Orientador: Kleber Tomás de Resende / Co-orientadora: Marcia H. M. R. Fernandes / Banca: Juliana Duarte Messana / Banca: Luiz Gustavo Ribeiro Pereira / Resumo: O experimento foi conduzido no Laboratório de Estudos em Caprinocultura, UNESP / FCAV, Jaboticabal, SP. Foram utilizadas 15 cabras não lactantes e não gestantes, adultas, da raça Anglo Nubiana. Foram realizados dois estudos. O primeiro foi dividido em duas fases. Na primeira fase os animais foram submetidos à 3 niveis de restrição alimentar, a vontade - SR, restrição moderada - RM (~15% do consumo à vontade), e restrição severa - RS (~40% do consumo à vontade). Na segunda fase, os mesmos animais foram realimentados passando a ser alimentados todos à vontade. No segundo estudo, os animais foram submetidos a dietas com diferentes níveis de volumoso: concentrado (V:C) nas proporções de 25:75, 50:50, e 75:25. No primeiro estudo, durante a Fase 1 (restrição), os animais submetidos ao tratamento RS apresentaram menor consumo de matéria seca (CMS, g/dia) em relação aos animais do tratamento SR e RM. Ao contrário do esperado o CMS dos animais submetidos RM não diferiu daqueles que se alimentavam a vontade. Não houve diferença na digestibilidade da MS, dos nutrientes e da energia na Fase 1 (restrição) e na Fase 2 (realimentação) deste estudo. Já em relação ao balanço energético, a produção de metano (g/dia), na Fase 1 foi maior nos animais que se alimentavam a vontade.Na Fase 1 (restrição), a perda de metano foi 18% e 42% menor para os animais submetidos a RM e RS, respectivamente, em relação aos SR. A EM, EM/ED, qm foram maiores durante a Fase 2 (realimentação), em comparação à Fase 1 (restrição). No segundo estudo, o CMS, consumo de matéria orgânica (MO), proteína bruta e extrato etéreo aumentaram linearmente à medida que a relação V:C diminui. O consumo de fibra em detergente neutro apresentou um comportamento quadrático, aumentando até a proporção de V:C de 50:50 e decrescendo em seguida... / Abstract: The experiment was conducted in the Laboratory for Research on Goat , UNESP / FCAV , Jaboticabal , SP . 15 non-lactating and non-pregnant, adult , Anglo Nubian goats were used . Two experiments was conducted . The first was divided into two phases. In the first phase the animals were subjected to 3 levels of feed restriction , ad libitum , moderate restriction ( 15 % of ad libitum intake ) , and severe restriction ( 40 % of ad libitum intake ) . In the second phase , the animals were fed back through to be fed all the will . In the second experiment , animals were fed diets with different levels of roughage : concentrate ratios of 25:75 , 50:50 , and 75:25 . For the 1st and 2nd phase due to the treatment , the animals undergoing treatment RS had lower dry matter intake (DMI , g / day ) compared to animals receiving SR and MR . Contrary to expectations CMS animals undergoing moderate restriction does not differ from those fed the will. There was no difference in DM digestibility , nutrients and energy in Phase 1 ( restriction) and Phase 2 ( feedback) of this study . In relation to energy balance , methane production ( g / day) in Phase 1 was higher in animals fed the will . In Phase 1 ( restriction) the energy lost in feces ( kJ / kg BW 0.75 ) of animals undergoing RS was lower compared to animals receiving MR and SR . In Phase 1 ( restriction) , the loss was 18 % methane and 42 % lower for animals undergoing MR and RS . Variables EM, EM / ED , qm were higher during Phase 2 (feedback ) compared to Phase 1 ( restriction) . For the 2nd experiment was no influence of treatments on CMS , CMO , CP and EE which showed a linear behavior increased as the forage: concentrate ratio decreases . The NDF had a quadratic behavior, increasing until the ratio of V : C 50:50 and decreasing thereafter... / Mestre

