable phosphorus removal process. Nevertheless, the high efficiency of TKN oxidation, organic matter removal and denitrification, coupled with low solid production, show that SBRRIA is an interesting alternative for the post-treatment of anaerobic reactor effluents. However, when phosphorus removal is required, sequential batch reactor operation is the viable alternative.

Este trabalho buscou avaliar a influência da relação C/N e da fonte de carbono no processo de nitrificação e desnitrificação simultâneas em reator de fluxo contínuo e leito fixo estruturado. Foi utilizado um reator vertical de acrílico, com volume total de 11,0 L e volume útil de 5,5 L, com hastes cilíndricas verticais de espuma de poliuretano como suporte para a biomassa. O sistema foi operado com TDH de 11,2±0,6 horas, aeração intermitente (2 horas com aeração e 1 hora sem aeração) e razão de recirculação de efluente igual a 5. A carga carbonácea afluente foi mantida constante (1,07 kg DQO.m-3.dia-1), ao longo de todo o período experimental, sendo as relações C/N testadas (9,7±1; 7,6±1; 2,9±1 e 2,9±0,4) obtidas a partir da variação na carga nitrogenada aplicada. Duas fontes orgânicas foram avaliadas: sacarose e peptona de carne. A eficiência média de remoção de DQO manteve-se acima de 90%. A eficiência máxima de remoção de N-total (84,6±10,1%) foi obtida para relação C/N de 2,9±1, com concentrações efluentes médias de NTK e N-NH4 de 5,9 e 4,3 mg.L-1, respectivamente. A análise estatística da eficiência de remoção de N-total confirmou que a fonte de carbono não exerceu influência sobre os processos de remoção. A obtenção de eficiências de desnitrificação superiores às calculadas estequiometricamente, em função da fonte de carbono, indicou a ocorrência de possíveis vias complementares para remoção de nitrogênio, como o processo anammox. As velocidades de nitrificação e desnitrificação obtidas nos ensaios cinéticos foram similares para as duas fontes de carbono e para as relações C/N estudadas e da mesma ordem de grandeza das apresentadas na literatura, reforçando a ideia de que a configuração de reator utilizada, aliada às adequadas condições operacionais, permitiu a remoção concomitante de matéria carbonácea e nitrogenada. / This study aimed to evaluate the influence of COD/N ratio and organic source on the simultaneous nitrification and denitrification (SND) in an up-flow structured-bed reactor. The reactor was made of acrylic with a total volume of 11 L and a working volume of 5.5 L and filled with cylinders of polyurethane foam as support for biomass growth. The system was continuously operated with an HRT of 11.2±0.6 h, intermittent aeration (2h with aeration and 1h without aerationd) and a liquid recycle ratio equal to 5. The organic load rate was constant (1.07 kg COD.m-3d-1) during the entire experiment. The COD/N ratios (9.7±1; 7.6±1; 2.9±1 and 2.9±0,4) were obtained from the variation of nitrogen load rate. Two organic sources were evaluated: sucrose and meat peptone. The average COD removal efficiency was above 90%. The maximum total nitrogen removal efficiency was 84.6±10.1%, with average TKN and NH4+-N effluent concentrations of 5.9 and 4.3 mg.L-1, respectively. Statistical analysis of total nitrogen removal efficiency confirmed that the carbon source did not influence over the removal processes. The denitrification efficiencies higher than the stoichiometrically calculated in function of the carbon source, indicated the occurrence of possible paths for nitrogen removal of nitrogen as anammox process. The nitrification and denitrification rates obtained in kinetic experiments were similar for the two sources of carbon and all C/N ratio studied at the same order of magnitude in relation to those reported in the literature, enhancing that the reactor configuration tested combined with the proper operational conditions allowed the organic matter and nitrogen removal simultaneously.

