187 search hits
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(Na,K) Aluminosilicate Hollandites: Structures, Crystal Chemistry, and High-pressure Behaviour
(2007)
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Jun Liu
- Aluminosilicates with the composition (Na,K)AlSi3O8 and the dense hollandite-type structure, in which all Si and Al are in six-fold coordination, are considered as a possible repository of potassium and sodium in the Earth´s mantle. The aim of this research is to explore the phase relation of the K-Na system at different temperatures and pressures, and to determine the physical-chemical properties and high-pressure behaviour of silicate hollandite-type structures containing K and Na in different concentrations. The (Na,K)AlSi3O8 hollandite solid solution has been synthesised using multi-anvil apparatus in the pressure range between 13 and 26 GPa and temperatures between 1500 and 2200 °C, using (Na0-0.6, K1-0.4)AlSi3O8 glasses, NaAlSi3O8 glass, and Na0.75K0.05Ca0.1AlSi3O8 glass as starting materials. The solubility of Na component into the KAlSi3O8 hollandite end-member increases with increasing pressure and temperature. Homogeneous assemblages with a pure hollandite phase (and maximum 1-2% of stishovite) were synthesized at temperature of 1700 °C and different pressures with up to 50% of NaAlSi3O8 component. No pure NaAlSi3O8 hollandite end-member was succsessfully synthesized. Considering the difference in heat dissipation between the shock events in meteorites and the multi-anvil presses, it appears likely that NaAlSi3O8 hollandite forms as a result of local high pressure and high temperature conditions and really fast quenching under non-equilibrium conditions. All synthesized hollandite samples have tetragonal I4/m symmetry at ambient conditions. The unit-cell volume and lattice parameters of the (Na,K)AlSi3O8 hollandite decreases linearly with increasing Na content. The a cell parameter decreases more rapidly than the c cell parameter, suggesting that changing the cation size in the tunnels of the hollandite structure affects more the a axis than the c axis. Structural refinements of single-crystal data collected for KAlSi3O8 and K0.8Na0.2AlSi3O8 hollandites are consistent with Si and Al disorder among the octahedral sites. The major difference between the KAlSi3O8 hollandite end-member and the K0.8Na0.2AlSi3O8 sample is the presence in the latter of a split site away from the 4th-fold axis. This position, occupied by ~ 75% of the total Na content, is closer to the framework walls and has a very distorted coordination polyhedron with only 5 Na1-O bond distances between 2.4 and 2.6 Angström whereas all other Na1-O bond distances are larger than 3 Angström. The high pressure behaviour of hollandite samples with compositions of KAlSi3O8, K0.8Na0.2AlSi3O8, K0.6Na0.4AlSi3O8, and K0.5Na0.5AlSi3O8 have been studied using diamond anvil cells and different pressure transmitting media, by means of X-ray powder diffraction and Raman spectroscopy. High temperature behaviour of K0.5Na0.5AlSi3O8 hollandite at high pressures has also been explored by means of X-ray powder diffraction. At high pressures, all tetragonal hollandite samples transform to a monoclinic (hollandite II) structure with space group I2/m. The transition pressure decreases with increasing Na component. Na substitution, thus, stabilizes the monoclinic phase, likely because the framework walls are more distorted than in the tetragonal phase and therefore more apt to accommodate the smaller Na atom. Second order Birch- Murnaghan equations of state were calculated for the tetragonal and monoclinic phases. If only experiments using He as pressure transmitting medium are compared, it appears that Na has little effect on the bulk modulus value of the tetragonal aluminosilicate hollandite, but increases the axial anisotropy. Monoclinic hollandites are more compressible, and are stable up to the highest pressures reached during the experiments, suggesting that they may be possible host minerals for Na and K in transition zone and even down to the Earth´s lower mantle. The lattice strains associated with the tetragonal I4/m to monoclinic I2/m transition have been determined. The phase transition is proper ferroelastic with negligible volume strain. The symmetry breaking strains e1-e2=a-b/a0 and e6=a/a0 x cos gamma are proportional to the order parameter Q associated with the transition and their squared values vary linearly with pressure indicating that the transition is second-order in character. The variation with pressure of the symmetry breaking strains is similar in K0.8Na0.2AlSi3O8 and KAlSi3O8 hollandites, suggesting that Na substitution mainly affects the transition pressure but not the transition mechanism. Results from the high pressure experiments show that the tetragonal to monoclinic phase transition is very sensitive to deviatoric stresses present during the experiments due to the different pressure transmitting media. These results might also give an indication of the possible effects arising from stresses on the mineral transitions in the Earth´s mantle.
