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The scientific drilling campaign PALEOVAN was conducted in the summer of 2010 and was part of the international continental drilling programme (ICDP). The main goal of the campaign was the recovery of a sensitive climate archive in the East of Anatolia. Lacustrine deposits underneath the lake floor of ‘Lake Van’ constitute this archive. The drilled core material was recovered from two locations: the Ahlat Ridge and the Northern Basin. A composite core was constructed from cored material of seven parallel boreholes at the Ahlat Ridge and covers an almost complete lacustrine history of Lake Van. The composite record offered sensitive climate proxies such as variations of total organic carbon, K/Ca ratios, or a relative abundance of arboreal pollen. These proxies revealed patterns that are similar to climate proxy variations from Greenland ice cores. Climate variations in Greenland ice cores have been dated by modelling the timing of orbital forces to affect the climate. Volatiles from melted ice aliquots are often taken as high-resolution proxies and provide a base for fitting the according temporal models.
The ICDP PALEOVAN scientific team fitted proxy data from the lacustrine drilling record to ice core data and constructed an age model. Embedded volcaniclastic layers had to be dated radiometrically in order to provide independent age constraints to the climate-stratigraphic age model. Solving this task by an application of the 40Ar/39Ar method was the main objective of this thesis. Earlier efforts to apply the 40Ar/39Ar dating resulted in inaccuracies that could not be explained satisfactorily.
The absence of K-rich feldspars in suitable tephra layers implied that feldspar crystals needed to be 500 μm in size minimum, in order to apply single-crystal 40Ar/39Ar dating. Some of the samples did not contain any of these grain sizes or only very few crystals of that size. In order to overcome this problem this study applied a combined single-crystal and multi-crystal approach with different crystal fractions from the same sample. The preferred method of a stepwise heating analysis of an aliquot of feldspar crystals has been applied to three samples. The Na-rich crystals and their young geological age required 20 mg of inclusion-free, non-corroded feldspars. Small sample volumes (usually 25 % aliquots of 5 cm3 of sample material – a spoon full of tephra) and the widespread presence of melt-inclusion led to the application of combined single- and multigrain total fusion analyses. 40Ar/39Ar analyses on single crystals have the advantage of being able to monitor the presence of excess 40Ar and detrital or xenocrystic contamination in the samples. Multigrain analyses may hide the effects from these obstacles. The results from the multigrain analyses are therefore discussed with respect to the findings from the respective cogenetic single crystal ages. Some of the samples in this study were dated by 40Ar/39Ar on feldspars on multigrain separates and (if available) in combination with only a few single crystals. 40Ar/39Ar ages from two of the samples deviated statistically from the age model. All other samples resulted in identical ages. The deviations displayed older ages than those obtained from the age model. t-Tests compared radiometric ages with available age control points from various proxies and from the relative paleointensity of the earth magnetic field within a stratigraphic range of ± 10 m. Concordant age control points from different relative chronometers indicated that deviations are a result of erroneous 40Ar/39Ar ages. The thesis argues two potential reasons for these ages: (1) the irregular appearance of 40Ar from rare melt- and fluid- inclusions and (2) the contamination of the samples with older crystals due to a rapid combination of assimilation and ejection.
Another aliquot of feldspar crystals that underwent separation for the application of 40Ar/39Ar dating was investigated for geochemical inhomogeneities. Magmatic zoning is ubiquitous in the volcaniclastic feldspar crystals. Four different types of magmatic zoning were detected. The zoning types are compositional zoning (C-type zoning), pseudo-oscillatory zoning of trace ele- ment concentrations (PO-type zoning), chaotic and patchy zoning of major and trace element concentrations (R-type zoning) and concentric zoning of trace elements (CC-type zoning). Sam- ples that deviated in 40Ar/39Ar ages showed C-type zoning, R-type zoning or a mix of different types of zoning (C-type and PO-type). Feldspars showing PO-type zoning typically represent the smallest grain size fractions in the samples. The constant major element compositions of these crystals are interpreted to represent the latest stages in the compositional evolution of feldspars in a peralkaline melt. PO-type crystals contain less melt- inclusions than other zoning types and are rarely corroded. This thesis concludes that feldspars that show PO-type zoning are most promising chronometers for the 40Ar/39Ar method, if samples provide mixed zoning types of Quaternary anorthoclase feldspars.