Made available in DSpace on 2016-12-23T14:04:34Z (GMT). No. of bitstreams: 1 Gabriel Hector Fontana.pdf: 3326725 bytes, checksum: 0537b69671db327278e7294ee7cfec00 (MD5) Previous issue date: 2012-12-03 / Monitoring water quality in the inner Continental Shelf (CS) has shown to be costly when conventional methods are employed. Orbital Remote Sensing appears as an alternative tool to monitoring important variables such as sea surface temperature (SST) and suspended sediment concentration (SSC). This study aims at assessing spatial distribution of SST and SSC in the continental shelf area of the Brazilian State of Espírito Santo using, respectively, Band 2 (0.569μm) and Band 6 (11.435μm) data from Thematic Mapper (TM) sensor on board of satellite Landsat 5. Thus, a data bank was built out of 127 images pre-processed and registered by the TM sensor. Of these 127 images, only 4 were selected for SST and SSC analyses. During image pre-processing, geometric and reflectance corrections are made. Geometric correction is carried out based on a second image orthorectified so that there is correct georeferencing. Reflectance correction is performed using an atmospheric compensation model. Through this model, sea surface reflectance is obtained. SST is estimated based on the adjustment of Brightness Temperature (BT) derived from Band 6 with data from the Multi-scale Ultra-high Resolution Sea Surface Temperature (MURSST). In case of not enough sediment field data to carry out curve adjustment, SSC calculation is performed using the empirical logarithm algorithm proposed by Tassan (1987), which uses Band 2 data. The corrected reflectance spectrum is compared to TOA reflectance spectrum. The corrected spectrum complied with the literature on natural targets analyzed: cloud, vegetation, water and water with sediments. Landsat BT adjustment with SST of MURSST showed to be significant, according to statistical F-test and to r2 = 0.87. Results of the 4 scenes for SST and SSC fields. For winter SST, a more homogeneous temperature of ~23ºC is observed, whereas the summer scene is characterized by thermal contrasts between the area closer to the coast (~21ºC) and the area further from the coast (~26ºC). Further, hotspot plumes associated to the mouths of Jucu and Doce Rivers and Espírito Santo Bay are also verified. For the SSC fields, higher-concentration plumes are observed, which are advected southeast. The highest concentrations are associated to the Doce River (over 60 mg/L). SSC values comply with the values reported in the relevant literature, i.e. close to the coastal line, in the summer scene, values of ~15mg/L were verified. On the other hand, for autumn and winter scenes, these values are about ~35mg/L. Both atmospheric correction and SSC distribution values found in this study are according to the data and studies reported in the relevant literature. Therefore, we can conclude that the method employed showed to be functional to process the data gathered in this study / O monitoramento da qualidade da água nas regiões internas à Plataforma Continental (PC) apresenta-se dispendioso quando são usados métodos convencionais. O Sensoriamento Remoto Orbital apresenta-se como uma ferramenta alternativa ao monitoramento de variáveis importantes como a Temperatura da Superfície do Mar (TSM) e a Concentração de Sedimentos em Suspensão (CSS). Este trabalho tem como objetivo avaliar a distribuição espacial da TSM e da CSS na região da PC capixaba usando, respectivamente, os dados da Banda 2 (0,569μm) e da Banda 6 (11,435μm) do sensor Thematic Mapper (TM) abordo do satélite Landsat 5. Sendo assim, é construído um banco de dados a partir de 127 imagens pré-processadas e registradas pelo sensor TM, e destas imagens, 4 foram selecionadas para a análise dos campos de TSM e CSS. No pré-processamento é realizada a correção geométrica e a correção da reflectância. A correção geométrica é realizada tomando como referência uma segunda imagem ortoretificada para que haja um correto georreferenciamento. A correção da reflectância é feita utilizando