5 Naturwissenschaften und Mathematik
- Bayreuther Graduiertenschule für Mathematik und Naturwissenschaften (BayNAT) (6)
Budget and fluxes of nitrogen in mountainous agroecosystems in a summer monsoonal climate under intensive land use
- A balanced nitrogen (N) cycle in intensively managed ecosystems is necessary as it underpins other ecosystem services. This study evaluated the agricultural practices in a typical mountainous catchment in South Korea in respect to N dynamics and their potential effect on water quality with the aim to develop options for a more sustainable catchment management.
In the 1st study, we used two approaches to calculate N budgets for the 5 key crops of the basin at the field scale. The gross and net N budgets for all crop types were found to be positive. Based on the small differences between the results of the two approaches we identified fertilizer N as well as soil Nmin as the dominant N input sources. As fertilizer N application was the major N input source (>50%), its reduction is the major scope of action for N savings at the field scale. A closely linked action is the synchronization of fertilizer N with soil Nmin. The large amount of fertilizer that is applied prior to planting (>60%) at the beginning of the monsoon season revealed that split applications could help reducing the fertilizer N additions and increase the low N use efficiencies (NUE). Based on the significant differences between gross and net N surplus for rice and bean fields, we identified the high amount of plant residues remaining after harvesting (>100 kg N ha-1) as a further factor for potential N savings. The 5 main crops accounted for over 80% of the total catchment N surplus (>400 Mg), even though their contribution to the area was only around 20%. A land use shift to perennial crops with lower N inputs was therefore found to be a possible but spatially limited chance to reduce N surpluses at the catchment scale. The comparison of catchment N surplus with stream N export revealed that 73-86% of the agricultural N surpluses were transported to water bodies in the catchment by either leaching or surface runoff.
In the 2nd study, we followed the fate of fertilizer N in a ridge and furrow (R/F) cultivation with polyethylene (PE) mulch by using 15N tracer. N leaching was simulated with Hydrus 2D. The comparison of 4 N fertilization levels (0, 150, 250 and 350 kg N ha-1) revealed that already 150 kg N ha-1 is sufficient to reach the maximal yield of radishes. Based on the low results of fertilizer N use efficiency (FNUE), we recommend two applications during the first 25 days of growth and a further application around day 50. These split applications adjusted to the plants’ needs increase the FNUE of the radish and decrease the fertilizer N losses during the growing season. However, split applications might be impractical in plastic covered R/F cultivations because mechanical equipment to apply fertilizer under the PE mulch is required. Based on the finding that 15N retention in soil and nitrate concentration in seepage water decreased similarly for ridges and furrows during the entire growing season, we conclude that the PE mulch had no significant effect on 15N retention in soil and on nitrate concentration in seepage water and did therefore not effectively protect the fertilizer in the ridges from percolation. Based on the simulation results, we found that the ridges and furrows contributed approximately an equal amount of leached N to the total amount. We therefore conclude that the PE mulch provided little protection for the fertilizer N in the ridges during heavy rainfall. N leaching amounts were further found to increase linearly with an increase in N addition rate as it is well known for R/F cultivations without PE mulch. The PE mulch did therefore not prevent the linear increase in leaching with an increase in fertilizer N addition. We summarize that without the use of additional measures such as split applications of fertilizer, the application of PE mulch in a summer monsoon climate with heavy rainfall events does not positively influence the N leaching rates.
In the 3rd study, we monitored soil water dynamics in the field and used this data set to simulate the influence of PE mulch on water fluxes with Hydrus 2D. We simulated soil water dynamics in 1) conventional flat tillage (CT); 2) R/F cultivation without PE mulched ridges (RT); and 3) R/F cultivation with PE mulched ridges (RTpm). The comparison of the simulated pressure heads during dry and wet periods revealed that the PE mulch induced significant soil moisture patterns only during the dry periods. During monsoon events, the effect of the PE mulch was dependent on the soil texture and the hydraulic conductivity. Summarizing the advantages and disadvantages of the R/F cultivation with PE mulch on sloped fields, the practice was observed to have the lowest amount of drainage water, the lowest evaporation rates but also the highest surface runoff rates. Hence, PE mulching might be assessed as a tool to reduce percolating water, but it concurrently increases water contribution to the river network by surface runoff.
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.
"The New Chemistry" - Sustainable Catalysis with Alcohols
- Subject of the thesis are new iridium complexes stabilized by anionic P,N- or P,N,P-ligands. These complexes were used in homogeneous catalysis. Furthermore, mechanistic studies were performed to provide an insight into the catalytic cycles. Synthesis protocols for a multitude of different product classes have been developed.
The iridium complex 1, stabilized by a neutral P,N-ligand, reacts under basic conditions with 2-aminopyridines. By elimination of dipyridylamine the new catalyst species 2a was formed, which is more stable than catalyst 1.
Based on this finding eight new anionic P,N-ligands and the resulting iridium complexes were synthesized.
After optimization of the reaction conditions (solvent, base, temperature and catalyst loading) these catalysts were used in BH (borrowing hydrogen)/HA (hydrogen autotransfer) reactions. The selective monoalkylation of anilines with primary alcohols was investigated. In comparative experiments the superiority of the new class of catalysts versus the original catalyst 1 was clearly shown. Under mild reaction conditions (70 °C) the selectivity profile with respect to the monoalkylation has been preserved.
The catalytic protocol was subsequently extended to the alkylation of aromatic diamines. Therefore various diaminobenzenes were used as substrates. Also Dapsone®, an important drug in treatment of leprosy could be used as starting material. We succeeded in both symmetric and unsymmetric monoalkylations of diamines. Due to the selectivity profile of the catalyst regarding aromatic amines, also unprotected amino alcohols could be used as alkylating reagents.
