Geração de sulcos em meio coesivo e caracterização hidrossedimentométrica de sua evolução

Na pesquisa em erosão, nas últimas décadas, está se formando um consenso de que é importante entender os processos básicos que regem o fenômeno. Uma alternativas para tentar compreender melhor as etapas do processo erosivo é separá-lo na fase de sulco (fluxo concentrado) e de entressulco. Dentro desse enfoque foi construído no Laboratório de Processos Erosivos e Deposicionais (LaPED) do IPH/UFRGS um canal de declividade para estudar o processo de incisão e o desenvolvimento dos sulcos de erosão. A estrutura experimental projetada e construída permite que seja controlada a vazão através de um medidor eletromagnético e que seja alterada a declividade do canal através de um sistema hidráulico associado a um nível digital. O solo colocado no canal foi um Latossolo Vermelho distrófico típico, as declividades de trabalho foram 3,0; 6,0 e 9,0% e a seqüência de vazões aplicadas foi 10,0; 18,5; 25,5; 38,5 e 51,0L.min-1. A estrutura experimental montada se mostrou de fácil operação e eficiente para permitir o avanço no entendimento dos processos de desagregação e de transporte de partículas sólidas pela ação do escoamento superficial, além de possibilitar a geração de sulco(s) de erosão na superfície do solo. O escoamento passou da condição de difuso para concentrado a partir do momento em que a velocidade superficial do fluxo alcançou 0,26m.s-1, a altura de lâmina atingiu 0,0102m, a velocidade de cisalhamento superou os 0,059m.s-1, a tensão de cisalhamento chegou a 3,50Pa e que a potência do escoamento atingiu pelo menos 0,22N.s-1. O processo de incisão iniciou-se com o canal experimental colocado em baixa declividade e em regime de escoamento sub-crítico e de transição. A velocidade de cisalhamento, no momento da incisão, foi, praticamente, o dobro daquela encontrada na literatura para solos siltosos e arenosos. Entretanto, para as três declividades a fase de sulco definido ocorreu somente em regime de escoamento turbulento. A tensão de cisalhamento foi o parâmetro que melhor descreveu a evolução da perda de solo. A potência do escoamento foi o parâmetro hidráulico que mostrou maior eficiência para separar as fases evolutivas dos sulcos. O desenvolvimento do(s) sulco(s) teve o seu início em uma condição de escoamento difuso (ausência de sulcos) e com a potência do escoamento oscilando entre 0,057 e 0,198N.s-1. O avanço do(s) sulco(s) começou com uma zona de transição (fase de incisão e de aprofundamento) onde a potência do escoamento varia entre 0,220 e 0,278N.s-1 e, logo em seguida, teve início a fase de sulco definido, com a potência do escoamento entre 0,314 e 0,544N.s-1. Na fase de escoamento concentrado foi preponderante o papel do processo de erosão regressiva para aumentar tanto o tamanho como o peso das partículas sólidas em transporte pelo escoamento superficial e assim fazer com que predominasse o transporte via fundo sobre o transporte via suspensão. As cargas de sedimento geradas nos solos de diferentes classes texturais foram separadas em grupos distintos em função da potência unitária do escoamento.

Rotação diferencial em estrelas do tipo solar

Stellar differential rotation is an important key to understand hydromagnetic stellar dynamos, instabilities, and transport processes in stellar interiors as well as for a better treatment of tides in close binary and star-planet systems. The space-borne high-precision photometry with MOST, CoRoT, and Kepler has provided large and homogeneous datasets. This allows, for the first time, the study of differential rotation statistically robust samples covering almost all stages of stellar evolution. In this sense, we introduce a method to measure a lower limit to the amplitude of surface differential rotation from high-precision evenly sampled photometric time series such as those obtained by space-borne telescopes. It is designed for application to main-sequence late-type stars whose optical flux modulation is dominated by starspots. An autocorrelation of the time series is used to select stars that allow an accurate determination of spot rotation periods. A simple two-spot model is applied together with a Bayesian Information Criterion to preliminarily select intervals of the time series showing evidence of differential rotation with starspots of almost constant area. Finally, the significance of the differential rotation detection and a measurement of its amplitude and uncertainty are obtained by an a posteriori Bayesian analysis based on a Monte Carlo Markov Chain (hereafter MCMC) approach. We apply our method to the Sun and eight other stars for which previous spot modelling has been performed to compare our results with previous ones. The selected stars are of spectral type F, G and K. Among the main results of this work, We find that autocorrelation is a simple method for selecting stars with a coherent rotational signal that is a prerequisite to a successful measurement of differential rotation through spot modelling. For a proper MCMC analysis, it is necessary to take into account the strong correlations among different parameters that exists in spot modelling. For the planethosting star Kepler-30, we derive a lower limit to the relative amplitude of the differential rotation. We confirm that the Sun as a star in the optical passband is not suitable for a measurement of the differential rotation owing to the rapid evolution of its photospheric active regions. In general, our method performs well in comparison with more sophisticated procedures used until now in the study of stellar differential rotation