Five samples were dated by applying the 40Ar/39Ar method to volcanic glass. High fractions of atmospheric Ar (typically > 98%) significantly hampered the precision of the 40Ar/39Ar ages and resulted in rough age estimates that widely overlap the age model. Ar isotopes indicated that the glasses bore a chorine-rich Ar-end member. The chlorine-derived 38Ar indicated chlorine-rich fluid-inclusions or the hydration of the volcanic glass shards. This indication strengthened the evidence that irregularly distributed melt-inclusions and thus irregular distributed excess 40Ar influenced the problematic feldspar 40Ar/39Ar ages. Whether a connection between a corrected initial 40Ar/36Ar ratio from glasses to the 40Ar/36Ar ratios from pore waters exists remains unclear.
This thesis offers another age model, which is similarly based on the interpolation of the temporal tie points from geophysical and climate-stratigraphic data. The model used a PCHIP- interpolation (piecewise cubic hermite interpolating polynomial) whereas the older age model used a spline-interpolation. Samples that match in ages from 40Ar/39Ar dating of feldspars with the earlier published age model were additionally assigned with an age from the PCHIP- interpolation. These modelled ages allowed a recalculation of the Alder Creek sanidine mineral standard. The climate-stratigraphic calibration of an 40Ar/39Ar mineral standard proved that the age versus depth interpolations from PAELOVAN drilling cores were accurate, and that the applied chronometers recorded the temporal evolution of Lake Van synchronously.
Petrochemical discrimination of the sampled volcaniclastic material is also given in this thesis. 41 from 57 sampled volcaniclastic layers indicate Nemrut as their provenance. Criteria that served for the provenance assignment are provided and reviewed critically. Detailed correlations of selected PALEOVAN volcaniclastics to onshore samples that were described in detail by earlier studies are also discussed. The sampled volcaniclastics dominantly have a thickness of < 40 cm and have been ejected by small to medium sized eruptions. Onshore deposits from these types of eruptions are potentially eroded due to predominant strong winds on Nemrut and Süphan slopes. An exact correlation with the data presented here is therefore equivocal or not possible at all.
Deviating feldspar 40Ar/39Ar ages can possibly be explained by inherited 40Ar from feldspar xenocrysts contaminating the samples. In order to test this hypothesis diffusion couples of Ba were investigated in compositionally zoned feldspar crystals. The diffusive behaviour of Ba in feldspar is known, and gradients in the changing concentrations allowed for the calculation of the duration of the crystal’s magmatic development since the formation of the zoning interface. Durations were compared with degassing scenarios that model the Ar-loss during assimilation and subsequent ejection of the xenocrystals. Diffusive equilibration of the contrasting Ba concentrations is assumed to generate maximum durations as the gradient could have been developed in several growth and heating stages. The modelling does not show any indication of an involvement of inherited 40Ar in any of the deviating samples. However, the analytical set-up represents the lower limit of the required spatial resolution. Therefore, it cannot be excluded that the degassing modelling relies on a significant overestimation of the maximum duration of the magmatic history. Nevertheless, the modelling of xenocrystal degassing evidences that the irregular incorporation of excess 40Ar by melt- and fluid inclusions represents the most critical problem that needs to be overcome in dating volcaniclastic feldspars from the PALEOVAN drill cores. This thesis provides the complete background in generating and presenting 40Ar/39Ar ages that are compared to age data from a climate-stratigraphic model. Deviations are identified statistically and then discussed in order to find explanations from the age model and/or from 40Ar/39Ar geochronology. Most of the PALEOVAN stratigraphy provides several chronometers that have been proven for their synchronicity. Lacustrine deposits from Lake Van represent a key archive for reconstructing climate evolution in the eastern Mediterranean and in the Near East. The PALEOVAN record offers a climate-stratigraphic age model with a remarkable accuracy and resolution.
