5 Naturwissenschaften und Mathematik
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.
Soil erosion and conservation potential of row crop farming in mountainous landscapes of South Korea
- Soils play an essential role for mankind because they provide fundamental ecosystem services required for human life, primarily for the production of food by providing the environment for plant growth. However, soils worldwide became highly threatened by human induced degradation, especially as a consequence of accelerated erosion by water during recent decades. In consideration of climate change and an increasing food demand of a rising population, there is an urgent need to conserve the soil resources by implementing effective erosion control measures for agricultural production. The effective implementation of those measures strongly depends on the specific conditions of particular regions and requires the analysis of the existing farming systems and their capability for erosion control.
Objective of this thesis is the analysis of the major agricultural practices applied for row crop cultivation in mountainous watersheds of South Korea with respect to water erosion and the identification of their conservation potential. Our first two studies analyze the subsurface flow processes, the runoff patterns, and the associated erosion rates of the widely applied plastic covered ridge-furrow system (plastic mulch), and our third study investigates the impact of herbicide applications on erosion associated with conventional and organic farming. To analyze the flow processes induced by the plastic mulch cultivation, we conducted four irrigation experiments on potato fields that represent a smooth surface, uncovered ridges, and plastic covered ridges with and without a developed crop canopy. With an automatic sprinkler, we irrigated small plots with a dye tracer solution of Brilliant Blue and potassium iodide, collected surface runoff, and excavated soil profiles to visualize the subsurface flow patterns, which were subsequently analyzed by image index functions. We found that the ridge-furrow system, especially when ridges are covered with plastic, decreased infiltration and generated high amounts of surface runoff, whereas a developed crop canopy increased infiltration due to interception and stem flow. The analyses of the subsurface flow patterns show that the plastic covered ridge-furrow system induces preferential infiltration in furrows and planting holes due to its topography and the impermeable covers, but that the impact on flow processes in the soils is relatively small compared to the impact on runoff generation. To identify the patterns of overland flow and the erosion rates associated with the plastic mulch system, we installed runoff collectors to monitor runoff and sediment transport of two potato fields with concave and convex topographies, and we applied the EROSION 3D model to compare the plastic covered ridge-furrow system to uncovered ridges and a smooth surface. We found that plastic mulch cultivation considerably increases soil erosion compared to uncovered ridges as a consequence of high amounts of surface runoff. Our results show that the ridge-furrow system concentrated overland flow on the concave field, resulting in severe gully erosion, but prevented flow accumulation and reduced erosion on the convex field, which demonstrates that the effect of this cultivation strategy is primarily controlled by the field topography and its orientation. To analyze the effects of conventional and organic farming on water erosion, we measured multiple vegetation parameters of crops and weeds of conventional and organic farms cultivating bean, potato, radish, and cabbage, and we simulated long-term soil loss rates with the Revised Universal Soil Loss Equation (RUSLE). We found that organic farming reduced erosion for radish, as a result of an increased weed biomass due to the absence of herbicides, but that it increased erosion for potato due to lower crop coverage, presumably as a consequence of crop-weed competition or herbivory associated with the absence of agricultural chemicals. Although we demonstrated that a developed weed cover in the furrows can potentially decrease the erosion risk for row crops, our results show that the average annual erosion rates of both farming systems exceed by far any tolerable soil loss.
In consideration of the generally high soil loss found in our studies, we conclude that the applied farming practices are not capable for effective erosion control and soil conservation in this region. However, based on our findings, we could identify possible modifications of those practices that can help to reduce the risk of erosion in the future. We recommend perforated plastic covers for ridges to reduce runoff generation, and the orientation of the ridge-furrow system along the contours or towards field edges to prevent flow accumulation and gully formation. Additionally, we suggest residue mulching of furrows to protect the soil surface from overland flow, and the cultivation of winter cover crops after harvest to maintain a better soil cover throughout the year.
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.