Monitoramento costeiro das praias de São Bento do Norte e Caiçara do Norte RN: implicações para o pólo petrolífero de Guamaré

This dissertation the results of a research developed in the area of São Bento do Norte and Caiçara do Norte, northern coast of the State of Rio Grande do Norte, during the period of June of 2000 to August of 2001, in the ambit of the projects MAMBMARÉ (CNPq/CTPETRO) and PROBRAL (CAPES/DAAD).The objective principal of this research was the characterization of the sedimentary dynamics of this coast, with base in data of coastal process (winds, currents, waves and tides), with topographical risings (beach profiles and dunes), satellite images and sedimentary analyses. The more specific objectives were accomplished the coastal monitoring of this coast, to verify the maintenance of an erosive tendency or progradacional after the groynes construction for contention of the erosion in the beach of Caiçara do Norte, as well as to verify the influence of the features of bottom of the platform interns adjacent on the pole petroliferous of Guamaré. The executed monitoramento allowed to identify that the movement of the sediments, along the year, in that area, is cyclical, reaching the largest oscillations during the months of winter (deposition) and they will summer (erosion). The sedimentologic studies indicated a general tendency for sands quartzosas, with gravel presence, moderately to good selected, with asymmetry predominantly negative. In agreement with the parameter of Dean (1957), used in the identification of the state morfodinâmico of the beaches, monitored beaches, are basically reflectivas with tendency to middlemen, what frames that space of the coast norteriograndense, as a space strongly vulnerable to erosive processes. The studies developed in the platform, it interns of this area, allowed to visualize for the first time, in large scale, the distribution of the features of the submarine bottom to the batométrico coat of 25 meters. Being pointed out the presence of a high one topographical submerged, with about 5 meters of height, 1 km of width and more than 24 meters of extension, located in the platform it interns in front of São Bento do Norte; coincident with the trend of the system of flaws of Carnaubais. This feature relay an important paper on the control of the sedimentary processes and oceanographic, as well as in the coastal evolution of this area of the RN state, and they affect the area of the pole petroliferous of Guamaré directly. These results contribute to a better knowledge of the processes in the area, and consequently as subsidies implantation of measures of coastal and environmental protection for the cities of São Bento do Norte and Caiçara do Norte, as well as to understand how the geological-sedimentary processes and oceanographic, in this area, are influencing the characteristics geoambientais of the pole petroliferous of Guamaré