um modelo de compensação atmosférica, e através desse modelo é obtida a reflectância superficial da água do mar. A TSM é estimada a partir do ajuste da Temperatura de Brilho (TB) derivada da Banda 6 com os dados do produto Multi-scale Ultra-high Resolution Sea Surface Temperature (MURSST). Na falta de dados de campo de sedimento para realizar o ajuste de curva, o cálculo da CSS é feito utilizando o algoritmo logarítmico empírico proposto por Tassan (1987) que usa os dados da Banda 2. O espectro da reflectância corrigida é comparado com o espectro da reflectância TOA. O espectro corrigido mostrou-se condizente com o da literatura para os alvos naturais analisados: nuvem, vegetação, água e água com sedimento. O ajuste da TB do Landsat com a TSM do MURSST apresentou-se significante, segundo a Estatística teste F e com um r2 = 0,87. Os resultados das 4 cenas para os campos de TSM e CSS. Para a TSM de inverno observa-se uma distribuição de temperatura mais homogênea de ~23ºC, enquanto a cena de verão é caracterizada por contrates térmicos entre a região junto da costa (~21ºC) e a região mais afastada (~26ºC). Além disso, verificam-se plumas térmicas associadas às desembocaduras de rios, Jucu e Doce, e à Baía do Espírito Santo. Para os campos de CSS são observadas plumas de maior concentração sendo advectadas para sudoeste, sendo as maiores concentrações associadas ao Rio Doce, acima de 60 mg/L. Os valores de CSS apresentam-se em concordância com os valores reportados na literatura, de forma que, próximo à linha de costa, na cena de verão, são observados valores de~15mg/L. Já para cenas de outono e inverno os valores são entorno de ~35mg/L. Ambos os resultados, de correção atmosférica e de distribuição da CSS, apresentam-se em conformidade com os dados e trabalhos da literatura e portanto, concluiu-se que o método utilizado se mostrou funcional para o processamento dos dados deste trabalho

The present status of the environment, including environmental problems such as heavy metal accumulation in aquatic and terrestrial ecosystems, is in part the consequence of long-term changes. Cores from peatlands and other natural archives provide us with the potential to study aspects of the atmospheric cycling of elements, such as metal pollutants, on timescales much longer than the decade or two available to us with atmospheric deposition monitoring programs. The past decade especially has seen a rapid increase in interest in the biogeochemical record preserved in peat, particularly as it relates to environmental changes (e.g. climate and pollution). Importantly, recent studies have shown that carbon dynamics, i.e., organic matter decomposition, may influence the record of atmospherically derived elements such as halogens and mercury. Other studies have shown that under certain conditions some downward movement of atmospherically deposited elements may also occur, which adds complexity to establishing reliable chronologies as well as inherent problems of estimating accurate accumulation rates of peat and past metal deposition. Thus, we still lack a complete understanding of the basic biogeochemical processes and their effects on trace element distributions. While many studies have validated the general temporal patterns of peat records, there has been a limited critical examination of accumulation records in quantitative terms. To be certain that we extract not only a qualitative record from peat, it is important that we establish a quantitative link between the archive and the few to several decades of data that are available from contemporary monitoring and research. The main objective of this doctoral thesis was to focus on improving the link between the long-term paleorecord and the contemporary monitoring data available from biomonitoring and direct deposition observations. The main research questions have therefore been: Are peat archives an absolute or relative record? And how are geochemical signals, including dating, incorporated in the peat archive? What temporal resolution is realistic to interpret by using peat cores?