On 6 June 1982, Israel invaded Lebanon to fight the Palestinian
Liberation Organization (PLO). Between August 1982 and February
1984, the US, France, Britain and Italy deployed a Multinational
Force (MNF) to Beirut. Its task was to act as an interposition force to
bolster the government and to bring peace to the people. The
mission is often forgotten or merely remembered in context with
the bombing of US Marines’ barracks. However, an analysis of the
Italian contingent shows that the MNF was not doomed to fail and
could accomplish its task when operational and diplomatic efforts
were coordinated. The Italian commander in Beirut, General Franco
Angioni, followed a successful approach that sustained neutrality,
respectful behaviour and minimal force, which resulted in a
qualified success of the Italian efforts.
The aim of this doctoral thesis was to establish a technique for the analysis of biomolecules with infrared matrix-assisted laser dispersion (IR-MALDI) ion mobility (IM) spectrometry. The main components of the work were the characterization of the IR-MALDI process, the development and characterization of different ion mobility spectrometers, the use of IR-MALDI-IM spectrometry as a robust, standalone spectrometer and the development of a collision cross-section estimation approach for peptides based on molecular dynamics and thermodynamic reweighting.
First, the IR-MALDI source was studied with atmospheric pressure ion mobility spectrometry and shadowgraphy. It consisted of a metal capillary, at the tip of which a self-renewing droplet of analyte solution was met by an IR laser beam. A relationship between peak shape, ion desolvation, diffusion and extraction pulse delay time (pulse delay) was established. First order desolvation kinetics were observed and related to peak broadening by diffusion, both influenced by the pulse delay. The transport mechanisms in IR-MALDI were then studied by relating different laser impact positions on the droplet surface to the corresponding ion mobility spectra. Two different transport mechanisms were determined: phase explosion due to the laser pulse and electrical transport due to delayed ion extraction. The velocity of the ions stemming from the phase explosion was then measured by ion mobility and shadowgraphy at different time scales and distances from the source capillary, showing an initially very high but rapidly decaying velocity. Finally, the anatomy of the dispersion plume was observed in detail with shadowgraphy and general conclusions over the process were drawn.
Understanding the IR-MALDI process enabled the optimization of the different IM spectrometers at atmospheric and reduced pressure (AP and RP, respectively). At reduced pressure, both an AP and an RP IR-MALDI source were used. The influence of the pulsed ion extraction parameters (pulse delay, width and amplitude) on peak shape, resolution and area was systematically studied in both AP and RP IM spectrometers and discussed in the context of the IR-MALDI process. Under RP conditions, the influence of the closing field and of the pressure was also examined for both AP and RP sources. For the AP ionization RP IM spectrometer, the influence of the inlet field (IF) in the source region was also examined. All of these studies led to the determination of the optimal analytical parameters as well as to a better understanding of the initial ion cloud anatomy.
The analytical performance of the spectrometer was then studied. Limits of detection (LOD) and linear ranges were determined under static and pulsed ion injection conditions and interpreted in the context of the IR-MALDI mechanism. Applications in the separation of simple mixtures were also illustrated, demonstrating good isomer separation capabilities and the advantages of singly charged peaks. The possibility to couple high performance liquid chromatography (HPLC) to IR-MALDI-IM spectrometry was also demonstrated. Finally, the reduced pressure spectrometer was used to study the effect of high reduced field strength on the mobility of polyatomic ions in polyatomic gases.