Simulação numérica da gaseificação de biomassa em leito fixo

O objetivo deste trabalho foi avaliar a potencialidade das sementes de açaí rejeitadas após beneficiamento em Belém – Pará, a fim de ser usada como fonte de biomassa para a produção de energia por gaseificação. Resultados da análise elementar obtidas no LABCAT – UNB em base seca foram obtidas com percentuais de Carbono, 46,06 %, Hidrogênio 6,01 % Oxigênio 43,37 %, Nitrogênio 4,33 % e Enxofre 0,08%. Tais valores entre outros parâmetros obtidos em estudo experimental realizados por Santos 2011 e Cruz, 2010, foram utilizados para realizar uma simulação numérica do processo de gaseificação por meio de um código FORTRAN zero dimensional desenvolvido especificamente para esta finalidade. Variações da influência da razão de equivalência e teor de umidade nas concentrações de CO, H2 e CH4 foram comparados a resultados experimentais. Um modelo transiente unidimensional também foi analisado. Utilizando a aplicação de um mecanismo de pirólise de dois passos onde o alcatrão primário (ou oxigenados) são inicialmente formados e então craqueados em alcatrão secundário (ou hidrocarbonetos) e outros gases combustíveis. Assim se revela a complexidade dos processos físicos e químicos que ocorrem no reator pelo uso do balanço de energia e massa e com informações das taxas de reação das reções químicas e os processos de transporte físicos. O modelo computacional é capaz de prever o perfil da composição de gases, temperatura, alcatrão primário e secundário ao longo do eixo longitudinal do gaseificador. Foram obtidos resultados para simulações realizadas nos dois modelos e posteriormente analisado tal comportamento em comparação ao resultado experimental obtidos por Santos (2011).

Depósitos sedimentares neoproterozoicos do Grupo Tucuruí - Cinturão Araguaia, Nordeste do Pará

O Grupo Tucuruí de idade do final do Neoproterozoico aflora na região de Tucuruí, nordeste do Pará, ao longo da zona de transição entre o Cráton Amazônico e o Cinturão Araguaia, e constitui uma sucessão vulcanossedimentar contendo derrames basálticos e sills de diabásio intercalados com depósitos siliciclásticos. A Falha de Tucuruí, por cavalgamento, projetou estes conjuntos rochosos para oeste, resultando em cisalhamento e percolação de fluidos. Os depósitos siliciclásticos são constituídos por subarcóseos e siltitos amalgamados, cujas camadas orientam-se na direção NNE-SSW com mergulho baixo para SE, além de apresentar granocrescência e espessamento ascendente. Foram reconhecidas duas associações de fácies sedimentares: depósitos de antepraia e tempestitos de face litorânea. Estas associações de fáceis sugerem processos de transporte e sedimentação ligados a um ambiente marinho raso, seguindo da zona de foreshore até a zona de shoreface, sob influência de onda de tempestade. A análise petrográfica revelou a imaturidade textural e composicional dos arenitos e siltitos arcosianos, indicando, sobretudo, área fonte com proveniência próxima, predominantemente constituída de rochas ígneas de composição máfica a intermediária que estiveram sujeitas a condições mesodiagenéticas. Assim, os depósitos siliciclásticos do Grupo Tucuruí representam a porção preservada de um segmento costeiro influenciado por ondas de tempestade em uma bacia do tipo rifte ou antepaís, com área fonte próxima, forte gradiente de relevo e deposição rápida, marcada predominantemente por intemperismo físico, e que foi atingida durante sua formação por vulcanismo efusivo.

Estudo comparativo entre o modelo analítico de Domenico (1987) e Wexler (1992) e suas implicações no gerenciamento de passivos ambientais

Pós-graduação em Geociências e Meio Ambiente - IGCE

Soil greenhouse gas emissions and their relations to soil attributes in a sugarcane area

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Records of sedimentary dynamics in the continental shelf and upper slope between Aveiro-Espinho (N Portugal)

