Drivers of forest dynamics: Joint effects of climate and competition
- The present dissertation thesis addresses different aspects of forest dynamics and possible changes due to climate change. Various modelling approaches are used to explore joint effects of climate and competition on forest dynamics with a focus on temperate forests. Motivated by scientific interest, this thesis is aimed at contributing to the establishment of fundamental knowledge for proper ecosystem management. Each of the research projects of this thesis explores a facet of forest dynamics. It appears that for projections of forest dynamics under climate change particularly, it is critical to consider competition among trees.
In the first study, the joint effect of climate and competition on forest dynamics in a mountain forest of New Zealand was investigated. The landscape simulation model LandClim was calibrated based on empirical data and applied to reproduce a 1700 years forest succession under stationary climate at the slope of Mt. Hauhungatahi, North Island. Although designed for European temperate forests, LandClim was capable of simulating NZ´s forest dynamics.
Under non-stationary climate, forests likely remain in disequilibrium with climate for some time due to the longevity of trees and competitive prevention of establishment. This aspect was investigated in a mixed beech-oak forest in Germany, using LandClim and the forest gap model SILVA in a cooperation study. Furthermore, a possible ‘climatic turning point’ was investigated, the point at which species dominances change due to changes in competitiveness caused by climate change. Both models projected a potential climatic turning point at a mean annual temperature of 11-12 °C and precipitation sum of 500‑530 mm. However, the change of species composition in existing mixed stands was much slower since the turning point also depended on inherited stand structure. Based on these projections the promotion of oak at dry sites seems advisable due to its superior resistance and resilience to drought.
The applied simulation models consider joint effects of climate and competition but no changes in species sensitivity to competition along climatic gradients. The Spanish National Forest Inventories provided a solid basis to develop a statistical model for the influence of climate and competition on tree growth. The results indicated that in Mediterranean forests the effect of competition increases with aridity potentially resulting in an additional disadvantage for drought sensitive oaks compared to pines under climate change.
Under the prerequisite that forest dynamics will be affected by climate change, different forest management strategies on adaptation are currently discussed. One option is the promotion of tree species that are better adapted to anticipated future climates (such as oak instead of beech in Germany) and also the introduction of non-local ecotypes of local species. This increase in biodiversity intuitively appears promising because it is in line with the insurance hypothesis and the portfolio effect theory. Within this thesis the effect of ecotype mixing as an increase of within stand diversity under consideration of self-thinning was assessed. It was shown that ecotype mixing in forest stands might lower the risk of yield losses and at the same time might exempt the portfolio effect from its drawback of lower chances for high yields.
Climate not only affects demographic rates of tree species but also all other ecosystem components. Disturbances are an important component of forest dynamics because they initiate successions and thereby influence species coexistence. Climate will alter disturbance regimes not only directly but also due to interactions among disturbances, for example an increased risk of insect outbreaks due to weak tree defence caused by severe drought stress. Most disturbance interactions have been observed to be positive, implying that increases of disturbances in quality and quantity due to climate change will be amplified. Furthermore, systems containing positive feedback loops are considered to be mostly unstable, which would result in forest collapse. A theoretical study on disturbance interactions showed why positive feedback loops of disturbances do not necessarily lead to a forest collapse. Disturbance interactions might cause only a minor part of disturbances, whereas direct changes due to climate change are of much higher importance.
The described studies reflect the diversity of the research field forest dynamics and innovative ecological methodology. Nevertheless, the present thesis is not an exhaustive discussion of drivers of forest dynamics under climate change. Forest dynamics and its drivers provide a range of open research questions posing a challenge for fundamental an applied research of high relevance for society.
Plasticity, Intraspecific Variability and Local Adaptation to Climatic Extreme Events of Ecotypes/Provenances of Key Plant Species
- Climate change, and especially an increase of magnitude and frequency of climatic extreme events such as drought periods or heatwaves, will alter growing conditions for plants in the future. Persistent ecosystems, with long-living organisms, such as forest or permanent grassland will be particularly impacted by this development. The velocity of these changes is likely to occur at a pace, which species may not be able to keep track with by natural dispersal or genetic adaptation. Agriculture, forestry and ecosystem management must develop counteracting practices to secure the persistence and functioning of these ecosystems and thus their provision of goods and services. Therefore it is important to develop a better understanding how species and ecosystems may respond to future climatic stressors. Impact assessments, e.g. via climatic envelope modelling are prone to misinterpretations of the adaptive capacity of species, as they do not incorporate the intraspecific genetic and phenotypic differences that exist within the populations accross the distribution range of a species.