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A macroscopic and microscopic investigation of the magnesite – otavite solid soluition
(2004)
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Fiona Bromiley
- The magnesite (MgCO3) – calcite (CaCO3) system is the most geologically important of the carbonate minerals. At intermediate compositions a distinct ordered phase exists, dolomite [MgCa(CO3)2], which has symmetry. A complete, disordered ( c symmetry) solid solution exists, but at temperatures in excess of 1400°C. Unmixing and ordering processes that occur at high temperatures in the magnesite – calcite system make experimental work difficult. However, the use of an analogue system allows syntheses under more accessible experimental conditions. The effects of cation substitution and ordering in the magnesite (MgCO3) – otavite (CdCO3) solid solution have, therefore, been investigated using X-ray powder diffraction and Hard Mode Infrared Spectroscopy (HMIS). The results from Rietveld refinements of the X-ray powder diffraction data show that the variation of the a-axis is linear as a function of composition and is not affected by different degrees of order at intermediate compositions. However, the c-axis shows a positive deviation from linearity as a function of composition for the 800°C series. The observed deviation decreases with increasing degree of order for samples of composition Mg0.5Cd0.5CO3. Oxygen-carbon-oxygen bond angles for samples with symmetry showed a decrease in bond angle from 120° (constrained by symmetry in samples with the c structure) with increase in degree of order. Site occupancies were used to determine the long-range order parameter, Q, for samples with symmetry. The square of the order parameter varies linearly as a function of temperature, suggesting a second-order phase transition, and a critical transition temperature of Tc = 719°C. Intensity ratios between reflections present only in the low symmetry phase and reflections present in both the low and high symmetry phases can be used to determine a value proportional to the square of the long-range order parameter, Q. Intensity ratios, between the (101) and (202) reflections for samples of composition Mg0.5Cd0.5CO3, were determined from X-ray powder diffraction patterns and show a linear variation as a function of temperature, with a critical transition temperature, Tc = 716°C. The local mixing and ordering behaviour of the magnesite – otavite solid soluition has been characterised using infrared powder absorption spectroscopy. Phonon bands due to cadmium-oxygen translations, and magnesium-oxygen translations were both observed in the IR spectra for samples of intermediate composition. Band positions for cadmium-oxygen translations remained constant as a function of composition, whereas band positions for magnesium-oxygen translations showed a decrease in wavenumber as a function of composition. Vibrational bands in other spectral regions (libration and translation of carbonate groups and doubly degenetrate in-plane bending and out-of-plane bending of carbonate groups) vary linearly as a function of composition and no effect of order on band position is observed. At high frequencies the samples with c symmetry (800°C series) show a linear shift in band position as a function of composition, whereas, samples in the cadmium dolomite stability field, with symmetry, show a marked increase in frequency compared to their c symmetry counterparts. Cation substitution, or disordering causes broadening of IR vibrational bands for a given material. In this study an alternative method was used, which makes use of the autocorrelation function to establish average line widths for six spectral regions. The autocorrelation results, delta corr, can be interpreted in terms of local strain fields present in the structure due to cation substitution and disordering. In the low frequency region, the delta corr values show a positive deviation from linearity as a function of composition. For samples of composition Mg0.5Cd0.5CO3 the delta corr values are virtually all the same, independent of the degree of order. Over all the spectral regions, the addition of 10mol% MgCO3 (1 Mg atom every 2 unit cells) to the otavite results in a large increase in line width. It is, therefore, suggested that the strain fields surrounding the substituting magnesium atoms into the otavite structure are on the order of 30Å. In the low MIR and at a composition of Mg0.5Cd0.5CO3, an effect of order is observed as a reduction in delta corr values with respect to the sample with c symmetry. The difference in delta corr values between the ordered and disordered samples was used to determine the local-order parameter, q, which scales linearly with the long-range order parameter, Q.
