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Causes for slow weathering and erosion in the steep, warm, monsoon-subjected Highlands of Sri Lanka
(2018)
In the Highlands of Sri Lanka, erosion and chemical weathering rates are among the lowest for global mountain denudation. In this tropical humid setting, highly weathered deep saprolite profiles have developed from high-grade metamorphic charnockite during spheroidal weathering of the bedrock. The spheroidal weathering produces rounded corestones and spalled rindlets at the rock-saprolite interface. I used detailed textural, mineralogical, chemical, and electron-microscopic (SEM, FIB, TEM) analyses to identify the factors limiting the rate of weathering front advance in the profile, the sequence of weathering reactions, and the underlying mechanisms. The first mineral attacked by weathering was found to be pyroxene initiated by in situ Fe oxidation, followed by in situ biotite oxidation. Bulk dissolution of the primary minerals is best described with a dissolution – re-precipitation process, as no chemical gradients towards the mineral surface and sharp structural boundaries are observed at the nm scale. Only the local oxidation in pyroxene and biotite is better described with an ion by ion process. The first secondary phases are oxides and amorphous precipitates from which secondary minerals (mainly smectite and kaolinite) form. Only for biotite direct solid state transformation to kaolinite is likely. The initial oxidation of pyroxene and biotite takes place in locally restricted areas and is relatively fast: log J = -11 molmin/(m2 s). However, calculated corestone-scale mineral oxidation rates are comparable to corestone-scale mineral dissolution rates: log R = -13 molpx/(m2 s) and log R = -15 molbt/(m2 s). The oxidation reaction results in a volume increase. Volumetric calculations suggest that this observed oxidation leads to the generation of porosity due to the formation of micro-fractures in the minerals and the bedrock allowing for fluid transport and subsequent dissolution of plagioclase. At the scale of the corestone, this fracture reaction is responsible for the larger fractures that lead to spheroidal weathering and to the formation of rindlets. Since these fractures have their origin from the initial oxidational induced volume increase, oxidation is the rate limiting parameter for weathering to take place. The ensuing plagioclase weathering leads to formation of high secondary porosity in the corestone over a distance of only a few cm and eventually to the final disaggregation of bedrock to saprolite. As oxidation is the first weathering reaction, the supply of O2 is a rate-limiting factor for chemical weathering. Hence, the supply of O2 and its consumption at depth connects processes at the weathering front with erosion at the surface in a feedback mechanism. The strength of the feedback depends on the relative weight of advective versus diffusive transport of O2 through the weathering profile. The feedback will be stronger with dominating diffusive transport. The low weathering rate ultimately depends on the transport of O2 through the whole regolith, and on lithological factors such as low bedrock porosity and the amount of Fe-bearing primary minerals. In this regard the low-porosity charnockite with its low content of Fe(II) bearing minerals impedes fast weathering reactions. Fresh weatherable surfaces are a pre-requisite for chemical weathering. However, in the case of the charnockite found in the Sri Lankan Highlands, the only process that generates these surfaces is the fracturing induced by oxidation. Tectonic quiescence in this region and low pre-anthropogenic erosion rate (attributed to a dense vegetation cover) minimize the rejuvenation of the thick and cohesive regolith column, and lowers weathering through the feedback with erosion.
Investigating the role of fluorinated amino acids on protein structure and function using simulation
(2018)
The Milky Way is only one out of billions of galaxies in the universe. However, it is a special galaxy because it allows to explore the main mechanisms involved in its evolution and formation history by unpicking the system star-by-star. Especially, the chemical fingerprints of its stars provide clues and evidence of past events in the Galaxy’s lifetime. These information help not only to decipher the current structure and building blocks of the Milky Way, but to learn more about the general formation process of galaxies.
In the past decade a multitude of stellar spectroscopic Galactic surveys have scanned millions of stars far beyond the rim of the solar neighbourhood. The obtained spectroscopic information provide unprecedented insights to the chemo-dynamics of the Milky Way. In addition analytic models and numerical simulations of the Milky Way provide necessary descriptions and predictions suited for comparison with observations in order to decode the physical properties that underlie the complex system of the Galaxy.
In the thesis various approaches are taken to connect modern theoretical modelling of galaxy formation and evolution with observations from Galactic stellar surveys. With its focus on the chemo-kinematics of the Galactic disk this work aims to determine new observational constraints on the formation of the Milky Way providing also proper comparisons with two different models. These are the population synthesis model TRILEGAL based on analytical distribution functions, which aims to simulate the number and distribution of stars in the Milky Way and its different components, and a hybrid model (MCM) that combines an N-body simulation of a Milky Way like galaxy in the cosmological framework with a semi-analytic chemical evolution model for the Milky Way. The major observational data sets in use come from two surveys, namely the “Radial Velocity Experiment” (RAVE) and the “Sloan Extension for Galactic Understanding and Exploration” (SEGUE).