The last focus point was on the study of peptide ions. A dataset obtained with electrospray IM spectrometry was characterized and used for the calibration of a collision cross-section (CCS) determination method based on molecular dynamics (MD) simulations at high temperature. Instead of producing candidate structures which are evaluated one by one, this semi-automated method uses the simulation as a whole to determine a single average collision cross-section value by reweighting the CCS of a few representative structures. The method was compared to the intrinsic size parameter (ISP) method and to experimental results. Additional MD data obtained from the simulations was also used to further analyze the peptides and understand the experimental results, an advantage with regard to the ISP method. Finally, the CCS of peptide ions analyzed by IR-MALDI were also evaluated with both ISP and MD methods and the results compared to experiment, resulting in a first validation of the MD method. Thus, this thesis brings together the soft ionization technique that is IR-MALDI, which produces mostly singly charged peaks, with ion mobility spectrometry, which can distinguish between isomers, and a collision cross-section determination method which also provides structural information on the analyte at hand.
In this paper two groups supporting different views on the mechanism of light induced polymer deformation argue about the respective underlying theoretical conceptions, in order to bring this interesting debate to the attention of the scientific community. The group of Prof. Nicolae Hurduc supports the model claiming that the cyclic isomerization of azobenzenes may cause an athermal transition of the glassy azobenzene containing polymer into a fluid state, the so-called photo-fluidization concept. This concept is quite convenient for an intuitive understanding of the deformation process as an anisotropic flow of the polymer material. The group of Prof. Svetlana Santer supports the re-orientational model where the mass-transport of the polymer material accomplished during polymer deformation is stated to be generated by the light-induced re-orientation of the azobenzene side chains and as a consequence of the polymer backbone that in turn results in local mechanical stress, which is enough to irreversibly deform an azobenzene containing material even in the glassy state. For the debate we chose three polymers differing in the glass transition temperature, 32 °C, 87 °C and 95 °C, representing extreme cases of flexible and rigid materials. Polymer film deformation occurring during irradiation with different interference patterns is recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. We also demonstrated the unique behaviour of azobenzene containing polymeric films to switch the topography in situ and reversibly by changing the irradiation conditions. We discuss the results of reversible deformation of three polymers induced by irradiation with intensity (IIP) and polarization (PIP) interference patterns, and the light of homogeneous intensity in terms of two approaches: the re-orientational and the photo-fluidization concepts. Both agree in that the formation of opto-mechanically induced stresses is a necessary prerequisite for the process of deformation. Using this argument, the deformation process can be characterized either as a flow or mass transport.
This work reviews the literature on an alleged global warming 'pause' in global mean surface temperature (GMST) to determine how it has been defined, what time intervals are used to characterise it, what data are used to measure it, and what methods used to assess it. We test for 'pauses', both in the normally understood meaning of the term to mean no warming trend, as well as for a 'pause' defined as a substantially slower trend in GMST. The tests are carried out with the historical versions of GMST that existed for each pause-interval tested, and with current versions of each of the GMST datasets. The tests are conducted following the common (but questionable) practice of breaking the linear fit at the start of the trend interval ('broken' trends), and also with trends that are continuous with the data bordering the trend interval. We also compare results when appropriate allowance is made for the selection bias problem. The results show that there is little or no statistical evidence for a lack of trend or slower trend in GMST using either the historical data or the current data. The perception that there was a 'pause' in GMST was bolstered by earlier biases in the data in combination with incomplete statistical testing.
