TY - THES A1 - Svirejeva-Hopkins, Anastasia T1 - Urbanised territories as a specific component of the global carbon cycle N2 - Wir betrachten folgende Teile: die zusätzlichen Kohlenstoff(C)-emissionen, welche aus der Umwandlung von natürlichem Umland durch Stadtwachstum resultieren, und die Änderung des C-Flusses durch 'urbanisierte' Ökosysteme, soweit atmosphärisches C durch diese in umliegende natürliche Ökosysteme entlang der Kette “Atmosphäre -> Vegetation -> abgestorbene organische Substanzen” gepumpt wird: d.h. C-Export; für den Zeitraum von 1980 bis 2050. Als Szenario nutzen wir Prognosen der regionalen Stadtbevölkerung, welche durch ein 'Hybridmodell' generiert werden für acht Regionen. Alle Schätzungen der C-Flüsse basieren auf zwei Modellen: das Regression Modell und das sogenannte G-Modell. Die Siedlungsfläche, welche mit dem Wachstum der Stadtbevölkerung zunimmt, wird in 'Grünflächen' (Parks, usw.), Gebäudeflächen und informell städtisch genutzte Flächen (Slums, illegale Lagerplätze, usw.) unterteilt. Es werden jährlich die regionale und globale Dynamik der C-Emissionen und des C-Exports sowie die C-Gesamtbilanz berechnet. Dabei liefern beide Modelle qualitativ ähnliche Ergebnisse, jedoch gibt es einige quantitative Unterschiede. Im ersten Modell erreicht die globale Jahresemission für die Dekade 2020-2030 resultierend aus der Landnutzungsänderung ein Maximum von 205 Mt/a. Die maximalen Beiträge zur globalen Emission werden durch China, die asiatische und die pazifische Region erbracht. Im zweiten Modell erhöht sich die jährliche globale Emission von 1.12 GtC/a für 1980 auf 1.25 GtC/a für 2005 (1Gt = 109 t). Danach beginnt eine Reduzierung. Vergleichen wir das Emissionmaximum mit der Emission durch Abholzung im Jahre 1980 (1.36 GtC/a), können wir konstatieren, daß die Urbanisierung damit in vergleichbarer Grösse zur Emission beiträgt. Bezogen auf die globale Dynamik des jährlichen C-Exports durch Urbanisierung beobachten wir ein monotones Wachstum bis zum nahezu dreifachen Wert von 24 MtC/a für 1980 auf 66 MtC/a für 2050 im ersten Modell, bzw. im zweiten Modell von 249 MtC/a für 1980 auf 505 MtC/a für 2050. Damit ist im zweiten Fall die Transportleistung der Siedlungsgebiete mit dem C-Transport durch Flüsse in die Ozeane (196 .. 537 MtC/a) vergleichbar. Bei der Abschätzung der Gesamtbilanz finden wir, daß die Urbanisierung die Bilanz in Richtung zu einer 'Senke' verschiebt. Entsprechend dem zweiten Modell beginnt sich die C-Gesamtbilanz (nach annähernder Konstanz) ab dem Jahre 2000 mit einer fast konstanten Rate zu verringern. Wenn das Maximum im Jahre 2000 bei 905MtC/a liegt, fällt dieser Wert anschliessend bis zum Jahre 2050 auf 118 MtC/a. Bei Extrapolation dieser Dynamik in die Zukunft können wir annehmen, daß am Ende des 21. Jahrhunderts die “urbane” C-Gesamtbilanz Null bzw. negative Werte erreicht. N2 - We calculate the additional carbon emissions as a result of the conversion of natural land in a process of urbanisation; and the change of carbon flows by “urbanised” ecosystems, when the atmospheric carbon is exported to the neighboring territories, from 1980 till 2050 for the eight regions of the world. As a scenario we use combined UN and demographic model′s prognoses for regional total and urban population growth. The calculations of urban areas dynamics are based on two models: the regression model and the Gamma-model. The urbanised area is sub-divided on built-up, „green“ (parks, etc.) and informal settlements (favelas) areas. The next step is to calculate the regional and world dynamics of carbon emission and export, and the annual total carbon balance. Both models give similar results with some quantitative differences. In the first model, the world annual emissions attain a maximum of 205 MtC/year between 2020-2030. Emissions will then slowly decrease. The maximum contributions are given by China and the Asia and Pacific regions. In the second model, world annual emissions increase to 1.25 GtC in 2005, beginning to decrease afterwards. If we compare the emission maximum with