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.
Soil organic matter (SOM) controls large part of the processes occurring at biogeochemical interfaces in soil and may contribute to sequestration of organic chemicals. Our central hypothesis is that sequestration of organic chemicals is driven by physicochemical SOM matrix aging. The underlying processes are the formation and disruption of intermolecular bridges of water molecules (WAMB) and of multivalent cations (CAB) between individual SOM segments or between SOM and minerals in close interaction with hydration and dehydration mechanisms. Understanding the role of these mediated interactions will shed new light on the processes controlling functioning and dynamics of biogeochemical interfaces (BGI). We will assess mobility of SOM structural elements and sorbed organic chemicals via advanced solid state NMR techniques and desorption kinetics and combine these with 1H-NMR-Relaxometry and advanced methods of thermal analysis including DSC, TGADSC- MS and AFM-nanothermal analysis. Via controlled heating/cooling cycles, moistening/drying cycles and targeted modification of SOM, reconstruction of our model hypotheses by computational chemistry (collaboration Gerzabek) and participation at two larger joint experiments within the SPP, we will establish the relation between SOM sequestration potential, SOM structural characteristics, hydration-dehydration mechanisms, biological activity and biogechemical functioning. This will link processes operative on the molecular scale to phenomena on higher scales.
The detritusphere is an excellent model to study microbial-physicochemical interactions during degradation of the herbicide MCPA. Whereas during the first phase of SPP 1315 we focused on bacterial and fungal abundance at the soil litter interface and carbon flow between different compartments, the second phase will be devoted to elucidating complex regulation mechanisms of MCPA degradation in the detritusphere: (1) At the cellular level, co-substrate availability and laccase abundance might be important regulators, (2) at the community level, bacteria harbouring different classes of tfdA genes might control degradation of MCPA and (3) at the microhabitat level, interaction between MCPA degraders and organo-mineral surfaces as well as transport processes might be important regulators. The concept of hierarchical regulation of MCPA degradation will be included into the modelling of small-scale microbial growth, MCPA transport and MCPA degradation near the soil-litter interface.
This subproject aims at the development of spectral electrical impedance tomography (EIT) as a non-destructive tool for the imaging, characterization and monitoring of root structure and function in the subsoil at the field scale. The approach takes advantage of the capacitive properties of the soil-root interface associated with induced electrical polarization processes at the root membrane. These give rise to a characteristic electrical signature (impedance spectrum), which is measurable in an imaging framework using EIT. In the first project phase, the methodology is developed by means of controlled rhizotron experiments in the laboratory. The goal is to establish quantitative relationships between characteristics of the measured impedance spectra and parameters describing root system morphology, root growth and activity in dependence on root type, soil type and structure (with/without biopores), as well as ambient conditions. Parallel to this work, sophisticated EIT inversion algorithms, which take the natural characteristics of root system architecture into account when solving the inherent inverse problem, will be developed and tested in numerical experiments. Thus the project will provide an understanding of electrical impedance spectra in terms of root structure and function, as well as specifically adapted EIT inversion algorithms for the imaging and monitoring of root dynamics. The method will be applied at the field scale (central field trial in Klein-Altendorf), where non-destructive tools for the imaging and monitoring of subsoil root dynamics are strongly desired, but at present still lacking.
Mit den Daten zur Umwelt stellt das UBA ein großes Angebot an aktuellen Daten zum Zustand der Umwelt bereit. Ein neues System – der UBA Data Cube – verbessert die Nutzbarkeit dieser Daten. Die Schnittstelle (API) dient zum programmatischen Abruf der Daten aus dem Data Cube des Umweltbundesamtes.
Existing models of soil organic matter (SOM) formation consider plant material as the main source of SOM. Recent results from nuclear magnetic resonance analyses of SOM and from own incubation studies, however, show that microbial residues also contribute to a large extent to SOM formation. Scanning electron microscopy showed that the soil mineral sur-faces are covered by numerous small patchy fragments (100 - 500 nm) deriving from microbial cell wall residues. We will study the formation and fate of these patchy fragments as continuously produced interfaces in artificial soil systems (quartz, montmorillonite, iron oxides, bacteria and carbon sources). We will quantify the relative contributions of different types of soil organisms to patchy fragment formation and elucidate the effect of redox con-ditions and iron mineralogy on the formation and turnover of patchy fragments. The develop-ment of patchy fragments during pedogenesis will be followed by studying soil samples from a chronosequence in the forefield of the retreating Damma glacier. We will characterize chemical and physical properties of the patchy fragments by nanothermal analysis and microscale condensation experiments in an environmental scanning electron microscope. The results will help understanding the processes at and characteristics of biogeochemical interfaces.
