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Floodplains and other wetlands depend on seasonal river flooding and play an important role in the terrestrial water cycle. They influence evapotranspiration, water storage and river discharge dynamics, and they are the habitat of a large number of animals and plants. Thus, to assess the Earth’s system and its changes, a robust understanding of the dynamics of floodplain wetlands including inundated areas, water storages, and water flows is required.
This PhD thesis aims at improving the modeling of large floodplains and wetlands within the global-scale hydrological model WaterGAP, in order to better estimate water flows and water storage variations in different storage compartments. Within the scope of this thesis, I have developed a new approach to simulate dynamic floodplain inundation on a global-scale. This approach introduces an algorithm into WaterGAP, which has a spatial resolution of 0.5 degree (longitude and latitude) globally. The new approach uses subgrid-scale topography, based on high-resolution digital elevation models, to describe the floodplain elevation profile within each grid cell by applying a hypsographic curve. The approach comprises the modeling of a two-way river-floodplain interaction, the separate downstream water transport within the river and the floodplain – both with temporally and spatially different variable flow velocities – and the floodplain-groundwater interactions. The WaterGAP version that includes the floodplain algorithm, WaterGAP 2.2b_fpl, estimates floodplain and river water storage, inundated area and water table elevation, and also simulates backwater effects.
WaterGAP 2.2b_fpl was applied to model river discharge, river flow velocity, water storages, water heights and surface water extent on a global-scale. Model results were comprehensively validated against ground observations and remote sensing data. Overall, the modeled and observed data are in agreement. In comparison to the former version WaterGAP 2.2b, the model performance has improved significantly. The improvements are most remarkable in the Amazon River basin. However, the seasonal variation of surface water extent and total water storage anomalies are still too low in many regions on the globe when compared to observations. A detailed analysis of the simulated results suggests that in the Amazon River basin the introduction of backwater effects is important for realistically simulating water storages and surface water extent. Future efforts should focus on the simulation of water levels in order to better model the flow routing according to water slope. To further improve the model performance in specific regions, I recommend that the globally constant model parameters that affect inundation initiation, river-floodplain interaction, DEM correction for vegetation, and backwater amount at basin or subbasin-scale be adjusted.
Air-sea feedbacks between the Mediterranean Sea and the atmosphere on various temporal and spatial scales play a major role in the Mediterranean regional climate system and beyond. The Mediterranean Sea is a source of moisture due to excess evaporation and, on a long-term average, is associated with a warming of the lower atmosphere in contact with the sea surface due to heat loss at the air-sea interface. The complex air-sea interactions and feedbacks in the Mediterranean basin strongly modulate the sea surface fluxes and favor several cyclogenetic activities under certain meteorological conditions. Examples of such cyclonic activities are medicanes (Mediterranean hurricanes) and Vb-cyclones. Medicanes are mesoscale, marine, and warm-core Mediterranean cyclones that exhibit some similarities to tropical cyclones, while Vb-cyclones are extra-tropical cyclones, that propagate from the Western Mediterranean Sea and travel across the Eastern European Alps into the Central European region. Extremely strong winds and heavy precipitation associated with these cyclones can lead to severe destruction and flooding. Changes in the intensity and frequency of these cyclones are also projected under changing future climate conditions, where the Mediterranean region has been identified as a hotspot in terms of rising temperatures.
The development of high-resolution regional climate models (RCMs) has progressed our understanding of the processes characterizing the Mediterranean climate. However, large uncertainties still exist regarding the estimates of air-sea fluxes, which, in turn, affect the simulation of the Mediterranean climate. Several factors can be attributed to such discrepancies, such as data quality, temporal and spatial resolution, and the misrepresentation of physical processes. To overcome some of these inconsistencies and deficiencies of the existing climate simulations, a new high-resolution atmosphere-ocean regional coupled model (AORCM) has been developed to simulate the air-sea feedback mechanisms. This coupled model incorporates the coupling of RCM COSMO-CLM (CCLM) and the regional ocean model NEMO-MED12 for the Mediterranean Sea (MED) as well as NEMO-NORDIC for the North- and Baltic Sea (NORDIC). Several experiments were performed using both the coupled and uncoupled models to investigate the impact of air-sea interactions and feedbacks on sea surface heat fluxes, wind speed, and on the formation of Mediterranean cyclones (i.e., medicanes and Vb-cyclones). These experiments were performed using different horizontal atmospheric grid resolutions to analyze the effect of resolution on sea surface heat fluxes, wind speed, and the development of medicanes.