Yet, intraspecific variation may exhibit potential tools for the development of climate change adaptation strategies. Here, I focus on key ecosystems in Central Europe. In particular the selective use of plant provenances or ecotypes may help to make ecosystems climate-resilient without a potentially more problematic introduction of exotic species. Especially provenances from warmer, drought-prone regions, with a current climate similar to the projected one for Central Europe recently came into focus as potential substitutes for local provenances, as they might have developed local adaptations to climate conditions at their location of origin. Insights about the response of these provenances to changing averages and extreme event regimes are crucial for a reasonable use of within-species diversity in climate change adaptation.
First, the concept of assisted colonization or migration of species or ecotypes and the role it can play as an adaptation strategy in agriculture, forestry or nature conservation is introduced (Manuscript1). It is suggested that a focus should be laid on keystone species that ensure ecosystem persistence and functioning as they govern the habitat structure and microclimate of a site. The assisted colonization of pre-adapted ecotypes of keystone species from climates similar to future projections for the target site is proposed.
Furthermore, provenances of selected grassland and forest key-species were exposed to drought and warming in two experiments in Bayreuth and Landau, and their ecological responses were analysed. Results suggest that local adaptations to climatic stressors exist. However, the magnitude and direction of responses strongly depend on species and climatic variables. For grassland species, e.g. differences in drought sensitivity could be demonstrated in some cases (Manuscript 4). Fagus sylvatica exhibited differences between the provenances in response to drought conditions, as well (Manuscript 3). It seems that marginal provenances, from the dry margins of the distribution range, show less increment reduction due to the drought treatment. Yet, under more favourable conditions of water supply these provenances did not yield the same high increment rates than more central provenances, indicating a trade-off between stability under stress and yield under non-stress conditions. A pine species that is generally considered to be rather drought-resistant, Pinus nigra, which is a potential substitute for climate-threatened conifers on dry sites in Central Europe, did not show any differences in response to drought and warming (Manuscript 2), maybe due to a weak selective pressure as a result of high drought-resistance across the whole distribution range. The impacts of drought on increment became not visible before the second year after the treatment, stressing the need for more long-time experiments in climate impact research.
Even in a generally warmer environment, cold extremes in winter or spring are expected still to prevail in the future. Therefore, the provenances of the selected species were tested for their cold-hardiness and late frost resistance (Manuscripts 5-7). Growth of the grassland species and F. sylvatica were negatively impacted by a late frost event and differences in late-frost sensitivity between provenances or ecotypes were identified. The (sub-) mediterranean species P. nigra showed differences between provenances in their winter cold hardiness. Correlations between performance under cold stress and winter conditions or late frost proneness of the places of origin could be established for almost all species. However, preceding climate experience, such as the warming or drought treatment of the plants altered their reaction to cold extremes compared to the control treatment, indicating the complexity of the interactive impacts of climate factors on ecosystem and plant performance.
The uncertainty of climate projections and the multitude of changing climatic stressors, though, make the prospect of an easy and rapid success in the search for single “best-adapted” provenances very questionable. In economics the portfolio effect shows that a diversification of investments decreases the risk of a total loss of profits. Hence, in a modelling procedure based on the increment data from the above mentioned experiment it was tested if a “portfolio investment” in several provenances in one stand decreases the risk of yield losses (Manuscript 8). Results indicate that the higher the number of provenances the higher the chance for a “best-performer” to be included in the set. So the likelihood of higher yields, under different climatic conditions increases, yet the risk of low yields stays stable.
Generally, it seems that the selective use of plant species and ecotypes in climate change adaptation can be a feasible tool to maintain ecosystem functionality and productivity. However, the uncertain projections, the multitude of climatic stressors and their interplay with other environmental factors and the potential impacts of assisted colonization of ecotypes on the genetic diversity within species and populations require further research.