The sedimentary unconsolidated cover of the Aveiro-Espinho continental shelf and upper slope (NW Portugal) records a complex interplay of processes including wave energy and currents, fluvial input, sediment transport alongshore and cross-shelf, geological and oceanographic processes and sediment sources and sinks. In order to study this record, a set of surface sediment samples was studied. Sediment grain size and composition, as well as the mineralogical composition (by XRD) of the fine (<63 mu m) and clay (<2 mu m) fractions and benthic microfaunal (foraminifera) data were analysed. Cluster analysis applied to the sedimentological data (grain size, sediment composition and mineralogy) allowed the establishment of three main zones corresponding to the: inner-, mid- and outer-shelf/upper slope. On the inner-shelf, the sedimentary coverture is composed of siliciclastic fine to very fine sand, essentially comprising modern (immature) terrigenous particles. The sediment grain size, as well as mineralogical and microfaunal composition, denote the high energetic conditions of this sector in which the alongshore transport of sand is predominantly southward and occurs mostly during the spring-summer oceanographic regime, when the main river providing sediments to this area, the River Douro, undergoes periods of drought. This effect may emphasize the erosive character of this coastal sector at present, since the Ria de Aveiro provides the shelf with few sediments. On the mid-shelf, an alongshore siliciclastic band of coarse sand and gravel can be found between the 40 m and 60 m isobaths. This gravelly deposit includes relic sediments deposited during lower sea-level stands. This structure stays on the surface due to the high bottom energy, which promotes the remobilization of the fine-grained sediments, and/or events of sediments bypassing. Benthic foraminifera density and "Benthic Foraminifera High Productivity" (BFHP) proxy values are in general low, which is consistent with the overall small supply of organic matter to the oceanic bottom in the inner- and mid-shelf. However, the Ria de Aveiro outflow, which delivers organic matter to the shelf, leaves its imprint mainly on the mid-shelf, identifiable by the increase in foraminifera density and BFHP values in front of the lagoon mouth. The higher values of BFHP along the 100 m isobath trace the present position of an oceanic thermal front whose situation may have changed in the last 3/5 ka BP. This zone marks a clear difference in the density, diversity and composition of benthic foraminifera assemblages. Here, in addition, sediment composition changes significantly, giving rise to carbonate-rich fine to medium sand in the deeper sector. The low bottom energy and the small sedimentation rate of the outer-shelf contributed to the preservation of a discontinuous carbonate-rich gravel band, between the 100 m and 140 m isobaths, also related to paleo-littorals, following the transgression that has occurred since the Last Glacial Maximum. The winter oceanographic regime favours the transport of fine grained sediments to the outer-shelf and upper slope. The inner- and mid-shelf, however, have low amounts of this kind of sediment and the Cretacic carbonated complexes Pontal da Galega and Pontal da Cartola, rocky outcrops located at the mid- and outer-shelf, act as morphological barriers to the cross-shelf transport of sediments. Thus a reduced sedimentation rate occurs in these deeper sectors, as indicated by the lower abundance of detrital minerals, which is compensated for the high sedimentary content of biogenic carbonates. The relatively high BFHP and Shannon Index values indicate water column stratification, high supply of organic matter and environmental stability, which provide favourable conditions for a diversified benthic fauna to flourish. These conditions also encourage authigenic chemical changes, favourable to glauconite formation, as well as illite and kaolinite degradation. Benthic foraminifera and clay mineral assemblages also reveal the effect of the internal waves pushing upward, and downslope losses of the sediments on the outer-shelf and upper slope.

Morphology and surface sedimentation on the upper and middle continental slope off Uruguay

This paper presents for the first time a morphological and surface sediment characterization of the Uruguayan outer continental shelf and slope. The study is based on a high-resolution coverage using hydrographical, geomorphological and sedimentological sampling and several textural and productivity proxies. Along slope terraces and an important canyon system characterizes continental slope morphology, indicating that across- and down-slope sedimentary processes control large-scale sedimentation. Terraces represent the prolongation of the Argentinean Contouritic Depositional System that vanishes in the study area, presumably as a result of the dynamic of the Brazil-Malvinas confluence. Canyons incised in the upper slope are likely related to low-stand sea level conditions. At the outer shelf and shallow upper slope (170-250 m depth), off-shelf sand transport is inferred from the distribution of relict sand and reworked biogenic gravel. In the upper continental slope, the northern region is characterized by an erosive environment controlled by a steep slope and the southward flowing Brazil current. In the south, a depositional environment is enhanced by the presence of a gentler slope and seaward incised canyons and is mainly controlled by hemipelagic processes associated with nutrient-rich Sub-Antarctic Waters (SAW), by its confluence with South Atlantic Central Waters (SACW) and by the Rio de la Plata’s (RdlP) influence. Additionally, within the upper slope, the occurrence of igneous-metamorphic cobbles and pebbles in canyon and mound lag deposits suggests the influence of glacial fluvial discharge and/or iceberg transport processes. In the middle slope, sedimentation is controlled by thermohaline-induced deep-water bottom currents. The decreasing influence of the erosive Antarctic Intermediate Water (AAIW) is evident in a northward diminution in grain size. The variety of transport and sedimentary processes identified reflect the control of the Brazil-Malvinas confluence zone and the Rio de la Plata’s discharge.

Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.

Flugzeuggetragene Spurengasmessungen in der Tropopausenregion

ZusammenfassungIm Rahmen der EU-Projekte POLSTAR (Polar StratosphericAerosol Experiment) und STREAM (Stratosphere TroposphereExperiment by Airborne Measurements) wurden flugzeuggetragene Spurengasmessungen in verschiedenen geografischen Breiten durchgeführt. Zwei Messkampagnen fanden im Januar (POLSTAR 97) und März (STREAM 97) 1997 über Kiruna (Schweden, 67°N, 20°O) statt, eine Kampagne wurde im Juli 1998 von Timmins (Kanada, 47°N, 81°W) aus durchgeführt (STREAM 98).CO und N2O wurden mittels TDLAS (Tunable Diode Laser Absorption Spectroscopy) nachgewiesen, CO2 wurde mit einem modifizierten kommerziellen Messgerät breitbandig gemessen. Zur Untersuchung von Mischungsvorgängen in der Tropopausenregion wurden Korrelationenzwischen CO, O3, N2O, CO2 und NOy herangezogen.Dabei konnte festgestellt werden, dass im Winter in der untersten Stratosphäre Mischung mit troposphärischen Luftmassen durch isentropen Transport im Bereich der Polarfront bis zu potentiellen Temperaturen von Theta=335K auftritt. Im Sommer lässt sich Mischung mit troposphärischen Luftmassen bis mindestens Theta=360K nachweisen, die effektiver als im Winter abläuft.Exemplarisch kann an einem Flug gezeigt werden, dassbis Theta=349K die Ausbildung der Mischungsschicht durchLuftmassenaustausch an der Polarfront verursacht wird, während oberhalb von Theta=349K Signaturen subtropischertroposphärischer Luftmassen gefunden werden.Der stratosphärische Hintergrund wird mitbestimmt durch photochemisch gealterte Luftmassen, die ihren Ursprung höchstwahrscheinlich in der Vortexregion des vorangegangenen Winters haben.

Realisierung einer 3D-Kreuzkorrelationsanlage zur Untersuchung von Struktur und Dynamik hochkonzentrierter Kolloide

Realisierung einer 3D-Kreuzkorrelationsanlage zur Untersuchung von Struktur und Dynamik hochkonzentrierter Kolloide Im Rahmen dieser Arbeit wird eine neuartige 3D-Kreuzkorrelationsanlage zur mehrfachstreufreien Untersuchung des diffusiven Verhaltens hochkonzentrierter kolloidaler Suspensionen vorgestellt. Hierzu werden zwei Lichtstreuexperimente gleichzeitig am gleichen Streuvolumen und mit dem gleichen Streuvektor durchgeführt. Aus der so gewonnenen Kreuzkorrelationsfunktion kann das dynamische Verhalten der Kolloide bestimmt werden. Für die Diffusion der Partikel spielen neben der direkten Wechselwirkung elektroviskoser Effekt und die hydrodynamische Wechselwirkung eine entscheidende Rolle. Insbesondere bei hohen Konzentrationen kann keiner der drei Effekte vernachlässigt werden. Die zu messenden Unterschiede in den Diffusionskoeffizienten sind sehr klein. Daher wurde der experimentelle Aufbau detailliert charakterisiert. Hierbei konnten theoretische Überlegungen hinsichtlich des Nachpulsens und der Totzeit der verwendeten Si-Avalanche-Photodioden überprüft werden. Der Kurzzeitselbstdiffusionskoeffizient hochkonzentrierter geladener kolloidaler Suspensionen wurde gemessen. Um die Daten bei hohen Konzentrationen korrekt zu normieren, wurde der elektroviskose Effekt bei geringen Konzentrationen ausführlich untersucht. Hierbei zeigte sich, dass der elektroviskose Einzelteilcheneffekt zu einer monotonen Abnahme des Diffusionskoeffizienten bei abnehmender Ionenstärke führt. Anhand der volumenbruchabhängigen Daten des Kurzzeitselbstdiffusionskoeffizienten konnte zum ersten Mal gezeigt werden, dass die hydrodynamische Wechselwirkung einen geringeren Einfluss auf die Diffusion hat, falls das direkte Wechselwirkungspotential ein Coulomb-Potential anstelle eines Harte-Kugel-Potentials ist.