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Adoption of footprint methods for the quality control of eddy-covariance measurements
(2004)
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Mathias Göckede
- Footprint models determine the spatial context of a measurement by defining a transfer function between sources or sinks of the signal and the sensor position. The resulting source area provides an important quality control tool to improve the interpretation of micrometeorological data sets. However, to date no approaches have been presented in the literature that provide a standardised footprint-based methodology that allows observers to include terrain characteristics into quality assessment and quality control strategies. One problem in this context is the small number of studies that concentrate on the validation of footprint models under the non-ideal conditions in which they are frequently being used. Therefore, for many applications, the accuracy of the source areas computed by the footprint models cannot be evaluated. To further increase the acceptance of footprint-based studies, a stronger focus on footprint validation studies for a wide variety of experimental designs is needed. This dissertation focuses on the development of a footprint-based evaluation tool for complex measurement sites that allows the combination of quality assessment results for micrometeorological measurements with characteristics of the surrounding terrain. The standardised method is easy-to-use in order to encourage its application on a large number of sites. To improve the interpretation of the obtained results, a second objective of this thesis was to develop and test approaches to validation experiments for footprint models. Göckede et al. (2004) presented an approach for the evaluation of micrometeorological measurement sites in complex terrain, which combined a method for quality assessment of eddy-covariance measurements with an analytic footprint model. Their software package provided micrometeorologists a practical tool for determining the average flux contributions from the land use type intended to observe at a specific site, or to identify footprint areas for which a high data quality could be assumed. Rebmann et al. (2005) proved the efficiency of this evaluation approach for extensive studies on a large number of sites organised in a network. Their results may serve as a tool for an improved determination of yearly sums of the net ecosystem exchange, because fluxes originating from sectors of minor quality could be excluded from the analysis. Because of these important contributions to quality control, Foken et al. (2004) integrated the site evaluation approach into a comprehensive survey on micrometeorological post-field data quality control techniques. The experiences obtained during the extensive study by Rebmann et al. (2005) allowed us identification of the major weak points of the approach, which we were able to improve in subsequent studies. Using remote sensing methods Reithmaier et al. (2005) studied the influence of the characteristics of the land use maps and different roughness length assignment schemes on the performance of the site evaluation approach. Finally, Göckede et al. (2005a) developed an updated version of the site evaluation approach, which improved the basic method by replacing the analytic footprint model with a Lagrangian stochastic footprint model that is more suitable for studies above high vegetation, and by applying a more sophisticated microscale flux aggregation method for the determination of areally-averaged roughness lengths. Although the implemented models are far more sophisticated than in the original version, the approach by Göckede et al. (2005a) still permits a practical application that allows for comparative studies of a large number of sites. With respect to the development of validation methods for footprint models using natural tracer measurements from field scale experiments, Göckede et al. (2005b) presented two different experimental approaches. Firstly, a comparison of measured flux differences and modelled land use differences for pairs of measurement positions revealed general correlations between measurement data and model results. Secondly, Göckede et al. (2005b) tested a correlation analysis between measured and modelled parameters using reference measurements and footprint results. This approach resulted in an objective quantitative evaluation of the accuracy of the footprint model. The study by Reth et al. (2005) could not be employed for footprint validation purposes because of a large systemic scatter between these measurement systems. Overall, both the paper by Göckede et al. (2005b) and by Reth et al. (2005) provided successful methods to testing the suitability of natural tracer experiments in the validation of footprint models. Although experimental deficits prevented the working out of significant differences between the results of the employed footprint models, their studies developed an improved design for natural tracer experiments that are especially designed for footprint validation purposes.
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Advection at a forest site – an updated approach
(2010)
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Lukas Siebicke
- The exchange of carbon dioxide (CO2) across the vegetation-atmosphere interface of a spruce forest was investigated. Horizontal and vertical advection are recognized as important terms of the Net Ecosystem Exchange (NEE) budget in addition to the commonly measured turbulent flux and storage flux. Direct advection measurements are challenging because of the instrumental accuracy required to observe small concentration gradients and small wind velocities and because of the spatio-temporal measurement resolution required to observe complex 3-D flow phenomena. This work presents an experimental multi-analyzer setup for the observation of horizontal CO2 concentration gradients with high temporal resolution and good spatial resolution with no tradeoff between the two. A statistical approach was developed to correct for inter-instrument bias by applying a conditional time dependent bias correction. This approach relies on properties of probability density distributions of concentration differences between one sample point and the spatial average of the sample point field. Sub-canopy CO2 concentration gradients observed with the above presented system showed a high spatial variability which was dependent on vegetation structure. Local concentration perturbations correlated with statistical properties of coherent structures and were explained by vertical exchange between CO2 enriched sub-canopy air and low concentration above-canopy air. The small-scale variability of CO2 concentration gradients brings into question the representativity of horizontal advection measurements for the control volume if observed with a low spatial resolution. Vertical advection estimates rely on accurate measurements of vertical wind velocity (w). Different procedures were applied during coordinate rotation to align the coordinate system of the sonic anemometer with the long-term stream lines. Spatial variability of the wind field was addressed by a sector-wise coordinate rotation. An investigation of temporal aspects of vertical wind velocity showed significant contributions from low frequencies in the spectrum of w. The impact of the data set length used for coordinate rotation on w and on vertical advection was investigated and observed to be large. A sequential coordinate rotation with controlled window length was proposed. Advection contributed significantly to NEE during the night and during transition periods at the Waldstein-Weidenbrunnen (DE-Bay) FLUXNET site. Daily NEE budgets were more realistic, compared to NEE from turbulent flux and storage change alone, if direct advection measurements from continuous and bias corrected gradient sampling were included, reducing the estimated daily carbon sequestration of the forest by almost 50 %.
