The development of sustainable and efficient energy conversion processes at interfaces is at the center of the rapidly growing field of basic energy science. How successful this challenge can be addressed will ultimately depend on the acquired degree of molecular-level understanding. In this respect, the severe knowledge gap in electro- or photocatalytic conversions compared to corresponding thermal processes in heterogeneous catalysis is staggering. This discrepancy is most blatant in the present status of predictive-quality, viz. first-principles based modelling in the two fields, which largely owes to multifactorial methodological issues connected with the treatment of the electrochemical environment and the description of the surface redox chemistry driven by the photo-excited charges or external potentials.Successfully tackling these complexities will advance modelling methodology in (photo)electrocatalysis to a similar level as already established in heterogeneous catalysis, with an impact that likely even supersedes the one seen there in the last decade. A corresponding method development is the core objective of the present proposal, with particular emphasis on numerically efficient approaches that will ultimately allow to reach comprehensive microkinetic formulations. Synergistically combining the methodological expertise of the two participating groups we specifically aim to implement and advance implicit and mixed implicit/explicit solvation models, as well as QM/MM approaches to describe energy-related processes at solid-liquid interfaces. With the clear objective to develop general-purpose methodology we will illustrate their use with applications to hydrogen generation through water splitting. Disentangling the electro- resp. photocatalytic effect with respect to the corresponding dark reaction, this concerns both the hydrogen evolution reaction at metal electrodes like Pt and direct water splitting at oxide photocatalysts like TiO2. Through this we expect to arrive at a detailed mechanistic understanding that will culminate in the formulation of comprehensive microkinetic models of the light- or potential-driven redox process. Evaluating these models with kinetic Monte Carlo simulations will unambiguously identify the rate-determining and overpotential-creating steps and therewith provide the basis for a rational optimization of the overall process. As such our study will provide a key example of how systematic method development in computational approaches to basic energy sciences leads to breakthrough progress and serves both fundamental understanding and cutting-edge application.
Bamboos (Poaceae) are widespread in tropical and subtropical forests. Particularly in Asia, bamboos are cultivated by smallholders and increasingly in large plantations. In contrast to trees, reliable assessments of water use characteristics for bamboo are very scarce. Recently we tested a set of methods for assessing bamboo water use and obtained first results. Objectives of the proposed project are (1) to further test and develop the methods, (2) to compare the water use of different bamboo species, (3) to analyze the water use to bamboo size relationship across species, and (4) to assess effects of bamboo culm density on the stand-level transpiration. The study shall be conducted in South China where bamboos are very abundant. It is planned to work in a common garden (method testing), a botanical garden (species comparison, water use to size relationship), and on-farm (effects of culm density). Method testing will include a variety of approaches (thermal dissipation probes, stem heat balance, deuterium tracing and gravimetry), whereas subsequent steps will be based on thermal methods. The results may contribute to an improved understanding of bamboo water use characteristics and a more appropriate management of bamboo with respect to water resources.
Beach sand deposits are widespread in the area around Sandefjord, at the western coast of the Oslofjord, southern Norway. The age of the deposits continuously increases with elevation, as the area has been subject to steady glacio-isostatic uplift throughout the Holocene. Existing local sea level curves provide age control related to elevation. Thus, the area offers excellent conditions to test hypotheses on soil formation and OSL dating. A chronosequence covering the last 10 000 years will be established. A preliminary study showed that soil formation leads to Podzols within 4300 - 6600 years. Micromorphological analyses suggest that clay illuviation takes place before and below podzolisation. It is hypothesised that clay translocation goes on contemporarily with podzolisation, but at greater soil depth, where the chemical conditions are suitable. This hypothesis will be proved by more detailed micromorphological investigation and chemical analyses. The factors controlling soil forming processes and their rates, will be determined by analyzing elemental composition, primary minerals and clay mineralogy. Preliminary OSL dating tests suggest that the beach sand deposits are OSL dateable despite the high latitude. This hypothesis will be checked by comparing OSL datings to ages derived from the 14C-based sea level curves.
