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Ökoeffizienz der Entsorgung in Bayern, Deutschland und der Schweiz

Im Auftrag des Bayerischen Landesamtes für Umwelt hat bifa den erstmals 2003 durchgeführten Ökoeffizienzvergleich der Entsorgungsstrukturen Bayerns, Deutschlands und der Schweiz erweitert und aktualisiert. Die Ergebnisse aus dem Jahr 2003 zeigten, dass der bayerische Weg zur Gestaltung der Abfallwirtschaft in seiner Ökoeffizienz im Vergleich mit den Entsorgungsstrukturen der Schweiz und dem deutschen Durchschnitt am besten abschnitt. Nach der, im Rahmen der aktuellen Beauftragung, durchgeführten Datenaktualisierung, der Bilanzierung zusätzlicher Wertstoffströme und der Berücksichtigung des Verbots der Ablagerung nicht vorbehandelter Abfälle rücken die Entsorgungsstrukturen hinsichtlich Ihrer Ökoeffizienz deutlich enger zusammen. Die Entsorgungsstruktur Bayerns weist im Vergleich zur Entsorgungsstruktur Deutschlands zwar noch ein geringfügig besseres ökologisches Gesamtergebnis auf, ist aber gleichzeitig mit leicht höheren Gesamtkosten verbunden. Die Entsorgungsstruktur der Schweiz ist etwas weniger ökoeffizient. Die Ursachen dafür sind eine geringere Umweltentlastung im ökologischen Gesamtergebnis, gepaart mit vergleichsweise hohen Entsorgungskosten. Methoden: Analyse und Moderation sozialer Prozesse, Ökobilanzierung und Systemanalyse, Ökonomie und Managementberatung.

First-principles kinetic modeling for solar hydrogen production

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.

Quantification of small-scale physicochemical properties of intact macropore surfaces in structured soils

In structured soils, the interaction of percolating water and reactive solutes with the soil matrix is mostly restricted to the surfaces of preferential flow paths. Flow paths, i.e., macropores, are formed by worm burrows, decayed root channels, cracks, and inter-aggregate spaces. While biopores are covered by earthworm casts and mucilage or by root residues, aggregates and cracks are often coated by soil organic matter (SOM), oxides, and clay minerals especially in the clay illuviation horizons of Luvisols. The SOM as well as the clay mineral composition and concentration strongly determine the wettability and sorption capacity of the coatings and thus control water and solute movement as well as the mass exchange between the preferential flow paths and the soil matrix. The objective of this proposal is the quantitative description of the small-scale distribution of physicochemical properties of intact structural surfaces and flow path surfaces and of their distribution in the soil volume. Samples of Bt horizons of Luvisols from Loess will be compared with those from glacial till. At intact structural surfaces prepared from soil clods, the spatial distribution (mm-scale) of SOM and clay mineral composition will be characterized with DRIFT (Diffuse reflectance infrared Fourier transform) spectroscopy using a self-developed mapping technique. For samples manually separated from coated surfaces and biopore walls, the contents of organic carbon (Corg) and the cation exchange capacity (CEC) will be analyzed and related to the intensities of specific signals in DRIFT spectra using Partial Least Square Regression (PLSR) analysis. The signal intensities of the DRIFT mapping spectra will be used to quantify the spatial distribution of Corg and CEC at these structural surfaces. The DRIFT mapping data will also be used for qualitatively characterizing the small scale distribution of the recalcitrance, humification, and microbial activity of the SOM from structural surfaces. The clay mineral composition of defined surface regions will be characterized by combining DRIFT spectroscopic with X-ray diffractometric analysis of manually separated samples. Subsequently, the spatial distribution of the clay mineral composition at structural surfaces will be determined from the intensities of clay mineral-specific signals in the DRIFT mapping spectra and exemplarily compared to scanning electron microscopic and infrared microscopic analysis of thin sections and thin polished micro-sections. The three-dimensional spatial distribution of the total structural surfaces in the volume of the Bt horizons will be quantified using X-ray computed tomography (CT) analysis of soil cores. The active preferential flow paths will be visualized and quantified by field tracer experiments. These CT and tracer data will be used to transfer the properties of the structural surfaces characterized by DRIFT mapping onto the active preferential flow paths in the Bt horizons.

Carbon and Chorine Isotope Effect Study to Investigate Chlorinated Ethylene Dehalogenation Mechanisms

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.