Orientador: Américo garcia da Silva Sobrinho / Banca: Giovani Fiorentini / Banca: Sarita Bonagurio Gallo / Resumo: O objetivo desta pesquisa foi avaliar a digestibilidade aparente da matéria seca e dos nutrientes, o balanço aparente de nitrogênio, a produção de gases in vitro com a determinação dos ácidos graxos de cadeia curta, o desempenho, os parâmetros quantitativos in vivo e da carcaça, assim como a avaliação econômica de dietas com coprodutos do biodiesel na alimentação de cordeiros. Para o ensaio in vivo utilizaram-se 40 cordeiros Ile de France, recém-desmamados, pesando 17,15 ± 1,56 kg e para o in vitro 4 cordeiros Santa Inês, com 31,2 ± 0,75 kg de peso corporal, como doadores de fluido ruminal. Os tratamentos foram compostos por dietas com 40% de silagem de milho e 60% dos concentrados: Cont: concentrado padrão; FAm: concentrado com 20% de farelo de amendoim na matéria seca; Gli: concentrado com 25% de glicerina bruta na matéria seca e FGl: concentrado com 10% de farelo de amendoim e 12,5% de glicerina bruta na matéria seca. O delineamento experimental foi inteiramente casualizado em ambos os ensaios, com uso do procedimento GLM do programa SAS (2003), sendo as comparações das médias dos tratamentos feitas pelo teste de Tukey a 5% de significância. O consumo de nutrientes, o balanço aparente de nitrogênio e as quantificações de metano e ácidos graxos de cadeia curta foram semelhantes. A inclusão de glicerina bruta resultou em maior (P<0,05) digestibilidade aparente da matéria seca (79,87%) e de nutrientes, exceto extrato etéreo (80,82%), se comparada às demais dietas. O desempenho dos cordeiros, as características quantitativas da carcaça e medidas no músculo Longissimus thoracis não diferiram (P>0,05) entre as dietas, enquanto que a largura da garupa in vivo, a compacidade corporal, o perímetro do tórax na carcaça e o peso dos cortes (paleta e lombo) diferiram (P<0,05). Na análise da alteração do rendimento líquido o farelo de amendoim resultou em maior... / Abstract: The objective this study was to evaluate the apparent digestibility of dry matter and nutrients, the nitrogen balance, the total in vitro gas production with shortchain fat acids determination, the performance, the quantitative parameters in vivo and in carcass, as the economic evaluation of diets with biodiesel coproducts in feeding lambs. For in vivo trial were used 40 Ile de France lambs, weaning, weighing 17.15 ± 1.56 kg and for in vitro trial four Santa Inês lambs, with 31.2 ± 0.75 kg of body weight, as suppliers of ruminal fluid. The treatments were composed for diets with 40% of corn silage and 60% of concentrates: Cont: standard concentrate; PMe: concentrate with 20% of peanut meal on dry matter; CGl: concentrate with 25% of crude glycerin on dry matter and PGl: concentrate with 10% of peanut meal and 12.5% of crude glycerin on dry matter. The experimental design was completely randomized in both trials, with use of GLM procedure of SAS (2003) software and comparisons between the treatments means were made by Tukey test at 5 % significance. The nutrients intake, the nitrogen balance and concentration of methane and short-chain fat acids were similar. The crude glycerin inclusion resulted higher (P<0.05) apparent digestibility of dry matter (79.87%) and nutrients, except ether extract (80.82%), compared to other diets. The lambs performance, the carcass characteristics quantitatives and measurement in Longissimus thoracis muscle were not different (P>0.05) between the diets, while the rump width in vivo, the body compactness, the chest girth in carcass and the cuts weigh (shoulder and back) were changed (P<0.05). In evaluate of change in net income the peanut meal resulted in higher economic value (R$ 16.23.head-1 ). The inclusion of crude glycerin was the viable nutritional alternative due the improvements on apparent digestibility. The coproducts used decreased the total costs of ... / Mestre

Orientador: Heloise de Oliveira Pastore / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T11:21:11Z (GMT). No. of bitstreams: 1 Strauss_Mathias_M.pdf: 12828792 bytes, checksum: 704e6ce09b644ccacab0bb51fa7baf10 (MD5) Previous issue date: 2008 / Resumo: A busca por fontes de energia mais limpas do que aquelas provenientes do petróleo tem sido a razão de estudo de diversos grupos de pesquisa. É também com este intuito que a síntese de novos catalisadores microporosos com metais de transição estruturais vem sendo estudada. Neste trabalho é apresentada a síntese de catalisadores originais para a combustão catalítica de metano denominados [M]-CAL-2 sendo estes materiais microporosos do tipo MeAPSO com estrutura chabasita análoga ao SAPO-34. Os catalisadores foram preparados utilizando diferentes metais de transição (Co, Mn e Fe) e em diferentes razões molares durante a preparação do gel de síntese. São apresentadas, nesta dissertação, as caracterizações estruturais, a composição, os estudos espectroscópicos e os testes catalíticos da combustão de CH4 para os sólidos obtidos. / Abstract: The search for cleaner energy sources than oil is the reason for studies conducted by several groups around the world. It is also with this intention that the synthesis of new microporous catalyst with structural transition metals is explored. In this work is presented the synthesis of new methane combustion catalysts called [M]-CAL-2, they are MeAPSO-type microporous materials with chabazite like structure analogous to the SAPO-34. The catalysts were prepared using different transition metals (Co, Mn and Fe) in different molar ratios in the synthesis gel. The morphology and composition, the spectroscopic studies and the catalytic tests for the CH4 combustion reaction are presented for the obtained solids. / Mestrado / Quimica Inorganica / Mestre em Química

