Efeito do teor em Y2O3 nos catalisadores suportados de 8%Ni/α-Al2O3 durante a reação de oxidação parcial do Metano para produção de Hidrogénio

Neste trabalho avaliou-se o desempenho de cinco catalisadores de Níquel suportados em α-Alumina, com diferentes teores em Ítria, durante a reação de Oxidação Parcial do Metano para a produção de Hidrogénio: 8%Ni/α-Al2O3, 8%Ni/2%Y2O3.α-Al2O3, 8%Ni/2,5%Y2O3.α-Al2O3, 8%Ni/5%Y2O3.α-Al2O3 e 8%Ni/Y2O3. Foram realizados testes catalíticos numa Unidade de Reação acoplada a um equipamento de análise, microGC. A reação decorreu à temperatura de 800 °C, num reator laboratorial de quartzo, durante 18 horas, com uma mistura pura de CH4 e O2 (Condição Concentrada). Os resultados demonstraram um aumento de atividade para os catalisadores de suporte misto com maior teor em Y2O3. Usando o mesmo procedimento, a reação de OPM foi realizada também para outra mistura reacional de CH4 e O2, mas agora diluída em Hélio (Condição Diluída). Estes resultados permitiram avaliar a velocidade de reação e a atividade dos catalisadores (TOF), para diferentes valores de temperatura, numa situação inicial de ausência de coque. Numa segunda etapa, avaliou-se o desempenho dos mesmos materiais durante 2 horas de reação à temperatura constante de 800 ℃. Finalmente, através da técnica de caraterização de XPS, identificaram-se as espécies presentes na superfície dos catalisadores. Os resultados sugerem que há formação de um composto intermediário NiYO3 formado entre o metal e o promotor Y2O3, conferindo atividade e estabilidade aos catalisadores e reduzindo a deposição de coque. O catalisador com maior teor em Y2O3 (8%Ni/5%Y2O3.α-Al2O3) foi o mais beneficiado com a adição do promotor, demonstrando melhor desempenho para a produção de H2 na Reação de Oxidação Parcial do Metano.

Modeling and optimization of extracellular polysaccharides production by Enterobacter A47

Polysaccharides are gaining increasing attention as potential environmental friendly and sustainable building blocks in many fields of the (bio)chemical industry. The microbial production of polysaccharides is envisioned as a promising path, since higher biomass growth rates are possible and therefore higher productivities may be achieved compared to vegetable or animal polysaccharides sources. This Ph.D. thesis focuses on the modeling and optimization of a particular microbial polysaccharide, namely the production of extracellular polysaccharides (EPS) by the bacterial strain Enterobacter A47. Enterobacter A47 was found to be a metabolically versatile organism in terms of its adaptability to complex media, notably capable of achieving high growth rates in media containing glycerol byproduct from the biodiesel industry. However, the industrial implementation of this production process is still hampered due to a largely unoptimized process. Kinetic rates from the bioreactor operation are heavily dependent on operational parameters such as temperature, pH, stirring and aeration rate. The increase of culture broth viscosity is a common feature of this culture and has a major impact on the overall performance. This fact complicates the mathematical modeling of the process, limiting the possibility to understand, control and optimize productivity. In order to tackle this difficulty, data-driven mathematical methodologies such as Artificial Neural Networks can be employed to incorporate additional process data to complement the known mathematical description of the fermentation kinetics. In this Ph.D. thesis, we have adopted such an hybrid modeling framework that enabled the incorporation of temperature, pH and viscosity effects on the fermentation kinetics in order to improve the dynamical modeling and optimization of the process. A model-based optimization method was implemented that enabled to design bioreactor optimal control strategies in the sense of EPS productivity maximization. It is also critical to understand EPS synthesis at the level of the bacterial metabolism, since the production of EPS is a tightly regulated process. Methods of pathway analysis provide a means to unravel the fundamental pathways and their controls in bioprocesses. In the present Ph.D. thesis, a novel methodology called Principal Elementary Mode Analysis (PEMA) was developed and implemented that enabled to identify which cellular fluxes are activated under different conditions of temperature and pH. It is shown that differences in these two parameters affect the chemical composition of EPS, hence they are critical for the regulation of the product synthesis. In future studies, the knowledge provided by PEMA could foster the development of metabolically meaningful control strategies that target the EPS sugar content and oder product quality parameters.