Transport of EINP through soil affected by the dynamics of infiltration flux and particle properties

In this project we experimentally explore the transport of engineered inorganic nanoparticles (EINP) through soils. This is done for original EINPs and some pre-aged form. Transport of NPs in soil is expected to be different from that of reactive solutes, in that hydrodynamic drag, inertial and shear forces as well as the affinity to water-gas interfaces are expected to be more relevant. Hence, the mobility of EINPs in soil is highly sensitive to the morphology of the porous structure and the dynamics of water saturation.This project provides the pore network structure for natural soils using X-ray micro-tomography to allow for an up-scaling of pore-scale interactions explored by project partners to the scale of soil horizons. The pore structure is represented by a network model suitable for pore scale simulations including the dynamics of water-gas interfaces.Pore network simulations will be compared to column experiments for conservative tracers as well as for unaltered and pre-aged EINPs (obtained from INTERFACE). This includes steady state flow scenarios for saturated (ponding) and unsaturated conditions as well as for transient flow to explore the impact of moving water-gas interfaces. The final goal is to arrive at a consistent interpretation of experimental findings and numerical simulations to develop a module for modelling EINP transfer through soil as a function of particle properties, soil structural characteristics and external forcing in terms of flux boundary conditions.

Schwerpunktprogramm (SPP) 1315: Biogeochemische Grenzflächen in Böden; Biogeochemical Interfaces in Soil, Quantification of active interfaces with respect to dissolved chemicals in unsaturated structured soil

During the first project period we developed a general approach to quantify soil pore structure based on X-ray micro-tomography Vogel et al. (2010) which is applicable at various scales to cover soil pores larger that 0.05 mm in a representative way. Based on this method we generated equivalent network models to numerically simulate flow and transport of dissolved chemicals. The existing network model was extended to handle reactive transport and infiltration processes which are especially critical for matter flux in soil. The results were compared to experimental findings. The original research question 'what does a particle see on its way through soil' could be answered quantitatively for various boundary conditions including steady state flux and infiltration. However, we identified various critical aspects of the proposed modeling concept which will be in the focus of the second period. This includes 1) the spatial arrangement of interfaces having different quality which is crucial for chemical interactions and pore scale water dynamics, 2) the realistic multiphase dynamics at the pore scale which need to reflect the dynamic pressure and movement of trapped non-wetting phase and 3) the parametrization of structural complexity which need to be developed beyond the measurement of continuous Minkowski functions to allow the development of quantitative relations between structure and function. These aspects will be explored in a joint experiments in cooperation with partners within the SPP.

Water use characteristics of bamboo (South China)

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.

Biopores in the subsoil: Formation, nutrient turnover and effects on crops with distinct rooting systems (BioFoNT)

Perennial fodder cropping potentially increases subsoil biopore density by formation of extensive root systems and temporary soil rest. We will quantify root length density, earthworm abundance and biopore size classes after Medicago sativa, Cichorium intybus and Festuca arundinacea grown for 1, 2 and 3 years respectively in the applied research unit's Central Field Trial (CeFiT) which is established and maintained by our working group. Shoot parameters including transpiration, gas exchange and chlorophyll fluorescence will frequently be recorded. Precrop effects on oilseed rape and cereals will be quantified with regard to crop yield, nutrient transfer and H2-release. The soil associated with biopores (i.e. the driloshpere) is generally rich in nutrients as compared to the bulk soil and is therefore supposed to be a potential hot spot for nutrient acquisition. However, contact areas between roots and the pore wall have been reported to be low. It is still unclear to which extent the nutrients present in the drilosphere are used and which potential relevance subsoil biopores may have for the nutrient supply of crops. We will use a flexible videoscope to determine the root-soil contact in biopores. Nitrogen input into the drilosphere by earthworms and potential re-uptake of nitrogen from the drilosphere by subsequent crops with different rooting systems (oilseed rape vs. cereals) will be quantified using 15N as a tracer.

Beach sand deposits on the coast of southern Norway as a natural experimental setup to test hypotheses on soil development and luminescence dating

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.

Regulation der photosynthetischen Effizienz der Biomassebildung im dynamischen Lichtklima bei exemplarischen Grünalgen und Diatomeen

In dem Vorhaben wird untersucht, wie wirksam die absorbierte Lichtenergie in Biomasse konvertiert wird. Vergleichend werden Grünalgen und Diatomeen unter verschiedenen Licht- und Nährstoffbedingungen studiert. Auf diese Weise können die metabolischen Kosten unter Nährstoffmangel oder anderen produktivitätsbegrenzenden Bedingungen studiert werden. So wird auch die Säureanpassung ausgewählter Phytoplankter untersucht, um die Biomassebildung in extrem sauren Tagebaurestseen auf physiologischer Ebene zu verstehen. Es konnte gezeigt werden, dass unter Stickstoffmangel die Überführung anorganischen Kohlenstoffs in Biomassebildung durch eine Veränderung der makromolekularen Zusammensetzung der Zellen ähnlicher Effizienz stattfindet, wie unter optimaler Stickstoffversorgung. Dies führt zu einer ökologisch bedeutsamen Teilentkopplung des C und N Kreislaufs im Ökosystem. Ähnliches beobachtet man auch bei der Anpassung von Phytoplanktonalgen an extrem saure Bedingungen wie man sie in sauren Tagebaurestseen vorfindet.

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