935 resultados para pyroclastic deposit


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Oxygenic photosynthesis fundamentally transformed our planet by releasing molecular oxygen and altering major biogeochemical cycles, and this exceptional metabolism relies on a redox-active cubane cluster of four manganese atoms. Not only is manganese essential for producing oxygen, but manganese is also only oxidized by oxygen and oxygen-derived species. Thus the history of manganese oxidation provides a valuable perspective on our planet’s environmental past, the ancient availability of oxygen, and the evolution of oxygenic photosynthesis. Broadly, the general trends of the geologic record of manganese deposition is a chronicle of ancient manganese oxidation: manganese is introduced into the fluid Earth as Mn(II) and it will remain only a trace component in sedimentary rocks until it is oxidized, forming Mn(III,IV) insoluble precipitates that are concentrated in the rock record. Because these manganese oxides are highly favorable electron acceptors, they often undergo reduction in sediments through anaerobic respiration and abiotic reaction pathways.

The following dissertation presents five chapters investigating manganese cycling both by examining ancient examples of manganese enrichments in the geologic record and exploring the mineralogical products of various pathways of manganese oxide reduction that may occur in sediments. The first chapter explores the mineralogical record of manganese and reports abundant manganese reduction recorded in six representative manganese-enriched sedimentary sequences. This is followed by a second chapter that further analyzes the earliest significant manganese deposit 2.4 billon years ago, and determines that it predated the origin of oxygenic photosynthesis and thus is supporting evidence for manganese-oxidizing photosynthesis as an evolutionary precursor prior to oxygenic photosynthesis. The lack of oxygen during this early manganese deposition was partially established using oxygen-sensitive detrital grains, and so a third chapter delves into what these grains mean for oxygen constraints using a mathematical model. The fourth chapter returns to processes affecting manganese post-deposition, and explores the relationships between manganese mineral products and (bio)geochemical reduction processes to understand how various manganese minerals can reveal ancient environmental conditions and biological metabolisms. Finally, a fifth chapter considers whether manganese can be mobilized and enriched in sedimentary rocks and determines that manganese was concentrated secondarily in a 2.5 billion-year-old example from South Africa. Overall, this thesis demonstrates how microbial processes, namely photosynthesis and metal oxide-reducing metabolisms, are linked to and recorded in the rich complexity of the manganese mineralogical record.

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Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NOx and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH4)2SO4 seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

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Os estudos destinados à aplicação de uma tecnologia mais limpa ao tratamento de águas em sistemas de resfriamento abertos com recirculação resultaram no desenvolvimento de uma filosofia de tratamento baseada na busca de uma operação com ciclo de concentração ideal. Assim, por meio do controle do balanço material no sistema de resfriamento, seria alcançado um nível de concentração em que a água de circulação apresentaria, naturalmente e ao mesmo tempo, baixa tendência à corrosão do ferro e baixa tendência à formação de incrustação de carbonato de cálcio. O tratamento com inibidores de corrosão e de formação de depósitos seria apenas complementar e, conseqüentemente, reduzido o emprego de produtos químicos para o condicionamento da água. O presente trabalho procura demonstrar que o critério de tratamento baseado apenas no índice de estabilidade não leva em conta o fato de que as espécies solúveis em água não se concentram de uma mesma forma, principalmente como decorrência de reações de conversão envolvendo o íon bicarbonato e de precipitação do íon cálcio. Como suporte desse trabalho, foram realizados ensaios de campo em um sistema de resfriamento aberto com recirculação em operação normal, porém sem tratamento químico da água. Foi possível, desse modo, observar a variação da concentração de cada espécie crítica presente na água com a vazão de descarga efetuada. Os resultados obtidos e o estudo realizado mostram que a metodologia tradicional pode apresentar desvios da realidade que podem comprometer a qualidade do tratamento, obrigando o emprego de maiores concentrações de produtos químicos para condicionamento da água, contrariando, assim, o próprio propósito original de execução de um tratamento dentro dos princípios de uma produção mais limpa. Este trabalho procura, ainda, salientar a importância qualitativa e quantitativa das espécies presentes, na água de reposição, na qualidade do tratamento, alertando que o emprego de reúso de água, como reposição de um sistema de resfriamento, deve ser criteriosamente analisado, pois uma água de má qualidade pode tornar o tratamento interno impraticável, exigindo a execução de um tratamento prévio muitas vezes inviável do ponto de vista econômico e causador de impacto ambiental

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Absolute f-values for 7 transitions in the first spectra of 4 elements have been measured using the atomic beam absorption technique. The equivalent widths of the absorption lines are measured with a photoelectric scanner and the atomic beam density is determined by continuously weighing a part of it with a sensitive automatic microbalance. The complete theory is presented and corrections are calculated to cope with gas absorption by the deposit on the microbalance pan and atoms which do not stick to the pan. An additional correction for the failure of the assumption of effusive flow in the formation of the atomic beam at large densities has been measured experimentally.

