The proposal addresses the potential of subsoil to contribute to K nutrition of crops. More specifically we will address the processes controlling release of K from interlayer of 2:1 clay minerals as this is expected to be the dominant K fraction in the subsoil. While it has been shown in the past that this so called 'non-exchangeable' K can be released due to root activity, there are controversial results concerning the role of soil solution K concentration in the rhizosphere required to trigger the process. Likewise little information is available about the concentration dynamics of other cations (NH4, Ca) in the rhizosphere and their impact on K release and vermiculitization supposed to be associated with this process. Model studies with substrate from the central field trial will be conducted in compartment systems equipped with micro suction cups. The measurement of dynamic changes of soil solution composition with increasing distance from the root surface will be combined with investigations of changes in mineralogy by XRD, TEM and SEM-EDX. Changes of mineralogy as a result of plant induced K release from interlayer will also be studied on bulk soil and rhizosphere samples collected within the central field and the central microcosm experiment and with mineral bags exposed in the field during a cropping cycle. Finally, X-ray CT will be used to access changes in soil texture, i.e. clay distribution around roots and the temporal spread of roots in biopores which is a prerequisite for K uptake from such structures.
Outbreaks of foodborne illness linked to consumptions of fresh, or partially processed, agricultural products are a growing concern in industrialized and developing countries. The incidence of human pathogens on fresh fruits and vegetables is often related to the use of recycled wastewaster in surface irrigation as well as high amounts of animal manure in agricultural management practice. Thereby the soil inhabiting fauna plays an important role in the transport and dissemination of microorganisms. The focus of the proposed project is on nematodes, well known vectors for bacteria and viruses in soil. The major goals are to: (1) survey human pathogens in soil and on/in free-living and plant parasitic nematodes in agriculture field sites irrigated with recycled wastewater or fertilized with fresh animal manure in Israel and the Palestinian Authority, (2) assess the function of nematodes as vectors in transmitting bacteria from microbial hot spots to plants, and (3) localize bacteria on and/or within the nematode and identify bacterial factors required for survival in the nematode host. Understanding the mechanisms involved in dissemination of human pathogens by nematodes will enhance the ability to develop practical means to minimize contamination of fresh produce and increase safety in food production.
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.
Rain-cracking limits the production of many soft and fleshy fruit including sweet cherries world wide. Cracking is thought to result from increased water uptake through surface and pedicel. Water uptake increases fruit volume, and hence, turgor of cells (Pcell) and the pressure inside the fruit (Pfruit) and subjects the skin to tangential stress and hence, strain. When the strain exceeds the limits of extensibility the fruit cracks. This hypothesis is referred to as the Pfruit driven strain cracking. Based on this hypothesis cracking is related to two independent groups of factors: (1) water transport characteristics and (2) the intrinsic cracking susceptibility of the fruit defined as the amount of cracking per unit water uptake. The intrinsic cracking susceptibility thus reflects the mechanical constitution of the fruit. Most studies focussed on water transport through the fruit surface (factors 1), but only little information is available on the mechanical constitution (i.e., Pfruit and Pcell, tensile properties such as fracture strain, fracture pressure and modulus of elasticity of the exocarp; factors 2). The few published estimates of Pfruit in sweet cherry are all obtained indirectly (calculated from fruit water potential and osmotic potentials of juice extracts) and unrealistically high. They exceed those measured by pressure probe techniques in mature grape berry by several orders of magnitude. The objective of the proposed project is to test the hypothesis of the Pfruit driven strain cracking. Initially we will focus on establishing systems of widely differing intrinsic cracking susceptibility by varying species (sweet and sour cherry, Ribes and Vaccinium berries, plum, tomato), genotype (within sweet cherry), stage of development and temperature. These systems will then be used for testing the hypothesis of Pfruit driven strain cracking. We will quantify Pfruit und Pcell by pressure probe techniques and compression tests and the mechanical properties of the exocarp using biaxial tensile tests. When the presence of high Pfruit and Pcell is confirmed by direct measurements, subsequent studies will focus on the mode of failure of the exocarp (fracture along vs. across cell walls) and the relationship between failure thresholds and morphometric characteristics of the exocarp. However, when Pfruit und Pcell are low, the hypothesis of Pfruit driven strain cracking must be rejected and the mechanistic basis for low pressures (presence of apoplastic solutes) clarified on a temporal (in the course of development) and a spatial scale (exocarp vs. mesocarp). We focus on sweet cherry, because detailed information on this species and experience in extending the short harvest period is available. Where appropriate, other cracking susceptible species (sour cherry, plum, Vaccinium, Ribes, tomato) will be included to further extend the experimental period and to maximize the range in intrinsic cracking susceptibility.