Quantifying water use by temperate deciduous forests in South Korea: roles of species diversity, canopy structure, and complex terrain
- About seventy percent of South Korea is covered with forests, most of which are found in the mountain regions since mountains receive more rainfall and are difficult terrains not suitable for agriculture. Because mountains are important water sources for cities and human population downstream, performing water balance for forest catchments has become a research priority. The ongoing shift from coniferous to species-rich deciduous forests due to a changing government policy and the anticipated changes in future climate, associated with increasing amount of rainfall and temperature will also impact forest water use, calling for an urgent need to understand how forests, in their current status, use water. The knowledge is vital for predicting water requirements for the future forest. The warm-deciduous temperate forests found in South Korea, however, have a high diversity of tree species, have multi-layered canopies and are mostly located on rugged mountainous terrains, which make it difficult to quantify forest water use, a basic requirement for catchment water budgeting. The main objectives of this study were to: (1) identify the roles of species diversity in tree and forest water use, (2) examine the impact of canopy structure on forest transpiration, and (3) evaluate the influence of terrain on forest water use.
Site-specific studies were carried out in three different natural deciduous forests, namely, Gyebang (GB), Gwangneung (GN) and Haean (HA) forest sites, representing the general structure of S. Korean forests. GB site is known for its high species diversity, GN site is an old forest growth at climax, with clearly defined understory and overstory canopy layers while the HA site was located with in a catchment, with strong elevation changes within short horizontal distances, rising from 400 to 1,000 m a.s.l., and in different aspects. Four locations with varying elevations and aspects were chosen in the HA site. Tree water use (TWU) and canopy transpiration (EC) were estimated from sap flux density measured with thermal dissipation probes. Understory transpiration (EU) was measured using stem heat balance while ecosystem evapotranspiration (Eeco) was determined using eddy covariance technique. Air temperatures (Ta), precipitation, solar radiation, vapor pressure deficit (VPD), wind speed were measured from weather stations and soil water content was measured from frequency domain reflectometry (FDR) sensors at the respective study sites. Vegetation surveys, including diameter at breast height (DBH), tree density, species composition, sapwood area (AS), and leaf area index were performed in all the sites. Canopy conductance (GC) and stomatal sensitivity to VPD were assessed based on transpiration and microclimate measured at each site.
A functional allometric relationship was established between AS and DBH, and also between TWU and DBH for all the study sites; first for single species and then combining all the species either in a single site or in all the sites. Irrespective of tree species, AS and maximum TWU were significantly correlated with DBH in a power function for AS (R2 = 0.77, P <0.0001) and both in power (R2 = 0.63, P <0.0001) and sigmoid functions (R2 = 0.66, P <0.0001) for TWU, for the co-occurring species as well as across the sites, suggesting that DBH can be a good predictor of stand AS and maximum TWU, based on the established allometric functions.
Early bud break and development of the understory compared to the overstory canopy resulted in an earlier onset of forest transpiration, with EU contributing 22% and 14% between April and May to the total forest transpiration. This high contribution was favored by high radiation and VPD in the understory, since the overstory was still undeveloped and open. Despite diminishing VPD and light conditions in the understory between June and August, the understory continued to transpire a substantial amount of water, contributing 10% of the total transpiration. The seasonal patterns of both EO and EU were synchronized to canopy development, while VPD and radiation determined daily trends. EO and EU accounted for 80% of Eeco in spring but only 60% during the monsoon period due to lowered radiation input, VPD, and plant area index (PAI). Thus, Eeco is largely influenced by transpiration rate and its seasonal variation and also canopy structure.
Early saturation of EC at relatively low VPD and also a rapid decrease in GC with increasing VPD were observed in the forest stand located at the highest elevation studied (950 m) in the HA site, compared to the GN and the other forest stands in HA. These differences in transpiration rates and stomatal response can be explained by greater stomatal sensitivity to VPD of 0.83 found at the 950 m site compared to 0.63–0.66 in the other study sites. However, the main controlling factor of the change in stomatal sensitivity at the 950 m stand is uncertain. Although maximum daily EC were correlated with AS of the forest stands at different sites (R2 = 0.78, P <0.01), annual EC declined with increasing elevation, i.e., 176 >175 >110 >90 mm year−1 at 340 >450 >650 >950 m, respectively. Decline in total EC was due to the decline in annual Ta, daytime VPD, and length of growing season at higher elevations. The GB site, which was located at 960 m elevation, however, did not display a same response pattern as those observed at the 950 m site. It is likely because these sites were under different environmental conditions, i.e., GB site is exposed to higher Ta and higher humidity, and is sheltered (lower wind speeds). These observations emphasize the complexity associated with estimation of transpiration in rugged terrains, since general principles do not always apply and the spatial patterns of forest transpiration are complex.