Cell functional enviromics: applications to Pichia pastoris

The present PhD thesis develops the cell functional enviromics (CFE) method to investigate the relationship between environment and cellular physiology. CFE may be defined as the envirome-wide cellular function reconstruction through the collection and systems-level analysis of dynamic envirome data. Throughout the thesis, CFE is illustrated by two main applications to cultures of a constitutive P. pastoris X33 strain expressing a scFv antibody fragment. The first application addresses the challenge of culture media development. A dataset was built from 26 shake flask experiments, with variations in trace elements concentrations and basal medium dilution based on the standard BSM+PTM1. Protein yield showed high sensitivity to culture medium variations, while biomass was essentially determined by BSM dilution. High scFv yield was associated with high overall metabolic fluxes through central carbon pathways concomitantly with a relative shift of carbon flux from biosynthetic towards energy-generating pathways. CFE identified three cellular functions (growth, energy generation and by-product formation) that together described 98.8% of the variance in observed fluxes. Analyses of how medium factors relate to identified cellular functions showed iron and manganese at concentrations close to PTM1 inhibit overall metabolic activity. The second application addresses bioreactor operation. Pilot 50 L fed-batch cultivations, followed by 1H-NMR exometabolite profiling, allowed the acquisition of data for 21 environmental factors over time. CFE identified five major metabolic pathway groups that are frequently activated by the environment. The resulting functional enviromics map may serve as template for future optimization of media composition and feeding strategies for Pichia pastoris. The present PhD thesis is a step forward towards establishing the foundations of CFE that is still at its infancy. The methods developed herein are a contribution for changing the culture media and process development paradigm towards a holistic and systematic discipline in the future.

Observations of air composition in Brazil between the Equator and 20°s during the dry season.

Field measurement programs in Brazil during the dry season months of August and September in 1979 and 1980 have demonstrated the great importance of the continental tropics in global air chemistry. Especially in the mixed layer, the air composition over land is much different from that over the ocean and the land areas are clearly longe scale sources of many inportant trace gases. During the dry season much biomass, burning takes place especially in the cerrado regions leading to substantial emission of air pollutants, such as CO, NOx, N2O, CH4 and other hydrocarbons. Ozone concentrations are alsoenhanced due to photochemical reactions. Biogenic organic emissions from tropical forests play likewise an important role in the photochemistry of the atmosphere. Carbon monoxide was found to be present in high concentrations in the boundary layer of the tropical forest, but ozone concentrations were much lower than in the cerrado.

A hidroquímica do Rio Solimões - Amazonas

Neste trabalho apresentamos os resultados dos estudos físicos-químicos do rio Solimões-Amazonas, em onze (11) locais e em trinta e um (31) afluentes e subafluentes, desde a fronteira do Brasil-Peru-Colômbia, em Tabatinga, até a amostragem, de frente a cidade de Santarém, no Estado do Pará, com uma distância de 2457 km. Os afluentes e subafluentes do rio Solimões-Amazonas ficam reduzidos a pequenos córregos nos seus altos cursos; apenas os rios Juruá, Purus, Negro e Madeira em alguns locais ficam com uma lâmina d'água de dois (2) metros, na região navegável, isto dependendo da estiagem. Todos os rios de água barrenta formam várzeas, que são ricas em nutrientes minerais, várzeas essas que possuem em toda a sua extensão lagos, paranás, igapós, forma-se grande abundância de capim flutuante que, em parte entre em decomposição, produzindo gases tóxicos, como H2S, CH4, CO2, etc. Os lagos e a várzea funcionam como se fossem uma esponja do rio, absolvendo sedimentos suspensos, nutrientes minerais e orgânicos, e liberando uma parte, no período de esvaziamento (seca). Os rios de água preta não formam várzeas e sim praias, e igapós no período da cheia, por possuírem pouco sedimentos; a cor escura é devida a substancias coloridas, como material húmico, que limitam a produção de fitoplancton. Os rios de água clara, também não formam várzeas e sim praias com poucos igapós; eles apresentam uma coloração verde azulada dada a grande formações de algas do tipo Cyanophyta. Os rios de água barrenta que apresentam maiores concentrações de sedimentos nos meses de novembro e abril tem como abastecedora a mobilização, com resuspensão, dos sedimentos, devidos ao aumento da vazão e, em parte, ao fenômeno das terras caldas. É possível que o rio Solimões-Amazonas receba suprimentos minerais e orgânicos dos rios de água barrenta, de pequenos rios que são represados na sua foz, de rios com pequenos afloramentos de calcáreo e de rios com elevados teores de substancias coloridas. As menores temperaturas no rio Solimões-Amazonas ocorrem no período de enchimento do Canal principal e as maiores no verão; quanto ao oxigênio as menores concentrações aparecem nos meses de abril a julho, são de vidas as águas oxidadas provenientes das várzeas e lagos.