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Aerob-thermophile Reinigung mineralölkontaminierter Abwässer
(2004)
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Alexandra Oberthür
- Unter aeroben Bedingungen ist der thermophile Mikroorganismus Geobacillus thermoleovorans im Labor- und Pilotmaßstab fähig, verschiedene mit Mineralölen kontaminierte Abwässer als einzige Kohlenstoffquelle zu nutzen. Die Verwertbarkeit eines synthetischen Dieselöls sowie eines Kühlschmierstoffs standardisierter Zusammensetzung durch die Kultur wurde untersucht. Des Weiteren wurden Kühlschmieremulsionen aus Kfz-Produktionsstätten und Spüllösungen zum Reinigen von Lackleitungen auf deren biologische Abbaubarkeit hin geprüft. Der Nachweis von Metaboliten erfolgte an einem GC-FID-System (Gaschromatograph mit Flammenionisationsdetektor). Im Vergleich zum Standardsubstrat Olivenöl wurden ähnliche, in Einzelfällen sogar höhere Wachstumsraten und Zelldichten erzielt. Hierbei wurde nachgewiesen, dass die Initialisierung der Lipaseexpression durch Triglyceride Voraussetzung für den effizienten Abbau von Mineralölkohlenwasserstoffen (MKW) durch Geobacillus thermoleovorans ist. Da MKW in der Praxis nahezu ausschließlich in Verbindung mit einer Vielzahl von Additiven gebraucht werden, wurde der Einfluss verschiedener Zusatzstoffe auf die Mikroorganismen erforscht. Als Kohlenstoffquelle diente das synthetische Dieselöl, als Zusatzstoffe wurden insbesondere Tenside, Flockungsmittel, Komplexbildner und Entschäumer verwendet. Es zeigte sich, dass alle eingesetzten anionischen Tenside (Natrimlaurylsulfat = SDS, Natriumlaurylbenzolsulfonat = SDBS) und nichtionischen Tenside (Tergitol NPX, Triton X 100) in Konzentrationen unterhalb der kritischen Mizellenbildungskonzentration (CMC, engl. Critical Micelle Concentration) nachweislich das Wachstum der Kultur durch die Verbesserung der Substrat-Bioverfügbarkeit stimulieren. Oberhalb der CMC fördern anionische Tenside das Wachstum der Kultur; nichtionische Tenside wirken mit ansteigender Konzentration zunehmend inhibierend. Triton X 100 unterdrückt in Konzentrationen oberhalb der CMC die extrazelluläre Lipaseaktivität vollständig. Positive und negative Effekte auf das Wachstumsverhalten der Kultur sind gleichermaßen das Resultat von Tensid-Membran-Interaktionen. Durch Einlagerung in die Zellmembranen erhöhen die Tenside die Permeabilität der Membranen für Enzyme, was wiederum zu einer Beschleunigung des MKW-Abbaus führt. Der inhibierende Einfluss von Triton X 100 hingegen kann auf die Konformation des Tensids zurückgeführt werden, die entweder die Ausscheidung von Enzymen behindert oder Zellmembran oder Enzyme direkt schädigt. Die experimentell ermittelten CMC im aerob-thermophilen System betrugen 50 mg/L für SDS und SDBS, 90 mg/L für Tergitol NPX® und 108 mg/L für Triton X 100. Darüber hinaus wurde nachgewiesen, dass SDBS in Anwesenheit von MKW metabolisiert wird. In Abwesenheit anderer Kohlenstoffquellen kann auch SDS von Geobacillus thermoleovorans verwertet werden. Ein Abbau nichtionischer Tenside wurde hingegen nicht beobachtet. Die Anwesenheit nichtionischer Tenside ist daher, wie nach der Durchführung einer Diskriminanzanalyse bestätigt wurde, das wichtigste Entscheidungskriterium bzgl. der Anwendbarkeit des Verfahrens zur Reinigung bislang nicht experimentell untersuchter MKW-haltiger Abwässer. Basierend auf den versuchsbegleitend erhobenen Wachstumsparametern wurde ein Vorhersagemodell zur Übertragbarkeit des aerob-thermophilen Verfahrens entwickelt. Geobacillus thermoleovorans weist eine hohe Resistenz gegenüber Bioziden, Schwermetallen und weiteren in Reinigungs- und Schmiermitteln eingesetzten Zusatzstoffen auf. Erst in Konzentrationen ab 1.500 mg/L bewirkt Antimon(III)oxid eine Inhibierung des Wachstums. Eine Anreicherung der genannten Substanzen im Abstrom der Anlage ist daher zu erwarten. Weiterer Forschungsbedarf besteht hinsichtlich der Aufklärung der Metabolisierungspfade von Geobacillus thermoleovorans in Bezug auf (Poly-)Ether und Biozide. Bei der weiteren Verfahrensoptimierung ist insbesondere die Reduktion des Energiebedarfs der Anlage anzustreben. Darüber hinaus empfiehlt sich der Einsatz des Verfahrens in (sub)tropischen Ländern sowie die Ausnutzung von Prozesswärme. Die Entsorgung metallbelasteter Schlämme und anderer nicht abbaubarer Feststoffe ist sicher zu stellen. Bei der Behandlung von Kühlschmierstoffen und ähnlich hoch CSB-belasteten Abwässern (CSB: Chemischer Sauerstoffbedarf) ist die Bereitstellung von Verdünnungswasser notwendig, da eine Raumlast von 13 kg CSB/m -3 d -3 die Belastungsobergrenze für das Verfahren darstellt. Aufgrund der hohen Prozess-Stabilität, der kurzen Anlaufzeiten, der hohen Wachstumsraten und der einfachen Betreuung ist das Verfahren sehr flexibel und vielfältig einsetzbar. Eine weitere Vertiefung dieses innovativen Ansatzes in der Abwasserreinigung ist von daher wünschenswert.