In the first approach the chemo-kinematic properties of the thin and thick disk of the Galaxy as traced by a selection of about 20000 SEGUE G-dwarf stars are directly compared to the predictions by the MCM model. As a necessary condition for this, SEGUE's selection function and its survey volume are evaluated in detail to correct the spectroscopic observations for their survey specific selection biases. Also, based on a Bayesian method spectro-photometric distances with uncertainties below 15% are computed for the selection of SEGUE G-dwarfs that are studied up to a distance of 3 kpc from the Sun.
For the second approach two synthetic versions of the SEGUE survey are generated based on the above models. The obtained synthetic stellar catalogues are then used to create mock samples best resembling the compiled sample of observed SEGUE G-dwarfs. Generally, mock samples are not only ideal to compare predictions from various models. They also allow validation of the models' quality and improvement as with this work could be especially achieved for TRILEGAL. While TRILEGAL reproduces the statistical properties of the thin and thick disk as seen in the observations, the MCM model has shown to be more suitable in reproducing many chemo-kinematic correlations as revealed by the SEGUE stars. However, evidence has been found that the MCM model may be missing a stellar component with the properties of the thick disk that the observations clearly show. While the SEGUE stars do indicate a thin-thick dichotomy of the stellar Galactic disk in agreement with other spectroscopic stellar studies, no sign for a distinct metal-poor disk is seen in the MCM model.
Usually stellar spectroscopic surveys are limited to a certain volume around the Sun covering different regions of the Galaxy’s disk. This often prevents to obtain a global view on the chemo-dynamics of the Galactic disk. Hence, a suitable combination of stellar samples from independent surveys is not only useful for the verification of results but it also helps to complete the picture of the Milky Way. Therefore, the thesis closes with a comparison of the SEGUE G-dwarfs and a sample of RAVE giants. The comparison reveals that the chemo-kinematic relations agree in disk regions where the samples of both surveys show a similar number of stars. For those parts of the survey volumes where one of the surveys lacks statistics they beautifully complement each other. This demonstrates that the comparison of theoretical models on the one side, and the combined observational data gathered by multiple surveys on the other side, are key ingredients to understand and disentangle the structure and formation history of the Milky Way.
We extend the scope of European palaeogenomics by sequencing the genomes of Late Upper Palaeolithic (13,300 years old, 1.4-fold coverage) and Mesolithic (9,700 years old, 15.4-fold) males from western Georgia in the Caucasus and a Late Upper Palaeolithic (13,700 years old, 9.5-fold) male from Switzerland. While we detect Late Palaeolithic-Mesolithic genomic continuity in both regions, we find that Caucasus hunter-gatherers (CHG) belong to a distinct ancient clade that split from western hunter-gatherers similar to 45 kya, shortly after the expansion of anatomically modern humans into Europe and from the ancestors of Neolithic farmers similar to 25 kya, around the Last Glacial Maximum. CHG genomes significantly contributed to the Yamnaya steppe herders who migrated into Europe similar to 3,000 BC, supporting a formative Caucasus influence on this important Early Bronze age culture. CHG left their imprint on modern populations from the Caucasus and also central and south Asia possibly marking the arrival of Indo-Aryan languages.
Understanding heat transport in sedimentary basins requires an assessment of the regional 3D heat distribution and of the main physical mechanisms responsible for the transport of heat. We review results from different 3D numerical simulations of heat transport based on 3D basin models of the Central European Basin System (CEBS). Therefore we compare differently detailed 3D structural models of the area, previously published individually, to assess the influence of (1) different configurations of the deeper lithosphere, (2) the mechanism of heat transport considered and (3) large faults dissecting the sedimentary succession on the resulting thermal field and groundwater flow. Based on this comparison we propose a modelling strategy linking the regional and lithosphere-scale to the sub-basin and basin-fill scale and appropriately considering the effective heat transport processes. We find that conduction as the dominant mechanism of heat transport in sedimentary basins is controlled by the distribution of thermal conductivities, compositional and thickness variations of both the conductive and radiogenic crystalline crust as well as the insulating sediments and by variations in the depth to the thermal lithosphere-asthenosphere boundary. Variations of these factors cause thermal anomalies of specific wavelength and must be accounted for in regional thermal studies. In addition advective heat transport also exerts control on the thermal field on the regional scale. In contrast, convective heat transport and heat transport along faults is only locally important and needs to be considered for exploration on the reservoir scale. The general applicability of the proposed workflow makes it of interest for a broad range of application in geosciences including oil and gas exploration, geothermal utilization or carbon capture and sequestration issues. (C) 2014 Elsevier Ltd. All rights reserved.