A new credit monitoring framework for agents' networks

The purpose of this work is to develop a practicable approach for Telecom firms to manage the credit risk exposition to their commercial agents’ network. Particularly it will try to approach the problem of credit concession to clients’ from a corporation perspective and explore the particular scenario of agents that are part of the commercial chain of the corporation and therefore are not end-users. The agents’ network that served as a model for the presented study is composed by companies that, at the same time, are both clients and suppliers of the Telecommunication Company. In that sense the credit exposition analysis must took into consideration all financial fluxes, both inbound and outbound. The current strain on the Financial Sector in Portugal, and other peripheral European economies, combined with the high leverage situation of most companies, generates an environment prone to credit default risk. Due to these circumstances managing credit risk exposure is becoming increasingly a critical function for every company Financial Department. The approach designed in the current study combined two traditional risk monitoring tools: credit risk scoring and credit limitation policies. The objective was to design a new credit monitoring framework that is more flexible, uses both external and internal relationship history to assess risk and takes into consideration commercial objectives inside the agents’ network. Although not explored at length, the blueprint of a Credit Governance model was created for implementing the new credit monitoring framework inside the telecom firm. The Telecom Company that served as a model for the present work decided to implement the new Credit Monitoring framework after this was presented to its Executive Commission.

Incêndios na Amazônia Brasileira: estimativa da emissão de gases do efeito estufa pela queima de diferentes ecossistemas de Roraima na passagem do evento “El Nino” (1997/98)

Foi estimada a área queimada, a biomassa vegetal total acima e abaixo do solo, a formação de carvão, a eficiência de queimada e a concentração de carbono de diferentes paisagens naturais e agroecossistemas que foram atingidos pelos incêndios ocorridos durante a passagem do “El Niño” em 1997/98 no Estado de Roraima, extremo norte da Amazônia Brasileira. O objetivo foi o de calcular a emissão bruta de gases do efeito estufa liberados por combustão das diversas classes de biomassa que compõem cada tipo fitofisionômico atingido. A área total efetivamente queimada foi estimada entre 38.144-40.678 km2, sendo 11.394-13.928 km2 de florestas primárias (intactas, em pé) e, o restante, de savanas (22.583 km2), campinas / campinaranas (1.388 km2) e ambientes florestais já transformados como pastagens, área agrícolas e florestas secundárias (2.780 km2). O total de carbono afetado pelos incêndios foi de 42,558 milhões de toneladas, sendo que 19,73 milhões foram liberados por combustão, 22,33 milhões seguiram para a classe de decomposição e 0,52 milhões foram depositados nos sistemas na forma de carvão (estoque de longo prazo). A emissão bruta de gases do efeito estufa, em milhões de toneladas do gás, considerando apenas o emitido por combustão foi de 17,3 de CO2, 0,21-0,35 de CH4, 1,99-3,68 de CO, 0,001-0,003 de N,O, 0,06-0,09 de NOx e 0,25 de hidrocarbonetos não-metânicos (HCNM). O total de carbono equivalente a CO2 emitido por combustão, quando considerado o potencial de aquecimento global de cada gás em um horizonte de tempo de 100 anos utilizado pelo IPCC, foi de 6,1-7,0 milhões de toneladas.

Improvement of in silico strain engineering methods in Saccharomyces cerevisiae

PhD thesis in Bioengineering

Modelling Amazonian forest eddy covariance data: a comparison of big leaf versus sun/shade models for the C-14 tower at Manaus I. Canopy photosynthesis

In this study, we concentrate on modelling gross primary productivity using two simple approaches to simulate canopy photosynthesis: "big leaf" and "sun/shade" models. Two approaches for calibration are used: scaling up of canopy photosynthetic parameters from the leaf to the canopy level and fitting canopy biochemistry to eddy covariance fluxes. Validation of the models is achieved by using eddy covariance data from the LBA site C14. Comparing the performance of both models we conclude that numerically (in terms of goodness of fit) and qualitatively, (in terms of residual response to different environmental variables) sun/shade does a better job. Compared to the sun/shade model, the big leaf model shows a lower goodness of fit and fails to respond to variations in the diffuse fraction, also having skewed responses to temperature and VPD. The separate treatment of sun and shade leaves in combination with the separation of the incoming light into direct beam and diffuse make sun/shade a strong modelling tool that catches more of the observed variability in canopy fluxes as measured by eddy covariance. In conclusion, the sun/shade approach is a relatively simple and effective tool for modelling photosynthetic carbon uptake that could be easily included in many terrestrial carbon models.