Prozessorientierte Modellierung des Wassertransports zur Bewertung von Hochwasserschutzmaßnahmen in bewaldeten Entstehungsgebieten

Im der vorliegenden Arbeit wurden die Einflüsse verschiedener wasserwirtschaftlicher und forstwirtschaftlicher Maßnahmen auf das Abflussverhalten von bewaldeten Gebieten untersucht. Der Schwerpunkt lag auf der Erfassung der Veränderungen im natürlichen System durch die jeweilige Maßnahme. Der Wassertransport wurde dabei auf der Prozessebene im Hangmaßstab betrachtet. Wichtige Erkenntnisse hinsichtlich der Hochwasserentstehung in bewaldeten Gebieten wurden gewonnen. Daraus abgeleitet wurde eine Bewertung sowohl der natürlich gegebenen Systemgrößen als auch der einzelnen Maßnahmen bezüglich einer Hochwasservorsorge in Wäldern.Berücksichtigt wurden Änderungen in der Bestockung und in der Feinerschließung der bewaldeten Flächen durch Wege und Wirtschaftstrecken. Die Wassertransportprozesse wurden im Gelände untersucht und in Abhängigkeit der globalen klimatischen Randbedingungen sowie den bodenhydraulischen und landnutzungsspezifischen Parameter mit dem Niederschlag-Abfluss-Modell CATFLOW simuliert.Die Abflussdynamik wird im untersuchten Maßstab im wesentlichen durch die gegebene Bodenhydraulik, die Vorfeuchte des Bodens bei einem Niederschlag und durch die Niederschlagsintensität bestimmt. Die vergleichende Untersuchung von zwei rheinland-pfälzischen Waldstandorten ergab, dass im Bereich Soonwald ein relativ hohes Hochwasserrisiko besteht. Hier wirken sich Eingriffe durch forstwirtschaftliche Bewirtschaftungsmaßnahmen stark aus. Im Bereich des Pfälzerwaldes ist nur ein sehr geringes Hochwasserrisiko gegeben, da hier die natürlichen Gebietseigenschaften die Eingriffe durch Bewirtschaftungsmaßnahmen überprägen.

Wasserfreie, polymere Protonenleiter für Brennstoffzellen durch Immobilisierung von Imidazol

Es werden neuartige, polymere Protonenleiter vorgestellt die nach dem 'Konzept des polymergebunden Protonensolvens' realisiert wurden. Sie zeigen protonische Leitfähigkeit als intrinsische Eigenschaft, sodass keine zweite, flüssige Phase zur Protonenleitung nötig ist. Verwirklicht wurde das Konzept anhand von kammartigen Siloxanoligomeren und -polymeren, wobei Imidazol als Protonensolvens durch flexible Spacer kovalent an das Rückgrat gebunden ist. Durch Pfropfung mit imidazoltragenden Spacereinheiten wurden ferner Kieselgelnanopartikel oberflächenmodifiziert. Um die Auswirkungen der Immobilisierung von Imidazol auf die Leitfähigkeit zu untersuchen, wurden neben unterschiedlichen Molekulargewichten, die Verbindungen auch jeweils mit verschiedenen Spacerlängen synthetisiert. Die Materialien wurden umfassend charakterisiert und auf ihr thermisches Verhalten, Stabilität, Leitfähigkeit, Diffusion und dielektrisches Verhalten sowie auch nach Dotierung mit Säure untersucht. Thermisch stabil sind die Materialien bis ca. 200°C. Die Leitfähigkeiten betragen bis zu 1,5E-3 S/cm bei 160°C, welche aufgrund der Immobilisierung des Imidazols ausschließlich auf Strukturdiffusion zurückzuführen sind. Die Strukturdiffusion ist vergleichbar mit dem Grotthus-Mechanismus in Wasser und wird durch die lokale Mobilität der Imidazolmoleküle, d.h. durch die Glasübergangstemperatur des Systems bestimmt. Entsprechend wird das für Glasbildner typische Vogel-Tamman-Fulcher-Verhalten für alle untersuchten Transportprozesse gefunden. Die mit abnehmender Glasübergangstemperatur abnehmende mechanische Stabilität der Materialien kann, wie gezeigt ist, durch Compoundierung mit Kieselgelnanopartikeln entscheidend verbessert werden, was eine kostengünstige und aussichtsreiche Möglichkeit zur Herstellung von Membranen für Brennstoffzellen darstellt.