The results of the present study indicate that a finer atmospheric grid resolution ([is as appreciated as]9 vs. [is as appreciated as]50 km) improved the wind speed simulations (particularly near coastal areas) and subsequently improved the simulations of the turbulent heat fluxes. Both parameters were better simulated in the coupled simulations than in the uncoupled simulations, but coupling introduced a warm SST bias in winter. Radiation fluxes were slightly better represented in coarse-grid simulations than in fine-grid simulations. However, the higher-resolution coupled model could reproduce the observed net outgoing total surface heat flux over the Mediterranean Sea. In addition to that sub diurnal SST variations have a strong effect on sub-daily heat fluxes and wind speed but minor effects at longer timescales. Regarding the impact of atmospheric grid resolution ([is as appreciated as]50, 25, and [is as appreciated as]9 km) and ocean coupling on medicanes, it was detected that the coupled model with a finer atmospheric grid ([is as appreciated as]9 km) was able to not only reproduce most medicane events, but also improved the track length, warm core, and wind speed compared to the uncoupled model. The coupled model with the coarse-grid ([is as appreciated as]50 and [is as appreciated as]25 km) did not show any improvement in simulating medicanes compared to the uncoupled model. The spectral nudging technique, applied on the wind components above 850 hPa in the interior domain to keep large-scale circulation close to the driving data (i.e., ERAInterim reanalysis), improved the accuracy of the times and locations of generated medicanes, but no improvement was found in the track length and intensity.
Concerning the role of the Mediterranean Sea coupling on Vb cyclones, the investigation showed that atmosphere-ocean coupling had an overall positive impact, although with a strong case-by-case variation, on the trajectories and intensity of Vb-cyclones as a result of the variation in moisture source for each event. In general, all model configurations could replicate Vbcyclones, their trajectories, and associated precipitation fields. The average structure of the precipitation field was best represented in the coupled simulations. Coupling of the North- and Baltic Seas also showed an improvement in some of the simulated Vb-cyclones.
The atmosphere-ocean coupling showed an overall positive impact on the simulation of sea surface heat fluxes and Mediterranean cyclones (medicanes and Vb-cyclones). Moreover, the representation of sea surface heat fluxes, wind speed, and medicane features was more realistic when using a finer atmospheric grid resolution (less than 10 km). The present study suggests that the combination of a finer atmospheric grid resolution together with atmosphere-ocean coupling is advantageous in simulating the Mediterranean climate system.
The current state of research about ancient settlements within the Nile Delta allows the hypothesizing of fluvial connections to ancient settlements all over the Nile Delta. Previous studies suggest a larger Nile branch close to Kom el-Gir, an ancient settlement hill in the northwestern Nile Delta. To contribute new knowledge to this little-known site and prove this hypothesis, this study aims at using small-scale paleogeographic investigations to reconstruct an ancient channel system in the surroundings of Kom el-Gir. The study pursues the following: (1) the identification of sedimentary environments via stratigraphic and portable X-ray fluorescence (pXRF) analyses of the sediments, (2) the detection of fluvial elements via electrical resistivity tomography (ERT), and (3) the synthesis of all results to provide a comprehensive reconstruction of a former fluvial network in the surroundings of Kom el-Gir. Therefore, auger core drillings, pXRF analyses, and ERT were conducted to examine the sediments within the study area. Based on the evaluation of the results, the study presents clear evidence of a former channel system in the surroundings of Kom el-Gir. Thereby, it is the combination of both methods, 1-D corings and 2-D ERT profiles, that derives a more detailed illustration of previous environmental conditions which other studies can adopt. Especially within the Nile Delta which comprises a large number of smaller and larger ancient settlement hills, this study's approach can contribute to paleogeographic investigations to improve the general understanding of the former fluvial landscape.
One of the most important events in human history occurred during the Early Pleistocene: the dispersal of early hominins out of Africa and into Europe and Asia. In Western Europe, the earliest evidences of the genus Homo have been found in the Baza Basin, at the sites of Orce in the SE of the Iberian Peninsula. These sites contain fossils and lithic industry dated approximately as 1.4–1.3 Ma.While hominin remains and artifacts at Orce, as well as the accompanying fauna, have been extensively studied, the properties and evolution of the Early Pleistocene vegetation in the basin remain unknown. The general effect of climate change on the expansion of early hominins from Africa into Eurasia still remains unclear. It is not known if the Early Pleistocene climate changes and the development of glacials periods led to the extirpation of European communities, or if those communities were able to endure and persist through such adverse climatic periods. This open question highlights the need for climate and environmental analyses for the time before, during and after the first presence of Homo in Europe. This PhD thesis contributes to that need by the presentation of the first long pollen record of the Baza Basin, where the oldest hominin sites in Western Europe are found.