In my project I aim at a better understanding of the evolution of malacostracan crustaceans, which includes very different groups such as mantis shrimps, krill and lobsters. Previous studies on Malacostraca, on extant as well as on fossil representatives, focussed on adult morphology.In contrast to such approaches, I will apply a Palaeo-Evo-Devo approach to shed new light on the evolution of Malacostraca. Palaeo-Evo-Devo uses data of different developmental stages of fossil malacostracan crustaceans, such as larval and juvenile stages. With this approach I aim at bridging morphological gaps between the different diverse lineages of modern malacostracans by providing new insights into the character evolution in these lineages.An extensive number of larval and juvenile malacostracans is present in the fossil record, but which have only scarcely been studied. The backbone of this project will be on malacostracans from the Solnhofen Lithographic Limestones (ca. 150 million years old), which are especially well preserved and exhibit minute details. During previous studies, I developed new documentation methods for tiny fossils from these deposits, e.g., fluorescence composite microscopy, and also discovered the first fossil mantis shrimp larvae. For malcostracan groups that do not occur in Solnhofen, I will investigate fossils from other lagerstätten, e.g., Mazon Creek and Bear Gulch (USA), or Montceaules- Mines and La-Voulte-sur-Rhône (France). The main groups in focus are mantis shrimps and certain other shrimps (e.g., mysids, caridoids), as well as the bottom-living ten-footed crustaceans (reptantians). Examples for studied structures are leg details, including the feeding apparatus, but also eyes. The results will contribute to the reconstruction of 3D computer models.The data collected in this project will be used for evaluating the relationships within Malacostraca, but mainly for providing plausible evolutionary scenarios, how the modern malacostracan diversity evolved. With the Palaeo-Evo-Devo approach, I am also able to detect shifts in developmental timing, called heterochrony, which is interpreted as one of the major driving forces of evolution. Finally, the reconstructed evolutionary patterns can be compared between the different lineages for convergencies. These comparisons might help to explain the convergent adaptation to similar ecological niches in different malacostracan groups, e.g., life in the deep sea, life on the sea bottom, evolution of metamorphosis or of predatory larvae.As the project requires the investigation of a large number of specimens in different groups, I will assign distinct sub-projects to three doctoral researchers. The results of this project will not only be published in peer-reviewed journals, but will also be presented to the non-scientific public, e.g., during fossil fairs or museum exhibitions with 3D models engraved in glass blocks.
Magnetic resonance tomography (MRT) on microcosm soil cores (200 mm Ø) used for CeMiX, comprising naturally stacked subsoil down to 700 mm plus topsoil from CeFiT, will be implemented at a laterally partially open Split 1.5 T magnet, with intended final in-plane spatial resolution of 200 Micro m. Three-dimensional biopore distributions and dynamics of their formation within the cores will be determined non-invasively and compared to complementing CT analyses of SP 2. One major aim is a non-invasive differentiation of the biopores into earthworm- and root system-originating ones and currently air-, water-, root- and earthwormfilled ones, based on NMR relaxation parameters. Attempts will additionally be made to classify different wall coatings of the biopores with regard to their water affinity. Dynamics of water distribution within the microcosm core and its biopore structures, starting from initial values taken from CeFiT (SP 3), will be documented with an in-plane resolution of 5 mm, in parallel to measurements of root growth dynamics for calculation of biomass and root surface area. Special emphasis will be put on the role of the plant root system for a re-distribution of water/D2O (and solutes) between different soil layers. Finally we will attempt MRT-controlled sample collection from the microcosm cores, to get - together with our research unit partners of SPs 4-8 - repeated access to minimally invasively acquired data on nutrient and microorganism distributions in concert with non-invasively collected water and root distribution data as a basis for dynamic modelling of water and solute circuits in SP 10. Beside the microcosm cores, flat rhizotrons as used in SP 3 will be employed to enable measurements of root and shoot hydrostatic pressure profiles with pressure probes, in addition to MRT measurements. In this way water distributions and corresponding driving forces and growth dynamics will be measured altogether in a minimally invasive manner.
Chlorinated ethylenes are prevalent groundwater contaminants. Numerous studies have addressed the mechanism of their reductive dehalogenation during biodegradation and reaction with zero-valent iron. However, despite insight with purified enzymes and well-characterized chemical model systems, conclusive evidence has been missing that the same mechanisms do indeed prevail in real-world transformations. While dual kinetic isotope effect measurements can provide such lines of evidence, until now this approach has not been possible for chlorinated ethylenes because an adequate method for continuous flow compound specific chlorine isotope analysis has been missing. This study attempts to close this prevalent research gap by a combination of two complementary approaches. (1) A novel analytical method to measure isotope effects for carbon and chlorine. (2) A carefully chosen set of well-defined model reactants representing distinct dehalogenation mechanisms believed to be important in real-world systems. Isotope trends observed in biotic and abiotic environmental dehalogenation will be compared to these model reactions, and the respective mechanistic hypotheses will be confirmed or discarded. With this hypothesis-driven approach it is our goal to elucidate for the first timdehalogenation reactions.