Complexity arising from multiple tree species composition when estimating forest water use can be reduced by applying functional allometric relationship linking tree size and water use. Forest canopy structure and physical location should be taken into account since they influence the way forests use water resources by altering microclimate and plant physiology. Based on our findings, estimation of forest water use on rugged terrains require repeated measurements at relatively small spatial scales since the driving factors change rapidly over very narrow vertical distances.
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.
Monte Carlo Simulation Methods for Studying the Thermodynamics of Ligand Binding & Transfer Processes in Biomolecules
R. Thomas Ullmann
- The binding and transfer of ligands is of central
importance for the function of many biomolecular
systems. The main topic of this thesis is the
development and application of Monte Carlo (MC)
simulation methods for studying complex ligand
binding equilibria which can also involve
conformational changes. The simulated systems
were described by microstates within a continuum
electrostatics/molecular mechanics (CE/MM) model
of the receptor-ligand system. The CE/MM modeling
methodology was improved. The improvements led to
more detailed molecular models that enable a more
realistic reproduction of system properties and
environmental conditions. The developed simulation
methods were applied to biomolecular systems whose
function involves aspects that are important for
the understanding of bioenergetic energy
transduction. The results of this thesis are
presented in five articles that are published in
peer reviewed scientific journals.
Manuscript A presents the Monte Carlo simulation
software GMCT which was largely developed in this
thesis. The software offers a variety of different
simulation methods that allow the user to harness
the full potential of CE/MM models in the simulation
of complex receptor systems.
Manuscript B presents a novel theoretical framework
for free energy calculations with the free energy
perturbation method. The novel framework is more
broadly applicable and can lead to more efficient
simulations than previous formulations. The
derivation of the formalism also led to interesting
insights into general statistical mechanics. The
formalism was implemented in GMCT and could already
be used fruitfully for the free energy calculations
presented in Manuscripts C and D.
Manuscript C demonstrates the application of free
energy measures of cooperativity to study the
coupling of protonation, reduction and conformational
change in azurin from Pseudomonas aeruginosa (PaAz).
Such a coupling is prototypic for bioenergetic systems
because it forms the thermodynamic basis of their
energy transducing function. PaAz is an experimentally
well characterized, small electron transport protein.
For this reason, PaAz was used here as model system
to demonstrate the usefulness of cooperativity free
energies in detecting and quantifying thermodynamic
coupling between events in complex biomolecular
systems. The results of this study led to new insight
that could help to determine the still enigmatic
physiological role of PaAz.
In Manuscript D, free energy calculations were
applied to study the thermodynamics of transport
through the ammonium transporter Amt-1 from
Archaeoglobus fulgidus (AfAmt-1). Ammonium is the most
directly utilizable nitrogen source for plants and
microorganisms. AfAmt-1 and its homologues facilitate
the transport of ammonia/ammonium across biological
membranes in living beings from all domains of life.
It is intensely debated how these proteins perform
their function and whether ammonia or its protonated
form ammonium is actually transported. The study
extended upon previous theoretical studies by
including the effects of substrate concentration,
electrochemical transmembrane gradients,
proton-coupled binding equilibria and competitive
binding of different ligand species. It was found
that the transported species is most likely the
ammonium ion. An ammonia/proton symport mechanism
that involves a pair of coplanar histidine residues
at the center of the transmembrane pore as transient
proton acceptor is made plausible by the high
genetic conservation of these residues.