Le but de ce travail est d'élaborer de nouveaux revêtements anti-usure à base de nitrure de chrome, de carbure et de carbonitrure de titane par dépôt physique en phase vapeur afin d'améliorer la résistance à l'usure à sec des outils de coupe du bois.Des revêtements binaires de CrN et de MoN, ternaires de Cr-Mo-N et de Ti-W-C et quaternaires de Ti-W-C-N ont été déposés sur des outils de coupe en carbure de tungstène et en acier et sur des substrats de silicium par pulvérisation magnétron RF en utilisant différentes cibles (Cr, Mo, Ti et WC) sous différentes atmosphères (Ar, Ar + N2, Ar + CH4 et Ar + N2 + CH4).L'influence de la pression de travail, des ratios des gaz plasmagènes, des tensions d'auto-polarisation des cibles, de la température des substrats et de celle du recuit sur les propriétés des revêtements ont été étudiées, en utilisant l'EDS, la WDS, l'XPS, la DRX, le MEB, le MET, l'AFM, la microscopie optique, l'interférométrie optique (2D et 3D), le Scratch test, l'essai Daimler, la nanoindentation et la tribométrie alternative et rotative. L'objectif est d'établir une corrélation entre le comportement tribologique des revêtements étudiés et leurs propriétés physico-chimiques et mécaniques.Les revêtements optimaux présentant la meilleure résistance à l'usure à sec ont été testés en usinage de l'épinette noire à l'échelle industrielle dans des conditions sévères (-20/-25 °C). Les résultats montrent que grâce à l'emploi des revêtements de Cr-Mo-N, Ti-W-C et de Ti-W-C-N, la durée de vie des outils coupants a été augmentée de 47 à 77 % par rapport à l'outil non revêtu.Mots clés: revêtement, (Cr-Mo)N, (Ti-W)(C,N), propriétés physico-chimiques, propriétés mécaniques, comportement tribologique, usinage bois

The Dong research group is interested in harnessing the power of transition metal catalysis to transform simple molecules and reagents (such as carbon monoxide, hydrogen gas, olefins, and C–H and C–O bonds) into valuable products (such as functionalized heterocycles, chiral carbonyl compounds and natural products). This thesis will describe our continual effort to achieve this goal. Part I describes the Pd-catalyzed functionalization of sp2 and sp3 C–H bonds. Carbon monoxide is used as a stoichiometric reductant in the cyclization of diarylnitroalkenes to afford biologically relevant 3-arylindoles and other N-containing heterocycles with carbon dioxide as the only stoichiometric byproduct. Also, an aryl sulfoxide moiety is shown to direct the arylation of sp3 C–H bonds to afford beta-functionalized amides. Part II describes the Ru-catalyzed sp3 C–O bond activation of alkoxypyridines and related heterocycles. In this transformation, an O- to N-alkyl migratory rearrangement occurs to afford N-alkylated pyridones which are structures found in many natural products and pharmaceutical agents. Part III describes our pursuit of metal-catalyzed asymmetric synthesis. Readily available benzylic bromides are carbonylated with carbon monoxide in alcoholic solvent mixtures. The resulting medicinally relevant 2-arylpropionic esters are obtained with moderate to good enantioselectivities. Preliminary results for the asymmetric hydrogenation of gem-diarylethylenes and novel ligand development are also disclosed. Part IV describes our efforts towards the total synthesis of 6-deoxyerythronolide B. Our retrosynthetic analysis of the macrolide antibiotic involves disconnections at the lactone linkage and between C7 and C8. The two equally complex fragments were prepared via reliable aldol, hydroboration, crotylation and redox chemistry. Rather than the typical macrolactonization method to form the 14-membered ring, we propose an alternative strategy where we plan to cyclize with a metal-catalyzed ring-closing metathesis event. Currently, this step is under investigation by other members in the group.

The Dong research group is interested in harnessing the power of transition metal catalysis to transform simple molecules and reagents (such as carbon monoxide, hydrogen gas, olefins, and C–H and C–O bonds) into valuable products (such as functionalized heterocycles, chiral carbonyl compounds and natural products). This thesis will describe our continual effort to achieve this goal. Part I describes the Pd-catalyzed functionalization of sp2 and sp3 C–H bonds. Carbon monoxide is used as a stoichiometric reductant in the cyclization of diarylnitroalkenes to afford biologically relevant 3-arylindoles and other N-containing heterocycles with carbon dioxide as the only stoichiometric byproduct. Also, an aryl sulfoxide moiety is shown to direct the arylation of sp3 C–H bonds to afford beta-functionalized amides. Part II describes the Ru-catalyzed sp3 C–O bond activation of alkoxypyridines and related heterocycles. In this transformation, an O- to N-alkyl migratory rearrangement occurs to afford N-alkylated pyridones which are structures found in many natural products and pharmaceutical agents. Part III describes our pursuit of metal-catalyzed asymmetric synthesis. Readily available benzylic bromides are carbonylated with carbon monoxide in alcoholic solvent mixtures. The resulting medicinally relevant 2-arylpropionic esters are obtained with moderate to good enantioselectivities. Preliminary results for the asymmetric hydrogenation of gem-diarylethylenes and novel ligand development are also disclosed. Part IV describes our efforts towards the total synthesis of 6-deoxyerythronolide B. Our retrosynthetic analysis of the macrolide antibiotic involves disconnections at the lactone linkage and between C7 and C8. The two equally complex fragments were prepared via reliable aldol, hydroboration, crotylation and redox chemistry. Rather than the typical macrolactonization method to form the 14-membered ring, we propose an alternative strategy where we plan to cyclize with a metal-catalyzed ring-closing metathesis event. Currently, this step is under investigation by other members in the group.