The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.
When released into surface waters, engineered inorganic nanoparticles (EINP) can be subject to multiple transformations. The objectives of MASK are to understand under which conditions EINP in aquatic systems will attach to suspended matter, under which conditions and in which time scale EINP are coated by NOM present in freshwater systems, how these coated colloidal particles are stabilized in the aquatic system and to which extent the aquatic aging processes are reversible. Homo-aggregation, coating changes, biological interactions and hetero-aggregation are hypothesized as key processes governing EINP aging in water bodies. In process orientated laboratory incubation experiments (50 ml to 6 l) with increasing complexity, MASK unravels the relevance and the interplay of inorganic colloids, aquagenic and pedogenic organic matter and solution physicochemistry for stability of EINP. These systems will successively approach situations in real waters. MASK thus provides information on EINP fluxes in the aquatic compartment, their time scales, reversibility and relative relevance. EINP will be analysed by standard light scattering techniques, ICP-MS, ESEM/EDX, WetSTEM and AFM. A method coupling hydrodynamic radius chromatography (HDC) with ICPMS recently developed by K. Tiede for nAg0 will be optimized and developed for further EINP analysis, MASK is further responsible for the virtual subproject ANALYSIS, the development and optimization of joint research unit methods of EINP analysis, sample preparation and sample storage, the exchange of methods and coordinates the joint analyses and the central EINP database.
The broad objective of the research is to gain a fundamental understanding of the surface reaction chemistry of exhaust catalysts operating under cycling conditions. Using an integrated theoretical approach we specifically target NOx abatement, with particular emphasis on the appearance and destruction of surface oxide phases as the reactor conditions cycle from oxidative to reductive during the operation of the NOx Storage Reduction (NSR) catalyst system. Methodologically this requires material-specific, quantitative and explicitly time-dependent simulation tools that can follow the evolution of the system over the macroscopic time-scales of NSR cycles, while simultaneously accounting for the atomic-scale site heterogeneity and spatial distributions at the evolving surface. To meet these challenging demands we will develop a novel multi-scale methodology relying on a multi-lattice first-principles kinetic Monte Carlo (kMC) approach. As representative example the simulations will be carried out on a PdO(101)/Pd(100) surface oxide model, but care will be taken to ensure a generalization of the multi-lattice first-principles kMC approach to other systems in which phase transformations may occur and result in a change in the surface lattice structure depending upon environmental variables.
Organic matter (OM) composition and dynamic in subsoils is thought to be significantly different from those in surface soils. This has been suggested by increasing apparent 14C ages of bulk soil OM with depth suggesting that the amount of fresh, more easily degradable components is declining. Compositional changes have been inferred from declining ä13C values and C/N ratios indicative for stronger OM transformation. Beside these bulk OM data more specific results on OM composition and preservation mechanisms are very limited but modelling studies and results from incubation experiments suggest the presence and mineralization of younger, 'reactive carbon pool in subsoils. Less refractory OM components may be protected against degradation by interaction with soil mineral particles and within aggregates as suggested by the very limited number of more specific OM analysis e.g., identification of organic compound in soil fractions. The objective of this project is to characterize the composition, transformation, stabilization and bioavailability of OM in subsurface horizons on the molecular level: 1) major sources and compositional changes with depth will be identified by analysis of different lipid compound classes in surface and subsoil horizons, 2) the origin and stabilization of 'reactive OM will be revealed by lipid distributions and 14C values of soil fractions and of selected plant-specific lipids, and 3) organic substrates metabolized by microbial communities in subsoils are identified by distributional and 14C analysis of microbial membrane lipids. Besides detailed analyses of three soil profiles at the subsoil observatory site (Grinderwald), information on regional variability will be gained from analyses of soil profiles at sites with different parent material.