Waste-Management in Mazabuka, Sambia - „Southern Wings Environmental Recovery Service – angepasste Lösung mit Modellcharakter, oder nicht konkurrenzfähiges Kleinunternehmen?“
- Im Rahmen dieser Arbeit wird das Abfallmanagement einer Mittelstadt Sambias analysiert. Dabei werden rechtlichte, institutionelle, kulturelle, ökonomische und ökologische Aspekte untersucht. So werden exemplarisch charakteristische Herausforderungen des Abfallmanagements in den Ländern des Südens (LdS) dargestellt. Explizit wird eine Organisationsanalyse eines abfallwirtschaftlichen Kleinunternehmens durchgeführt, um die Frage zu beantworten, ob das praktizierte und in der gängigen Literatur als Best-Practice bezeichnete Betreibermodell einer Handkarren-Müllabholung tatsächlich Vorbildcharakter hat. Letztlich werden auf die Analyse aufbauend spezifische Handlungsempfehlungen in Bezug auf das Wirtschaftsunternehmen, sowie allgemeingültige Erkenntnisse in Bezug auf das Abfallmanagement in den LdS aufgeführt.
Silicon and oxygen self-diffusion in forsterite and implications to upper-mantle rheology
- (1) Silicon lattice diffusion coefficient in dry forsterite
The high temperature creep of olivine is believed to be controlled by self-diffusion of olivine. However, the experimentally measured silicon diffusion coefficients (DSi) [Dohmen et al., 2002; Jaoul et al., 1981] were about 2-3 orders of magnitude lower than those estimated from dislocation creep rates by deformation experiments [Durham and Goetze, 1977a; Goetze and Kohlstedt, 1973]. In order to resolve this discrepancy, we measured DSi in a dry forsterite single crystal at 1600-1800 K, 1 atm -13 GPa using an ambient pressure furnace and Kawai-type multi-anvil apparatus. The water contents in the samples were carefully controlled at <1 wt. ppm. The results of DSi showed small negative pressure dependence with an activation volume of 1.7±0.4 cm3/mol. The activation energy is found to be 410±30 kJ/mol. LogDSi at 1600 and 1800 K at ambient pressure are -19.7±0.4 and -18.1±0.3 (DSi in m2/s), respectively, which are ~2.4 orders of magnitude higher than those reported by Jaoul et al. . Their low DSi might reflect the effects of a horizontal migration of the isotopically enriched thin films applied on the sample surfaces, which may inhibit diffusion into the substrate during annealing. Our results resolved the discrepancy of DSi measured in diffusion experiments with those deduced from creep rates measured in deformation experiments.
(2) Effect of water on silicon self-diffusion coefficient in forsterite
Water has been considered to largely affect geodynamical processes in the Earth’s interior. In particular, experimental deformation studies suggested that even several tens wt. ppm of water can enhanced creep in olivine by several orders of magnitude. However, those deformation results are doubtful because of the experimental limitations, e.g., considering only a limited range of water content and very high stresses applied to the samples. Because the high temperature creep of silicate minerals is controlled by silicon self-diffusion, we systematically measured DSi in iron-free forsterite at 8 GPa, 1600 - 1800 K, and water content (CH2O) from <1 up to ~800 wt. ppm, showing a relationship, DSi ∝ (CH2O)0.32±0.07. This CH2O exponent is strikingly lower than 1.2, which has been obtained by deformation experiments [Hirth and Kohlstedt, 2003]. The high nominal creep rates in the deformation studies under wet conditions may be caused by excess grain boundary water. Thus, the effect of water on olivine rheology is much smaller than that it has been considered before and many geodynamic problems should be reconsidered. The viscosity in the upper mantle calculated from DSi continuously decreases with increasing depth without appearing a minimum zone by mineral hydration, and therefore, the asthenosphere softening cannot be caused by water effect. The CH2O differences between the source of hotspots and their surrounding regions only causes a viscosity contrast by a factor of two, which is rather small in comparison with that caused by temperature differences. Therefore, CH2O differences cannot be the major reason that leads to the immobility of hotspots.