Au cours de ce travail de nouvelles méthodes pour la formation de liaison C-N ont été développées. Dans la première partie de cette thèse une application de catalyse métal-ligand bifonctionnelle pour la réaction énantiosélective aza-Michael est démontrée. Dans la deuxième partie nous présentons le travail sur les cyclisations, en utilisant des alcaloïdes du quinquina facilement disponibles, comme catalyseurs des plus prometteurs, fournissant des β-amino-acides d’indoline avec jusqu'à 98% ee. Parmi eux, l’hydroquinidine ressort du lot comme étant le catalyseur donnant le meilleur excès énatiomérique. La troisième partie est liée à l'élaboration d'un nouveau processus intermoléculaires de diamination de styrènes, diènes et triènes, utilisant des bis-sulfonylimides comme source d'azote, en combinaison avec le diacétate de iodosobenzène, qui fournit une approche intéressante et efficace de diamines vicinales biologiquement et chimiquement important. La réaction peut être effectuée à température ambiante sans avoir besoin de protection par atmosphère inerte. / The concept of metal-ligand bifunctionality was successfully applied for an enantioselective aza-Michael reaction by employing well-defined ruthenium amido complexes. The catalyst was optimised and the corresponding chiral indoline β-amino acid derivatives were obtained with high enantioselectivities. Next, a straightforward enantioselective bifunctional organocatalytic approach was also developed. Employing hydroquinidine as catalyst the corresponding cyclic products were obtained in excellent enantioselectivities and quantitative yields. These compounds can be selectively deprotected and applied to peptide synthesis. Finally, we have developed unprecedented diamination reactions of styrenes, butadienes and hexatrienes employing easily accessible hypervalent iodine(III) reagents under robust reaction conditions. The first examples of the metal-free 1,2-diamination of butadienes were demonstrated and this oxidation methodology was further extended to the highly attractive 1,4 installation of two nitrogen atoms within a single step.

Este trabalho buscou avaliar a influência da relação C/N e da fonte de carbono no processo de nitrificação e desnitrificação simultâneas em reator de fluxo contínuo e leito fixo estruturado. Foi utilizado um reator vertical de acrílico, com volume total de 11,0 L e volume útil de 5,5 L, com hastes cilíndricas verticais de espuma de poliuretano como suporte para a biomassa. O sistema foi operado com TDH de 11,2±0,6 horas, aeração intermitente (2 horas com aeração e 1 hora sem aeração) e razão de recirculação de efluente igual a 5. A carga carbonácea afluente foi mantida constante (1,07 kg DQO.m-3.dia-1), ao longo de todo o período experimental, sendo as relações C/N testadas (9,7±1; 7,6±1; 2,9±1 e 2,9±0,4) obtidas a partir da variação na carga nitrogenada aplicada. Duas fontes orgânicas foram avaliadas: sacarose e peptona de carne. A eficiência média de remoção de DQO manteve-se acima de 90%. A eficiência máxima de remoção de N-total (84,6±10,1%) foi obtida para relação C/N de 2,9±1, com concentrações efluentes médias de NTK e N-NH4 de 5,9 e 4,3 mg.L-1, respectivamente. A análise estatística da eficiência de remoção de N-total confirmou que a fonte de carbono não exerceu influência sobre os processos de remoção. A obtenção de eficiências de desnitrificação superiores às calculadas estequiometricamente, em função da fonte de carbono, indicou a ocorrência de possíveis vias complementares para remoção de nitrogênio, como o processo anammox. As velocidades de nitrificação e desnitrificação obtidas nos ensaios cinéticos foram similares para as duas fontes de carbono e para as relações C/N estudadas e da mesma ordem de grandeza das apresentadas na literatura, reforçando a ideia de que a configuração de reator utilizada, aliada às adequadas condições operacionais, permitiu