The following f-values were measured:

Fe: fλ3720 = 0.0430 ± 8%

Cu: fλ3247 = 0.427 ± 4.5%, fλ3274 = 0.206 ± 4.7%, fλ2492 = 0.0037 ± 9%

Cd: fλ3261 = 0.00190 ± 7%, fλ2288 = 1.38 ± 12%

Au: fλ2428 = 0.283 ± 5.3%

Comparison with other accurately measured f-values, where they exist, shows agreement within experimental errors.

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Some of the metallogenic provinces of the southwestern United States and northern Mexico are defined by the geographic distribution of trace elements in the primary sulfide minerals chalcopyrite and sphalerite. The elements investigated include antimony, arsenic, bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, molybdenum, nickel, silver, tellurium, thallium, and tin. Of these elements, cobalt, gallium, germanium, indium, nickel, silver, and tin exhibit the best defined geographic distribution.

The data indicate that chalcopyrite is the preferred host for tin and perhaps molybdenum; sphalerite is the preferred host for cadmium, gallium, germanium, indium, and manganese; galena is the preferred host for antimony, bismuth, silver, tellurium, and thallium; and pyrite is the preferred host for cobalt, nickel, and perhaps arsenic. With respect to the two minerals chalcopyrite and sphalerite, antimony, arsenic, molybdenum, nickel, silver, and tin prefer chalcopyrite; and bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, and thallium prefer sphalerite. This distribution probably is the result of the interaction of several factors, among which are these: the various radii of the elements, the association due to chemical similarities of the major and trace elements, and the degree of ionic versus covalent and metallic character of the metal-sulfur bonds in chalcopyrite and sphalerite. The type of deposit, according to a temperature classification, appears to be of minor importance in determining the trace element content of chalcopyrite and sphalerite.

A preliminary investigation of large single crystals of sphalerite and chalcopyrite indicates that the distribution within a single crystal of some elements such as cadmium in sphalerite and indium and silver in chalcopyrite is relatively uniform, whereas the distribution of some other elements such as cobalt and manganese in sphalerite is somewhat less uniform and the distribution of tin in sphalerite is extremely erratic. The variations in trace element content probably are due largely to variations in the composition of the fluids during the growth of the crystals, but the erratic behavior of tin in sphalerite perhaps is related to the presence of numerous cavities and inclusions in the crystal studied.

Maps of the geographic distribution of trace elements in chalcopyrite and sphalerite exhibit three main belts of greater than average trace element content, which are called the Eastern, Central, and Western belts. These belts are consistent in trend and position with a beltlike distribution of copper, gold, lead, zinc, silver, and tungsten deposits and with most of the major tectonic features. However, there appear to be no definite time relationships, for as many as four metallogenic epochs, from Precambrian to late Tertiary, are represented by ore deposits within the Central belt.

The evidence suggests that the beltlike features have a deep seated origin, perhaps in the sub-crust or outer parts of the mantle, and that the deposits within each belt might be genetically related through a beltlike compositional heterogeneity in the source regions of the ores. Hence, the belts are regarded as metallogenic provinces.

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I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO2 conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH2/pH2O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH2O in the furnace atmosphere and is independent of fO2 and pH2/pH2O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H2 in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH2/pH2O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO2 conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO2 conditions from IW-2.2 to IW+6.7 and over a range of pH2/pH2O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D*water) is assumed to be constant. The relationship between D*water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D*water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH2/pH2O from 0.007 to 9.7, a range of fO2 from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D*water to variations in pH2 suggests that H2 diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D*water during dehydration and hydration in H2/CO2 gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO2 and CO/CO2 gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D*water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr2O3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H2O, and F, components with a lower concentration in the host olivine than in the melt (Al2O3, SiO2, Na2O, K2O, TiO2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na2O, K2O) by coupling to slow diffusing components such as SiO2 and Al2O3. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

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A proposta do referente estudo foi medir a espessura do depósito de um metal em outro metal base, ou seja, utilizar o processo eletroquímico de Galvanoplastia ou eletrodeposição deste metal, por meio da técnica de fluorescência de raios X (XRF). O uso desta técnica justificou-se pelo interesse em reduzir os custos excessivos durante o processo eletroquímico, bem como, minimizar as possíveis margens de erros para obter resultados satisfatórios nas medidas. Neste trabalho, incluíram-se as medidas da espessura do Níquel (Ni) e análises da intensidade de radiação incidentes e a radiação atenuante, em função da espessura dos elementos Cromo (Cr) e Zinco (Zn), considerando como metal base o elemento Ferro (Fe). Em decorrência disso, em todos os casos foram simulados os processos de deposição do metal onde foram incluídos os resultados de absorção de raios X, além de desprezar a influência de outros fatores como a temperatura, o pH, o tratamento de superfície, entre outros, os quais são necessários para considerar em cada caso.