Spatial-temporal variation of dissolved inorganic material in the Amazon basin

The Amazon River basin is important in the contribution of dissolved material to oceans (4% worldwide). The aim of this work was to study the spatial and the temporal variability of dissolved inorganic materials in the main rivers of the Amazon basin. Data from 2003 to 2011 from six gauging stations of the ORE-HYBAM localized in Solimões, Purus, Madeira and Amazon rivers were used for this study. The concentrations of Ca2+, Na+, K+, Mg2+, Cl-, SO4 -2, HCO3 - and SiO2 were analyzed. At the stations of Solimões and Amazon rivers, the concentrations of Ca2+, Mg2+, HCO3 - and SO4 -2 had heterogeneous distribution over the years and did not show seasonality. At the stations of Madeira river, the concentration of these ions had seasonality inversely proportional to water discharge (dilution-concentration effect). Similar behavior was observed for the concentrations of Cl- and Na+ at the stations of the Solimões, Amazon and Madeira rivers, indicating almost constant release of Cl- and Na+ fluxes during the hydrological cycle. K+ and SiO2 showed almost constant concentrations throughout the years and all the stations, indicating that their flows depend on the river discharge variation. Therefore, the temporal variability of the dissolved inorganic material fluxes in the Solimões and Amazon rivers depends on the hydro-climatic factor and on the heterogeneity of the sources. In the Madeira and Purus rivers there is less influence of these factors, indicating that dissolved load fluxes are mainly associated to silicates weathering. As the Solimões basin contributes approximately 84% of the total flux of dissolved materials in the basin and is mainly under the influence of a hydro-climatic factor, we conclude that the temporal variability of this factor controls the temporal variability of the dissolved material fluxes of the Amazon basin.

Algorithms and computational tools for metabolic flux analysis

PhD thesis in Biomedical Engineering

Particle transport in fouling caused by kaolin-water suspensions on copper tubes

Particulate fouling tests were carried out using kaolin-water suspensions flowing through an annular heat exchanger with a copper inner tube. The flow rate was changed from test to test, but the fluid temperature and pH, as well as the particle concentration, were maintained constant. In the lower range of fluid velocities (<0.5 m/s), the deposition process seemed to be controlled by mass transfer. The corresponding experimental transport fluxes were compared to the predictions obtained with several models, showing that diffusion governed particle transport. The absolute values of the mass transfer fluxes and their dependences on the Reynolds number were satisfactorily predicted by some of the models.

Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source

The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with 13C-labeled CH4 (13CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, 13C-labeled CO2 (13CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with 13CO2 production and no methanogenesis occurred, excluding TMO as a possible source for 13CO2 production from 13CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment.

Between specialization and globalization. The marketing of agrarian products and its environmental impacts seen from a historical perspective: the province of Barcelona in the mid-nineteenth century

Ecological economics has five good reasons to consider that economic globalisation, spurred by commercial and financial fluxes, to be one of the main driving forces responsible for causing environmental degradation to our planet. The first, is the energy consumption and the socio-environmental impacts which long-distance haulage entails. The second, is the ever-increasing flow of goods to far-away destinations which renders their recycling practically impossible. This is particularly significant, because it prevents the metabolic lock of the nutrients present in food and other agrarian products from taking place. The third, is that the high degree of specialization attained in agriculture, forestry, cattle, mining and industry in each region, generates deleterious effects not only on the eco-landscape structure of the uses of the soil, but on the capability to provide habitat and environmental functions to maintain biodiversity as well

Patterns of oxygen consumption during establishment of cephalocaudal polarity in the early chick embryo.

Oxygen uptake was studied during the establishment of cephalocaudal polarity in the very early chick embryo, i.e., 10 hr before (stage VI) and at laying (stage X). Oxygen fluxes in minute regions of the intact blastoderms were measured in vitro by scanning microspectrophotometry in the presence or absence of glucose. The oxygen consumption of the whole blastoderm remained constant (6 nmol O2 X hr-1) throughout the period studied, although the number of cells increased more than twofold. The regional oxygen fluxes varied from 0.41 to 1.13 nmol O2 X hr-1 X mm-2 at stage VI and from 0.42 to 0.70 nmol O2 X hr-1 X mm-2 at stage X. At stage VI, the oxygen flux in the center of the blastoderm was significantly higher than that in its periphery. This pattern remained evident when the values were corrected for cell number or for cytoplasmic volume. At stage X, there was a tendency for the oxygen fluxes to decrease from the posterior to the anterior regions of the area pellucida. Thus the pattern of oxidative metabolism in the late uterine embryos seems to change from radial to bilateral. This change of symmetry probably reflects the process of formation of the embryonic axis. In addition, the fact that the oxygen uptake was similar in the presence or absence of glucose suggests that early chick embryos metabolize essentially intracellular stores.