It is well-documented that strength training (ST) improves measures of muscle strength in young athletes. Less is known on transfer effects of ST on proxies of muscle power and the underlying dose-response relationships. The objectives of this meta-analysis were to quantify the effects of ST on lower limb muscle power in young athletes and to provide dose-response relationships for ST modalities such as frequency, intensity, and volume. A systematic literature search of electronic databases identified 895 records. Studies were eligible for inclusion if (i) healthy trained children (girls aged 6–11 y, boys aged 6–13 y) or adolescents (girls aged 12–18 y, boys aged 14–18 y) were examined, (ii) ST was compared with an active control, and (iii) at least one proxy of muscle power [squat jump (SJ) and countermovement jump height (CMJ)] was reported. Weighted mean standardized mean differences (SMDwm) between subjects were calculated. Based on the findings from 15 statistically aggregated studies, ST produced significant but small effects on CMJ height (SMDwm = 0.65; 95% CI 0.34–0.96) and moderate effects on SJ height (SMDwm = 0.80; 95% CI 0.23–1.37). The sub-analyses revealed that the moderating variable expertise level (CMJ height: p = 0.06; SJ height: N/A) did not significantly influence ST-related effects on proxies of muscle power. “Age” and “sex” moderated ST effects on SJ (p = 0.005) and CMJ height (p = 0.03), respectively. With regard to the dose-response relationships, findings from the meta-regression showed that none of the included training modalities predicted ST effects on CMJ height. For SJ height, the meta-regression indicated that the training modality “training duration” significantly predicted the observed gains (p = 0.02), with longer training durations (>8 weeks) showing larger improvements. This meta-analysis clearly proved the general effectiveness of ST on lower-limb muscle power in young athletes, irrespective of the moderating variables. Dose-response analyses revealed that longer training durations (>8 weeks) are more effective to improve SJ height. No such training modalities were found for CMJ height. Thus, there appear to be other training modalities besides the ones that were included in our analyses that may have an effect on SJ and particularly CMJ height. ST monitoring through rating of perceived exertion, movement velocity or force-velocity profile could be promising monitoring tools for lower-limb muscle power development in young athletes.
Spatio-temporal data denotes a category of data that contains spatial as well as temporal components. For example, time-series of geo-data, thematic maps that change over time, or tracking data of moving entities can be interpreted as spatio-temporal data.
In today's automated world, an increasing number of data sources exist, which constantly generate spatio-temporal data. This includes for example traffic surveillance systems, which gather movement data about human or vehicle movements, remote-sensing systems, which frequently scan our surroundings and produce digital representations of cities and landscapes, as well as sensor networks in different domains, such as logistics, animal behavior study, or climate research.
For the analysis of spatio-temporal data, in addition to automatic statistical and data mining methods, exploratory analysis methods are employed, which are based on interactive visualization. These analysis methods let users explore a data set by interactively manipulating a visualization, thereby employing the human cognitive system and knowledge of the users to find patterns and gain insight into the data.
This thesis describes a software framework for the visualization of spatio-temporal data, which consists of GPU-based techniques to enable the interactive visualization and exploration of large spatio-temporal data sets. The developed techniques include data management, processing, and rendering, facilitating real-time processing and visualization of large geo-temporal data sets. It includes three main contributions:
- Concept and Implementation of a GPU-Based Visualization Pipeline.
The developed visualization methods are based on the concept of a GPU-based visualization pipeline, in which all steps -- processing, mapping, and rendering -- are implemented on the GPU. With this concept, spatio-temporal data is represented directly in GPU memory, using shader programs to process and filter the data, apply mappings to visual properties, and finally generate the geometric representations for a visualization during the rendering process. Data processing, filtering, and mapping are thereby executed in real-time, enabling dynamic control over the mapping and a visualization process which can be controlled interactively by a user.
- Attributed 3D Trajectory Visualization.
A visualization method has been developed for the interactive exploration of large numbers of 3D movement trajectories. The trajectories are visualized in a virtual geographic environment, supporting basic geometries such as lines, ribbons, spheres, or tubes. Interactive mapping can be applied to visualize the values of per-node or per-trajectory attributes, supporting shape, height, size, color, texturing, and animation as visual properties. Using the dynamic mapping system, several kind of visualization methods have been implemented, such as focus+context visualization of trajectories using interactive density maps, and space-time cube visualization to focus on the temporal aspects of individual movements.
- Geographic Network Visualization.
A method for the interactive exploration of geo-referenced networks has been developed, which enables the visualization of large numbers of nodes and edges in a geographic context. Several geographic environments are supported, such as a 3D globe, as well as 2D maps using different map projections, to enable the analysis of networks in different contexts and scales. Interactive filtering, mapping, and selection can be applied to analyze these geographic networks, and visualization methods for specific types of networks, such as coupled 3D networks or temporal networks have been implemented.