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Aluminium stabilizes dissolved organic matter by precipitation
(2008)
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Thorsten Scheel
- It is well known that carbon mineralization in acidic forest soils can be reduced by large Al concentrations. Precipitation of dissolved organic matter (DOM) by dissolved Al could contribute substantially to C retention in acidic forest soils. However, no information is available on the properties of precipitated organic matter (OM) and its stability against microbial decay although that might be an important mechanism for long-term carbon storage in soils. Therefore, I investigated the influence of (i) the DOM composition, (ii) the pH of precipitation, and (iii) the Al/C ratio in solution on the amount of OM precipitated, the associated changes in its composition, and the resulting stability of precipitated OM against microbial decay. Between 13 and 84% of the C in solution was precipitated, depending on pH, Al/C ratio, and the composition of DOM. I observed preferential precipitation of aromatic compounds and enrichment of carboxylic C in precipitated OM, being associated by depletion in N and enrichment in P. The type of bonds between OM functional groups and the Al cations was independent of pH, Al/C ratios and solution composition. FTIR spectra indicated ligand exchange as possible binding mechanism. Furthermore, exoenzymes were present in a functional state in precipitated OM. Carbon mineralization of DOM was up to 28 times larger than that of the respective precipitated OM. Only 0.5-7.7% of precipitated C was mineralized during 7 weeks of incubation. When precipitated OM remained in solution the reduction in C degradation by precipitation amounted up to 65%. This increase in stability by precipitation was significantly correlated with the amount of C precipitated. Thus, the bonds between Al and carboxylic groups of aromatic compounds with low N contents resulted in a reduced bioavailability of C. I found no indication for toxic effects of Al. The enzyme activity found in precipitates significantly increased the percentage of C mineralized of precipitated OM. However, after eight weeks of incubation the correlations between enzyme activity and C mineralization disappeared, despite substantial enzyme activity and C being still present. Thus, degradation of precipitated OM seems to be governed by enzyme activity during the first degradation phase, but the long term stability of precipitated OM is probably related to its chemical properties and structure, e.g. floc size. The Al cations linked a large number of molecules of OM up to floc sizes of 110 µm in diameter, with smaller sizes on average at pH 3.8 (16.6 µm) than at pH 4.5 (27.6 µm). For a floc of 10 µm about 80 million molecules needed to be spatially aggregated. Thus, the spatial accessibility of OM was considerably reduced in these flocs leading to additional stabilization, besides the intrinsic stability of the organic compounds and the complexation by Al. The observation that only a certain fraction of precipitated OM is prone to degradation by enzymes supports this. I conclude that precipitation of DOM is an important mechanism for the long-term carbon stabilization in mineral horizons of acidic forest soils. Changing environmental conditions can affect both the amount of OM precipitated and the degradability of the precipitate. Thus, more focus should be laid on the influence of OM precipitation on C retention and sequestration in acidic forest soils.
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Analysis of flow patterns and flow mechanisms in soils
(2009)
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Christina Bogner
- Matrix flow and preferential flow can occur concurrently in the same soil. Both flow regimes produce typical flow patterns that can be visualised in dye tracer experiments. To extract quantitative information from dye tracer studies a vast variability of approaches exists. One of them is to describe dye patterns by the so called dye coverage function, i.e. the percentage of stained area per soil depth. Based on extreme value statistics the dye coverage function can be reinterpreted as a probability function to find the tracer in a certain depth. Therefore, the two-parametric probability distribution 1 – H, H being the generalised Pareto distribution, can be fitted to the dye coverage function. The form parameter of this distribution serves as a risk index for vertical solute propagation. We did tracer experiments with Brilliant Blue FCF at three study sites: in a Norway spruce forest in southeast Germany, in a tropical mountain rainforest in southern Ecuador and on an agricultural field in southern France. We tested the ability of the risk index to summarise main information obtained in dye tracer studies and characterise flow patterns in different soils. Our results suggest that the risk index is to some degree invariant to changing experimental conditions (such as irrigation rate). The initial soil moisture, however, seems to have a large influence on the risk index. It is difficult to adjust the parameters of the generalised Pareto distribution when the dye coverage function fluctuates or does not decrease monotonically. This might be due to tortuosity of paths, varying flow mechanism or changing soil physical properties. Thus, we restricted the analysis to the lowest part of the profile. Since the theory of the risk index is based on extreme values of vertical solute propagation it is the lowest part of the profile that is the most interesting. We propose to combine the two parameters of the generalized Pareto distribution and to use the complete distribution 1 - H to estimate the risk of vertical solute propagation in soils. Despite a certain resistance to changes of experimental conditions, the risk index is not an intrinsic soil parameter. Since the flow regime in the same soil can be dominated either by preferential flow or by uniform matrix flow, the risk of vertical solute propagation will change. The adjusted parameters