Shallow groundwater of the huge deltaic systems of Asia like the Red River Delta in Vietnam is often enriched in inorganic arsenic (As), threatening the health of millions of residents. The massive abstraction of groundwater in these areas locally causes an irreversible mixing of arsenic-free groundwater resources with arsenic-rich groundwater. Increased concentrations of competitive anions, especially phosphate (PO43-), decrease the immobilization capacity of the sediments. During transport, the mobility of dissolved As in local aquifers is strongly influenced by adsorption to sedimentary and ubiquitously occurring iron(oxyhydr)oxides. Additionally, arsenic-rich groundwater is often enriched in reduced iron (Fe2+) as well, which is capable to react with iron(oxyhydr)oxides, thereby inducing mineral transformations. Such transformations permanently affect the arsenic adsorption and immobilization capacity of the sediments.Within the scope of this research project, the underlying mechanisms related to As transport and the resulting threat to arsenic-free groundwater resources will be characterized in cooperation with the Swiss Federal Institute of Aquatic Science and Technology (Eawag). The research concept aims at assessing the complex interactions within the arsenic-iron-phosphate-system under field conditions at a study site next to the Red River. First, filtration experiments using local groundwater enriched in As and PO43- will be used to determine the As adsorption capacity of different and previously geochemically characterized iron(oxyhydr)oxides. In a second step, sample carrier containing As loaded iron(oxyhydr)oxides will be introduced into surface near aquifer parts of the study site (via existing groundwater monitoring wells). These samples will be exposed to local groundwater characterized by increased As, Fe2+ and PO43- concentrations for the following nine months. Using the in situ exposition of predefined iron(oxyhydr)oxides, it will be possible to distinguish potential mineral transformations and their influences on the As immobilization capacity of the respective iron(oxyhydr)oxides. By combining the results and outcomes of the field experiments, new and important conclusions regarding the mobility of As can be drawn. The data can be used to create a hydrochemical transport model describing reactive As transport within the investigation area. In addition, the results of the in situ exposition experiments will allow to draw conclusions in respective to the long term As immobilization capacity of different iron(oxyhydr)oxides, which is an essential information regarding in situ decontamination techniques.
Agriculture is the major contributor of nitrogen to ecosystems, both by organic and inorganic fertilizers. Percolation of nitrate to groundwater and further transport to surface waters is assumed to be one of the major pathways in the fate of this nitrogen. The quantification of groundwater and associated nitrate flux to streams is still challenging. In particular because we lack understanding of the spatial distribution and temporal variability of groundwater and associated NO3- fluxes. In this preliminary study we will focus on the identification and quantification of groundwater and associated nitrate fluxes by combining high resolution distributed fiber-optic temperature sensing (DTS) with in situ UV photometry (ProPS). DTS is a new technique that is capable to measure temperature over distances of km with a spatial resolution of ca1 m and an accuracy of 0.01 K. It has been applied successfully to identify and quantify sources of groundwater discharge to streams. ProPS is a submersible UV process photometer, which uses high precision spectral analyses to provide single substance concentrations, in our case NO3-, at minute intervals and a detection limit of less than 0.05 mg l-1 (ca.0.01 mg NO3--Nl-1). We will conduct field experiments using artificial point sources of lateral inflow to test DTS and ProPS based quantification approaches and estimate their uncertainty. The selected study area is the Schwingbach catchment in Hessen, Germany, which has a good monitoring infrastructure. Preliminary research on hydrological fluxes and field observations indicate that the catchment favors the intended study.
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