The weather in Eurasia, Australia, and North and South America is largely controlled by the strength and position of extratropical storm tracks. Future climate change will likely affect these storm tracks and the associated transport of energy, momentum, and water vapour. Many recent studies have analyzed how storm tracks will change under climate change, and how these changes are related to atmospheric dynamics. However, there are still discrepancies between different studies on how storm tracks will change under future climate scenarios. Here, we show that under global warming the CMIP5 ensemble of coupled climate models projects only little relative changes in vertically averaged mid-latitude mean storm track activity during the northern winter, but agree in projecting a substantial decrease during summer. Seasonal changes in the Southern Hemisphere show the opposite behaviour, with an intensification in winter and no change during summer. These distinct seasonal changes in northern summer and southern winter storm tracks lead to an amplified seasonal cycle in a future climate. Similar changes are seen in the mid-latitude mean Eady growth rate maximum, a measure that combines changes in vertical shear and static stability based on baroclinic instability theory. Regression analysis between changes in the storm tracks and changes in the maximum Eady growth rate reveal that most models agree in a positive association between the two quantities over mid-latitude regions.
The Great Hungarian Plain was a crossroads of cultural transformations that have shaped European prehistory. Here we analyse a 5,000-year transect of human genomes, sampled from petrous bones giving consistently excellent endogenous DNA yields, from 13 Hungarian Neolithic, Copper, Bronze and Iron Age burials including two to high (similar to 22x) and seven to similar to 1x coverage, to investigate the impact of these on Europe's genetic landscape. These data suggest genomic shifts with the advent of the Neolithic, Bronze and Iron Ages, with interleaved periods of genome stability. The earliest Neolithic context genome shows a European hunter-gatherer genetic signature and a restricted ancestral population size, suggesting direct contact between cultures after the arrival of the first farmers into Europe. The latest, Iron Age, sample reveals an eastern genomic influence concordant with introduced Steppe burial rites. We observe transition towards lighter pigmentation and surprisingly, no Neolithic presence of lactase persistence.
1,4-Di(homo)allyl-2,5-diketopiperazines are synthesized and polymerized via ADMET using the Hoveyda-Grubbs 2nd generation catalyst. The but-3-enylated diketopiperazine can be converted into unsaturated tertiary polyamide with molar mass of <3000 g mol(-1), whereas the allylated diketopiperazine cannot. Double-bond isomerization occurs regardless of whether or not benzoquinone is present. A polyesteramide with a higher molar mass of ca. 4800 g mol(-1) is obtained by the alternating copolymerization (ALTMET) of 1,4-di(but-3-enyl)-2,5-di ketopiperazine and ethylene glycol diacrylate. A post-polymerization modification of the poly(ester)amides via radical thiol-ene chemistry, however, fails.
The mid- to late Holocene interval is characterised by a highly variable climate in response to a gradual change in orbital insolation. The seasonal impact of these changes on the Eifel Maar region is not yet well documented largely due to uncertainties about the completeness of this archive ("missing varves" in the well known Lake Holzmaar) and a limited understanding of the factors (e.g. temperature, precipitation) influencing the seasonality archived within the lamination/varves. In this study we approach these challenges from a different perspective. Using detailed microfacies investigations we: (1) demonstrate that the ambiguity about the "missing varves" is related to the climate induced complex biotic and abiotic laminations that led to mis-identification of varves; (2) use a combination of detailed microfacies investigations (varve structure, seasonality of biotic and abiotic signals), lamination quality, varve counts on multiple cores, published and new radiocarbon dates to develop a continuous master chronology based on the Bayesian modelling approach. The dates of major climate, volcanic, and archaeological event(s) determined using our model are in good agreement with the independently determined ages of the same events from other archives, confirming the accuracy of our age model; (3) test the sensitivity of the seasonal proxies to the available data on mid-Holocene changes in temperature and precipitation; (4) demonstrate that the changes in lake eutrophicity are correlative with temperature changes in NW Europe and probably triggered by solar variability; and (5) show that the early Iron Age onset of eutrophication in Lake Holzmaar was climate induced and began several decades before the impact of anthropogenic activity was seen in the form of intensified detrital erosion in the catchment area. Our work has implications for understanding the impact of climate change and anthropogenic activities on limnological systems. (C) 2014 Elsevier B.V. All rights reserved.