By the use of tridentate P,N,P-ligands, a novel class of more stable catalysts compared to complexes 2a-9a, could be developed. Due to sealing the synthesis reactor with a semipermeable membrane, the retransfer of the “borrowed” hydrogen could be prevented and H2 is released. Dehydrogenation and condensation steps are now possible instead of BH/HA. By reacting secondary alcohols with β-amino alcohols, pyrroles were accessible.
After adapting the synthesis protocol to this new class of products the tolerance of functional groups was tested. Diversely functionalized alcohols were used. Under mild reaction conditions (90 °C) and very low catalyst loadings (down to 0.03 mol% iridium), a large number of novel pyrroles was accessible. Using this protocol 21 differently substituted α,α-pyrroles, 12 bicyclic pyrroles, symmetrically as well as non-symmetrically substituted oligopyrroles and three β-aminopyrroles were synthesized. The catalyst resting state was identified by NMR experiments and X-ray structure analysis to be an iridium trihydride. This trihydride is formed under catalytic conditions, by treatment of the pre-catalyst with alcohols or in hydrogen atmosphere.
In the final part of the work, a catalytic pyridine synthesis was developed. In this so far unknown heterocycle synthesis up to four different substituents could be introduced within a single reaction step. 2,6-, 2,5-, 2,4- and 2,3-substituted pyridines were synthesized selectively by using variously substituted primary or secondary alcohols and γ-amino alcohols. Furthermore, both the synthesis of bicyclic pyridines as well as the synthesis of pyridines that bear chiral substituents is possible.
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.
Dual-Responsive Polymer and Hybrid Systems: Applications for Gene Delivery and Hydrogels
- This thesis focused on the synthesis of functional materials based on water-soluble and responsive polymers, in particular poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA). The dual-responsive behavior and polycationic character at physiological pH of PDMAEMA lead to outstanding properties and thus, to a versatile component for water-based applications. The main concept of the thesis was to combine the ability for gene delivery of PDMAEMA with the magnetic properties of iron oxide nanoparticles to enable an activity of the gene vector in an applied external magnetic field. Another point was to apply the dual-responsive behavior of PDMAEMA (temperature and pH) for physically cross-linked hydrogels.
Initial studies on magnetic dual-responsive gene vectors revealed a facile synthesis of PDMAEMA-grafted iron oxide nanoparticles utilizing dopamine as physically binding anchor group for the polymer chains. Here, a dopamine-based ATRP initiator was applied for the surface modification of the nanoparticles, which enabled a controlled polymerization technique via the “grafting-from” approach. Gene transfection experiments with CHO-K1 cells show that the transfection efficiency is significantly higher than for poly(ethyleneimine) (PEI), which is regarded as the “gold standard” among the polycationic gene vectors. Although the hybrid particles show a considerably high molecular weight (4.3 MDa), which should lead to a significant increase of the cytotoxicity as observed for linear PDMAEMA their cytotoxicity is remarkably low, lower than that of PEI. Thus, the excellent performance in gene delivery experiments can be attributed to the star-like architecture of the PDMAEMA. Moreover, the uptake of our superparamagnetic gene vector into the cells enables a magnetic cell separation by applying an external magnetic field.
However, due to the non-covalent bonds of dopamine to the iron oxide nanoparticles, the PDMAEMA chains undergo a detachment with time from the nanoparticle surface. This led to the synthesis of PDMAEMA-based magnetic core-shell-corona nanoparticles. Here, the iron oxide nanoparticles were covered with a thin silica shell in order to link the PDMAEMA chains covalently to the inorganic core via silane chemistry. This approach revealed stable dual-responsive hybrid nanoparticles with irreversible binding of the polymer chains and a high long-term stability in aqueous media. These hybrid star-like particles also show excellent gene delivery. The inter-polyelectrolyte complex formation between the PDMAEMA corona of the core-shell-corona particles and pDNA showed that the pDNA molecules are individually complexed with single nanoparticles at N/P ratios (polymer nitrogen / pDNA phosphorous) where the best transfection results are obtained. The magnetic cell separation was further improved by using a Magnetic Activated Cell Sorting system (MACSTM). The magnetically separated cells maintain a high transfection efficiency as well as viability and could even be further cultivated.
Another aspect of this thesis was to include PDMAEMA as stimuli-responsive block in a double switchable block copolymer-based hydrogel. For this purpose, we chose a physically cross-linked ABCBA pentablock terpolymer system, which was polymerized via sequential ATRP and consist of a water-soluble PEO middle block, two dual-responsive (temperature/pH) PDMAEMA B-blocks as well as two thermo-responsive poly(di(ethylene glycol) methyl ether methacrylate) (PDEGMA) A-blocks (PDEGMA-b-PDMAEMA-b-PEO-b-PDMAEMA-b-PDEGMA). The aggregation behavior in dilute solution was investigated via temperature-dependent Dynamic Light Scattering (DLS) revealing that both stimuli-responsive blocks can be triggered separately and the coil-to-globule transition temperatures of the stimuli-responsive blocks were found to be strongly dependent on the block lengths for low molecular weights. In concentrated solutions, however, rheology studies did not show a further change in the mechanical properties after gelation for the investigated ABCBA pentablock terpolymer compositions. As a result, the principle of our complex system points towards a successful synthesis of a dual-responsive ABCBA pentablock terpolymer hydrogel system, which may show two distinct phase transition even for the gel state, if longer block lengths of the outer A- and B-blocks would be applied.
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.