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Über alle Erwartungen
(2022)
You be a Mensch
(2022)
Climate change is one of the greatest challenges to humanity in this century, and most noticeable consequences are expected to be impacts on the water cycle – in particular the distribution and availability of water, which is fundamental for all life on Earth. In this context, it is essential to better understand where and when water is available and what processes influence variations in water storages. While estimates of the overall terrestrial water storage (TWS) variations are available from the GRACE satellites, these represent the vertically integrated signal over all water stored in ice, snow, soil moisture, groundwater and surface water bodies. Therefore, complementary observational data and hydrological models are still required to determine the partitioning of the measured signal among different water storages and to understand the underlying processes. However, the application of large-scale observational data is limited by their specific uncertainties and the incapacity to measure certain water fluxes and storages. Hydrological models, on the other hand, vary widely in their structure and process-representation, and rarely incorporate additional observational data to minimize uncertainties that arise from their simplified representation of the complex hydrologic cycle.
In this context, this thesis aims to contribute to improving the understanding of global water storage variability by combining simple hydrological models with a variety of complementary Earth observation-based data. To this end, a model-data integration approach is developed, in which the parameters of a parsimonious hydrological model are calibrated against several observational constraints, inducing GRACE TWS, simultaneously, while taking into account each data’s specific strengths and uncertainties. This approach is used to investigate 3 specific aspects that are relevant for modelling and understanding the composition of large-scale TWS variations.
The first study focusses on Northern latitudes, where snow and cold-region processes define the hydrological cycle. While the study confirms previous findings that seasonal dynamics of TWS are dominated by the cyclic accumulation and melt of snow, it reveals that inter-annual TWS variations on the contrary, are determined by variations in liquid water storages. Additionally, it is found to be important to consider the impact of compensatory effects of spatially heterogeneous hydrological variables when aggregating the contribution of different storage components over large areas. Hence, the determinants of TWS variations are scale-dependent and underlying driving mechanism cannot be simply transferred between spatial and temporal scales. These findings are supported by the second study for the global land areas beyond the Northern latitudes as well.
This second study further identifies the considerable impact of how vegetation is represented in hydrological models on the partitioning of TWS variations. Using spatio-temporal varying fields of Earth observation-based data to parameterize vegetation activity not only significantly improves model performance, but also reduces parameter equifinality and process uncertainties. Moreover, the representation of vegetation drastically changes the contribution of different water storages to overall TWS variability, emphasizing the key role of vegetation for water allocation, especially between sub-surface and delayed water storages. However, the study also identifies parameter equifinality regarding the decay of sub-surface and delayed water storages by either evapotranspiration or runoff, and thus emphasizes the need for further constraints hereof.
The third study focuses on the role of river water storage, in particular whether it is necessary to include computationally expensive river routing for model calibration and validation against the integrated GRACE TWS. The results suggest that river routing is not required for model calibration in such a global model-data integration approach, due to the larger influence other observational constraints, and the determinability of certain model parameters and associated processes are identified as issues of greater relevance. In contrast to model calibration, considering river water storage derived from routing schemes can already significantly improve modelled TWS compared to GRACE observations, and thus should be considered for model evaluation against GRACE data.
Beyond these specific findings that contribute to improved understanding and modelling of large-scale TWS variations, this thesis demonstrates the potential of combining simple modeling approaches with diverse Earth observational data to improve model simulations, overcome inconsistencies of different observational data sets, and identify areas that require further research. These findings encourage future efforts to take advantage of the increasing number of diverse global observational data.
