Catalytic decomposition of formic acid using supported metal nanoparticles

Upgrade of hydrogen to valuable fuel is a central topic in modern research due to its high availability and low price. For the difficulties in hydrogen storage, different pathways are still under investigation. A promising way is in the liquid-phase chemical hydrogen storage materials, because they can lead to greener transformation processes with the on line development of hydrogen for fuel cells. The aim of my work was the optimization of catalysts for the decomposition of formic acid made by sol immobilisation method (a typical colloidal method). Formic acid was selected because of the following features: it is a versatile renewable reagent for green synthesis studies. The first aim of my research was the synthesis and optimisation of Pd nanoparticles by sol-immobilisation to achieve better catalytic performances and investigate the effect of particle size, oxidation state, role of stabiliser and nature of the support. Palladium was chosen because it is a well-known active metal for the catalytic decomposition of formic acid. Noble metal nanoparticles of palladium were immobilized on carbon charcoal and on titania. In the second part the catalytic performance of the “homemade” catalyst Pd/C to a commercial Pd/C and the effect of different monometallic and bimetallic systems (AuxPdy) in the catalytic formic acid decomposition was investigated. The training period for the production of this work was carried out at the University of Cardiff (Group of Dr. N. Dimitratos).

A bio-coke for anode production and the manufacturing method thereof

Dans l’industrie de l’aluminium, le coke de pétrole calciné est considéré comme étant le composant principal de l’anode. Une diminution dans la qualité du coke de pétrole a été observée suite à une augmentation de sa concentration en impuretés. Cela est très important pour les alumineries car ces impuretés, en plus d’avoir un effet réducteur sur la performance des anodes, contaminent le métal produit. Le coke de pétrole est aussi une source de carbone fossile et, durant sa consommation, lors du processus d’électrolyse, il y a production de CO2. Ce dernier est considéré comme un gaz à effet de serre et il est bien connu pour son rôle dans le réchauffement planétaire et aussi dans les changements climatiques. Le charbon de bois est disponible et est produit mondialement en grande quantité. Il pourrait être une alternative attrayante pour le coke de pétrole dans la fabrication des anodes de carbone utilisées dans les cuves d’électrolyse pour la production de l’aluminium. Toutefois, puisqu’il ne répond pas aux critères de fabrication des anodes, son utilisation représente donc un grand défi. En effet, ses principaux désavantages connus sont sa grande porosité, sa structure désordonnée et son haut taux de minéraux. De plus, sa densité et sa conductivité électrique ont été rapportées comme étant inférieures à celles du coke de pétrole. L’objectif de ce travail est d’explorer l’effet du traitement de chaleur sur les propriétés du charbon de bois et cela, dans le but de trouver celles qui s’approchent le plus des spécifications requises pour la production des anodes. L’évolution de la structure du charbon de bois calciné à haute température a été suivie à l’aide de différentes techniques. La réduction de son contenu en minéraux a été obtenue suite à des traitements avec de l’acide chlorhydrique utilisé à différentes concentrations. Finalement, différentes combinaisons de ces deux traitements, calcination et lixiviation, ont été essayées dans le but de trouver les meilleures conditions de traitement.

Socio-economic aspects of the fisheries of Nabugabo lakes and implications for management