The impact of precipitation in shallow cumulus convection on the moisture variance and third-order moments of moisture is investigated with the help of large-eddy simulations. Three idealized simulations based on the Rain in Cumulus over the Ocean field experiment are analyzed: one nonprecipitating, on a smaller domain, and two precipitating cases, on a larger domain with different initial profiles of moisture. Results show that precipitation and the associated cloud organization lead to increased generation of higher-order moments (HOM) of moisture compared to the nonprecipitating case. To understand the physical mechanism and the role of individual processes in this increase, budgets of HOM of moisture are studied. Microphysics directly decreases the generation of HOM of moisture, but this effect is not dominant. The gradient production term is identified as the main source term in the HOM budgets. The influence of the gradient production term on moisture variance is further examined separately in cloud active and nonactive regions. The main contribution to the gradient production term comes from the smaller cloud active region because of the stronger moisture flux. Further analyses of the horizontal and vertical cross sections of moisture fluctuations show that the precipitation-induced downdrafts and updrafts are the main mechanism for the generation of moisture variance. The variance increase is linked to shallow dry downdraft regions with horizontal divergence in the subcloud layer, moist updrafts with horizontal convergence in the bulk cloud layer, and finally wider areas of horizontal divergence in the cloud inversion layer.
The modern precipitation balance in southeastern (SE) Brazil is regulated by the South American summer Monsoon and threatened by global climate change. On glacial-interglacial timescales, monsoon intensity was strongly controlled by precession-forced changes in insolation. To date, relatively little is known about the spatiotemporal distribution of tropical precipitation in SE Brazil and the resulting variability of fluvial discharge on glacial-interglacial timescales. Here, we present X-ray diffraction-derived mineralogical data for the 150–70 ka period (marine isotope stage (MIS) 6 to MIS 5) from the Doce River basin. This area was sensitive to changes in monsoonal precipitation intensity due to its proximity to the South Atlantic Convergence Zone. The data, obtained from a marine sediment core (M125-55–7) close to the Doce river mouth (20°S), show pronounced changes in the Doce River suspension load’s mineralogical composition on glacial-interglacial and precessional timescales. While the ratio of silicates to carbonates displays precession-paced changes, the mineralogical composition of the carbonate-free fraction discriminates between two assemblages which strongly vary between glacial and interglacial time scales, with precession-forced variability only visible in MIS 5. The first assemblage, dominated by high contents of kaolinite and gibbsite, indicates intensified lowland erosion of mature tropical soils. The second one, characterized by higher contents of the well-ordered illite, quartz and albite, points to intensified erosion of immature soils in the upper Doce Basin. High kaolinite contents in the silicate fraction prevailed in late MIS 6 and indicate pronounced lowland soil erosion along a steepened topographic gradient. The illite-rich mineral assemblage was more abundant in MIS 5, particularly during times of high austral summer insolation, indicating strong monsoonal rainfall and intense physical erosion in the upper catchment. When the summer monsoon weakened in times of lower insolation, the mineral assemblage was dominated by kaolinite again, indicative of lower precipitation and runoff in the upper catchment and dominant lowland erosion.
The metasomatised continental mantle may play a key role in the generation of some ore deposits, in particular mineral systems enriched in platinum-group elements (PGE) and Au. The cratonic lithosphere is the longest-lived potential source for these elements, but the processes that facilitate their pre-concentration in the mantle and their later remobilisation to the crust are not yet well-established. Here, we report new results on the petrography, major-element, and siderophile- and chalcophile-element composition of native Ni, base metal sulphides (BMS), and spinels in a suite of well-characterised, highly metasomatised and weakly serpentinised peridotite xenoliths from the Bultfontein kimberlite in the Kaapvaal Craton, and integrate these data with published analyses. Pentlandite in polymict breccias (failed kimberlite intrusions at mantle depth) has lower trace-element contents (e.g., median total PGE 0.72 ppm) than pentlandite in phlogopite peridotites and Mica-Amphibole-Rutile-Ilmenite-Diopside (MARID) rocks (median 1.6 ppm). Spinel is an insignificant host for all elements except Zn, and BMS and native Ni account for typically <25% of the bulk-rock PGE and Au. High bulk-rock Te/S suggest a role for PGE-bearing tellurides, which, along with other compounds of metasomatic origin, may host the missing As, Ag, Cd, Sb, Te and, in part, Bi that are unaccounted for by the main assemblage.