The Andes are a ~7000 km long N-S trending mountain range developed along the South American western continental margin. Driven by the subduction of the oceanic Nazca plate beneath the continental South American plate, the formation of the northern and central parts of the orogen is a type case for a non-collisional orogeny. In the southern Central Andes (SCA, 29°S-39°S), the oceanic plate changes the subduction angle between 33°S and 35°S from almost horizontal (< 5° dip) in the north to a steeper angle (~30° dip) in the south. This sector of the Andes also displays remarkable along- and across- strike variations of the tectonic deformation patterns. These include a systematic decrease of topographic elevation, of crustal shortening and foreland and orogenic width, as well as an alternation of the foreland deformation style between thick-skinned and thin-skinned recorded along- and across the strike of the subduction zone. Moreover, the SCA are a very seismically active region. The continental plate is characterized by a relatively shallow seismicity (< 30 km depth) which is mainly focussed at the transition from the orogen to the lowland areas of the foreland and the forearc; in contrast, deeper seismicity occurs below the interiors of the northern foreland. Additionally, frequent seismicity is also recorded in the shallow parts of the oceanic plate and in a sector of the flat slab segment between 31°S and 33°S. The observed spatial heterogeneity in tectonic and seismic deformation in the SCA has been attributed to multiple causes, including variations in sediment thickness, the presence of inherited structures and changes in the subduction angle of the oceanic slab. However, there is no study that inquired the relationship between the long-term rheological configuration of the SCA and the spatial deformation patterns. Moreover, the effects of the density and thickness configuration of the continental plate and of variations in the slab dip angle in the rheological state of the lithosphere have been not thoroughly investigated yet. Since rheology depends on composition, pressure and temperature, a detailed characterization of the compositional, structural and thermal fields of the lithosphere is needed. Therefore, by using multiple geophysical approaches and data sources, I constructed the following 3D models of the SCA lithosphere: (i) a seismically-constrained structural and density model that was tested against the gravity field; (ii) a thermal model integrating the conversion of mantle shear-wave velocities to temperature with steady-state conductive calculations in the uppermost lithosphere (< 50 km depth), validated by temperature and heat-flow measurements; and (iii) a rheological model of the long-term lithospheric strength using as input the previously-generated models.
The results of this dissertation indicate that the present-day thermal and rheological fields of the SCA are controlled by different mechanisms at different depths. At shallow depths (< 50 km), the thermomechanical field is modulated by the heterogeneous composition of the continental lithosphere. The overprint of the oceanic slab is detectable where the oceanic plate is shallow (< 85 km depth) and the radiogenic crust is thin, resulting in overall lower temperatures and higher strength compared to regions where the slab is steep and the radiogenic crust is thick. At depths > 50 km, largest temperatures variations occur where the descending slab is detected, which implies that the deep thermal field is mainly affected by the slab dip geometry.
The outcomes of this thesis suggests that long-term thermomechanical state of the lithosphere influences the spatial distribution of seismic deformation. Most of the seismicity within the continental plate occurs above the modelled transition from brittle to ductile conditions. Additionally, there is a spatial correlation between the location of these events and the transition from the mechanically strong domains of the forearc and foreland to the weak domain of the orogen. In contrast, seismicity within the oceanic plate is also detected where long-term ductile conditions are expected. I therefore analysed the possible influence of additional mechanisms triggering these earthquakes, including the compaction of sediments in the subduction interface and dehydration reactions in the slab. To that aim, I carried out a qualitative analysis of the state of hydration in the mantle using the ratio between compressional- and shear-wave velocity (vp/vs ratio) from a previous seismic tomography. The results from this analysis indicate that the majority of the seismicity spatially correlates with hydrated areas of the slab and overlying continental mantle, with the exception of the cluster within the flat slab segment. In this region, earthquakes are likely triggered by flexural processes where the slab changes from a flat to a steep subduction angle.
First-order variations in the observed tectonic patterns also seem to be influenced by the thermomechanical configuration of the lithosphere. The mechanically strong domains of the forearc and foreland, due to their resistance to deformation, display smaller amounts of shortening than the relatively weak orogenic domain. In addition, the structural and thermomechanical characteristics modelled in this dissertation confirm previous analyses from geodynamic models pointing to the control of the observed heterogeneities in the orogen and foreland deformation style. These characteristics include the lithospheric and crustal thickness, the presence of weak sediments and the variations in gravitational potential energy.