Microbial production of natural gas in subsurface organic-rich reservoirs (e.g. coal, shale, oil) can be enhanced by the introduction of limiting nutrients to stimulate microbial communities to generate “new” methane resources on human timescales. The few successful field experiments of Microbial Enhancement of Coalbed Methane (MECoM) relied on relatively qualitative approaches for estimating the amount of “new” methane produced during the stimulation process (i.e. extrapolation of pre-stimulation gas production curves). We have tested deuterated water as a tracer, initially in the laboratory, to more directly quantify the amount of “new” methane generated and the effectiveness of MECoM stimulation approaches. Microorganisms, formation water, and coal obtained during a previous drilling project in the Powder River Basin, Birney, Montana were used to set up a series of benchtop stimulation experiments where we added incremental amounts of deuterated water to triplicate sets of stimulated microbes (methanogens). We hypothesized that as MECoM progresses, methanogens will incorporate the heavy water into new methane produced, as methanogens naturally uptake hydrogen during methanogenesis. The amount of hydrogen incorporated into methane from water is dependent on the methanogenic pathway (hydrogenotropic vs acetoclastic/methylotrophic). During the experiments, we saw a shift in the methanogenic pathway towards acetoclastic methanogenesis, which was indicated by a consistent shift in the enrichment of deuterium in the methane produced, methanogenic community, and a large kinetic fractionation. The enrichment of the methane as compared to the deuterium content of the water the microbes used followed a narrowly confined, predictable range of values. This predictable enrichment of the methane allows us to propose a quantification scheme for the amount of methane produced in larger field scale stimulations, as we can compare the change in the overall deuterium content of the in-situ methane with the known value before the stimulation. The success of our proof-of-concept laboratory experiments suggests that deuterium may be used as a tracer of “new” natural gas resources in field- to commercial-scale MECoM projects. In addition, additions of deuterated water may also be useful as a tracer in bioremediation projects where large background pools of contaminants or degradation products hamper traditional quantification techniques, microbial enhanced oil recovery, or other subsurface carbon cycling pathways.

Abstract The present thesis deals with the nuclear magnetic resonance (NMR) spectroscopy of small solutes applied to the studies of liquid crystals and molecular sieves. In this method, changes induced by the investigated environment to the static spectral parameters (i.e. nuclear shielding, indirect and direct spin-spin coupling and quadrupole coupling) of the solute are measured. The nuclear shielding of dissolved noble gases is utilized for the studies of thermotropic liquid crystals. The relation between the symmetry properties of mesophases and the nuclear shielding is described. The different interaction mechanisms perturbing the observed noble gas nuclear shielding are discussed, particularly, the role of long-range attractive van der Waals interactions is brought out. The suitability of the noble gas NMR spectroscopy to the studies of lyotropic liquid crystals is investigated in terms of nuclear shielding and quadrupole coupling interactions. In molecular sieve systems, the effect of inter- and intracrystalline motions of solutes on their NMR spectra is discussed. A novel method for the measurement of the intracrystalline motions is developed. The distinctions in the 13C shielding of methane adsorbed in AlPO4-11 and SAPO-11, two structurally similar molecular sieves differing in composition, are indicated.

Climate change is expected to have significant and uncertain impacts on methane (CH4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specificCH(4) measurements to larger scales and predict responses of CH4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydro-genotrophic methanogenesis (AM and HM) to CH4 production, and predicts the C isotopic signature (delta C-13) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH4 production pathways and delta C-13 in emitted CH4 (delta C-13-CH4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated delta C-13-CH4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (alpha(AM) and alpha(HM)), CH4 oxidation (alpha(MO)), and plant-mediated CH4 transport (alpha(TP)). The sensitivity analysis indicated that the delta C-13-CH4 is highly sensitive to the factors associated with microbial metabolism (alpha(AM), alpha(HM), and alpha(MO)). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH4 cycling in peatlands.