(3) Effect of water on oxygen self-diffusion coefficient in forsterite
Oxygen is the second slowest diffusion species in olivine with similar diffusion coefficients as silicon. Therefore, oxygen diffusion also plays essential role in rock deformation as well as silicon diffusion. In order to examine the effects of water on creep reported by rock deformation experiments, we also measured oxygen self-diffusion coefficient (DO) in forsterite at a pressure of 8 GPa and temperatures of 1600 - 1800 K as a function of CH2O from <1 up to ~800 wt. ppm. The experimental results showed DO ∝ (CH2O)0.06±0.1 ≈ (CH2O)0. Namely, water has no effect on DO. Together with the small effect of water on silicon self-diffusion coefficient, we conclude that the role of water on upper mantle rheology is insignificant.
(4) Silicon grain boundary diffusion coefficient in forstetrite
Dislocation creep causes non-Newtonian viscosity and seismic anisotropy whereas diffusion creep doesn’t. Determination of deformation mechanism in Earth’s interior is thus essential to understand mantle dynamics. We have measured silicon grain-boundary diffusion coefficient in forsterite as a function of pressure, temperature, and water content. The activation volume, activation energy, and water exponent are found to be 1.8±0.2 cm3/mol, 245±12 kJ/mol, and 0.22±0.05, respectively. The rates of dislocation creep, Coble diffusion creep, and Nabarro-Herring diffusion creep calculated from silicon lattice and grain-boundary diffusion coefficients suggest dominant diffusion creep in cold mantles and mantle wedges. In the asthenosphere, dislocation creep always dominates because of the high temperature. The deformation mechanism transition does not occur in the asthenosphere. In the lithosphere, diffusion creep dominates in shallow regions and dislocation creep dominates in lower regions. In mantle wedges, diffusion creep dominates and therefore olivine does not form lattice-preferred orientation: their strong anisotropy is caused not by olivine but by serpentine. The Newtonian rheology suggested by postglacial rebound and the seismically observed mid-lithospheric discontinuity should be attributed to the diffusion creep dominated cold continental lithosphere.
GrenzStattMiteinander. Zivilgesellschaftliche Raumproduktionen eines grenzüberschreitenden deutsch-polnischen Gemeinwesens in Görlitz und Zgorzelec.
- Während Pressevertreter sowie Politiker Görlitz (D) und Zgorzelec (PL), die sich seit 1998 als Europastadt bezeichnen, zum „Modellfall des europäischen Einigungsprozess“ (FAZ, 10.06.2006) erklären, sind damit verbundene Visionen in ihrer Differenz zum Alltagsleben in den nach dem Zweiten Weltkrieg geteilten Grenzstädten deutlich spür-bar. – Vollzieht sich die postulierte Konstruktion eines grenzüberschreitenden Ge-meinwesens auch als bottom-up-Prozess innerhalb von Alltagswelten beiderseits der Staatsgrenze? Davon ausgehend folgt die Arbeit mit einer ethnographischen For-schungshaltung der Perspektive zivilgesellschaftlicher Akteure im Bereich von Kultur und Bildung, die für das sogenannte „borderwork“ (Rumford 2008), der Konstruktion, Verschiebung und dem Abbau von Grenzen, eine aktive Position einnehmen. Als Zu-gang dient die doppelte Triade der Raumproduktion, die Lefebvre in La production de l'espace (1974) formuliert und aufgrund der Prämisse „(sozialer) Raum ist ein (soziales) Produkt“ sowohl territoriale als auch soziale bordering-Prozesse berücksichtigen kann.
The Effect of Spatial and Environmental Drivers on Patterns in Species Richness and Composition
- This thesis includes eight manuscripts with methodological, empirical and theoretical contributions that aim to enhance the understanding of species richness and composition patterns and their underlying drivers. Islands and isolated systems are in the focus of this work.
Islands provide optimal conditions to study biogeographic patterns. Theoretical advances in ecology have been initiated by island biogeography. Theory on island biogeography has particularly been improved by a better representation of time related components including speciation and environmental change. Oceanic islands are not stable systems but follow a characteristic ontogeny. After the volcanic emergence over the sea surface, erosion processes, shaping the island first more heterogeneous and then flatter, transform islands. This thesis shows how particular characteristics of the classic theory of island biogeography can be included in the currently most advanced theoretical framework. While MacArthur & Wilson (1963) particulary focussed on processes (colonisation and extinction) for generating species richness patterns, current theory assumes a defined upper limit for species richness (“carrying capacity”). By reinforcing the importance of processes in the current theory, as suggested in this thesis, it is much simpler to formulate hypothesis that can be tested by empirical data. Carrying capacity is linked to “habitat heterogeneity”, both, in the meaning of topographic variability as well as the number of vegetation units that are present in a given area. This thesis demonstrates that a clear terminology is a prerequisite for a profound understanding of the effects of “heterogeneity” on species diversity patterns in general and the underlying biogeographic processes in particular. The heterogeneity of surfaces influences species diversity not only on scales larger than kilometres but also is important on very fine scales of meters and smaller. Novel methods to measure different aspects of surface variability are introduced and discussed and their effect on species richness and composition of plant species groups in different ecological systems is presented.