Fisheries are very important to Uganda's economy. The sector provides a vital source of food, recreation, trade and socioeconomic well being for the people and community globally. The fisheries of small lakes are important for producing fish for local populations who are not near the large lakes. These satellite lakes support important fisheries and other economic activities like fishing, water for domestic purposes and tourism, besides socio-cultural values. A number-of fish;- species, some of which were found only in Lake Victoria have been depleted through over-exploitation, introduction of exotics especiaily Nile perch and environmental degradation. Some of these fishes have been observed to survive in satellite lakes in the Victoria and Kyoga Lake basins. The Nabugabo satellite lakes (Manywa, Kayugi and Kayanja) contain endemic Cichlid fish species acting as reservoirs and therefore very important for conservation of fish biodiversity. Despite the socio-economic importance and uniqueness of these satellite lakes little research on socio-economic studies has been carried out. The sustainability of the lake is being threatened by increasing human activities. The fish stocks and species diversity are declining and this poses a threat to the livelihood of the people who depend on fish for food and income. Arising from this need a study was carried out to establish the socio-economic aspects of Nabugabo fisheries and implications for management, on which basis resource users would be made aware of the impacts of their activities. It was hoped that this would go further to ensure wise use and management of the resources by the users. The specific objectives were identifying activities around the lake, establishing socioeconomic values attached to the lake, identifying problems of the lake and resource users and examining existing local based management institutions. Results show that the activities taking place around the lakes include fishing, farming, watering of animals, deforestation and charcoal burning, brick making, resort beach development and food and refreshment. The major problem facing the lake was found to be encroachment of Hippo grass (Vossia) on the lake, which is decreasing the size of the lake, and limiting open waters for fishing (this only applied to Lake Nabugabo). Other important problems include use of illegal fishing methods, declining fish stocks and loss of cultural identity. The resource users are most pressed by the low incomes resulting from poor fish catches, theft of gears and lack of market. On examining the resource base for the lakes, it was only Lake Nabugabo that had a Landing Management Committee. The other three lakes did not have leadership institutions in place except the local councils for the respective villages. This was probably due to observed limited fisheries activities. Majority of the respondents agreed that Government and other service providers should work jointly to supplement local beach management committees in the management of the lakes resources. This is a good gesture because with increase in fishing effort and rampant use of illegal fishing methods, there is need to strengthen management institutions present on the lake. This would require Government, local community and other service providers to work together in a participatory way to control environment-degrading activities and stop the use of illegal fishing methods. Burning of vegetation on the lake should be stopped since it enhances growth of this grass. Finally, traditional taboos; which are present on some of the Nabugabo lakes, should be enhanced, as away of preserving them.

Revisão do plano de segurança da água do sistema regional do Carvoeiro

Os Planos de Segurança da Água surgem com a necessidade de aumentar a segurança da água de abastecimento, superando a monitorização de conformidade de “fim de linha”, permitindo aumentar a confiança do consumidor na qualidade da água que lhe é fornecida. Esta nova abordagem recorre a uma metodologia de gestão baseada na identificação e no controlo de riscos em pontos críticos de um sistema de abastecimento, em complemento do controlo realizado através da monitorização da conformidade da água entregue aos consumidores. O Plano de Segurança da Água (PSA) encontra-se implementado no Sistema Regional do Carvoeiro (SRC) desde o ano de 2009. O SRC é um sistema de abastecimento de água em alta, sendo constituído por conjunto de infraestruturas de captação, tratamento, transporte e armazenamento de água desde a sua origem, localizada no rio Vouga, em Carvoeiro, até aos municípios integrados na Associação de Municípios do Carvoeiro-Vouga. Atendendo à obra de expansão do SRC, tornou-se imperativo efetuar uma revisão ao PSA, sendo este o objetivo primordial do trabalho de estágio desenvolvido na empresa Águas do Vouga S.A, concessionária responsável pela gestão do SRC. Para a prossecução deste objetivo, o trabalho desenvolvido envolveu os seguintes passos metodológicos: identificação das operações aplicadas no SRC; identificação de perigos e eventos perigosos em todos os órgãos constituintes do sistema; avaliação de riscos; identificação de pontos críticos de controlo; identificação de pontos de monitorização e medidas preventivas; elaboração do plano de monitorização, incluindo, procedimentos de controlo operacional em condições normais de funcionamento e em caso de desvio; validação deste plano. Deste trabalho resultou a identificação de 166 eventos perigosos, 17 tipologias de perigos, 3 pontos de controlo crítico e 17 pontos de monitorização. Os pontos de controlo crítico foram identificados nos processos de tratamento da ETA do Carvoeiro. O primeiro foi localizado na etapa de filtração com areia, antracite e zeólitos correspondendo aos perigos com metais (Fe e Mn), outros compostos químicos perigosos, partículas, turvação, matéria orgânica e alumínio. O segundo ponto foi identificado na etapa de filtração com filtros de carvão ativado granular relativo ao aparecimento de sabor e cianotoxinas. O terceiro ponto de controlo crítico foi encontrado na etapa de desinfeção referente aos microrganismos patogénicos. Os pontos de monitorização foram localizados ao longo do sistema em situações onde não se dispõem de nenhuma medida de controlo para eliminar o perigo e antes e após os pontos de controlo crítico. O plano de monitorização foi desenvolvido para estes pontos, embora os limites e procedimentos definidos devam ser alvo de revisão após a conclusão da obra de expansão do sistema. A validação da revisão do plano foi iniciada, mas cingiu-se apenas na avaliação preliminar de riscos, prévia ao início de operação da ETA do Carvoeiro. Para além da revisão deste plano, foram realizadas outras tarefas, nomeadamente uma análise à qualidade da água fornecida e distribuída pelo sistema, a elaboração do plano PCQA para o ano de 2016, a configuração da plataforma de gestão operacional NAVIATM e a revisão do Manual de Gestão da Águas do Vouga relativo ao processo de qualidade na captação, tratamento e distribuição e ao processo de qualidade na gestão do PSA.