Specific conditions occur in the cold and strong northern foreland, which is characterized by active seismicity and thick-skinned structures, although the modelled crustal strength exceeds the typical values of externally-applied tectonic stresses. The additional mechanisms that could explain the strain localization in a region that should resist deformation are: (i) increased tectonic forces coming from the steepening of the slab and (ii) enhanced weakening along inherited structures from pre-Andean deformation events. Finally, the thermomechanical conditions of this sector of the foreland could be a key factor influencing the preservation of the flat subduction angle at these latitudes of the SCA.
Sustainable urban growth
(2022)
This dissertation explores the determinants for sustainable and socially optimalgrowth in a city. Two general equilibrium models establish the base for this evaluation, each adding its puzzle piece to the urban sustainability discourse and examining the role of non-market-based and market-based policies for balanced growth and welfare improvements in different theory settings. Sustainable urban growth either calls for policy actions or a green energy transition. Further, R&D market failures can pose severe challenges to the sustainability of urban growth and the social optimality of decentralized allocation decisions. Still, a careful (holistic) combination of policy instruments can achieve sustainable growth and even be first best.
Stimuli-promoted in situ formation of hydrogels with thiol/thioester containing peptide precursors
(2022)
Hydrogels are potential synthetic ECM-like substitutes since they provide functional and structural similarities compared to soft tissues. They can be prepared by crosslinking of macromolecules or by polymerizing suitable precursors. The crosslinks are not necessarily covalent bonds, but could also be formed by physical interactions such as π-π interactions, hydrophobic interactions, or H-bonding. On demand in situ forming hydrogels have garnered increased interest especially for biomedical applications over preformed gels due to the relative ease of in vivo delivery and filling of cavities. The thiol-Michael addition reaction provides a straightforward and robust strategy for in situ gel formation with its fast reaction kinetics and ability to proceed under physiological conditions. The incorporation of a trigger function into a crosslinking system becomes even more interesting since gelling can be controlled with stimulus of choice. The use of small molar mass crosslinker precursors with active groups orthogonal to thiol-Michael reaction type electrophile provides the opportunity to implement an on-demand in situ crosslinking without compromising the fast reaction kinetics.
It was postulated that short peptide sequences due to the broad range structural-function relations available with the different constituent amino acids, can be exploited for the realisation of stimuli-promoted in situ covalent crosslinking and gelation applications. The advantages of this system over conventional polymer-polymer hydrogel systems are the ability tune and predict material property at the molecular level.
The main aim of this work was to develop a simplified and biologically-friendly stimuli-promoted in situ crosslinking and hydrogelation system using peptide mimetics as latent crosslinkers. The approach aims at using a single thiodepsipeptide sequence to achieve separate pH- and enzyme-promoted gelation systems with little modification to the thiodepsipeptide sequence. The realization of this aim required the completion of three milestones.
In the first place, after deciding on the thiol-Michael reaction as an effective in situ crosslinking strategy, a thiodepsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) with expected propensity towards pH-dependent thiol-thioester exchange (TTE) activation, was proposed as a suitable crosslinker precursor for pH-promoted gelation system. Prior to the synthesis of the proposed peptide-mimetic, knowledge of the thiol-Michael reactivity of the would-be activated thiol moiety SH-Leu, which is internally embedded in the thiodepsipeptide was required. In line with pKa requirements for a successful TTE, the reactivity of a more acidic thiol, SH-Phe was also investigated to aid the selection of the best thiol to be incorporated in the thioester bearing peptide based crosslinker precursor. Using ‘pseudo’ 2D-NMR investigations, it was found that only reactions involving SH-Leu yielded the expected thiol-Michael product, an observation that was attributed to the steric hindrance of the bulkier nature of SH-Phe. The fast reaction rates and complete acrylate/maleimide conversion obtained with SH-Leu at pH 7.2 and higher aided the direct elimination of SH-Phe as a potential thiol for the synthesis of the peptide mimetic.