Furthermore, this thesis highlights the isolating effect of elevation (elevation-driven ecological isolation hypothesis). Environmental filtering along an elevational gradient differentiates ecosystems. Isolation increases with elevation, as comparable ecosystems are much farther apart at high elevations than is the case for lowland ecosystems. In addition, ecosystems on neighbouring islands or on the continent that serve as source regions for colonising species are smaller in area in high elevations in comparison to low elevation ecosystems. Consequently, an above average speciation rate reflected in a high percentage of endemic species can be expected for higher elevations on islands and high mountains. The elevation driven ecological isolation hypothesis is tested for a number of islands and a new hypothesis indicating a complex interaction with isolation is developed. The difference in isolation between low and high elevation ecosystem diminishes as the overall isolation of the island increases. Thus the relation between the percentage of endemic species and elevation should reverse with an increase in isolation. On very isolated islands, low and high elevation ecosystems are alike isolated but low elevation ecosystems should have an above average speciation rate as they provide more area and higher temperatures relative to the ecosystems above (e.g. metabolic theory of ecology).
The scale dependence of diversity patterns are attributed to ecological processes that operate differently over varying extents and grain sizes. This thesis demonstrates that scale dependencies in distance-decay analyses cannot be traced back to processes that are specific for the ecological scale, but can largely be attributed to sampling design and are highly sensitive to grain size and study extent. Distance-decay analyses are an adequate method to assess spatial turnover in species composition. However, this thesis shows that frequent practise of making comparisons among studies is not possible within the current methodological framework.
Finally, this thesis provides an overview on patterns in species richness and composition and elaborates interconnections between associated theories and underling drivers. Promising novel research questions and directions are identified in the field of island biogeography and in an adequate formalisation of a “heterogeneity” concept.
Energy-domain synchrotron radiation Mössbauer source for physics under extreme conditions
- Iron is one of the most abundant elements on Earth, and it is an important component in minerals. Electronic and magnetic properties of iron-bearing materials significantly affect processes occurring in the deep interior of the Earth. In the materials that make up the Earth’s lower mantle iron may exist in different valence, spin states and crystallographic environments. Most of the existing experimental techniques either do not allow to separately follow evolution of different iron sites or are not suitable for measurements under high-pressure/high-temperature conditions. This makes studies of iron electronic structure under such conditions extremely challenging.
The current Ph.D. thesis is divided into two major parts. The first part is dedicated to the development of a Synchrotron Mössbauer Source (SMS). This device allows energy domain Mossbauer spectroscopy to be performed on a sample under pressures above 100 GPa in laser heated diamond anvil cells. The second part is dedicated to studying the behavior of iron in iron/alumina-bearing silicate perovskite under conditions of the Earth’s lower mantle.
1. Synchrotron Mössbauer Source
There are several techniques that allow magnetic and electronic properties of materials under extreme conditions to be probed: X-ray Emission Spectroscopy (XES), X-ray absorption near edge structure (XANES), Nuclear Resonance Spectroscopes, etc. For elements in which observation of Mössbauer effect is possible the most mature, sensitive, and suitable technique for studies of magnetic and electronic properties is energy-domain Mössbauer spectroscopy.
However, due to low brilliance of utilized radioactive sources and low natural abundance of iron in lower mantle minerals measurements using conventional energy- resolved Mössbauer spectroscopy require very long time and usually are limited to moderate pressures. The problem can be solved by combining the outstanding properties of synchrotron radiation (high brilliance, possibility for extreme focusing) with the energy-resolved approach. In brief, what is needed is a synchrotron source of Mössbauer radiation. Construction of such source was the primary task of my PhD work. The possibility to develop such a source was demonstrated at the Nuclear Resonance beamline ID18 at the European Synchrotron Radiation Facility (ESRF) by Smirnov et al. (1997). The source is based on pure nuclear reflections existing in antiferromagnetic 57FeBO3 crystals.