M.Sc. / The potential target areas for coalbed methane in South Africa are reviewed and a case study based on borehole data from the north-eastern Karoo basin was undertaken. The Early Permian coal seams of the Karoo Supergroup occur in several discrete sedimentary basins in South Africa, of which the Karoo basin is the largest. Using screening criteria based on geological, petrographical and analytical data some of the coal deposits can be excluded as potential coalbed methane producers. These include the Molteno Coalfield, large parts of the Karoo basin coal deposits and some of the Northern Province's coal deposits which are structurally disturbed. The traditional mining areas in the Free State, Witbank and Highveld coalfields are excluded from the coalbed methane study because the target seams occur at less than 200 metres below surface, too shallow for gas retention. Some of the coal seams in the Waterberg Coalfield occur at depths of several hundred metres below surface and these are unlikely to be mined by conventional means. These deep coals may be ideal coalbed methane producers. This regional overview was based on available, published data and two important parameters, permeability of coal and coalbed hydrology are unknown but important factors that will need to be taken into account in any future evaluations. The case study focused on an area close to Amersfoort that has a predicted potential for coalbed methane production. The study utilized 465 borehole descriptions from which isopach maps and geological cross-sections were constructed. Limited samples of borehole core provided lithological information from which a facies analyses was undertaken so as to establish the hydrodynamic origin of each facies types. The main lithofacies associated with the coal seams are mudstones, carbonaceous shales and fine- to coarse-grained sandstone. These data were combined with analyses from limited permeability data, petrographical data and proximate analyses for the Gus and Alfred seams. In addition to the sedimentary rocks, the role of dolerite intrusions was found to be significant as these occur as thick sills and dykes that occur below, within and above the coal seams. These may compartmentalize the seams into secondary targets within the study area. Thick sills overlying the coal zone also increase static loading and may be advantageous with respect to reducing the minimum depthbelow- surface requirements. Potential coalbed methane target areas are identified, although the entire study area is not suitable due to structural displacement of the coal seams, thinning of coal in places and devolatization caused by the dolerites.

Philosophiae Doctor - PhD / This thesis described the development of new catalytic system for the conversion of natural gas (methane) to liquid products such as methanol and formaldehyde. This technology can allow the exploitation of small and medium size gas fields without the need to build an expensive gas to liquid plants or long pipelines. The technology is based on a concept of non-separating membrane reactor where an inorganic membrane paper serves as a catalyst support through which a reaction mixture is flowing under mild conditions and short residence times. / South Africa

Master of Science / Department of Geology / Matthew Kirk / Biodegradation of crude oil to methane has long been known to exist in shallow petroleum reservoirs. It is only in the past decade, however, in which the concept of in-reservoir petroleum biodegradation has changed from a model emphasizing aerobic crude-oil degradation (with oxygen delivered down from meteoric waters) to a more recent model in which crude-oil degradation is driven by anaerobic processes (methanogenic microorganisms). In this study, we examine controls on microbial conversion of crude oil and coal into methane in middle-Pennsylvanian strata in the Cherokee Basin, Kansas, USA and how access to oil or coal influence microbial communities. Specifically, we considered the following hypotheses: 1) microorganisms in the basin are capable of generating methane by degrading crude oil or coal and 2) potential controls on the rate of methane formation include microbial diversity, formation water chemistry, nutrient abundance, and carbon dioxide abundance. To test these hypotheses, we used three sets of laboratory experiments constructed of materials from the Cherokee basin, Kansas. One set tested environmental controls on methane generation from oil, another from coal, and a third was a control experiment that utilized methanogenic substrates rather than oil or coal. In the experiments with oil and coal, environmental factors tested ammonium/phosphate availability, feedlot wastewater injection, and carbon dioxide abundance. Our experiments also tested the influence of salinity, by including materials from a well producing water with relatively low salinity and a well producing water with relatively high salinity. The cultures were allowed to incubate from approximately 75 to 170 days, during which headspace of oil and coal bioreactors were sampled periodically and analyzed for methane concentrations. Post incubation analyses included microbial DNA sequencing. We determined that a higher concertation of methanogens existed in the lower salinity well, which has higher potential for practical stimulatory injection. Of methane produced, the only significant (Mann Whitney) treatment had access to oil in lower salinity formation water. Access to coal resulted in no significant results. Microbial diversity, in the form of methanogenic archaea abundance, formation water chemistry (salinity), and wastewater nutrient often correlated with increased, yet insignificant, rates of methane production, while carbon dioxide abundance showed no benefit. Of methanogenic substrates consumed, we determined that most Cherokee basin methanogens preferred methanol over hydrogen and acetate.

The influence water levels have on CO2 and CH4 efflux were investigated at the Loxahatchee Impoundment Landscape Assessment (LILA) research facility, located in Boynton Beach, FL, USA. Measurements of CO2 efflux were taken for 24 h periods four times for one year from study plots. Laboratory incubations of intact soil cores were sampled for CO2, CH4, and redox potential. Additionally, soil cores from wet and dry condition were incubated for determination of enzyme activity and macronutrient limitation on decomposition of organic matter from study soils. Water levels had a significant negative influence on CO2 efflux and redox, but did not significantly influence CH4 efflux. Study plots were significantly different in CH4 efflux and redox potential. Labile carbon was more limiting to potential CO2 and CH4 production than phosphorus, with the effect significantly greater from dry conditions soils. Enzyme activity results were variable with greater macronutrient responses from dry condition soils.