Manuscript E presents a first application of the
microstate description within a CE/MM model to the
simulation of the non-equilibrium dynamics of a
molecular system. We simulated the re-reduction
kinetics of the primary electron donor in the
photocycle of the bacterial photosynthetic reaction
center from Blastochloris viridis. The simulation
results are in very good agreement with
experimentally measured data.
Mineral sequestration of CO2 by reaction with alkaline residues
- With the onset of industrialization within the last 150 years, a significant increase in the concentration of the greenhouse gas carbon dioxide (CO2) is recorded in the atmosphere. According to current scientific understanding the rising atmospheric CO2 levels can be linked with high probability to the observed phenomenon of global warming. Consequently, the reduction of anthropogenic greenhouse gas emissions has become a global challenge of environmental research and policy.
In this thesis, a novel approach to achieve a long-term mineral sequestration of CO2 was studied, using alkaline residue materials. This study examined for the first time a process that allows for rapid removal of CO2 from flue gas through reaction with lignite fly ashes in aqueous solution.
In this process the basicity of the residues is utilized for mineral trapping of CO2 by precipitating stable calcite. Lignite fly ashes are a cheap, inexpensive, highly reactive byproduct of coal combustion. Due to the exposure to heat, these waste streams generally contain high amounts of reactive Ca/Mg (hydr)oxides and thus offer a high alkalinity. The alkaline residues were therefore not considered as an environmental problem, but rather as useful reactants for technical CO2 neutralization in the context of combustion processes.
Carbonates are end-products of weathering processes at the earth surface and mineral carbonation is thus assessed to be a permanent and safe storage option of CO2. Compared to alternative forms of carbon storage (e.g. the injection into gas reservoirs) cost-intensive monitoring programs for safety reasons can be omitted. Also, the carbonation generally leads to heavy metal fixation in the residues, allowing for an environmentally less problematic disposal of the products or even their industrial re-use (e.g. road construction, cement industry). Due to the common high reactivity of alkaline fly ashes no pre-treatment (e.g. grinding, using chemical additives) is needed compared to the use of natural silicate minerals as feedstock material. For these reasons mineral carbonation of alkaline residues can be considered as a process with low costs and low energy consumption, thus making it an interesting CO2 reduction pathway from an economical point of view.
In Chapter 1, the mechanisms and rates of reactions between alkaline lignite fly ash and CO2 in aqueous suspensions were evaluated. Aqueous laboratory experiments showed that CO2 from flue gas can be bound directly as carbonate. Additionally, solutions with high dissolved inorganic carbon content are formed, which can be injected into aquifers for mineral CO2 sequestration. As the dissolution rates of the alkaline mineral phases are high, gas phase CO2 transfer into the aqueous phase is mostly the limiting factor for the overall carbonation process. CO2 dissolution is controlled by the solution pH, by the available surface area of the gas/water interface and by the gradient at that interface.
The maximum conversion of 5.2 moles of CO2 per kg fly ash (≈ 0.23 kg kg-1) obtained at 75 °C demonstrates the high potential of alkaline fly ashes to sequester CO2. This value accounts for a CO2 sequestration capacity of nearly 3.5 million t of CO2 in Germany alone based on the available lignite fly ash, which corresponds to 2 percents of the CO2 emissions from lignite power combustion (168 million t a-1 in 2009).
In Chapter 2, laboratory carbonation experiments are described, which were carried out with the individual mineral phases CaO and MgO in aqueous solution. The process showed parallels with the reactions observed during carbonation of lignite fly ashes, suggesting that Ca and Mg (hydr)oxides can be used as proxies to estimate alkaline waste reaction with CO2 in general.