The close spatial relationship between BMS and metasomatic minerals (e.g., phlogopite, ilmenite) indicates that the lithospheric mantle beneath Bultfontein was resulphidised by metasomatism after initial melt depletion during stabilisation of the cratonic lithosphere. Newly-formed BMS are markedly PGE-poor, as total PGE contents are <4.2 ppm in pentlandite from seven samples, compared to >26 ppm in BMS in other peridotite xenoliths from the Kaapvaal craton. This represents a strong dilution of the original PGE abundances at the mineral scale, perhaps starting from precursor PGE alloy and small volumes of residual BMS. The latter may have been the precursor to native Ni, which occurs in an unusual Ni-enriched zone in a harzburgite and displays strongly variable, but overall high PGE abundances (up to 81 ppm). In strongly metasomatised peridotites, Au is enriched relative to Pd, and was probably added along with S. A combination of net introduction of S, Au +/− PGE from the asthenosphere and intra-lithospheric redistribution, in part sourced from subducted materials, during metasomatic events may have led to sulphide precipitation at ~80–120 km beneath Bultfontein. This process locally enhanced the metallogenic fertility of this lithospheric reservoir. Further mobilisation of the metal budget stored in these S-rich domains and upwards transport into the crust may require interaction with sulphide-undersaturated melts that can dissolve sulphides along with the metals they store.
Cratonic eclogite is the product of oceanic crust subduction into the subcontinental lithospheric mantle, and it also is a fertile diamond source rock. In contrast to matrix minerals in magma-borne xenoliths, inclusions in diamond are shielded from external fluids, retaining more pristine information on the state of the eclogite source at the time of encapsulation. Vanadium is a multi-valent element and a widely used elemental redox proxy. Here, we show that that xenolithic garnet has lower average V abundances than garnet inclusions. This partly reflects crystal-chemical controls, whereby higher average temperatures recorded by inclusions, accompanied by enhanced Na2O and TiO2 partitioning into garnet, facilitate V incorporation at the expense of clinopyroxene. Unexpectedly, although diamond formation is strongly linked to metasomatism and xenoliths remained open systems, V concentrations are similar for bulk eclogites reconstructed from inclusions and from xenoliths. This suggests an oxygen-conserving mechanism for eclogitic diamond formation, and implies that eclogite is an efficient system to buffer fO2 over aeons of lithospheric mantle modification by subduction-derived and other fluids.
During my PhD, I was applying the clumped isotope technique to modern brachiopods and fossil belemnites, and I conducted methodological work. Carbonate clumped isotope thermometry is a tool to reconstruct carbonate precipitation temperatures. In contrast to oxygen isotope thermometry, i.e., the δ18O-thermometer, the carbonate clumped isotope thermometer does not require an estimate for the oxygen isotope composition of the seawater, as it considers the fractionation of isotopes exclusively amongst carbonate isotopologues. The ∆47 value of a carbonate expresses the abundance of the 13C–18O bond bearing carbonate isotopologue, within the carbonate, relative to its random distribution. In thermodynamic equilibrium, the ∆47 value of a given carbonate is solely a function of the carbonate precipitation temperature. However, kinetic isotope fractionations, i.e., vital effects, driven by diffusion, pH or incomplete oxygen isotope exchange between water and dissolved inorganic carbonate species can cause the carbonate to be precipitated with isotopic compositions that are offset from those predicted for thermodynamic equilibrium.
Brachiopods serve as important geochemical archives of past climate conditions. To investigate the nature and significance of kinetic controls on brachiopod shell δ18O and ∆47 values, in collaboration with the BASE-LiNE Earth ITN, I analysed the bulk and clumped isotope compositions of eighteen modern brachiopod shells, collected from different geographic locations and water depths that cover a substantial range of growth temperatures. Growth temperatures and seawater δ18O values for each brachiopod were independently determined. Most of the analysed brachiopods exhibit combined offsets from clumped and oxygen isotope equilibrium, and there is a significant negative correlation between the offset values. The observed correlation slope between offset ∆47 and offset δ18O point to the importance of kinetic effects associated with Knudsen diffusion and incomplete hydration and hydroxylation of CO2 (aq), occurring during biomineralisation. The correlations between the growth rates of the analysed brachiopods and both the offset ∆47 and the offset δ18O values provide further arguments for the presence of kinetic effects. In conclusion, the oxygen and clumped isotope composition of modern brachiopod shells are affected by growth rate-induced kinetic effects that hinder their use for palaeoceanography.