Conversion of sub-tropical native vegetation to introduced conifer forest: Impacts on below-ground and above-ground carbon pools

Land-use change can have a major influence on soil organic carbon (SOC) and above-ground C pools. We assessed a change from native vegetation to introduced Pinus species plantations on C pools using eight paired sites. At each site we determined the impacts on 0–50 cm below-ground (SOC, charcoal C, organic matter C, particulate organic C, humic organic C, resistant organic C) and above-ground (litter, coarse woody debris, standing trees and woody understorey plants) C pools. In an analysis across the different study sites there was no significant difference (P > 0.05) in SOC or above-ground tree C stocks between paired native vegetation and pine plantations, although significant differences did exist at specific sites. SOC (calculated based on an equivalent soil mass basis) was higher in the pine plantations at two sites, higher in the native vegetation at two sites and did not differ for the other four sites. The site to site variation in SOC across the landscape was far greater than the variation observed with a change from native vegetation to introduced Pinus plantation. Differences between sites were not explained by soil type, although tree basal area was positively correlated with 0–50 cm SOC. In fact, in the native vegetation there was a significant linear relationship between above-ground biomass and SOC that explained 88.8% of the variation in the data. Fine litter C (0–25 mm diameter) tended to be higher in the pine forest than in the adjacent native vegetation and was significantly higher in the pine forest at five of the eight paired sites. Total litter C (0–100 mm diameter) increased significantly with plantation age (R2 = 0.64). Carbon stored in understorey woody plants (2.5–10 cm DBH) was higher in the native vegetation than in the adjacent pine forest. Total site C varied greatly across the study area from 58.8 Mg ha−1 at a native heathland site to 497.8 Mg ha−1 at a native eucalypt forest site. Our findings suggest that the effects of change from native vegetation to introduced Pinus sp. forest are highly site-specific and may be positive, negative, or have no influence on various C pools, depending on local site characteristics (e.g. plantation age and type of native vegetation).

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Environmental Dynamics of Dissolved Black Carbon in Aquatic Ecosystems

Black carbon (BC), the incomplete combustion product from biomass and fossil fuel burning, is ubiquitously found in soils, sediments, ice, water and atmosphere. Because of its polyaromatic molecular characteristic, BC is believed to contribute significantly to the global carbon budget as a slow-cycling, refractory carbon pool. However, the mass balance between global BC generation and accumulation does not match, suggesting a removal mechanism of BC to the active carbon pool, most probable in a dissolved form. The presence of BC in waters as part of the dissolved organic matter (DOM) pool was recently confirmed via ultrahigh resolution mass spectrometry, and dissolved black carbon (DBC), a degradation product of charcoal, was found in marine and coastal environments. However, information on the loadings of DBC in freshwater environments and its global riverine flux from terrestrial systems to the oceans remained unclear. The main objectives of this study were to quantify DBC in diverse aquatic ecosystems and to determine its environmental dynamics. Surface water samples were collected from aquatic environments with a spatially significant global distribution, and DBC concentrations were determined by a chemical oxidation method coupled with HPLC detection. While it was clear that biomass burning was the main sources of BC, the translocation mechanism of BC to the dissolved phase was not well understood. Data from the regional studies and the developed global model revealed a strong positive correlation between DBC and dissolved organic carbon (DOC) dynamics, indicating a co-generation and co-translocation between soil OC and BC. In addition, a DOC-assistant DBC translocation mechanism was identified. Taking advantage of the DOC-DBC correlation model, a global riverine DBC flux to oceans on the order of 26.5 Mt C yr-1 (1 Mt = 1012 g) was determined, accounting for 10.6% of the global DOC flux. The results not only indicated that DOC was an important environmental intermediate for BC transfer and storage, but also provided an estimate of a major missing link in the global BC budget. The ever increasing DBC export caused by global warming will change the marine DOM quality and may have important consequences for carbon cycling in marine ecosystem.