Labor- und Feldstudien zeigen, dass die Oberflächengrenzschicht des Ozeans (â€Ìsurface microlayerâ€Ì, kurz SML) die biogeochemischen Kreisläufe von klimaaktiven und atmosphärisch wichtigen Spurengasen wie Kohlenstoffdioxid (CO2), Kohlenstoffmonoxid (CO), Methan (CH4), Lachgas (N2O) und Dimethylsulfid (DMS) stark beeinflusst: (i) Jüngste Studien aus den PASSME- und SOPRAN-Projekten haben hervorgehoben, dass Anreicherungen von oberflächenaktiven Substanzen (d.h. Tensiden) einen starken (dämpfenden) Effekt sowohl auf die CO2- als auch auf die N2O-Flüsse über die SML/Atmosphären-Grenzfläche hinweg haben und (ii) Spurengase können durch (mikro)biologische oder (photo)chemische Prozesse in der SML produziert und verbraucht werden. Daher kann der oberste Teil des Ozeans, einschließlich der SML, verglichen mit dem Wasser, das in der Mischungsschicht unterhalb der SML zu finden ist, eine bedeutende Quelle oder Senke für diese Gase sein, was von sehr großer Relevanz für die Forschungseinheit BASS ist. Die Konzentrationen von CO2, N2O und anderen gelösten Gasen in der SML (oder den oberen Zentimetern des Ozeans) unterscheiden sich nachweislich von ihren Konzentrationen unterhalb der SML. Typischerweise werden die Nettoquellen und -senken wichtiger atmosphärischer Spurengase mit Konzentrationen berechnet, die in der Mischungsschicht gemessen wurden und mit Gasaustauschgeschwindigkeiten, die die SML nicht berücksichtigen. Diese Diskrepanzen führen zu falsch berechneten Austauschflüssen, die in der Folge zu großen Unsicherheiten in den Berechnungen der Klima-Antrieben und der Luftqualität in Erdsystemmodellen führen können. Durch die Verknüpfung unserer Spurengasmessungen mit Messungen von (i) der Dynamik und den molekularen Eigenschaften der organischen Materie und speziell des organischen Kohlenstoffs (SP1.1; SP1.5), (ii) der biologischen Diversität und der Stoffwechselaktivität (SP1.2), (iii) den optischen Eigenschaften der organischen Materie (SP1.3), (iv) der photochemischen Umwandlung der organischen Materie (SP1.4) und (v) den physikalischen Transportprozessen (SP2.3) werden wir ein umfassendes Verständnis darüber erlangen, wie die SML die Variabilität der Spurengasflüsse beeinflusst.
Biogeochemical interfaces shape microbial community function in soil. On the other hand microbial communities influence the properties of biogeochemical interfaces. Despite the importance of this interplay, basic understanding of the role of biogeochemical interfaces for microbial performance is still missing. We postulate that biogeochemical interfaces in soil are important for the formation of functional consortia of microorganisms, which are able to shape their own microenvironment and therefore influence the properties of interfaces in soil. Furthermore biogeochemical interfaces act as genetic memory of soils, as they can store DNA from dead microbes and protect it from degradation. We propose that for the formation of functional biogeochemical interfaces microbial dispersal (e.g. along fungal networks) in response to quality and quantity of bioavailable carbon and/or water availability plays a major role, as the development of functional guilds of microbes requires energy and depends on the redox state of the habitat.To address these questions, hexadecane degradation will be studied in differently developed artificial and natural soils. To answer the question on the role of carbon quantity and quality, experiments will be performed with and without litter material at different water contents of the soil. Experiments will be performed with intact soil columns as well as soil samples where the developed interface structure has been artificially destroyed. Molecular analysis of hexadecane degrading microbial communties will be done in vitro as well as in situ. The corresponding toolbox has been successfully developed in the first phase of the priority program including methods for genome, transcriptome and proteome analysis.
In soils and sediments there is a strong coupling between local biogeochemical processes and the distribution of water, electron acceptors, acids, nutrients and pollutants. Both sides are closely related and affect each other from small scale to larger scale. Soil structures such as aggregates, roots, layers, macropores and wettability differences occurring in natural soils enhance the patchiness of these distributions. At the same time the spatial distribution and temporal dynamics of these important parameters is difficult to access. By applying non-destructive measurements it is possible to overcome these limitations. Our non-invasive fluorescence imaging technique can directly quantity distribution and changes of oxygen and pH. Similarly, the water content distribution can be visualized in situ also by optical imaging, but more precisely by neutron radiography. By applying a combined approach we will clarify the formation and architecture of interfaces induces by oxygen consumption, pH changes and water distribution. We will map and model the effects of microbial and plant root respiration for restricted oxygen supply due to locally high water saturation, in natural as well as artificial soils. Further aspects will be biologically induced pH changes, influence on fate of chemicals, and oxygen delivery from trapped gas phase.
We consider clay minerals, iron oxides and charcoal as major components controlling the formation of interfaces relevant for sorption of organic chemicals, as they control the assemblage of organic matter and mineral particles. We studied the formation of interfaces in batch incubation experiments with inoculated artificial soils consisting of model compounds (clay minerals, iron oxide, char) and natural soil samples. Results show a relevant contribution of both iron oxides and clay minerals to the formation of organic matter as sorptive interfaces for hydrophobic compounds. Thus, we intend to focus our work in the second phase on the characterization of the interface as formed by organic matter associated with clay minerals and iron oxides. The interfaces will be characterized by the BET-N2 and ethylene glycol monoethyl ether (EGME) methods and 129Xe and 13C NMR spectroscopy for determination of specific surface area, sorptive domains in the organic matter and microporosity. A major step forward is expected by the analysis of the composition of the interface at different resolution by reflected-light microscopy (mm scale), SEM (scanning electron microscopy, micrometer scale) and secondary ion mass spectrometry at the nanometer scale (nanoSIMS). The outcomes obtained in combination with findings from cooperation partners will help to unravel the contribution of different types of soil components on the formation and characteristics of the biogeochemical interfaces and their effect on organic chemical sorption.
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