For surface soils, the mechanisms controlling soil organic C turnover have been thoroughly investigated. The database on subsoil C dynamics, however, is scarce, although greater than 50 percent of SOC stocks are stored in deeper soil horizons. The transfer of results obtained from surface soil studies to deeper soil horizons is limited, because soil organic matter (SOM) in deeper soil layers is exposed to contrasting environmental conditions (e.g. more constant temperature and moisture regime, higher CO2 and lower O2 concentrations, increasing N and P limitation to C mineralization with soil depth) and differs in composition compared to SOM of the surface layer, which in turn entails differences in its decomposition. For a quantitative analysis of subsoil SOC dynamics, it is necessary to trace the origins of the soil organic compounds and the pathways of their transformations. Since SOM is composed of various C pools which turn over on different time scales, from hours to millennia, bulk measurements do not reflect the response of specific pools to both transient and long-term change and may significantly underestimate CO2 fluxes. More detailed information can be gained from the fractionation of subsoil SOM into different functional pools in combination with the use of stable and radioactive isotopes. Additionally, soil-respired CO2 isotopic signatures can be used to understand the role of environmental factors on the rate of SOM decomposition and the magnitude and source of CO2 fluxes. The aims of this study are to (i) determine CO2 production and subsoil C mineralization in situ, (ii) investigate the vertical distribution and origin of CO2 in the soil profile using 14CO2 and 13CO2 analyses in the Grinderwald, and to (iii) determine the effect of environmental controls (temperature, oxygen) on subsoil C turnover. We hypothesize that in-situ CO2 production in subsoils is mainly controlled by root distribution and activity and that CO2 produced in deeper soil depth derives to a large part from the mineralization of fresh root derived C inputs. Further, we hypothesize that a large part of the subsoil C is potentially degradable, but is mineralized slower compared with the surface soil due to possible temperature or oxygen limitation.
Research in 'silviculture' and 'forest economics' very often takes place largely independent from each other. While silviculture predominantly focuses on ecological aspects, forest eco-nomics is sometimes very theoretic. The applied bioeconomic models often lack biological realism. Investigating mixed forests this proposal tries to improve bioeconomic modelling and optimisation under uncertainty. The hypothesis is tested whether or not bioeconomic model-ling of interacting tree species and risk integration would implicitly lead to close-to-nature forestry. In a first part, economic consequences of interdependent tree species mixed at the stand level are modelled. This part is based on published literature, an improved model of timber quality and existing data on salvage harvests. A model of survival over age is then to be developed for mixed stands. A second section then builds upon data generated in part one and concentrates on the simultaneous optimisation of species proportions and harvest-ing ages. It starts with a mean-variance optimisation as a reference solution. The obtained results are compared with data from alternative approaches as stochastic dominance, down-side risk and information-gap robustness.