Based on the initial studies, for the pH-promoted gelation system, the proposed Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH was kept unmodified. The subtle difference in pKa values between SH-Leu (thioester thiol) and the terminal cysteamine thiol from theoretical conditions should be enough to effect a ‘pseudo’ intramolecular TTE. In polar protic solvents and under basic aqueous conditions, TDP successfully undergoes a ‘pseudo’ intramolecular TTE reaction to yield an α,ω-dithiol tripeptide, HSLeu-Leu-Gly-NEtSH. The pH dependence of thiolate ion generation by the cysteamine thiol aided the incorporation of the needed stimulus (pH) for the overall success of TTE (activation step) – thiol-Michael addition (crosslinking) strategy.
Secondly, with potential biomedical applications in focus, the susceptibility of TDP, like other thioesters, to intermolecular TTE reaction was probed with a group of thiols of varying thiol pKa values, since biological milieu characteristically contain peptide/protein thiols. L-cysteine, which is a biologically relevant thiol, and a small molecular weight thiol, methylthioglycolate both with relatively similar thiol pKa, values, led to an increase concentration of the dithiol crosslinker when reacted with TDP. In the presence of acidic thiols (p-NTP and 4MBA), a decrease in the dithiol concentration was observed, an observation that can be attributed to the inability of the TTE tetrahedral intermediate to dissociate into exchange products and is in line with pKa requirements for successful TTE reaction. These results additionally makes TDP more attractive and the potentially the first crosslinker precursor for applications in biologically relevant media.
Finally, the ability of TDP to promote pH-sensitive in situ gel formation was probed with maleimide functionalized 4-arm polyethylene glycol polymers in tris-buffered media of varying pHs. When a 1:1 thiol: maleimide molar ratio was used, TDP-PEG4MAL hydrogels formed within 3, 12 and 24 hours at pH values of 8.5, 8.0 and 7.5 respectively. However, gelation times of 3, 5 and 30 mins were observed for the same pH trend when the thiol: maleimide molar was increased to 2:1.
A direct correlation of thiol content with G’ of the gels at each pH could also be drawn by comparing gels with thiol: maleimide ratios of 1:1 to those with 2:1 thiol: maleimide mole ratios. This is supported by the fact that the storage modulus (G') is linearly dependent on the crosslinking density of the polymer. The values of initial G′ for all gels ranged between (200 – 5000 Pa), which falls in the range of elasticities of certain tissue microenvironments for example brain tissue 200 – 1000 Pa and adipose tissue (2500 – 3500 Pa).
Knowledge so far gained from the study on the ability to design and tune the exchange reaction of thioester containing peptide mimetic will give those working in the field further insight into the development of new sequences tailored towards specific applications.
TTE substrate design using peptide mimetic as presented in this work has revealed interesting new insights considering the state-of-the-art. Using the results obtained as reference, the strategy provides a possibility to extend the concept to the controlled delivery of active molecules needed for other robust and high yielding crosslinking reactions for biomedical applications. Application for this sequentially coupled functional system could be seen e.g. in the treatment of inflamed tissues associated with urinary tract like bladder infections for which pH levels above 7 were reported. By the inclusion of cell adhesion peptide motifs, the hydrogel network formed at this pH could act as a new support layer for the healing of damage epithelium as shown in interfacial gel formation experiments using TDP and PEG4MAL droplets.
The versatility of the thiodepsipeptide sequence, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-(TDPo) was extended for the design and synthesis of a MMP-sensitive 4-arm PEG-TDPo conjugate. The purported cleavage of TDPo at the Gly-SLeu bond yields active thiol units for subsequent reaction of orthogonal Michael acceptor moieties. One of the advantages of stimuli-promoted in situ crosslinking systems using short peptides should be the ease of design of required peptide molecules due to the predictability of peptide functions their sequence structure. Consequently the functionalisation of a 4-arm PEG core with the collagenase active TDPo sequence yielded an MMP-sensitive 4-arm thiodepsipeptide-PEG conjugate (PEG4TDPo) substrate.