Abstract: Subaqueous carbonates from the Devils Hole caves (southwestern USA) provide a continuous Holocene to Pleistocene North American paleoclimate record. The accuracy of this record relies on two assumptions: That carbonates precipitated close to isotope equilibrium and that groundwater temperature did not change significantly in the last 570 thousand years. Here, we investigate these assumptions using dual clumped isotope thermometry. This method relies on simultaneous analyses of carbonate ∆47 and ∆48 values and provides information on the existence and extent of kinetic isotope fractionation. Our results confirm the hypothesis that calcite precipitation occurred close to oxygen and clumped isotope equilibrium during the last half million years in Devils Hole. In addition, we provide evidence that aquifer temperatures varied by less than ±1°C during this interval. Thus, the Devils Hole calcite δ18O time series exclusively represents changes in groundwater δ18O values. Plain Language Summary: The oxygen isotope composition of cave carbonates records changes in Earth's climate. However, the reliability of such records depends on how stable the carbonate precipitation environment was. Here, we use a novel method called dual clumped isotope thermometry that can provide simultaneous information on a carbonate's growth temperature and whether any additional fractionation processes affected its oxygen and clumped isotope signatures. Specifically, we investigated the Devils Hole caves, which provide a reference oxygen isotope time series for North America. We find that groundwater temperature did not change significantly in the last half-million years. Variations in the oxygen isotope composition of the deposited carbonates solely reflect variations in the oxygen isotope composition of the groundwater.
Evidence of hydrothermal activity is reported for the Mesozoic pre- and syn-rift successions of the western Adriatic palaeomargin of the Alpine Tethys, preserved in the Western Southalpine Domain (NW Italy). The products of hydrothermal processes are represented by vein and breccia cements, as well as dolomitization and silicification of the host rocks. In the eastern part of the study area, interpreted as part of the necking zone of the continental margin, Middle Triassic dolostones and Lower Jurassic sediments are crossed by veins and hydrofracturing breccias cemented by saddle dolomite. The precipitation of dolomite cements occurred within the stratigraphic succession close to the sediment–water interface. Despite the shallow burial depth, fluid inclusion microthermometry and clumped isotopes show that hydrothermal fluids were relatively hot (80–150°C). In the western part of the study area, interpreted as part of the hyperextended distal zone, a polyphase history of host-rock fracturing is recorded, with at least two generations of veins cemented by calcite, dolomite and quartz. Vein opening and cementation occurred at shallow burial depth around the time of deposition of the syn-rift clastic succession. Fluid inclusion microthermometry on both quartz and dolomite cements indicates a fluid temperature of 90–130°C, again pointing to hydrothermal fluids. Both in Fenera-Sostegno and Montalto Dora areas, O, C and Sr isotope values, coupled with fluid inclusion and clumped isotope data, indicate that hydrothermal fluids derived from seawater interacted with crustal rocks during hydrothermal circulation. Stratigraphic and petrographic evidence, and U–Pb dating of dolomitized clasts within syn-rift sediments, document that hydrothermal fluids circulated through sediments from the latest Triassic to the Toarcian, corresponding to the entire syn-rift evolution of the western portion of the Adriatic palaeomargin. The documented hydrothermal processes are temporally correlated with regional-scale thermal events that took place in the same time interval at deeper crustal levels.
An update of the two-energy turbulence scheme is presented, the 2TE + APDF scheme. The original version of the two-energy scheme is able to successfully model shallow convection without the need of an additional parameterization for non-local fluxes. However, the performance of the two-energy scheme is worse in stratocumulus cases, where it tends to overestimate the erosion of the stable layers. We have identified the causes: the non-local stability parameter does not consider local stratification, the scheme lacks an internal parameter that could distinguish between a shallow convection regime and a stratocumulus regime, and it uses an inflexible turbulence length scale formulation. To alleviate this problem, we propose several modifications: an update of the stability parameter, a modified computation of the turbulence length scale, and the introduction of the entropy potential temperature to distinguish between a shallow convection and a stratocumulus regime. In addition, the two-energy scheme is coupled to a simplified assumed probability density function method in order to achieve a more universal representation of the cloudy regimes. The updated turbulence scheme is evaluated for several idealized cases and one selected real case in the ICOsahedral Nonhydrostatic (ICON) modeling framework. The results show that the updated scheme corrects the overmixing problem in the stratocumulus cases. The performance of the updated scheme is comparable to the operational setup, and can be thus used instead of the operational turbulence and shallow convection scheme in ICON. Additionally, the updated scheme improves the coupling with dynamics, which is beneficial for the modeling of coherent flow structures in the atmospheric boundary layer.
The segregation of refugees in collective accommodation centres represents an integral component of the European border regime and its complex interplay of inclusion and exclusion. The corresponding spatial, symbolic and discursive demarcations, however, are not simply implemented politically from above, but negotiated on the ground on a daily basis. One crucial group of actors in the German context are neighbourhood-based volunteers. These groups frequently accompany accommodation centres with support structures. Based on contributions in the field of critical border studies and on the example of a municipal accommodation facility in Frankfurt, Germany, this paper demonstrates how volunteers, through their practices and engagement with refugees and others, on one hand, and dominant discourses, institutions and regulations on the other, participate in the production of locally specific spaces of asylum that are marked by simultaneous and contradictory processes of bordering and debordering.