A Study of the Microwave Carbothermic Reduction of Chromite Ore

Microwave reduction testing using activated charcoal as a reducing agent was performed on a sample of Black Thor chromite ore from the Ring of Fire deposit in Northern Ontario. First, a thermodynamic model was constructed for the system. Activity coefficients for several species were found in the literature. The model predicted chromium grades of 61.60% and recoveries of 93.43% for a 15% carbon addition. Next, reduction testing on the chromite ore was performed. Tests were performed at increasing power levels and reduction times. Testing atmospheres used were air, argon, and vacuum. The reduced product had maximum grades of 72.89% and recoveries of 80.37%. These maximum values were obtained in the same test where an argon atmosphere was used, with a carbon addition of 15%, optimal power level of 1200 W (actual 1171 W), and a time of 400 seconds. During this test, 17.53% of the initial mass was lost as gas, a carbon grade of 1.95% was found for the sintered core product. Additional work is recommended to try and purify the sintered core product as well as reduce more of the initial sample. Changing reagent schemes or a two step reduction / separation process could be implemented.

Experimental and modeling studies of forced convection storage and drying systems for sweet potatoes

Sweet potato is an important strategic agricultural crop grown in many countries around the world. The roots and aerial vine components of the crop are used for both human consumption and, to some extent as a cheap source of animal feed. In spite of its economic value and growing contribution to health and nutrition, harvested sweet potato roots and aerial vine components has limited shelf-life and is easily susceptible to post-harvest losses. Although post-harvest losses of both sweet potato roots and aerial vine components is significant, there is no information available that will support the design and development of appropriate storage and preservation systems. In this context, the present study was initiated to improve scientific knowledge about sweet potato post-harvest handling. Additionally, the study also seeks to develop a PV ventilated mud storehouse for storage of sweet potato roots under tropical conditions. In study one, airflow resistance of sweet potato aerial vine components was investigated. The influence of different operating parameters such as airflow rate, moisture content and bulk depth at different levels on airflow resistance was analyzed. All the operating parameters were observed to have significant (P < 0.01) effect on airflow resistance. Prediction models were developed and were found to adequately describe the experimental pressure drop data. In study two, the resistance of airflow through unwashed and clean sweet potato roots was investigated. The effect of sweet potato roots shape factor, surface roughness, orientation to airflow, and presence of soil fraction on airflow resistance was also assessed. The pressure drop through unwashed and clean sweet potato roots was observed to increase with higher airflow, bed depth, root grade composition, and presence of soil fraction. The physical properties of the roots were incorporated into a modified Ergun model and compared with a modified Shedd’s model. The modified Ergun model provided the best fit to the experimental data when compared with the modified Shedd’s model. In study three, the effect of sweet potato root size (medium and large), different air velocity and temperature on the cooling/or heating rate and time of individual sweet potato roots were investigated. Also, a simulation model which is based on the fundamental solution of the transient equations was proposed for estimating the cooling and heating time at the centre of sweet potato roots. The results showed that increasing air velocity during cooling and heating significantly (P < 0.05) affects the cooling and heating times. Furthermore, the cooling and heating times were significantly different (P < 0.05) among medium and large size sweet potato roots. Comparison of the simulation results with experimental data confirmed that the transient simulation model can be used to accurately estimate the cooling and heating times of whole sweet potato roots under forced convection conditions. In study four, the performance of charcoal evaporative cooling pad configurations for integration into sweet potato roots storage systems was investigated. The experiments were carried out at different levels of air velocity, water flow rates, and three pad configurations: single layer pad (SLP), double layers pad (DLP) and triple layers pad (TLP) made out of small and large size charcoal particles. The results showed that higher air velocity has tremendous effect on pressure drop. Increasing the water flow rate above the range tested had no practical benefits in terms of cooling. It was observed that DLP and TLD configurations with larger wet surface area for both types of pads provided high cooling efficiencies. In study five, CFD technique in the ANSYS Fluent software was used to simulate airflow distribution in a low-cost mud storehouse. By theoretically investigating different geometries of air inlet, plenum chamber, and outlet as well as its placement using ANSYS Fluent software, an acceptable geometry with uniform air distribution was selected and constructed. Experimental measurements validated the selected design. In study six, the performance of the developed PV ventilated system was investigated. Field measurements showed satisfactory results of the directly coupled PV ventilated system. Furthermore, the option of integrating a low-cost evaporative cooling system into the mud storage structure was also investigated. The results showed a reduction of ambient temperature inside the mud storehouse while relative humidity was enhanced. The ability of the developed storage system to provide and maintain airflow, temperature and relative humidity which are the key parameters for shelf-life extension of sweet potato roots highlight its ability to reduce post-harvest losses at the farmer level, particularly under tropical climate conditions.