of the generalised Pareto distribution will capture the dominant flow regime as reflected by tracer flow patterns. Bearing in mind the boundary conditions of the tracer experiment like irrigation rate, the tracer employed, soil initial moisture or type of vegetation (permanent or seasonal, deep rooted or shallow rooted) it is possible to compare different study sites or to consider the same site at different boundary conditions and to access the risk of vertical solute propagation. Pattern analysis based on the risk index for vertical solute propagation revealed the occurrence of preferential flow at the German study site. To gain insight in flow mechanisms and possible impacts on soil chemistry we analysed soil texture, fine root density, soil bulk density, exchangeable cations, pH and total C and N contents in preferential flow paths and soil matrix. Results from linear mixed-effects models suggested that at this study site roots constituted main preferential flow paths and induced macropore flow, especially in the topsoil. In the subsoil root density decreased and inhomogeneous infiltration from preferential flow paths into the soil matrix caused non-uniform flow. There were no textural differences between the flow domains, but smaller bulk densities in preferential flow paths. This is probably due to a higher soil organic matter content in preferential flow paths. We found smaller pH values, more Ca, more Mg, more C and more N in preferential flow paths. Compared to the adjacent soil matrix, more Al and more Fe (but small absolute amounts) were found in the subsoil where macropore flow along root channels decreases and heterogeneous matrix flow dominates. These distinct chemical properties can be explained by root activity and translocation of solutes and DOC (dissolved organic carbon) via preferential flow paths. During transport along preferential flow paths contact time between DOC and soil is reduced so that DOC is transported to greater depth where it potentially forms organo-mineral associations. If this holds true, preferential flow is a mechanism that promotes C sequestration in subsoil and does not only influence its immediate environment around paths, but also underlying subsoil horizons.
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Applicability of weight-shift microlight aircraft for measuring the turbulent exchange above complex terrain
(2013)
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Stefan Metzger
- The possibility to reliably observe the exchange of heat and moisture between the land surface and the atmosphere is vital to our understanding of the regional and global cycling of energy and water. While ground-based flux measurements can be made continuously for long periods, they only represent a small landscape unit. On the other hand, aircraft-based measurements have the ability to directly measure the exchange over large areas. Especially over heterogeneous landscapes the spatio-temporal characteristics of both approaches complement each other. However, complex terrestrial ecosystems are sparsely investigated to date, in particular over topographically structured terrain. This can be attributed to; (i) limitations in the description of boundary layer processes over non-homogenous terrain, and (ii) a lack of applicable measurement platforms and techniques to study these processes. In pursue of a resolution strategy, this dissertation investigates the applicability of weight-shift microlight aircraft (WSMA) to gain new insights in the spatial variability of heat and moisture exchange over complex terrain.
WSMA are comparatively cheap in procurement and maintenance, and their unique structure provides exceptional transportability and climb rate. These structural features qualify the WSMA for terrain-following flight over complex and inaccessible terrain, but potentially influence measurements aboard the aircraft. In this dissertation a WSMA with a scientific payload enabling fast measurements of the 3D wind, temperature, water vapor concentration, position, and the radiative flux is used to;
(i) Quantify the WSMA wind measurement uncertainty. A novel time-domain procedure is developed, which improves the accuracy of the WSMA wind measurement by 63% for the horizontal- and 72% for the vertical wind components. The resulting precisions are ±0.09 m s−1 and ±0.04 m s−1, and the agreement with ground-based measurements is in the order of ±0.4 m s−1 and ±0.3 m s−1 (root mean square deviation), respectively.
(ii) Quantify the WSMA eddy-covariance flux measurement uncertainty. From uncertainty propagation the smallest resolvable changes in friction velocity (0.02 m s−1), and sensible- (5 W m−2) and latent (3 W m−2) heat flux are estimated. In comparison to tower measurements, the WSMA observes higher fluxes (17–21%). The differences are not statistically significant, and can be explained by the tower setup and non-propagating eddies.
(iii) Spatially resolve and regionalize the heat and moisture exchange above a complex landscape. Wavelet decomposition of the turbulence data is used to yield a flux observation each 90 m along the flight path. For each flux observation the biophysical surface properties in the flux footprint are determined. An environmental response function between the flux observations and biophysical and meteorological drivers is then inferred using a machine learning technique. This function is used to produce regional maps of the heat and moisture exchange to an accuracy of ≤18% and a precision of ≤5% for individual land covers.
Hence this dissertation provides the necessary basis for using WSMA to investigate the mechanisms of turbulent exchange over heterogeneous and topographically structured terrain. Moreover, the developed algorithms are generally applicable to (i) partitioning flux uncertainty and environmental variability, (ii) extrapolating flux measurements, (iii) assessing the spatial representativeness of long-term tower flux measurements, and (iv) designing, constraining and evaluating flux algorithms for remote sensing and numerical modeling applications.