a remoção concomitante de matéria carbonácea e nitrogenada. / This study aimed to evaluate the influence of COD/N ratio and organic source on the simultaneous nitrification and denitrification (SND) in an up-flow structured-bed reactor. The reactor was made of acrylic with a total volume of 11 L and a working volume of 5.5 L and filled with cylinders of polyurethane foam as support for biomass growth. The system was continuously operated with an HRT of 11.2±0.6 h, intermittent aeration (2h with aeration and 1h without aerationd) and a liquid recycle ratio equal to 5. The organic load rate was constant (1.07 kg COD.m-3d-1) during the entire experiment. The COD/N ratios (9.7±1; 7.6±1; 2.9±1 and 2.9±0,4) were obtained from the variation of nitrogen load rate. Two organic sources were evaluated: sucrose and meat peptone. The average COD removal efficiency was above 90%. The maximum total nitrogen removal efficiency was 84.6±10.1%, with average TKN and NH4+-N effluent concentrations of 5.9 and 4.3 mg.L-1, respectively. Statistical analysis of total nitrogen removal efficiency confirmed that the carbon source did not influence over the removal processes. The denitrification efficiencies higher than the stoichiometrically calculated in function of the carbon source, indicated the occurrence of possible paths for nitrogen removal of nitrogen as anammox process. The nitrification and denitrification rates obtained in kinetic experiments were similar for the two sources of carbon and all C/N ratio studied at the same order of magnitude in relation to those reported in the literature, enhancing that the reactor configuration tested combined with the proper operational conditions allowed the organic matter and nitrogen removal simultaneously.

Este trabalho buscou verificar a viabilidade do uso de fermentado de glicerol como fonte externa de carbono para a remoção biológica de nutrientes em um reator de leito estruturado, submetido à aeração intermitente (LEAI). O LEAI foi alimentado com efluente de reator UASB de bancada, usado no tratamento de esgoto sanitário. O reator LEAI possuía volume total de 12,3L e, devido às hastes cilíndricas verticais de espuma de poliuretano usadas como suporte para a biomassa, o volume útil foi de 8,6 L. Inicialmente, o reator foi operado sob aeração contínua com tempo de detenção hidráulica (TDH) de 24 horas e razão de recirculação de efluente igual a 3 para desenvolvimento de biomassa nitrificante no reator. Após a eficiência de nitrificação atingir 80%, o reator passou a ser operado com TDH de 12 horas e sob aeração intermitente, mantendo-se a razão de recirculação igual a 3. Foram então realizadas 4 fases em modo contínuo sob aeração intermitente (tempo de aeração/tempo sem aeração) de 2h/1h sem glicerol, 3h/1h sem glicerol, 2h/1h com glicerol, 3h/1h com glicerol. A adição de glicerol fermentado ocorreu somente durante os períodos não aerados. Em todas as fases, a DQO média efluente ao sistema variou entre 26±8 e 59±14 mg.L-1. Em relação à remoção de nitrogênio total (como NTK), verificou-se a baixa eficiência de remoção nas fases em que não houve a adição do fermentado, atingindo 49,6±13,5% (2h/1h) e 29,2±10,1% (3h/1h). Entretanto, nas fases em que houve a inserção do glicerol, as eficiências de remoção de N-total foram superiores, obtendo-se 64,9±21,6% (2h/1h) e 69,5±11,7% (3h/1h). Não foi observada remoção de fósforo em nenhuma das fases em que o reator foi operado com alimentação contínua. A fim de verificar a eficácia do fermentado de glicerol na remoção de N e P, o sistema foi modificado para que o reator LEAI operasse em bateladas sequenciais (RSB). Nessa etapa da pesquisa, observou-se o estabelecimento da comunidade acumuladora de fósforo no sistema, obtendo-se eficiência de remoção de fósforo de 56,1±8,5%. A eficiência de remoção de nitrogênio total também aumentou, atingindo 86,2±6,2%. Concluiu-se