Red de Conocimientos Campesinos: hilos de saberes, experiencias y tensiones en Zona Bananera

El conocimiento campesino se ha pensado como un cúmulo de saberes y prácticas tradicionales que las personas que trabajan la tierra han aprendido y transmitido de generación en generación. Pero para el análisis de las relaciones que construyen los campesinos con la tierra, el agua, las semillas, los cultivos, los químicos, las herramientas de trabajo y el dinero, es importante considerar el conocimiento campesino como una red de aprendizajes, saberes, experiencias, prácticas y relaciones territoriales. Aquella red se teje desde múltiples actores tales como funcionarios de instituciones estatales y bancarias, empresarios, familiares, vecinos y amigos, quienes inciden, influyen e intervienen en los recursos que manejan los campesinos. Esta tesis aborda la construcción, reconstrucción y materialización del conocimiento sobre el trabajo en la tierra que han configurado campesinos agricultores en el municipio de Zona Bananera, Magdalena. En las parcelas que poseen dichas personas, han confluido diferentes controles sobre el uso de recursos por parte de empresas bananeras y extractoras de aceite, trabajadores del Instituto Colombiano para la Reforma Agraria INCORA, gobiernos locales y docentes de educación superior. Allí, los campesinos por medio de su conocimiento han apropiado, negociado, disputado y resistido saberes que regulan, restringen y direccionan el manejo de recursos en sus tierras.

Tracing acidification induced by Deccan Phase 2 volcanism

The Deccan Volcanic Province (DVP) was built up by three major phases of eruptions; the most voluminous of which, the Deccan Phase 2, encompassed the Cretaceous–Palaeogene (KT) boundary. Deccan eruptions have been implicated as a contributor to the end-Cretaceous mass extinction, however, mechanism by which volcanic activity affected biota remains poorly understood. We applied a combination of rock magnetic techniques scanning electron microscopy to characterize mineral assemblages of three sections of intertrappean lacustrine sediments from the north-western Maharashtra Deccan Volcanic Provinces. Our results indicate that in sediments deposited during the early stages of the Deccan Phase 2, the Daïwal River and Dhapewada sequences, iron-bearing mineral association is dominated by detrital iron oxides (magnetite and hematite) sourced from the weathering of the surrounding basaltic bedrocks, with minor contribution form authigenic iron sulphides (framboidal pyrite, pyrrhotite and/or greigite). The sediments deposited during the final stages of Phase 2 (the Podgawan sequence) differ significantly in their characteristics. In particular, the Podgawan sediments have 1) very low magnetic susceptibility values, but higher terrigenous fraction (clays and shales) content; 2) more complex assemblage of magnetic minerals, 3) ubiquitous presence of Fe–Ca–Ce vanadates; and 4) unusual lithological variations in the middle part of the section (represented by a charcoal-rich level that is capped by a red clay layer containing fossilized bacterial colonies). We suggest that these unusual characteristics reflect increased acidity in the region during the deposition of the Podgawan sequence, likely due to cumulative effects of volcanic aerosols released during the Deccan Phase 2 eruptions. The combination of these features may be used to recognize episodes of increased acidity in the geological record. Our results also contribute to understanding of local vs. global effects of the Deccan volcanism.

Atrazine sorption in soil treated with biochar.

Biochar has been used worldwide as soil amendment. Due to the high sorption capacity of organic compounds by charcoal in general, the use of biochar can change the soil sorptive properties, that could result in a environmental protective strategy in one hand and/or in need of higher pesticides doses in another hand. However no data in the literature is available about the long term effect of biochar application in the sorptive properties of the soil, even studies about the sorptive properties of soil treated with biochar are scarce, the few available papers are with pure biochar. This unprecedented work, evaluating the sorption of atrazine in a clayed soil treated with biochar, under experimental field conditions, evaluated the sorption isotherms one and three years after the single biochar application (16 Mg ha-1 of biochar). One year after the biochar application the Kf was two times higher for the biochar amended soil than for the control one (without biochar). This effect decreases after three years from the application, but it is even significantly higher (50% higher) than the control treatment.