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Applying regional climate change projections for spatio-temporal risk analyses of vector-borne diseases
(2011)
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Dominik Fischer
- Bei vorliegender Dissertation handelt es sich um eine Abhandlung zu vektor-assoziierten Krankheiten in Zeiten des Klimawandels. Bei vektor-assoziierten Krankheiten wird ein Pathogen durch einen Vektor (Überträger), auf ein Wirtstier übertragen. Als solche Vektoren agieren meist Arthropoden. Klimatische Veränderungen beeinflussen vektor-assoziierte Krankheiten insbesondere dadurch, dass Arthropoden ihre Körpertemperatur nicht selbst regeln können und zudem bestimmte Temperaturansprüche zur Pathogenentwicklung im Vektor erfüllt sein müssen. Das Klimaänderungssignal des 21. Jahrhunderts wird von Klimamodellen in verschiedenen räumlichen und zeitlichen Auflösungen wiedergegeben. Die Projektionen beruhen auf Emissionsszenarien klimawirksamer Treibhausgase. In der Arbeit werden die Einsatzmöglichkeiten von regionalen Klimamodellen zur Gefährdungsabschätzung anhand verschiedener Fallbeispiele aufgezeigt. Deren Nutzen und Einsatzmöglichkeiten werden einführend aufgeführt. Für die Risikoanalysen werden regionalen Klimamodelle REMO und COSMO-CLM angewandt, die durch dynamisches „Downscaling“ globaler Modelle generiert wurden. Beide sind in ihrem neuesten Prozesslauf in das globale Modell ECHAM5 eingebettet. Der direkte Übertrag bekannter Temperaturansprüche von Vektor und/oder Pathogen auf künftig zu erwartende Bedingungen stellt den ersten methodologischen Schwerpunkt dieser Arbeit dar. Eine Amplifikation des Dengue-Virus im Überträger der Stechmücke Aedes aegypti könnte demnach zunächst in Südeuropa, im weiteren Verlauf des 21. Jhd. aber auch in weiteren europäischen Regionen möglich sein. Weiterhin verdeutlichen die Ergebnisse, dass sich auch das Zeitfenster einer potentiellen Übertragung des Dengue-Virus verlängern kann. Durch das Überlagern der bekannten Temperaturansprüchen von Sandmücken (Gattung Phlebotomus) und der von ihnen übertragbaren Erreger - Leishmania infantum Komplex - können potentielle Regionen Deutschlands identifiziert werden, in denen einer autochthone Übertragung der Leishmaniose möglich ist. Es ist zu erwarten, dass ein solches Risiko zunächst in südwestlichen und westlichen Regionen Deutschlands, im späteren Verlaufe des des 21. Jhd. jedoch auch für eher nördlich und östlich gelegene Regionen bestehen wird. Der zweite innerhalb dieser Arbeit gewählte methodologische Ansatz zeigt die Einsatzmöglichkeiten regionaler Klimaprojektion für die bioklimatische Nischenmodellierung von Krankheitsüberträgern auf. Die anhand statistischer Verfahren ermittelte bioklimatische Nische der jeweiligen Art wird hierbei auf zukünftig zu erwartende klimatische Bedingungen übertragen. Anhand dieser Analyse kann aufgezeigt werden, dass sich die klimatische Eignung für die invasive Stechmücke Aedes albopictus (Überträger mehrere human-pathogener Viren) ausgehend von westlichen Regionen Europas über Mitteleuropa und schließlich Osteuropas erhöhen wird. Der Transfer der ermittelten spezifischen klimatischen Nische ausgewählter Sandmücken-Arten (u.a. Überträger der zum Leishmania-Komplex zählenenden Pathogenen) auf künftige Bedingungen lässt vermuten, dass deren klimatische Eignung in Mitteleuropa - abgesehen von alpinen Regionen - zunehmen wird. Künftige potenzielle Ausbreitungswege der Sandmücken in einer sich verändernden Umwelt, werden via “least-cost analysis“ ermittelt. Die Ergebnisse deuten darauf hin, dass aufgrund der eingeschränkten natürlichen Ausbreitungsfähigkeit, einige der künftig potenziell geeigneten Lebensräume nicht erreicht werden. In den verschiedenen Fallstudien kann gezeigt werden, dass die zu erwartenden klimatischen Veränderungen im 21. Jhd. eine mögliche Ausbreitung der in dieser Arbeit adressierten Vektoren und vektor-assoziierter Krankheiten in Europa begünstigen werden. Als einheitliche Tendenz kann speziell für Mitteleuropa festgehalten werden, dass sich die Gefährdung, Ende des 21.Jhd. erhöhen wird. Dies begründet sich höchstwahrscheinlich durch die projizierte raschere Erwärmung in der zweiten Jahrhunderthälfte. Abschließend bleibt jedoch festzuhalten, dass es neben klimatischen Veränderungen weitere Faktoren für die Ausbreitung bzw. Neuetablierung von Vektoren und den damit verbundenen übertragbaren Infektionskrankheiten ausschlaggebend sind. Der Einfluss einzelner Faktoren auf die Etablierung bzw. Ausbreitung vektor-assoziierte Krankheiten variiert auf raum-zeitlichen Skalen. Für die ermittelten klimatisch-abgeleiteten Risikogebiete sollten in Folgestudien auf kleineren Skalen wirksam werdenden Faktoren integriert werden. Diese Ergebnisse können wiederum die Entwicklung von Surveillance- und Monitoringprogramme unterstützen, um somit Maßnahmen gegen die Ausbreitung von vektor-assoziierten Krankheiten initiieren zu können.