The carbonation of CaO happens fast, occurs at high pH values > 12 and is controlled at the mineral surface by the dissolution of Ca(OH)2. As long as Ca(OH)2 is available CO2 uptake by the system is high and leads to the simultaneous precipitation of calcite (CaCO3). Under similar conditions MgO carbonation is a slower and much more complex process. In the presence of MgO an initial pH of ~ 10.8, indicating solubility equilibrium, was reached. Subsequently, TDIC concentrations and EC increased almost linearly. The pool of MgO based alkalinity can be made available for mineral trapping if the kinetic restrictions for precipitation of Mg-carbonate can be overcome, e. g. by running the processes at higher temperature (> 50 °C) and higher s/l-ratio. Corresponding to related work the precipitation of hydromagnesite (Mg5(CO3)4 (OH)2 ∙ 4H2O) is found for temperatures above 50 ° C already at a suspended amount of 4 g L-1. Precipitation of nesquehonite (MgCO3 ∙ 3H2O)) starts upon a suspended amount of MgO of more than 10 g L-1 at 25 ° C.
In Chapter 3 the setup and the results of a model are shown, which was used to simulate and evaluate the process of alkaline material carbonation over time. Experimentally derived specific dissolution rates for CaO/MgO and CO2 are used for the development of a kinetic geochemical model based on the freely available PHREEQC algorithm. The software offers the access to databases, which containing thermodynamic constants of all common dissolved species in natural and industrial processes.
Experimental assays conducted in an aqueous carbonation reactor (see Chapter 1 and 2) were used as reference to test the model and evaluate its robustness and sensitivity.
The reaction course of the experiments based on the use of the pure phases (CaO and MgO) was successfully reproduced by our simulations. The developed model may thus be used as a valuable tool for the optimization of technical scenarios/facilities for CO2 sequestration. In order to study different mineral sequestration scenarios for calcite precipitation, we used the simulation to test the variation of process parameters and the addition of chemical additives (CaCl2, CaSO4). Finally, the simulation of the carbonation of lignite fly ash was tested using our simplified model based on CaO, MgO, calcite, anhydrite as kinetic reactants. It was shown that advanced techniques to determine the exact mineralogy of combustion residues and the extension of the availability of thermodynamic data of specific mineral phases are necessary to improve geochemical modelling in future work.
In Chapter 4, the potential contribution of lignite fly ash to mineral CO2 trapping in a high anhydrite (CaSO4) containing aquifer were analyzed. The study examined the possibility of combining underground CO2 storage and geothermal heat/energy production from an anhydrite rich aquifer. In such a scenario Ca2+ for the precipitation of calcite could be provided from the dissolution of the calcium sulfate. The dissolution of anhydrite concurrently releases acid, being counterproductive with respect to the formation of carbonates. The possibility of pH buffering by the addition of alkaline lignite fly ash is therefore appraised to optimize the conditions of carbonate precipitation.
The performed laboratory experiments, as basis for thermodynamic simulations with PHREEC, confirmed that the buffering capacity derived from the fly ashes is essential for calcite precipitation in such a system. Already with an addition of 0.1 weight percent of fly ash per volume of the injection solution the amount of precipitated calcite was maximized. The dissolution of anhydrite is associated with a concurrent increase in pore space and can balance the porespace reduction by precipitation of carbonates and secondary silicates in the geothermal reservoir.
