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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.
Subproject 3 will investigate the effect of shifting from continuously flooded rice cropping to crop rotation (including non-flooded systems) and diversified crops on the soil fauna communities and associated ecosystem functions. In both flooded and non-flooded systems, functional groups with a major impact on soil functions will be identified and their response to changing management regimes as well as their re-colonization capability after crop rotation will be quantified. Soil functions corresponding to specific functional groups, i.e. biogenic structural damage of the puddle layer, water loss and nutrient leaching, will be determined by correlating soil fauna data with soil service data of SP4, SP5 and SP7 and with data collected within this subproject (SP3). In addition to the field data acquired directly at the IRRI, microcosm experiments covering the broader range of environmental conditions expected under future climate conditions will be set up to determine the compositional and functional robustness of major components of the local soil fauna. Food webs will be modeled based on the soil animal data available to gain a thorough understanding of i) the factors shaping biological communities in rice cropping systems, and ii) C- and N-flow mediated by soil communities in rice fields. Advanced statistical modeling for quantification of species - environment relationships integrating all data subsets will specify the impact of crop diversification in rice agro-ecosystems on soil biota and on the related ecosystem services.
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.
Boron (B) is an essential microelement for plants. Despite the use of modern fertilization methods, B deficiency still causes losses in agricultural plant production. Even though many positive effects of B on plant growth and physiology have been reported, a large majority of B functions and the regulatory mechanisms controlling the B nutritional status remain unknown. The main objective of this project is to elucidate how the greatly B deficiency-sensitive Brassica crop plants process and regulate their B status during vegetative and reproductive growth. In this context, the project aims at identifying the mode of action of B in mechanisms regulating the B status itself and uncovering those mechanisms contributing to B efficiency in different genotypes. Plant species subjected to investigation will be the agronomically important oilseed and vegetable plant Brassica napus (rapeseed) and its close relative the genetic and molecular model plant Arabidopsis thaliana. Questions addressed within the scope of this project should lead to a detailed understanding of mechanisms controlling B uptake and allocation from the level of the whole plant down to the cellular level. B transport routes and rates will be determined in sink- and source tissues and in developmental periods with a particularly high B demand. A special focus will be on the identification of B transport bottlenecks and the analysis of B deficiency-sensitive transport processes to and within the highly B-demanding reproductive organs. Recent studies in Arabidopsis suggest that Nodulin26-like Intrinsic Proteins (NIPs), which belong to the aquaporin channel protein family, are essential for plant B uptake and distribution. The systematic focus on the molecular and physiological characterization of B. napus NIPs will clarify their role in B transport and will identify novel NIP-associated mechanisms playing key roles in the B response network.To further resolve the mostly unknown impact of the B nutritional status on gene regulation and metabolism, a transcript and metabolite profile of B-sufficient and B-deficient rapeseed plants will be generated. Additionally, an Arabidopsis transcription factor knockout collection (greater 300 lines) will be screened for abnormalities in responses to the B nutritional status. This will identify yet unknown B-responsive genes (transcription factors and their targets) and gene products (enzymes or metabolite variations) playing key roles in signalling pathways and mechanisms regulating the B homeostasis. Boron (in form of boric acid) and arsenite (As) share in all likelihood the same NIP-mediated transport pathways. To assess the consequences of this dual transport pathway the so far unstudied impact of the plants B nutritional status on the accumulation and distribution of As will be investigated in B. napus. Moreover, the current dimension of the As contamination of Brassica-based food products, to which consumers are exposed to, will be analyzed. usw.
Almond in California represents an agroecosystem pollinated solely by a single species, the European honey bee, a species that is becoming increasingly difficult and expensive to manage due to substantial, unpredictable mortality. Therefore, sustainable and high output production require a more integrated approach that diversifies sources of pollination. For this purpose, detailed data of our understanding how diversity can stabilize pollination are required. The project will identify alternative wild pollinator species and collect high quality data contributing to our understanding of how diversity (pollen and insects) can bolster honey bee pollination during stable and unstable climatic conditions. The research will be carried out on almond orchards in Northern California known to be either pollinator species rich (up to 30 species) or depauperate (honey bees only). The replicated extremes in pollinator diversity represent a unique opportunity to study the effects of diversity on pollination in real agroecosystems combined with laboratory and glasshouse experiments. The overall goal is to provide basic research that is essential for our general understanding of how insect diversity can affect high-quality pollination under land use and climate change.