As a demonstration of the developed visualization concepts, interactive visualization tools for two distinct use cases have been developed. The first contains the visualization of attributed 3D movement trajectories of airplanes around an airport. It allows users to explore and analyze the trajectories of approaching and departing aircrafts, which have been recorded over the period of a month. By applying the interactive visualization methods for trajectory visualization and interactive density maps, analysts can derive insight from the data, such as common flight paths, regular and irregular patterns, or uncommon incidents such as missed approaches on the airport.
The second use case involves the visualization of climate networks, which are geographic networks in the climate research domain. They represent the dynamics of the climate system using a network structure that expresses statistical interrelationships between different regions. The interactive tool allows climate analysts to explore these large networks, analyzing the network's structure and relating it to the geographic background. Interactive filtering and selection enables them to find patterns in the climate data and identify e.g. clusters in the networks or flow patterns.
The focus in this article, through a reading of the German-Australian
newspaper Der Kosmopolit, is on the legacies of entangled imperial
identities in the period of the nineteenth-century German
Enlightenment. Attention is drawn to members of the liberal
nationalist generation of 1848 who emigrated to the Australian
colonies and became involved in intellectual activities there. The
idea of entanglement is applied to the philosophical orientation
of the German-language newspaper that this group formed, Der
Kosmopolit, which was published between 1856 and 1957. Against
simplistic notions that would view cosmopolitanism as the
opposite of nationalism, it is argued that individuals like Gustav
Droege and Carl Muecke deployed an entangled ‘cosmo-
nationalism’ in ways that both advanced German nationalism and
facilitated their own engagement with and investment in
Australian colonial society.
Identifying abrupt transitions is a key question in various disciplines. Existing transition detection methods, however, do not rigorously account for time series uncertainties, often neglecting them altogether or assuming them to be independent and qualitatively similar. Here, we introduce a novel approach suited to handle uncertainties by representing the time series as a time-ordered sequence of probability density functions. We show how to detect abrupt transitions in such a sequence using the community structure of networks representing probabilities of recurrence. Using our approach, we detect transitions in global stock indices related to well-known periods of politico-economic volatility. We further uncover transitions in the El Nino-Southern Oscillation which coincide with periods of phase locking with the Pacific Decadal Oscillation. Finally, we provide for the first time an 'uncertainty-aware' framework which validates the hypothesis that ice-rafting events in the North Atlantic during the Holocene were synchronous with a weakened Asian summer monsoon.
Accuracy of training recommendations based on a treadmill multistage incremental exercise test
(2018)
Competitive runners will occasionally undergo exercise in a laboratory setting to obtain predictive and prescriptive information regarding their performance. The present research aimed to assess whether the physiological demands of lab-based treadmill running (TM) can simulate that of over-ground (OG) running using a commonly used protocol. Fifteen healthy volunteers with a weekly mileage of ≥ 20 km over the past 6 months and treadmill experience participated in this cross-sectional study. Two stepwise incremental tests until volitional exhaustion was performed in a fixed order within one week in an Outpatient Clinic research laboratory and outdoor athletic track. Running velocity (IATspeed), heart rate (IATHR) and lactate concentration at the individual anaerobic threshold (IATbLa) were primary endpoints. Additionally, distance covered (DIST), maximal heart rate (HRmax), maximal blood lactate concentration (bLamax) and rate of perceived exertion (RPE) at IATspeed were analyzed. IATspeed, DIST and HRmax were not statistically significantly different between conditions, whereas bLamax and RPE at IATspeed showed statistical significance (p < 0.05). Apart from RPE at IATspeed, IATspeed, DIST, HRmax and bLamax strongly correlate between conditions (r = 0.815–0.988). High reliability between conditions provides strong evidence to suggest that running on a treadmill are physiologically comparable to that of OG and that training recommendations and be made with assurance.