Cleavage studies using thiol flourometric assay in the presence of MMPs -2 and -9 confirmed the susceptibility of PEG4TDPo towards these enzymes. The resulting time-dependent increase in fluorescence intensity in the presence of thiol assay signifies the successful cleavage of TDPo at the Gly-SLeu bond as expected. It was observed that the cleavage studies with thiol flourometric assay introduces a sigmoid non-Michaelis-Menten type kinetic profile, hence making it difficult to accurately determine the enzyme cycling parameters, kcat and KM .
Gelation studies with PEG4MAL at 10 % wt. concentrations revealed faster gelation with MMP-2 than MMP-9 with 28 and 40 min gelation times respectively. Possible contributions by hydrolytic cleavage of PEG4TDPo has resulted in the gelation of PEG4MAL blank samples but only after 60 minutes of reaction. From theoretical considerations, the simultaneous gelation reaction would be expected to more negatively impact the enzymatic than hydrolytic cleavage. The exact contributions from hydrolytic cleavage of PEG4TDPo would however require additional studies.
In summary this new and simplified in situ crosslinking system using peptide-based crosslinker precursors with tuneable properties exhibited in situ crosslinking gelation kinetics on similar levels with already active dithiols reported. The advantageous on-demand functionality associated with its pH-sensitivity and physiological compatibility makes it a strong candidate worth further research as biomedical applications in general and on-demand material synthesis is concerned.
Results from MMP-promoted gelation system unveils a simple but unexplored approach for in situ synthesis of covalently crosslinked soft materials, that could lead to the development of an alternative pathway in addressing cancer metastasis by making use of MMP overexpression as a trigger. This goal has so far not being reach with MMP inhibitors despite the extensive work this regard.
Untersucht werden die von BulwienGesa erhobenen und aufbereiteten jahresdurchschnittlichen Mieten von Wohnungen und die Relation des Wiederverkaufswertes von Eigentumswohnungen zu den Wohnungsmieten (Preis-Miet-Relation) in 401 kreisfreien Städten und Landkreisen für die Jahre 2004–2017. Dabei zeigt sich bei den Wohnungsmieten eine Zunahme der regionalen Streuung im Zeitverlauf vor allem in der auf die Finanzkrise 2007–2009 folgenden Zeit. Bei der Preis-Miet-Relation nimmt die Streuung im Zeitverlauf ab 2010 ebenfalls zu. Im Durchschnitt der Regionen (Landkreise und kreisfreie Städte) steigen über den gesamten Zeitabschnitt die Mieten und in der überwiegenden Zahl der Regionen auch die Preis-Miet-Relation (allerdings erst ab 2010); sie entwickeln sich aber regional stark unterschiedlich. Dies führt auch zur Zunahme der Variationskoeffizienten, also der relativen Streuung der regionalen Mieten und – ab 2010 – auch der regionalen Preis-Miet-Relationen.
Dies deutet auf eine Zunahme der regionalen Disparitäten in der Bundesrepublik Deutschland hin. Besondere Divergenzen zeigen sich zwischen den alten und den neuen Bundesländern, wie auch zwischen prosperierenden kreisfreien Städten und deren Umland und ökonomisch schwächeren Städten und Landkreisen.
Mit den ›Nachträgen‹ liegt nun der letzte Schriftenband der Jubiläumsausgabe vor. Er ergänzt die ›Jubiläumsausgabe‹ um Texte und Briefe, die entweder erst nach Erscheinen des jeweiligen Bandes entdeckt wurden oder bei Fortsetzung der Ausgabe nach dem Krieg als verschollen galten. Bei den philosophischen Fragmenten handelt es sich u.a. um bisher unbekannte Entwürfe für die ›Morgenstunden‹ und ›An die Freunde Lessings‹. Zu den Judaica zählen Mendelssohns Übertragungen hebräischer Gedichte des 18. Jahrhunderts, seine Übersetzung der Grundartikel des Judentums und seine Anmerkungen zu Michaelis’ Rezension von Dohms ›Ueber die bürgerliche Verbesserung der Juden‹. Zu Mendelssohns Briefpartnern zählen u.a. Abbt, Iselin, Lessing, Friedrich II., Engel, Lavater, Michaelis, Penzel, Nicolai, Dohm, Kuh, Lowth, Carmer und Ramler.