The majority of the worlds forests has undergone some form of management, such as clear-cut or thinning. This management has direct relevance for global climate: Studies estimate that forest management emissions add a third to those from deforestation, while enhanced productivity in managed forests increases the capacity of the terrestrial biosphere to act as a sink for carbon dioxide emissions. However, uncertainties in the assessment of these fluxes are large. Moreover, forests influence climate also by altering the energy and water balance of the land surface. In many regions of historical deforestation, such biogeophysical effects have substantially counteracted warming due to carbon dioxide emissions. However, the effect of management on biogeophysical effects is largely unknown beyond local case studies. While the effects of climate on forest productivity is well established in forestry models, the effects of forest management on climate is less understood. Closing this feedback cycle is crucial to understand the driving forces behind past climate changes to be able to predict future climate responses and thus the required effort to adapt to it or avert it. To investigate the role of forest management in the climate system I propose to integrate a forest management module into a comprehensive Earth system model. The resulting model will be able to simultaneously address both directions of the interactions between climate and the managed land surface. My proposed work includes model development and implementation for key forest management processes, determining the growth and stock of living biomass, soil carbon cycle, and biophysical land surface properties. With this unique tool I will be able to improve estimates of terrestrial carbon source and sink terms and to assess the susceptibility of past and future climate to combined carbon cycle and biophysical effects of forest management. Furthermore, representing feedbacks between forest management and climate in a global climate model could advance efforts to combat climate change. Changes in forest management are inevitable to adapt to future climate change. In this process, is it possible to identify win-win strategies for which local management changes do not only help adaptation, but at the same time mitigate global warming by presenting favorable effects on climate? The proposed work opens a range of long-term research paths, with the aim of strengthening the climate perspective in the economic considerations of forest management and helping to improve local decisionmaking with respect to adaptation and mitigation.
Various species of pest insects cause substantial damage to agriculture every year, or transmit deadly diseases to animals and humans. A successful strategy to control pest insect populations is based on the Sterile Insect Technique (SIT), which uses the release of mass-reared, radiation sterilized male insects to cause infertile matings and thus reduce the pest population level. However, irradiation is not applicable to every insect species. Thus, new strategies based on genetic modifications of pest insects have been developed or are currently under investigation.The goal of the proposed research is to improve the development and ecological safety of genetically engineered (GE) insects created for enhanced biological control programs, including the SIT and new strategies based on conditional lethality. A major concern for GE insect release programs is transgene stability, and maintenance of their consistent expression. Transgene loss or intra-genomic movement could result in loss of strain attributes, and may ultimately lead to interspecies movement resulting in ecological risks. To address potential transgene instability, a new transposon vector that allows post-integration immobilization will be tested in the Mediterranean, Mexican and Oriental fruit fly tephritid pest species. In addition, the system will be established in the mosquito species Aedes and Anopheles - carriers of dengue and malaria.Random genomic insertion is also problematic for GE strain development due to genomic position effects that suppress transgene expression, and insertional mutations that negatively affect host fitness and viability. Diminished transgene expression could result in the unintended survival of conditional lethal individuals, or the inability to identify them. To target transgene vectors to defined genomic insertion sites having minimal negative effects on gene expression and host fitness, a recombinase-mediated cassette exchange (RMCE) strategy will be developed that. RMCE will also allow for stabilization of the target site, will be tested in tephritid and mosquito species, and will aid to the development of stabilized target-site strains for conditional lethal biocontrol. This will include a molecular and organismal evaluation of an RNAi-based lethality approach. Lethality based on an RNAi mechanism in the proposed insects would increase the species specificity and having multiple targets for lethality versus one target in existing systems. By seeking to improve transgene expressivity and stabilization of transposon-based vector systems, this proposal specifically addresses issues related to new GE insects by reducing their unintended spread after field release, and by limiting the possibilities for transgene introgression.
Magnetic properties of ferrimagnetic minerals depend on their crystal lattice, anisotropy, chemical composition and grain size. The latter parameter is strongly controlled by microstructures, which are significant for the interpretation of the magnetic properties of shocked magnetic minerals. Fracturing and lattice defects are the main causes for magnetic domain size reduction and generate an increase in coercivity and the suppression of magnetic transitions (e.g. 34 K transition in pyrrhotite, Verwey transition in magnetite).Especially for an adequate investigation of shock-induced modifications in ferromagnetic minerals, a combination of microstructural and magnetic measurements is therefore essential.This project focusses on two significant aspects of extreme conditions - the consequence of shock waves on natural material on Earth and on the magnetic mineralogy of exotic magnetic minerals in iron meteorites. In order to obtain general correlations between deformation structures and magnetic properties, the specific magnetic properties and carriers as well as microstructures of samples from two impact structures in marine targets (Lockne and Chesapeake Bay) will be compared with shocked magnetite ore and magnetite-bearing target lithologies from outside the crater (Lockne) as well as from undeformed megablocks within the crater (Chesapeake Bay). We will test the hypothesis if shock-related microstructures and associated magnetic properties can significantly be overprinted by postshock hydrothermal alteration. We especially want to focus on the Verwey transition (TV) as lower TVs are described for shocked impact lithologies. Hence, the main focus of this study lies on magneto-mineralogical investigations which combine low- and high-temperature magnetic susceptibility and saturation isothermal remanent magnetization with mineralogical and microstructural investigations. The same methods will then be used for the investigation of iron meteorites, whose magnetic properties are often controled by exotic magnetic minerals like cohenite, schreibersite and daubreelite in addition to the metal phases. Magnetic transition temperatures of those phases are poorly documented in relation to their chemical composition as well as to their crystallographic and microstructural configuration. For a general understanding of shock-related magnetization processes in extraterrestrial and terrestrial material, however, it is crucial to obtain a general correlation between the initial 'unshocked' state and the subsequent shock- and alteration-related overprints.
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