Iron spin crossovers at high pressures and temperatures and their effects on materials relevant tot he Earth’s lower mantle and core
- Iron is the most abundant element by mass in the Earth. The iron content and its spin or oxidation state have a major influence on the physical properties of the main phases in the Earth’s interior. Therefore it is of vast importance to understand the behavior of iron in mineral phases at the temperature and pressure conditions of the Earth’s interior. This cumulative thesis investigates Fe spin crossovers in iron-containing magnesium aluminum silicates, iron-bearing silicate glasses, the iron carbide Fe3C and the effect of Fe spin crossovers on the Fe/Mg partitioning between perovskite and ferropericlase in pyrolitic model system of the Earth’s lower mantle. The goal is first to understand the nature of the Fe spin crossover in respect to its oxidation state and second to estimate the consequences of their occurrence to processes and the structure in the Earth. Central tools in these studies are laser heated diamond anvil cells, to reach the pressure and temperature conditions of the Earth’s interior, Mössbauer spectroscopy, which is a sensitive probe for detecting structural and spin changes in Fe-bearing materials, and analytical transmission electron microscopy, as a probe of chemistry and oxidation state on the nm-scale. In this cumulative thesis I present the results of five research articles. For the analysis of conventional and recently developed synchrotron energy domain Mössbauer spectra the computer program MossA is introduced, which builds the basis for the analysis and interpretation of the results for the other studies. Based on synchrotron Mössbauer spectroscopy and electrical conductivity measurements of Fe-bearing silicate aluminum perovskite it is shown that Fe3+ occupies the dodecahedral A-site of the perovskite structure and remains in the high-spin state throughout the pressure and temperature conditions of the Earth’s lower mantle. Furthermore, a study on the electronic behavior of Fe in a Fe2+-rich aluminous silicate glass and a Fe3+-rich sodium silicate glass infers that no sharp high spin to low spin crossover occurs in silicate melts in the Earth’s lower mantle. This result excludes the possibility of negatively buoyant melts in the lower mantle in an early magma ocean solely due to strong preferential partitioning of iron into the melt phase, which would be induced by a Fe low-spin bearing melt. New insights into to decoupled partitioning behavior of Fe2+ and Fe3+ between the two dominant phases of the Earth’s lower mantle, perovskite and ferropericlase, are presented. The intermediate spin to low spin crossover of Fe2+ in perovskite at about 110 GPa seems to have a strong effect on partitioning and oxidation state of Fe. It leads to a change of the partitioning behavior of Fe between perovskite and ferropericlase and induces a reduction of Fe3+ to Fe2+ in perovskite. Finally, a Mössbauer spectroscopic and single-crystal x-ray diffraction study of Fe3C reveals a two-stage loss of magnetism in Fe3C at high pressures at room temperature: a ferro- to paramagnetic transition around 8-10 GPa and a para- to nonmagnetic transition at about 22 GPa.
Impact of time and spatial averages on the energy balance closure
- Secondary circulations are large and relatively stationary eddies, which are caused by the surface heterogeneity and normally reside away from the ground. They are believed to be the cause of the energy balance closure problem at the earth's surface, because their contribution to the turbulent fluxes is missed by a fixed eddy-covariance tower measurement that has a typical averaging time of 30 minutes. In this thesis, data from the LITFASS-2003 experiment was used to investigate the impact of time and spatial averages on the energy balance closure. This data consisted of many observations over a large heterogeneous landscape that could generate secondary circulations; some of which might be still near the earth's surface.
For the time average analysis, the averaging time was extended to increase the possibility that secondary circulations were picked up by the sensor. Two approaches, which were the modified ogive analysis and the block ensemble average, were applied to analyze the data from ground-based measurements. The modified ogive analysis requiring a steady state condition, could extend the averaging time up to a few hours and suggested that an averaging time of 30 minutes was still overall sufficient for the eddy-covariance measurement over low vegetation. The block ensemble average, on the contrary, did not require a steady state condition, but could extend the averaging time to several days. However, this approach could only improve the energy balance closure for some sites during specific periods, when secondary circulations existed in the vicinity of the sensor. Based on this approach, it was found that the near-surface secondary circulations mainly transported sensible heat, which led to an alternative energy balance correction by the buoyancy flux ratio approach, in which the attribution of the residual depended on the relative contribution of the sensible heat flux to the buoyancy flux. The fraction of the residual attributed to the sensible heat flux by this energy balance correction was larger than in the energy balance correction that preserved the Bowen ratio.
In the spatial average analysis, two energy balance correction approaches, the buoyancy flux ratio and the Bowen ratio approaches, were applied to the area-averaged fluxes (composite fluxes) in order to include contribution from secondary circulations. These composite fluxes were aggregated from multiple ground-based measurements. The energy balance corrected fluxes were validated against the spatial average fluxes, which were measured by an aircraft and a large aperture scintillometer (LAS). In this validation, the backward Lagrangian footprint model was used to estimate the source area of the measurement. It was found that both energy balance correction approaches did improve the agreement between time and spatial averages fluxes. This suggested that the contribution from secondary circulations could be properly accounted by the energy balance correction.