Im April 2012 führte PUMA das Rücknahmesystem Bring Me Back ein. Seither können Kunden in PUMA Stores weltweit gebrauchte Produkte zurückgeben, die dann durch die Firma I:CO der Weiterverwendung und Verwertung zugeführt werden. Auch die Produkte der neuen recyclefähigen und biologisch abbaubaren PUMA-InCycle-Kollektion, die seit März 2013 auf dem Markt sind, werden so erfasst. Hierzu gehört etwa das recycelbare PUMA Track Jacket, das zu 98 Prozent aus Polyester aus gebrauchten PET-Flaschen besteht. Der PUMA-Rucksack aus Polypropylen wird nach Gebrauch an den ursprünglichen Hersteller zurückgegeben, der das Material wieder zu neuen Rucksäcken verarbeitet. Durch solche Neuentwicklungen will PUMA seine Planungs- und Entscheidungsbasis verbessern. Deshalb hat sie bifa mit der Analyse abfallwirtschaftlicher Optionen für gebrauchte PUMA Produkte beauftragt. bifa untersuchte hierzu Referenzprodukte und Optionen für die Erfassung und Sortierung von Produkten und Materialien. 35 Pfade mit unterschiedlichen Verwertungs- und Beseitigungsansätzen wurden entwickelt und bewertet. Die Realisierungschancen der Pfade wurden dann dem zu erwartenden Nutzen insbes. für die Umwelt gegenübergestellt. Dabei wurde zwischen gut entwickelten und wenig entwickelten Abfallwirtschaften (Waste-Picking-Szenario W-P-Szenario) unterschieden. Es zeigte sich, dass Pfade, die im Szenario Abfallwirtschaft ökologisch nachteilig sind, im W-P-Szenario durchaus vorteilhaft sein können. Im W-P-Szenario sind zudem Pfade realisierbar, die in entwickelten Abfallwirtschaften keine Chance hätten. Die moderne Abfallverbrennung ist für W-P-Szenarien ökologisch vorteilhaft, aber dennoch eine schwierige Option. In entwickelten Abfallwirtschaften sollten Sammlung und Wiedereinsatz gebrauchter Schuhe und Textilien weiterentwickelt werden. Die folgenden generellen Empfehlungen wurden gegeben: - Der Einsatz von Recyclingmaterialien in PUMA-Produkten ist aus ökologischer Sicht zu empfehlen. Diese Erkenntnis wird auch durch die Ergebnisse der ersten ökologischen Gewinn-und-Verlust-Rechnung von PUMA belegt. Über die Hälfte aller Umweltauswirkungen entlang der gesamten Produktions- und Lieferkette des Unternehmens werden bei der Herstellung von Rohmaterialien verursacht - Das Produktdesign sollte auch für bestehende Verwertungspfade optimiert werden, da realistischerweise nur ein Teil der Produkte über das Sammelsystem erfasst werden kann - Die ökologischen Vorteile von Produkten, die aus nur einem Material bestehen, kommen nur dann zum Tragen, wenn das Produkt nach Gebrauch aussortiert und das Material tatsächlich recycelt wird - Biol. abbaubare Produkte können auch Nachteile haben, zum Beispiel die schnellere Entwicklung von klimaschädlichem Methan bei ungeordneter Deponierung - Eine Verlängerung der Produktlebensdauer über den gesamten Lebenszyklus einschl. der Verwendung als Gebrauchtprodukt ist der effektivste Weg, Umweltlasten zu reduzieren. Meth. Ökobilanzierung und Systemanalyse (Text gekürzt)
Dairy farming across Germany displays diverse production systems. Factor endowment, management, technology adoption as well as competitive dynamics in the local or regional land, agribusiness and dairy processing sectors contribute to this differentiation on farm level. These differences impact on the ability of dairy farms and regional dairy production systems to successfully respond to pressures arising from future market and policy changes. The overall objective of the research activities of which this project is a part of, is to develop a thorough understanding of the processes that govern the spatial dynamics of dairy farm development in different regions in Germany. The central hypothesis of this research project is that management system and technological choices differ systematically across local production and market conditions. The empirical approach will focus on the estimation of farm specific nonparametric cost functions for dairy farms located in across Germany differentiated by time and location. A spatially differentiated data base with information on input use, resource availability, as well as local market conditions for land and output markets will be compiled. The nonparametric approach is specifically suited to disclose a more accurate representation of dairy production system heterogeneity across locations and time compared to parametric concepts as it provides the necessary flexibility to accommodate non-linearities relevant for a wide domain of explanatory variables. The methodology employed goes beyond the state of the art of the literature as it combines kernel density estimation with a Bayesian sampling approach to provide theory consistent parameters for each farm in the data sample.The specific methodological hypothesis is that the nonparametric approach is superior to current parametric techniques and this hypothesis is tested using statistical model evaluation. Regarding the farm management and technological choices, we hypothesize that land suitability for feed production determines the farm intensity of dairy production and thus management and technological choices. With respect to the ability of farms to successfully respond to market pressures we hypothesize that farms at the upper and lower tail of the intensity distribution both can generate positive returns from dairy production. These last two hypotheses will be tested using the estimated spatially differentiated farm specific costs and marginal costs.The expected outcomes are of relevance for the agricultural sector and the food supply chain economy as a whole as fundamental market structure changes in the dairy sector are ongoing due to the abolition of the quota regulation in the years 2014/2015. Thus, exact knowledge about differences and development of dairy cost heterogeneity of farms within and between regions are an important factor for the actors involved in the market as well as the political support of this process.
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