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This work presents the basic elements for the analysis of decision under uncertainty: Expected Utility Theory and its citicisms and risk aversion and its measurement. The concepts of certainty equivalent, risk premium, absolute risk aversion and relative risk aversion, and the "more risk averse than" relation are discussed. The work is completed with several applications of decision making under uncertainty to different economic problems: investment in risky assets and portfolio selection, risk sharing, investment to reduce risk, insurance, taxes and income underreporting, deposit insurance and the value of information.

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O presente estudo aborda a caracterização faciológica e quimioestratigráfica do intervalo de folhelhos betuminosos da Formação Tremembé (Oligoceno da Bacia de Taubaté), bem como a avaliação econômica desses depósitos na região de Pindamonhangaba e Moreira César, SP. A partir da coleta sistemática de amostras de testemunhos do poço MOR-SP, foram determinados os teores de COT, S e RI, assim como dados de Pirólise Rock-Eval. Com base nesses dados seis unidades quimioestratigráficas(designadas de I a VI a partir da base) foram definidas no intervalo de cerca de 40 metros de espessura. Dados previamente estudados dos poços TMB-SP e PND-SP foram utilizados para correlação dessasunidades.Com base nos dados de Pirólise RockEval foi possível quantificar o volume de óleo potencialmente recuperável através do aproveitamento industrial dos folhelhos betuminosos. No intervalo mais promissor (unidades VI e V), compreendendo uma seção de cerca de 17 metros de espessura, o rendimento de óleo é de cerca de 25,7 milhões de barris por km2, na área do poço MOR-SP.Os dados obtidos apontam para uma importante jazida não convencional de folhelho betuminoso (oilshale), cujo aproveitamentoeconômico, se executado,requerirá, além de novas soluções tecnológicas, a implementação de ações de forma a minimizar os impactos sociais e ambientais de uma possível operação extrativa desse recurso.

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Different rearing facilities (concrete tanks, pens and ponds) were tested for suitability as spawning environments. The concrete tanks and the pens in the lagoon gave the best results as to the number of spawns obtained. Of the three types of spawning devices tested, containers with a 150 mm opening at one of the two ends were preferably used by the fish. The brooders in the spawning facilities spontaneously entered the spawning containers to deposit their eggs without external human intervention. Actual fecundity estimates ranged from 9805 to 40597.

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The hydrology of the Ebrie coastal lagoon in Abidjan area is summarized. The authors describe the oxygenation in that area during the two extreme seasons of the hydrological cycle: the low-water season (March-April) and the high-water season (Sept-Oct). The influences of the continental and oceanic waters, photosynthesis, exchanges with the atmosphere and pollution are considered. The oxigen consumption of primary organic pollution represents from 9 to 12% of the content of the waters that circulates in the area. It is geographically very heterogeneous. The central basin, swept by strong marine and fresh water currents, shows a rather high level of water oxygenation. In the peripheric bays, water circulation and mixing are less important and pollution accelerates the natural eutrophic processes. During the low-water season, a vertical stratification is responsible for a bottom anoxic layer and the deposit of reduced organic silts. On the contrary, supersaturations, up to 200%, are recorded on the surface layer. During the high-water season the break of the vertical stratification sets the loose reduced silts into suspension and partly reoxygenates the bottom waters. A classification of the different areas, based on the oxygen vertical profiles is proposed.

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使用倾斜角沉积(GLAD)的电子束蒸发技术,制备了倾斜角度在60°~85°之间的ZnS双折射雕塑薄膜(STF)。使用X射线衍射(XRD)和扫描电镜(SEM)检测了ZnS薄膜的结晶状态和断面形貌,使用Lamda-900分光光度计测量了薄膜在不同的偏振光入射时的透过率。研究发现,室温下倾斜沉积ZnS薄膜断面为倾斜柱状结构,且薄膜的结晶程度不高。在相同的监控厚度时,随倾斜角度增大,沉积到基片上的薄膜厚度逐渐变小,但仍然大于余弦曲线显示的理论厚度。根据偏振光垂直入射时薄膜的透过光谱计算了不同角度沉积的薄膜的折射率