The impact of local environment characteristics on individual cycling behaviour has been discussed in transport research for several years. Many previous studies have, however, primarily focused on the presence and distribution of built environment elements, considered using georeferenced or census data. This paper argues that not only is the objectively measured environment an influencing factor, but also the individual perception of this environment. Furthermore, besides built elements, the evaluation of perceived non-built attributes, such as discourses and policies, as well as the environment’s impact on cycling attitudes, should be taken into account for a more comprehensive view. For this purpose, this study examines the responses to a household survey in the German city of Offenbach am Main (n = 701). The impact of the perceived local environment on cycling behaviour and cycling attitudes has been analysed using 21 perception items as well as socio-demographics, travel mode availability and general travel attitudes. For a more detailed view on cycling behaviour, this study applies the stage model of self-regulated behavioural change (SSBC) indicating a level of openness to use a bicycle frequently in everyday life. The results of the multivariate analysis show that the perceptions of built and non-built environment characteristics interrelate. Furthermore, certain perceptions encourage bicycle use and positive attitudes towards cycling, such as perceived cycling safety and pleasure. Primarily, these perceptions are safe and appropriate cycling infrastructures, cycling as a common practice and the absence of vandalism, dirt and high car pressure.
Lightning climate change projections show large uncertainties caused by limited empirical knowledge and strong assumptions inherent to coarse-grid climate modeling. This study addresses the latter issue by implementing and applying the lightning potential index parameterization (LPI) into a fine-grid convection-permitting regional climate model (CPM). This setup takes advantage of the explicit representation of deep convection in CPMs and allows for process-oriented LPI inputs such as vertical velocity within convective cells and coexistence of microphysical hydrometeor types, which are known to contribute to charge separation mechanisms. The LPI output is compared to output from a simpler flash rate parameterization, namely the CAPE × PREC parameterization, applied in a non-CPM on a coarser grid. The LPI’s implementation into the regional climate model COSMO-CLM successfully reproduces the observed lightning climatology, including its latitudinal gradient, its daily and hourly probability distributions, and its diurnal and annual cycles. Besides, the simulated temperature dependence of lightning reflects the observed dependency. The LPI outperforms the CAPE × PREC parameterization in all applied diagnostics. Based on this satisfactory evaluation, we used the LPI to a climate change projection under the RCP8.5 scenario. For the domain under investigation centered over Germany, the LPI projects a decrease of 4.8% in flash rate by the end of the century, in opposition to a projected increase of 17.4% as projected using the CAPE × PREC parameterization. The future decrease of LPI occurs mostly during the summer afternoons and is related to (i) a change in convection occurrence and (ii) changes in the microphysical mixing. The two parameterizations differ because of different convection occurrences in the CPM and non-CPM and because of changes in the microphysical mixing, which is only represented in the LPI lightning parameterization.
Diamant hat besondere physikalische und optische Eigenschaften sowie eine starke Resistenz gegenüber Strahlenschädigung. Diese Eigenschaften ermöglichen eine vielfältige Anwendung von Diamant in Wissenschaft und Technik, wie zum Beispiel als Sensormaterial in Strahlungsdetektoren.
Kubisches Zirconiumdioxid (ZrO2) wird aufgrund seiner mechanisch und optisch ähnlichen Eigenschaften unter anderem an Stelle von Diamant eingesetzt. Es ist ebenfalls ein geeignetes Material für viele technische Anwendungen und wird durch seine Strahlenresistenz in Strahlungsumgebungen verwendet. Da beide Materialien in diesem Anwendungsbereich hoher energetischer Strahlung ausgesetzt sind, sind Reaktionen auf die Bestrahlung wie etwa strukturelle Veränderungen oder die Änderungen von Materialeigenschaften von großem Interesse.
In der vorliegenden Arbeit wurde die Morphologie, Struktur und physikalischen Eigenschaften von Diamant und Yttriumoxid-stabilisiertem kubischem ZrO2 nach der Bestrahlung mit 14 MeV Au-Ionen und 1.6 GeV Au-Ionen untersucht. Die durch die Bestrahlung verursachten Veränderungen der Oberflächen und der bestrahlten Volumina wurden mit diversen komplementären analytischen Methoden charakterisiert, bewertet und für die verschiedenen Materialien und Ionenenergien verglichen.