￼The major technical goals of my PhD work were to (a) construct a device that would be permanently ready for operation, and (b) optimize it to have the best possible resolution and highest possible intensity. In order to achieve these goals theoretical calculations were first conducted to understand how to best improve the performance. Second, several experiments were performed to confirm the theoretically predicted results. Third, several optical schemes of the SMS were tested in order to determine the optimal setup.
As a result of the research and development program a powerful Synchrotron Mössbauer Source (SMS) for high-pressure applications was constructed at the Nuclear Resonance beamline (ID18) of the ESRF. Using results obtained in the combined theoretical/experimental study of angular dependence of energy and temporal distributions of the pure nuclear reflections of iron borate crystal, the SMS was optimized for the highest possible intensity and best possible resolution. The bandwidth of radiation provided by the SMS is between 10-15 neV (2-3 Γ0, where Γ0 is a natural linewidth of Mössbauer resonance for Iron), the intensity is ~2.5×104 photons/s and the typical scanning velocity range is about ±12 mm/s (±0.6 μeV). In contrast to conventional radioactive sources, the SMS gives the possibility to focus the beam to tens of microns. SMS is the in-line monochromator, permanently located in the optics hutch and operational immediately after moving it into the incident beam position. The source can be used with all existing sample environments in the experimental hutches downstream of the beamline.
The implementation of this device opens the possibility for studying systems with complex hyperfine structure utilizing energy-resolved approach under various extreme conditions, for example at high-pressure. Furthermore, the SMS allows for very short collection times of only a few minutes, which enables data to be collected during laser heating. Several high-pressure and high-pressure/high-temperature studies that have already been performed are described in the second part of this Ph.D. thesis. The almost 100% recoilless resonant radiation delivered by the source and its high brightness allow a broad field of SMS applications. The SMS can be utilized in any mode of synchrotron storage ring operation.
2. Study of the spin state of Fe3+ ions in perovskite
Silicate perovskite (Mg,Fe)(Si,Al)O3 is the most abundant phase in the Earth’s lower mantle. Knowledge of its properties is indispensable for understanding lower mantle behavior. Dynamic, thermodynamic, and transport properties of silicate perovskite can be significantly affected by the valence and spin state of iron. Silicate perovskite with 5-10 mol% of Fe (where Fe3+/ΣFe ~50–75% (McCammon et al., ￼1997)) and Al, is dominant phase in Earth lower mantle (~75 vol%) (Zhang et al., 2006; Stackhouse et al., 2007). The behavior of Fe electronic properties under conditions close to those of the Earths lower mantle remains strongly controversial.
The second part of my Ph.D. work is dedicated to an investigation of the spin state of iron in Fe3+- rich silicate perovskite at high pressure. Four different silicate perovskite samples with different stoichiometry were studied using the Synchrotron Mössbauer Source. SMS spectra were collected at room temperature and pressures up to 122 GPa using diamond anvil cells, with or without laser annealing of the samples.
The hyperfine parameters, i.e., centre shift and quadrupole splitting, for the same phases, which were extracted from measured spectra for all perovskite samples studied in this work, are the same at each pressure within experimental error. Moreover, there is no change in Fe3+/ΣFe for individual samples over the entire pressure range of the experiment. The hyperfine parameters of the Fe3+ doublet are consistent with the high-spin state (Gütlich et al., 2011), and their smooth variation with pressure indicates that Fe3+ does not undergo spin crossover within the entire pressure range. All observed changes in the spectra are associated with abrupt changes in the electronic state of Fe2+. The hyperfine parameters of the low QS Fe2+ doublet correspond to the high-spin state (McCammon et al., 2008), while the doublet with high quadrupole splitting, whose intensity grows with pressure at the expense of the Fe2+ high-spin state, corresponds either to intermediate-spin (IS) Fe2+ (McCammon et al., 2008) or a distortion of the site occupied by high-spin Fe2+ (Hsu et al., 2010). Based on results presented in a work of Narygina (2010), we indentify changes in Fe2+ electronic structure as high-spin to intermediate spin transition. Irrespective of the interpretation of the Fe2+ spin state, conclusions regarding the absence of spin crossover in Fe3+ remain valid.