que o fermentado do glicerol apresenta potencial significativo para uso como fonte exógena de carbono no processo de remoção de fósforo e N-total. Concluiu-se também que, embora o glicerol fermentado contenha compostos favoráveis à remoção de fósforo em reatores de leito estruturado, a alimentação contínua do reator com aeração intermitente, não promove as condições ideais para o estabelecimento de processo estável de remoção de fósforo. No entanto, a elevada eficiência de oxidação de NTK, de remoção de matéria orgânica e de desnitrificação, aliadas à baixa produção sólida, mostram que o LEAI é uma alternativa interessante em comparação às tecnologias praticadas atualmente para pós-tratamento de efluentes de reatores anaeróbios. Contudo, quando a remoção de fósforo é necessária, a operação do reator em bateladas sequenciais é a alternativa viável. / This work aimed to verify the viability of the use of fermented glycerol as an external carbon source for the nutrient biological removal in structured-bed reactor subjected to recirculation and intermittent aeration (SBRRIA). The SBRRIA was fed effluent from UASB reactor bench scale, used in the treatment of domestic sewage. The SBTTIA reactor had a total volume of 12.3L and, due to the vertical cylindrical strips of polyurethane foam used as biomass support, the useful volume was 8.6 L. Initially, the reactor was operated under continuous aeration with hydraulic retention time (HRT) of 24 hours and effluent recirculation ratio of 3 for the development of nitrifying biomass in the reactor. After the nitrification efficiency reach 80%, the reactor started to be operated at the HRT of 12 h under intermittent aeration, maintaining the recirculation ratio equal to 3. Four phases were then carried out continuously under intermittent aeration (aeration / time without aeration) of 2h/1h without glycerol, 3h/1h without glycerol, 2h/1h with glycerol, 3h/1h with glycerol. The addition of fermented glycerol occurred only during time without aeration. In all phases, the average COD effluent of the system ranged between 26±8 and 59±14 mg.L-1. Low removal efficiency of total nitrogen (as TKN) was verified in the phases without addition of the fermented glycerol, reaching 49.6±13.5% (2h/1h) and 29.2±10.1% (3h/1h). However, the efficiency of total nitrogen removal efficiency was higher when fermented glycerol was added during the non-aerated period, attaining 64.9±21.6% (2h/1h) and 69.5±11.7% (3h/1h). No phosphorus removal was observed in any of the previous phases in which the reactor was operated under continuous feeding. In order to verify the feasibility of fermented glycerol in the removal of N and P, the system was modified so that the LEAI reactor operated in sequential batch mode (SRB). At this stage of the research, the establishment of the phosphorus accumulating community in the system was observed and phosphorus removal efficiency attained 56.1±8.5%. The efficiency of total nitrogen removal also increased up to 86.2±6.2%. It was concluded that the fermented glycerol presents significant potential for use as an exogenous carbon source in the process of phosphorus and nitrogen removal. It can be also concluded that fixed bed reactors can remove phosphorus from wastewaters using fermented glycerol presenting compounds favorable to the development of phosphorus accumulating microorganisms (PAO). However, reactors subjected to continuous feeding and intermittent aeration do not promote good conditions for the establishment of stable phosphorus removal process. Nevertheless, the high efficiency of TKN oxidation, organic matter removal and denitrification, coupled with low solid production, show that SBRRIA is an interesting alternative for the post-treatment of anaerobic reactor effluents. However, when phosphorus removal is required, sequential batch reactor operation is the viable alternative.