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The glancing angle deposition (GLAD) technique was used to deposit ZnS films by electron beam evaporation method. The cross sectional scanning electron microscopy (SEM) image illustrated a highly orientated microstructure composed of slanted column. The atomic force microscopy (APM) analysis indicated that incident flux angle had significant effects on the nodule size and surface roughness. Under identical nominal thickness, the actual thickness of the GLAD films is related to the incident flux angle. The refractive index and in-plane birefringence of the GLAD ZnS films were discussed, and the maximum bireffingence Delta n = 0.036 was obtained at incident flux angle of alpha = 80 degrees. Therefore, the glancing angle deposition technique is a promising way to create a columnar structure with enhanced birefringent property. (c) 2005 Elsevier B.V. All rights reserved.

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Os modelos para a formação de plútons alcalinos da Província Alcalina do Sudeste Brasileiro ou Alinhamento Poços de Caldas-Cabo Frio associam a gênese destas rochas a grandes reativações ou a passagem de uma pluma mantélica, registrada pelo traço de um hot spot. O objetivo desta tese é, apresentar novos dados e interpretações para contribuir com a melhor elucidação e discussão destes modelos. Os estudos incluem mapeamento, petrografia, litogeoquímica, geoquímica isotópica de Sr, Nd e Pb e datação 40Ar/39Ar. As intrusões selecionadas correspondem ao Morro Redondo, Mendanha e Morro de São João, no Rio de Janeiro, localizados em posições distintas no alinhamento Poços de Caldas-Cabo Frio. A intrusão alcalina do Morro Redondo é composta majoritariamente de nefelina sienitos e sienitos com nefelina, com rara ocorrência de rochas máficas e é caracterizada por uma suíte alcalina sódica insaturada em sílica, de caráter metaluminosa a peralcalina. Esta intrusão foi datada em aproximadamente 74 Ma (idade-platô 40Ar/39Ar). A intrusão alcalina do Mendanha é composta por diversos tipos de rochas sieníticas, além de brechas e estruturas subvulcânicas, como rochas piroclásticas e diques e caracteriza-se por ser uma suíte alcalina sódica saturada em sílica, de caráter metaluminosa, diferente do que ocorre no Marapicu, este subsaturado em sílica. Esta intrusão apresentou duas idades-platô 40Ar/39Ar distintas de magmatismo: 64 Ma para as rochas do Mendanha e 54 Ma em dique de lamprófiro, registrando magmatismo policíclico. O Morro do Marapicu foi datado em aproximadamente 80 Ma. Já a intrusão alcalina do Morro de São João possui uma ampla variedade de litotipos saturados a subsaturados em sílica, tais como sienitos, álcali-sienitos e monzossienitos (alguns portadores de pseudoleucita), com variedades melanocráticas, tais como malignitos e fergustios. Estas rochas definem suas distintas suítes alcalinas subsaturadas em sílica: Uma de composição sódica e outra potássica. Há também uma suíte alcalina saturada em sílica, definida por gabros alcalinos e shonkinitos. A petrogênese destas intrusões corresponde ao modelo de cristalização fracionada, com assimilação de rochas encaixantes (AFC) como indicado pela alta variabilidade de razões isotópicas de estrôncio. No Morro de São João é sugerido o modelo de mistura magmática. Estas intrusões foram geradas a partir de magmas mantélicos enriquecidos, possivelmente associados à antiga zona de subducção relacionada ao orógeno Ribeira. Em razão das novas idades obtidas, o modelo de hot spot proposto fica prejudicado, visto que o Marapicu é de idade mais antiga das intrusões analisadas, o que era esperado para o Morro Redondo. Alguns modelos projetam plumas mantélicas com aproximadamente 1000 km de diâmetro, o que poderia explicar o Mendanha ser contemporâneo ao Morro de São João. As assinaturas isotópicas obtidas para as intrusões não se associam à assinatura isotópica de Trindade e, caso o modelo de plumas mantélicas seja o correto, a pluma que teria maior semelhança de assinatura isotópica é a pluma de Tristão da Cunha.

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真空室内金属粒子污染是降低激光薄膜性能的一个重要因素。采用高真空残余气体分析仪,对薄膜沉积过程中的气氛进行分析。发现由黄铜制作的加热灯架在工作时会分解出Zn,在这种条件下沉积薄膜,会使薄膜中掺入金属杂质,导致薄膜激光破坏阈值降低。采用表面分析技术对薄膜的组分进行分析,证实薄膜中锌杂质的存在。激光破坏实验证明,含有锌杂质的薄膜的破坏阈值明显降低。