Mittels Röntgenfluoreszenzmessungen wurde die Verteilung und Menge an implantiertem Au semi-quantitativ ermittelt. Die Oberflächen der Proben wurden mit optischer Mikroskopie, Rasterkraftmikroskopie, Rasterelektronenmikroskopie, Röntgenreflektometrie und Elektronenrückstreubeugung untersucht. Strukturelle Veränderungen wurden mit Raman-Spektroskopie analysiert. Der elektrische Widerstand, die Dichte, die Härte sowie das Ätzverhalten der bestrahlten Proben wurden ermittelt und geben Auskunft über die Änderung physikalischer Eigenschaften der Materialien.
Diamant und kubisches ZrO2 reagieren sehr unterschiedlich auf die Bestrahlung mit Au-Ionen gleicher Energien und Fluenzen. Die Diamantproben zeigen nach der Bestrahlung mit 14 MeV Au-Ionen deutliche Veränderungen und Schädigungen der Oberfläche sowie des bestrahlten Volumens. Es wird eine Änderung der Struktur, der Dichte, der Härte, des elektrischen Widerstands sowie des Ätzverhaltens der Proben beobachtet, was auf die Amorphisierung von Diamant zurückgeführt wird. Kubisches ZrO2 ist deutlich strahlungsresistenter gegenüber der Bestrahlung mit 14 MeV Au-Ionen. Es werden keine signifikanten strukturellen Änderungen im getesteten Fluenzbereich beobachtet.
Die mit 1.6 GeV Au-Ionen bestrahlten Diamanten zeigen nur geringe Schädigungen und keine deutliche Änderung der Struktur oder der physikalischen Eigenschaften. Die kubischen ZrO2 Proben sind als Folge der Bestrahlung mit 1.6 GeV Au-Ionen zerbrochen, was auf hohe interne Spannung durch Defektbildung zurückgeführt wird.
This thesis is focusing on the impact of Paratethys and Mediterranean water bodies over the Eurasian climate and the interplay between climate, tectonics and biosphere during the late Miocene. This target was the interval between 12.7 and 7.65 Ma for Paratethys, following the Eastern Paratethys restriction and isolation, and 7.2−6.5 Ma (the early Messinian) in Mediterranean, zooming on the effects of gateway restrictions over the eastern Mediterranean and the new born Aegean domain. In both cases restriction is overlapping with large scale climatic changes and tectonic reconfiguration, leading a sort of symbiotic relationship.
Paratethys was a giant epicontinental sea that covered a large part of Eurasia since Paleogene. Due to the Eurasia-Afro-Arabia collision and formation of the Alpine-Himalayan belt (Rögl, 1999; Popov et al., 2006), the Paratethys was divided during the late Miocene in smaller basins that in time were isolated of each other. The protracted isolation and intense continentalisation of paratethyan realm led to changes in humidity distribution, basin connectivity, sediment sources and salinity. These changes had in turn major consequences over water circulation, water availability, vegetation cover and biota. These changes are more intense after 11.6 Ma, when the Eastern Paratethys lost any sustained marine connection, evolving into an enclosed system with endemic fauna (Harzhauser and Piller, 2007).
Mediterranean Sea is a Mezozoic oceanic relic squeezed between Africa, Europe, Anatolia and Arabia, as Africa continued to subduct beneath the European plate. As opposed to Paratethys, it maintained the open connection with the ocean until Messinian, when the two Atlantic gateways (Betic and Rifian corridors) closed for a short time, isolating the basin. The cut off resulted in a dramatic drop down and onset of evaporitic precipitation in marginal basins, the event receiving the name of Messinian Salinity Crisis (5.97−5.55). The restriction affected all marine ecosystems, due to changes in salinity and stratification of water column.
The main objectives of this thesis were:
(1) build valid paleo-temperatures records for both basins based on biomarkers;
(2) reconstruct the hydrology for the late Miocene time interval;
(3) identify vegetation composition and changes;
(4) identify paleo-fires in the late Miocene sediment records;
(5) identify the biotic response to the overall climate and tectonic changes.
All the above objectives were attained with results published in specific journals (Chapters 5−7).
Based on Panagia section (Taman Peninsula, Russia) the longest Paratethys temperature record was completed (~5 Myr), covering the interval between 12.7 and 7.65 Ma. A comprehensive SST and MAT records was obtained, as well as soil pH and carbon (δ13C) and hydrogen (δ2H) stable isotopic compositions on n-alkanes and alkenones. The main findings are concentrated around three prolonged periods with severe droughts affecting the late Miocene circum-Paratethys region peaking at 9.65, 9.4 and 7.9 Ma, associated with a transition towards open land vegetation, intensification of fire activity and enhanced evaporation and aridity.