the annual emission caused by deforestation, 1.36GtC per year, then we can say that the role of urbanised territories (UT) is of a comparable magnitude. Regarding the world annual export of carbon by UT, we observe its monotonous growth by three times, from 24 MtC to 66 MtC in the first model, and from 249 MtC to 505 MtC in the second one. The latter, is therefore comparable to the amount of carbon transported by rivers into the ocean (196-537 MtC). By estimating the total balance we find that urbanisation shifts the total balance towards a “sink” state. The urbanisation is inhibited in the interval 2020-2030, and by 2050 the growth of urbanised areas would almost stop. Hence, the total emission of natural carbon at that stage will stabilise at the level of the 1980s (80 MtC per year). As estimated by the second model, the total balance, being almost constant until 2000, then starts to decrease at an almost constant rate. We can say that by the end of the XXI century, the total carbon balance will be equal to zero, when the exchange flows are fully balanced, and may even be negative, when the system begins to take up carbon from the atmosphere, i.e., becomes a “sink”. T2 - Urbanised territories as a specific component of the global carbon cycle KW - Urbanisierung KW - C-Senke KW - Bilanz KW - Kohlenstoffzyklus KW - Städte KW - C-Fluss KW - Slums KW - Vegetation KW - Verteilung KW - urban KW - land conversion KW - carbon KW - sink KW - cities KW - urbanisation KW - emissions KW - favela KW - regional KW - population KW - density KW - distribution KW - flux KW - vegetation Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001512 ER - TY - JOUR A1 - Jay, Raphael M. A1 - Vaz da Cruz, Vinicius A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Mitzner, Rolf A1 - Föhlisch, Alexander T1 - Probing solute-solvent interactions of transition metal complexes using L-edge absorption spectroscopy JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - In order to tailor solution-phase chemical reactions involving transition metal complexes, it is critical to understand how their valence electronic charge distributions are affected by the solution environment. Here, solute-solvent interactions of a solvatochromic mixed-ligand iron complex were investigated using X-ray absorption spectroscopy at the transition metal L-2,L-3-edge. Due to the selectivity of the corresponding core excitations to the iron 3d orbitals, the method grants direct access to the valence electronic structure around the iron center and its response to interactions with the solvent environment. A linear increase of the total L-2,L-3-edge absorption cross section as a function of the solvent Lewis acidity is revealed. The effect is caused by relative changes in different metal-ligand-bonding channels, which preserve local charge densities while increasing the density of unoccupied states around the iron center. These conclusions are corroborated by a combination of molecular dynamics and spectrum simulations based on time-dependent density functional theory. The simulations reproduce the spectral trends observed in the X-ray but also optical absorption experiments. Our results underscore the importance of solute-solvent interactions when aiming for an accurate description of the valence electronic structure of solvated transition metal complexes and demonstrate how L-2,L-3-edge absorption spectroscopy can aid in understanding the impact of the solution environment on intramolecular covalency and the electronic charge distribution. KW - basis-sets KW - charge-transfer KW - density KW - dynamics KW - electron localization KW - iron KW - solvation KW - spin-crossover KW - tranfer excited-state KW - x-ray-absorption Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpcb.0c00638 SN - 1520-6106 SN - 1520-5207 VL - 124 IS - 27 SP - 5636 EP - 5645 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Cervantes, Sebastian A1 - Shprits, Yuri Y. A1 - Aseev, Nikita A1 - Drozdov, Alexander A1 - Castillo Tibocha, Angelica Maria A1 - Stolle, Claudia T1 - Identifying radiation belt electron source and loss processes by assimilating spacecraft data in a three-dimensional diffusion model JF - Journal of geophysical research : Space physics N2 - Data assimilation aims to blend incomplete and inaccurate data with physics-based dynamical models. In the Earth's radiation belts, it is used to reconstruct electron phase space density, and it has become an increasingly important tool in validating our current understanding of radiation belt dynamics, identifying new physical processes, and predicting the near-Earth hazardous radiation environment. In this study, we perform reanalysis of the sparse measurements from four spacecraft using the three-dimensional Versatile Electron Radiation Belt diffusion model and a split-operator Kalman filter over a 6-month period from 1 October 2012 to 1 April 2013. In comparison to previous works, our 3-D model accounts for more physical processes, namely, mixed pitch angle-energy diffusion, scattering by Electromagnetic Ion Cyclotron waves, and magnetopause shadowing. We describe how data assimilation, by means of the innovation vector, can be used to account for missing physics in the model. We use this method to identify the radial distances from the Earth and the geomagnetic conditions where our model is inconsistent with the measured phase space density for different values of the invariants mu and K. As a result, the Kalman filter adjusts the predictions in order to match the observations, and we interpret this as evidence of where and when additional source or loss processes are active. The current work demonstrates that 3-D data assimilation provides a comprehensive picture of the radiation belt electrons and is a crucial step toward performing reanalysis using measurements from ongoing and future missions. KW - acceleration KW - code KW - density KW - emic waves KW - energetic particle KW - mechanisms KW - reanalysis KW - ultrarelativistic electrons KW - weather Y1 - 2019 U6 - https://doi.org/10.1029/2019JA027514 SN - 2169-9380 SN - 2169-9402 VL - 125 IS - 1 PB - American Geophysical Union CY - Washington ER - TY - JOUR A1 - Awad, Emad A1 - Metzler, Ralf T1 - Closed-form multi-dimensional solutions and asymptotic behaviours for subdiffusive processes with crossovers: II. Accelerating case JF - Journal of physics : A, Mathematical and theoretical N2 - Anomalous diffusion with a power-law time dependence vertical bar R vertical bar(2)(t) similar or equal to t(alpha i) of the mean squared displacement occurs quite ubiquitously in numerous complex systems. Often, this anomalous diffusion is characterised by crossovers between regimes with different anomalous diffusion exponents alpha(i). Here we consider the case when such a crossover occurs from a first regime with alpha(1) to a second regime with alpha(2) such that alpha(2) > alpha(1), i.e., accelerating anomalous diffusion. A widely used framework to describe such crossovers in a one-dimensional setting is the bi-fractional diffusion equation of the so-called modified type, involving two time-fractional derivatives defined in the Riemann-Liouville sense. We here generalise this bi-fractional diffusion equation to higher dimensions and derive its multidimensional propagator (Green's function) for the general case when also a space fractional derivative is present, taking into consideration long-ranged jumps (Levy flights). We derive the asymptotic behaviours for this propagator in both the short- and long-time as well the short- and long-distance regimes. Finally, we also calculate the mean squared displacement, skewness and kurtosis in all dimensions, demonstrating that in the general case the non-Gaussian shape of the probability density function changes. KW - multidimensional fractional diffusion equation KW - continuous time random KW - walks KW - crossover anomalous diffusion dynamics KW - non-Gaussian probability KW - density Y1 - 2022 U6 - https://doi.org/10.1088/1751-8121/ac5a90 SN - 1751-8113 SN - 1751-8121 VL - 55 IS - 20 PB - IOP Publ. Ltd. CY - Bristol ER -