These results show that the previously reported spin crossover of Fe3+ ions does not occur when Fe3+ occupies the A-site. In both alumina-containing and alumina-free silicate perovskites Fe3+ ions remain in the high-spin state up to at least 122 GPa, i.e., almost up to the pressure corresponding to the lower mantle - outer core boundary. The results also indicate that Fe3+ ions do not diffuse from the A-site to the B-site in perovskite after high-temperature annealing at high pressure, Mössbauer spectra of before and after annealing are identical. There is also no evidence for high-spin to low-spin crossover of Fe3+ ions due to site change. In contrast, the results confirm that Fe2+ ions undergo a transition from a high-spin to an intermediate spin state, without reaching a low-spin state within the studied pressure range at room temperature. These results suggest that the seismic velocity anomalies in the lower mantle cannot be attributed to spin crossover in Fe3+.
Synthesis and investigation of boron phases at high pressures and temperatures
- Boron, discovered as an element in 1808 and produced in pure form in 1909, still remains one of the most complicated light elements full of surprises. Even the number of pure boron polymorphs is a subject of intensive discussions. It is proven the existence of α-, β- and γ-boron phases. Structural details of the most common boron phase (β-B) are still not fully revealed. For decades boron remained the last stable element in the periodic table, whose ground state was not determined. It has been a subject of a longstanding controversy, whether α-B or β-B is the thermodynamically stable phase at ambient pressure and temperature.
The existence of the α-tetragonal boron phase T-50 has been an open question since its first discovery. It was not clear if T-50 could be synthesized as a pure boron phase or its structure must be stabilized by the presence of carbon or nitrogen. Theorists claimed that T-50 could not exist at all because of its unstable electronic configuration.
We have developed a method of synthesis of single crystals of α-boron. They were crystallized from a boron-platinum melt at high pressures (6-11 GPa) and high temperatures (1450-1875 K). An average size of the as-grown isometric crystals was 60 μm to 80 μm in maximum dimension. The crystal structure is in good agreement with the literature data. Detailed investigation of single crystals of α-boron using Raman spectroscopy was performed under elevated pressures and temperatures. The behaviour of the Raman modes under pressure was studied both theoretically and experimentally. Single crystals of β-boron were grown at temperatures above 1550 K and pressures up to 11 GPa using the similar methodology like that worked out for synthesis of α-boron.
In a series of experiments above 8 GPa we synthesized single crystals of tetragonal δ-boron (also known in literature as α-tetragonal boron or T-50) and refined the crystal structure of this phase based on synchrotron X-ray diffraction data. The purity of δ-boron was confirmed by means of the microprobe analysis and the electron energy loss spectroscopy (EELS).
A new, so far unknown boron phase, ε-boron, was synthesized at pressures of 8-10 GPa and temperatures between 2000-2250 K. The microprobe analysis and EELS revealed that the samples were not contaminated. The crystal structure of the new phase was determined by means of single crystal X-ray diffraction. ε-boron crystallizes in a R-3m space group with the unit cell parameters a = 5.5940(7) Å and c = 12.0756(16) Å (in hexagonal setting). The unit cell contains 15 boron atoms. The structure can be presented by the network of B12 icosahedra with a group of three boron atoms in the inter-icosahedra space. This phase is isostructural to boron carbide B13C2 (if carbon atoms are substituted by boron ones). Measured hardness is ~60 GPa which places ε-boron in the family of superhard materials.
We have demonstrated that δ-boron and ε-boron are metastable polymorphs because (a) they were found only together with other stable boron phases (α-, β-, or γ-B), and (b) upon heating at high pressure, both δ-B and ε-B transform to β- or γ-B, if the PT conditions correspond to the fields of stability of the latter.