The time intervals with dryer conditions recorded in Panagia coincide with periods of mammal turnover and dispersal in Eurasia indicating that major environmental changes occurred in the circum-Paratethys region and Paratethys fragmentation had a great impact on the terrestrial ecosystems, when periods of prolonged droughts generated biotic crises and animal displacements across the Eurasian continent. The δ13CC29n-alkane values and charcoal morphologies from Panagia indicate an increased contribution of C4 plants adapted to drier conditions at 9.66 Ma. Similarly high δ13CC29n-alkane values continue until 9.4 Ma, when in Western Europe increased seasonality accelerated the demise of the evergreen subtropical woodlands and expansion of grasslands from Anatolia and Middle East to Europe.
As a result of basin fragmentation and climatic stress, the Eastern Paratethys sub-basins progressively lost their marine properties and turned into brackish-fresh water bodies fed primarily by riverine input. The shallower areas became in time emerged, obstructing connections and isolating the biota, inducing rapid adjusting or extinctions. Thus, the Paratethys harbored a highly endemic fauna (Rögl, 1999), such as dwarf whales, dolphins, seals (among mammals), as well as fish and other taxa (mollusks, ostracods, diatoms, foraminifera, algae, etc.).
Collectively the data structured and analyzed in chapter five support a model in which the Eastern Paratethys evolved as a largely (en)closed system, registering paleoenvironmental signals that are governed by interbasinal connectivity (or lack of it) and regional climate changes in the basin catchment. Acting as an important source of humidity for Western and Central Asia, the size and areal extent of the Paratethys water body is likely to have had a major impact on hydroclimate patterns in the Eurasian interior, with the cumulative fluctuations in both hydrology and surface temperature enhancing the aridity and seasonality, with different partition of moisture over the year. Our combined data suggests a decoupling of Paratethys from the global system as isolation advanced, dominated by regional tectonics and ultimately the Paratethys volume and areal extent reduction.
Atmospheric particles play an important role in the radiative balance of the Earth, as well as they affect human health and air quality. Hence, the chemical characterization constitutes a crucial task to determinate their properties, sources and fate. Particularly, the analysis of nanoparticles (d<100 nm) represents an analytical challenge, since these particles are abundant in number but have very little mass.
This accumulative thesis focuses on the chemical characterization of nanoparticles, performed in both laboratory and field studies. Here, I present four manuscripts, two of which are my main project as a lead author.
The first manuscript (Caudillo et al., 2021) focuses on the gas and the particle phase originated from biogenic precursor gases (α-pinene and isoprene). The experiments were performed in the CLOUD chamber at CERN to simulate pure biogenic new particle formation. Both gas and particle phases are measured with a nitrate CI-APi-TOF mass spectrometer, while the TD-DMA is coupled to it for particle-phase measurements, this setup allows a direct comparison as both measurements use the identical chemical ionization and detector. This study demonstrates the suitability of the TD-DMA for measuring newly formed nanoparticles and it confirms that isoprene suppresses new particle formation but contributes to the growth of newly formed particles.
The second manuscript (Caudillo et al., 2022) presents an intercomparison of four different techniques (including the TD-DMA) for measuring the chemical composition of SOA nanoparticles. The measurements were conducted in the CLOUD chamber. The intercomparison was done by contrasting the observed chemical composition, the calculated volatility, and the thermal desorption behavior (for the thermal desorption techniques). The methods generally agreed on the most important compounds that are found in the nanoparticles. However, they did see different parts of the organic spectrum. Potential explanations for these differences are suggested.
The third manuscript (Ungeheuer al., 2022) presents both laboratory and ambient measurements to investigate the ability of lubricant oil to form new particles. These new particles are an important source of ultrafine particles in the areas nearby large airports. The ambient measurements were performed downwind of Frankfurt International Airport, and it was found that the fraction of lubricant oil is largest in the smallest particles. In the laboratory, the main finding was that evaporated lubricant oil nucleates and forms new particles rapidly. The results suggest that nucleation of lubricant oil and subsequent particle growth can occur in the cooling exhaust plumes of aircraft-turbofans.
The fourth manuscript (Wang et al., 2022) is a new particle formation study in the CLOUD chamber at CERN. This study shows that nitric acid, sulfuric acid, and ammonia interact synergistically and rapidly form particles under upper free tropospheric conditions. These particles can grow by condensation (driven by the availability of ammonia) up to CCN sizes and INP particles. The ability of these particles to act as a CCN and INP was also investigated and it was found to be as efficient as for desert dust. This mechanism constitutes an important finding and it can account for previous observations of high concentrations of ammonia and ammonium nitrate over the Asia monsoon region.
Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.
Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.