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Assessment of the environmental acceptability of refrigerants by discrete mathematics: cluster analysis and Hasse diagram technique
(2008)
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Guillermo Restrepo
- The recognition of the adverse environmental impact of chlorofluorocarbons (CFCs), mainly used as refrigerants, has lead to look for environmentally acceptable CFC replacements. Main environmental concern CFCs face is their ability to deplete the stratospheric ozone layer, quantified by the ozone depletion potential (ODP). Some of the first replacements mooted were hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), which contribute to the global warming, quantified by the global warming potential (GWP). ODP and GWP are related to the atmospheric lifetime (ALT), a third indicator. Hence, the environmental impact of a refrigerant may be characterised by a triple of ODP, GWP and ALT values. In this respect, an acceptable refrigerant is a chemical with low ODP, GWP and ALT values. One of the first steps to assess the environmental acceptability of refrigerants is to classify them to find substances with common features. Hence, a supervised and unsupervised classification was performed over 40 refrigerants. First one was a classification based upon elemental composition and functional groups present in refrigerant molecules which leads to: CFCs, HCFCs, HFCs, hydrocarbons (HCs), hydrofluoro ethers (HFEs), chloromethanes (CMs), carbon dioxide, trifluoroiodomethane, dimethyl ether and ammonia. The unsupervised classification was performed using hierarchical cluster analysis. In this case, refrigerants were characterised by three kinds of descriptors: Environmental properties (ODP, GWP, ALT), thermodynamic features related to their refrigeration performance and molecular descriptors derived from their molecular structure. Eight clustering methodologies were applied to each kind of refrigerant descriptors. To assess the stability of these classifications, the cluster index, a method for quantifying classification similarities was developed and further applied to refrigerant results. It was found that environmental descriptors are the only case in which refrigerant classes are stable when varying the classification method. The chemotopological procedure, a method for studying similarity relationships, was applied to the environmental classification of refrigerants. It was found that CFCs are similar to themselves and also to 1,1,1,3,3,3-hexafluoropropane, a HFC. The most similar substances to all CFCs considered were trichlorofluoromethane and 1,1,2-trichloro-1,2,2-trifluoroethane. The other refrigerant families were found to be similar to many other substances, therefore there is no clear affiliation of refrigerants of one family to one certain class. It was found a disagreement between the supervised classification leading to refrigerant families and the three unsupervised classifications (environmental, thermodynamic and molecular ones). Therefore, refrigerant classification into families does not imply same classification based upon environmental properties, thermodynamic features and molecular descriptors. A different refrigerant classification was performed, i.e. the one based upon order relationships of refrigerant environmental properties. In this case the Hasse diagram technique, a method based on partial order theory, was applied to the 40 refrigerants characterised by environmental properties. A parameter free procedure for ordering classes based upon order relationships of their elements was developed. For that purpose, the dominance and separability degrees were introduced, first one indicates the extent to which members of one class hold higher descriptor values than the members of another class; while separability degree quantifies the lack of order relationships between two classes. Dominance and separability degrees were related by a theorem. By the application of dominance and separability degrees to refrigerant families three main classes were detected: problematic substances, gathering CFCs, octafluorocyclobutane and bromochlorodifluoromethane; least problematic ones, collecting HCs, CMs, carbon dioxide, trifluoroiodomethane, dimethyl ether and ammonia; and moderately problematic refrigerants, made from HCFCs, HFCs and HFEs. It was found that some HFEs are not dominated by CFCs, which raises the question on the applicability of these substances as environmentally acceptable replacements. METEOR (Method of evaluation by order theory), a procedure for prioritising descriptors and studying its effect on the order relationships of the objects considered was discussed. When applied to the refrigerants, the effect of prioritising ODP, GWP and ALT in the order relationships of these substances was studied. It was found that pentafluorodimethyl ether, a HFE, is one of the most problematic refrigerants under a large range of priorities of the environmental properties considered. Due to the mathematical generality of the methods here introduced, they are not restricted to the analysis of refrigerants but can be used to the study of different sets whose elements are characterised by various attributes.