Summarising, in the course of the present work the high-pressure high-temperature synthesis of the five boron polymorphs was established as a reproducible, verifiable and well-documented process. Following the synthesis prescription one can grow single crystals of α-B, β-B, γ-B, δ-B, and ε-B phases. Based on results of numerous HPHT experiments, the phase boundaries between the stable boron phases (α-B, β-B, γ-B) were found. Thus, our serial exploration of the pressure-temperature field using the large volume press synthesis technique resulted in establishing the phase diagram of boron (showing also the PT fields of the appearance of its two metastable phases, δ-B and ε-B) in the pressure interval of 3 GPa to 18 GPa at temperatures between 1073 K and 2423 K. Based on our experimental data and linear extrapolation of the α/β phase boundary down to ambient pressure we could resolve a longstanding controversy on the ground state of boron in favour of the α-B phase.
Documentation of the EVENT-HMMS Experiment 2012 – Microclimatological effects of rain-out shelters within EVENT II
- no abstract
Site-specific modelling of turbulent fluxes on the Tibetan Plateau
- The Tibetan Plateau attracts attention in recent decades due to its influence on the East-Asian Monsoon and regional hydrology. Therefore estimates of the regional energy and water balance have come into the focus, utilising remote sensing and regional model approaches, but such attempts require surface-specific flux data of high quality for validation. Eddy-covariance measurements are qualified for this task, but these are scarce on the Tibetan Plateau, incomplete due to quality filtering and potentially biased due to the well-known closure gap of the observed energy balance as well as small-scale heterogeneity. This thesis is related to the infrastructural EU project CEOP-AEGIS, aiming at a standardised processing of eddy-covariance data – including correction of the energy balance closure and gap-filling – on the Tibetan Plateau.
In a pre-analysis step, particular issues about data quality of turbulent fluxes (sensible heat flux and latent heat flux/evapotranspiration) at Tibetan Plateau sites have been addressed. One of them is the degradation of data quality due to the frequent occurrence of near-ground free convective conditions. Another issue arises from coordinate rotation for non-omnidirectional sonic anemometer, which requires a careful handling. In consequence, a sector-wise planar-fit is recommended, disregarding the sector influenced by the anemometer's mounting structure. This can reduce occurrences of invalid momentum flux data, whilst no effect on scalar fluxes can be seen.
As a main topic, this thesis investigates the application of process-based modelling to estimate turbulent flux exchange between the surface and the atmosphere for typical surface types on the Tibetan Plateau. Therefore a case study has been carried out at Nam Co, Tibetan Plateau. Turbulent flux measurements over dry and wet grassland as well as over a shallow lake have been conducted during the summer monsoon season of 2009, and modelled with the land surface scheme SEWAB and a hydrodynamic multilayer model for the lake. Adaptations were implemented to the land surface scheme with regard to the special conditions on the Tibetan Plateau, such as extreme diurnal variation of surface temperature and variation in soil moisture, further called TP version. The analysis includes a consequent model comparison with eddy-covariance data, using model parameters derived independently rather than applying optimisation strategies. Specific attention has been devoted to the impact of observed energy balance closure and its correction, establishing a new correction method according to the Buoyancy flux.
The land surface model reasonably represented the dry and the wet grassland site by only setting the site-specific model parameters, and the TP version performed overall better than the original version, while laboratory measurements of soil parameters failed to improve model performance in comparison to standard parameter values. Soil temperature and moisture measurements as well as field based knowledge of the soil type have been identified as minimum requirements for model parameter acquisition. Lake surface fluxes have been modelled reliably, the lake depth has been taken into account. These results can be transferred to any lake on the Tibetan Plateau given the required forcing data including a representative lake surface temperature.
The choice of the surface model and the selection of the energy balance closure correction method are inter-related problems. The correction partitions the balance residual to the sensible and latent heat flux. This can be typically done according to the Bowen ratio, or according to the presented new method which attributes a larger fraction to the sensible heat flux. Testing both methods leads to partly ambiguous model performance, especially with respect to the used parameter sets. It clearly leads to shifts in model bias, while the R² metric suggests higher model compatibility to the Bowen ratio correction. The latter agrees with previous findings with respect to SEWAB modelling, but is in contradiction with recent experimental findings, attributing the closure gap to secondary circulations, driven by buoyancy. Future research on model structure should account for such processes.
As expected, the flux measurements showed distinct differences between the investigated land use types in magnitude and dynamics. The used models were able to resolve these differences in general with contrasts between surface types exceeding model errors. This must be considered when validating regional flux estimates with eddy-covariance data from the dry Nam Co station. The findings from this thesis provide the basis to process eddy-covariance data on the required level as described above.