All findings in this thesis, therefore, depict that secondary circulations significantly transport energy in the atmospheric surface layer. The energy balance correction, accomplished by using either the Bowen ratio approach or the buoyancy flux ratio approach, is necessary to estimate the actual vertical transport of energy at the earth's surface.
Impact of extreme hydrological conditions on belowground carbon cycling and redox dynamics in peat soils from a northern temperate fen
Cristian Estop Aragonés
- Peatlands have an important role in the global carbon cycle and constitute the largest pool of carbon stored in terrestrial ecosystems due to their disproportionally high areal soil carbon density. This globally relevant carbon stock is the result of a process mostly initiated after the last glaciation period. A key factor for this long term carbon accumulation is the relative low decomposition of organic matter in these predominantly water logged ecosystems. Hydrological conditions play thus a fundamental role in peatlands and the feedback of carbon cycling in these ecosystems in response to climate change is under debate. Peatlands are important CO2 sinks but also constitute global sources of CH4. The atmospheric exchange and production rates of these greenhouse gases are strongly influenced by the hydrological regime. An increased frequency of extreme meteorological conditions resulting in drying and flooding events is predicted to occur in the future.
The major issue regarding the climate change debate at the global scale is how rapid these greenhouse gases are being released to the atmosphere. Despite the general consensus regarding the broad effects of drying and flooding on CO2 and CH4 exchange, belowground processes producing such greenhouse gases and their response to water table dynamics is underrepresented and usually simplified or overgeneralized. Temperature, moisture, oxygen content and nutrient content are among the major environmental controls for organic matter decomposition rates in peat soils. Another important and intrinsic control is peat quality or humification degree of organic matter. The interrelation and relevance of all these factors vary among sites and with hydrological condition in a temporal and spatial scale.
This work presents investigations focusing on belowground redox processes aiming to witness the dynamic interrelation of soil physical and chemical (soil gas and pore water chemistry) variables, and evaluates the relevance of some controls of organic matter decomposition during a wide range of hydrological conditions. Most of this work shows information under in situ conditions and complementary laboratory experiments were performed minding the in situ observations. The findings contribute to general knowledge by providing raw data in fen peats under fluctuating and contrasting water table conditions in a relatively high spatiotemporal resolved scale. Dryings led to increased air filled porosity, O2 intrusion, CO2 degassing, inhibition of methanogenesis and renewal of electron acceptors. The opposite trend occurred upon rewetting with pulses of iron and sulphate reduction and delayed methane production to a variable extent. Upon flooding, continued anaerobic conditions stimulated the accumulation of reduced products, methanogenic precursors (acetate and hydrogen) and CH4.
The general assumption that the water table directly controls the oxygen content in peat was relativized. This work shows that such relation is greatly influenced by peat physical properties, which partially control the changes in moisture. Based on these findings, the mineral content and the degree of compaction in organic soils can be implemented to more accurately represent the dynamics of aeration in peats upon water table changes. Another general assumption is that drying events, i.e. temporary decline of water table below mean position, lead to increased CO2 production and emission from peat soils to the atmosphere. Such statement was also relativized and must account for the depth distribution of respiration rates in relation to the mean water table of the peat deposit. Based on these findings, the high relative contribution of upper peat layers already exposed above the water table mask the effects of increased CO2 production in deeper peat upon water table drop. Additionally, the role of moisture was shown to be little for aerobic respiration. This work also evaluates the importance of drought severity by accounting for the post drought effects on methane production. More intense and prolonged drying events led to a greater regeneration of electron acceptors in peat soil, which broadly suppressed or limited methane production upon rewetting. This relation was not simple and several factors such as water table position, post drought water table fluctuations, temperature and organic matter content contributed to the recovery of methane production after drying. The provision of substrates by fermentation processes limited peat respiration during shallow water table and drying. In contrast, accumulation of acetate and hydrogen was observed during flooding indicating a decoupling of fermentation from terminal metabolism and favouring the co-occurrence of iron reduction, sulphate reduction and methanogenesis.