Ultrafeine Aerosolpartikel in der Stratosphäre

Ein neu konstruierter Kondensationskernzähler COPAS (COndensation PArticle counting System) für in-situ-Messungen der Konzentration von Aitken-Teilchen und ultrafeinen Aerosolpartikeln wurde im Rahmen dieser Arbeit erstmals erfolgreich bei Flugzeugmessungen eingesetzt. COPAS ist ein für flugzeuggestützte Messungen an Bord des Forschungsflugzeuges „Geophysica“ in der oberen Troposphäre und unteren Stratosphäre angepaßtes und voll automatisiertes System. Die Verfahrensweise, die Aerosolpartikel des Größenbereichs mit Durchmessern d < 100 nm zum Anwachsen zu bringen, um sie mittels optischer Detektion zu erfassen, ist im COPAS durch das Prinzip der thermischen Diffusion realisiert, wodurch eine kontinuierliche Messung der Aerosolkonzentration mit der untersten Nachweisgrenze für Partikeldurchmesser von d = 6 nm gewährleistet ist. Durch die Verwendung einer Aerosolheizung ist die Unterscheidung von volatilem und nichtvolatilem Anteil des Aerosols mit COPAS möglich. In umfassenden Laborversuchen wurde das COPAS-System hinsichtlich der unteren Nachweisgrenze in Abhängigkeit von der Betriebstemperatur und bei verschiedenen Druckbedingungen charakterisiert sowie die Effizienz der Aerosolheizung bestimmt. Flugzeuggestützte Messungen fanden in mittleren und polaren Breiten im Rahmen des EUPLEX-/ENVISAT-Validierungs–Projektes und in den Tropen während der TROCCINOX/ENVISAT-Kampagne statt. Die Messungen der vertikalen Konzentrationsverteilung des Aerosols ergaben in polaren Breiten eine Zunahme der Konzentration oberhalb von 17 km innerhalb des polaren Vortex mit hohem Anteil nichtvolatiler Partikel von bis zu 70 %. Als Ursache hierfür wird der Eintrag von meteoritischen Rauchpartikeln aus der Mesosphäre in die obere und mittlere Stratosphäre des Vortex angesehen. Ferner konnte in der unteren Stratosphäre des polaren Vortex der Einfluß troposphärischer Luft aus niedrigen Breiten festgestellt werden, die sich in einer hohen Variabilität der Aerosolpartikelkonzentration manifestiert. In tropischen Breiten wurde die Tropopausenregion untersucht. Dabei wurden Konzentrationen von bis zu 104 ultrafeiner Aerosolpartikel mit 6 nm < d < 14 nm pro cm-3 Luft gemessen, deren hoher volatiler Anteil einen sicheren Hinweis darauf gibt, daß die Partikel durch den Prozeß der homogenen Nukleation gebildet wurden. Damit konnte erstmals die Schlußfolgerungen von Brock et al. (1995) durch direkte Messungen der ultrafeinen Partikelkonzentration weitergehend belegt werden, daß in der tropischen Tropopausenregion die Neubildung von Aerosolpartikeln durch homogene Nukleation stattfindet. Die vertikalen Verteilungen der stratosphärischen Aerosolpartikelkonzentration mittlerer Breiten verdeutlichen die Ausbildung einer über 6 Jahre hinweg nahezu konstanten Hintergrundkonzentration des stratosphärischen Aerosols unter vulkanisch unbeeinflußten Bedingungen. Ferner gibt die vergleichende Untersuchung der stratosphärischen Aerosolpartikelkonzentration aus polaren, mittleren und tropischen Breiten Aufschluß über den Transport und die Prozessierung des stratosphärischen Aerosols und insbesondere über den Austausch von Luftmassen zwischen der Stratosphäre und der Troposphäre.