The Greenland Ice Sheet is the second-largest mass of ice on Earth. Being almost 2000 km long, more than 700 km wide, and more than 3 km thick at the summit, it holds enough ice to raise global sea levels by 7m if melted completely. Despite its massive size, it is particularly vulnerable to anthropogenic climate change: temperatures over the Greenland Ice Sheet have increased by more than 2.7◦C in the past 30 years, twice as much as the global mean temperature. Consequently, the ice sheet has been significantly losing mass since the 1980s and the rate of loss has increased sixfold since then. Moreover, it is one of the potential tipping elements of the Earth System, which might undergo irreversible change once a warming threshold is exceeded. This thesis aims at extending the understanding of the resilience of the Greenland Ice Sheet against global warming by analyzing processes and feedbacks relevant to its centennial to multi-millennial stability using ice sheet modeling.
One of these feedbacks, the melt-elevation-feedback is driven by the temperature rise with decreasing altitudes: As the ice sheet melts, its thickness and surface elevation decrease, exposing the ice surface to warmer air and thus increasing the melt rates even further. The glacial isostatic adjustment (GIA) can partly mitigate this melt-elevation feedback as the bedrock lifts in response to an ice load decrease, forming the negative GIA feedback. In my thesis, I show that the interaction between these two competing feedbacks can lead to qualitatively different dynamical responses of the Greenland Ice Sheet to warming – from permanent loss to incomplete recovery, depending on the feedback parameters. My research shows that the interaction of those feedbacks can initiate self-sustained oscillations of the ice volume while the climate forcing remains constant.
Furthermore, the increased surface melt changes the optical properties of the snow or ice surface, e.g. by lowering their albedo, which in turn enhances melt rates – a process known as the melt-albedo feedback. Process-based ice sheet models often neglect this melt-albedo feedback. To close this gap, I implemented a simplified version of the diurnal Energy Balance Model, a computationally efficient approach that can capture the first-order effects of the melt-albedo feedback, into the Parallel Ice Sheet Model (PISM). Using the coupled model, I show in warming experiments that the melt-albedo feedback almost doubles the ice loss until the year 2300 under the low greenhouse gas emission scenario RCP2.6, compared to simulations where the melt-albedo feedback is neglected,
and adds up to 58% additional ice loss under the high emission scenario RCP8.5. Moreover, I find that the melt-albedo feedback dominates the ice loss until 2300, compared to the melt-elevation feedback.
Another process that could influence the resilience of the Greenland Ice Sheet is the warming induced softening of the ice and the resulting increase in flow. In my thesis, I show with PISM how the uncertainty in Glen’s flow law impacts the simulated response to warming. In a flow line setup at fixed climatic mass balance, the uncertainty in flow parameters leads to a range of ice loss comparable to the range caused by different warming levels.
While I focus on fundamental processes, feedbacks, and their interactions in the first three projects of my thesis, I also explore the impact of specific climate scenarios on the sea level rise contribution of the Greenland Ice Sheet. To increase the carbon budget flexibility, some warming scenarios – while still staying within the limits of the Paris Agreement – include a temporal overshoot of global warming. I show that an overshoot by 0.4◦C increases the short-term and long-term ice loss from Greenland by several centimeters. The long-term increase is driven by the warming at high latitudes, which persists even when global warming is reversed. This leads to a substantial long-term commitment of the sea level rise contribution from the Greenland Ice Sheet.
Overall, in my thesis I show that the melt-albedo feedback is most relevant for the ice loss of the Greenland Ice Sheet on centennial timescales. In contrast, the melt-elevation feedback and its interplay with the GIA feedback become increasingly relevant on millennial timescales. All of these influence the resilience of the Greenland Ice Sheet against global warming, in the near future and on the long term.