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Schwerpunktprogramm (SPP) 1488: Planetary Magnetism (PlanetMag), Probing the Earth's subdecadal core-mantle dynamics based on satellite geomagnetic field models

The CHAMP mission provided a great amount of geomagnetic data all over the globe from 2000 to 2010. Its dense data coverage has allowed us to build GRIMM - GFZ Reference Internal Magnetic Model - which has the highest ever resolution for the core field in both space and time. We have already modeled the fluid flow in the Earth's outer core by applying the diffusionless magnetic induction equation to the latest version of GRIMM, to find that the flow evolves on subdecadal timescales, with a remarkable correlation to the observed fluctuation of Earth rotation. These flow models corroborated the presence of six-year torsional oscillations in the outer core fluid. Torsional oscillation (TO) is a type of hydromagnetic wave, theoretically considered to form the most important element of decadal or subdecadal core dynamics. It consists of relative azimuthal rotations of rigid fluid annuli coaxial with the mantle's rotation and dynamically coupled with the mantle and inner core. In preceding works, the TOs have been studied by numerical simulations, either with full numerical dynamos, or solving eigenvalue problems ideally representing the TO system. While these studies drew insights about dynamical aspects of the modeled TOs, they did not directly take into account the observations of geomagnetic field and Earth rotation. Particularly, there have been no observation-based studies for the TO using satellite magnetic data or models. In the proposed project, we aim at revealing the subdecadal dynamics and energetics of the Earth's core-mantle system on the basis of satellite magnetic observations. To that end, we will carry out four work packages (1) to (4), for all of which we use GRIMM. (1) We perform timeseries analyses of core field and flow models, to carefully extract the signals from TOs at different latitudes. (2) We refine the conventional flow modeling scheme by parameterizing the magnetic diffusion at the core surface. Here, the diffusion term is reinstated in the magnetic induction equation, which is dynamically constrained by relating it to the Lorentz term in the Navier-stokes equation. (3) We develop a method to compute the electromagnetic core-mantle coupling torque on the core fluid annuli, whereby the energy dissipation due to the Joule heating is evaluated for each annulus. This analysis would provide insights on whether the Earth's TOs are free or forced oscillations. (4) Bringing together physical implications and computational tools obtained by (1) to (3), we finally construct a dynamical model for the Earth's TOs and core-mantle coupling such that they are consistent with GRIMM and Earth rotation observation. This modeling is unique in that the force balances concerning the TOs are investigated in time domain, as well as that the modeling also aims at improving the observation-based core flow model by considering the core dynamics.

Vertical partitioning and sources of CO2 production and effects of temperature, oxygen and root location within the soil profile on C turnover

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.

Forschergruppe (FOR) 1320: Crop Sequence and Nutrient Acquisition from the Subsoil, Water as medium for nutrient distribution: Monitoring water distribution between subsoil and topsoil considering roles of biopores and plants, by MRT and pressure probes (WatMed)

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.

Forschergruppe (FOR) 1320: Crop Sequence and Nutrient Acquisition from the Subsoil, Plant induced weathering of minerals in the subsoil - release of 'non-exchangeable' potassium from 2:1 layer minerals (TransMinK)

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.

Linking internal pattern dynamics and integral responses - Identification of dominant controls with a strategic sampling design

In hydrology, the relationship between water storage and flow is still fundamental in characterizing and modeling hydrological systems. However, this simplification neglects important aspects of the variability of the hydrological system, such as stable or instable states, tipping points, connectivity, etc. and influences the predictability of hydrological systems, both for extreme events as well as long-term changes. We still lack appropriate data to develop theory linking internal pattern dynamics and integral responses and therefore to identify functionally similar hydrological areas and link this to structural features. We plan to investigate the similarities and differences of the dynamic patterns of state variables and the integral response in replicas of distinct landscape units. A strategic and systematic monitoring network is planned in this project, which contributes the essential dynamic datasets to the research group to characterize EFUs and DFUs and thus significantly improving the usual approach of subdividing the landscape into static entities such as the traditional HRUs. The planned monitoring network is unique and highly innovative in its linkage of surface and subsurface observations and its spatial and temporal resolution and the centerpiece of CAOS.

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

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.

The parent material as major factor for the properties of the biogeochemical interface: Integrative analysis

The formation of biogeochemical interfaces in soils is controlled, among other factors, by the type of particle surfaces present and the assemblage of organic matter and mineral particles. Therefore, the formation and maturation of interfaces is studied with artificial soils which are produced in long-term biogeochemical laboratory incubation experiments (3, 6, 12, 18 months. Clay minerals, iron oxides and charcoal are used as major model components controlling the formation of interfaces because they exhibit high surface area and microporosity. Soil interface characteristics have been analyzed by several groups involved in the priority program for formation of organo-mineral interfaces, sorptive and thermal interface properties, microbial community structure and function. Already after 6 months of incubation, the artificial soils exhibited different properties in relation to their composition. A unique dataset evolves on the development and the dynamics of interfaces in soil in the different projects contributing to this experiment. An integrated analysis based on a conceptual model and multivariate statistics will help to understand overall processes leading to the biogeochemical properties of interfaces in soil, that are the basis for their functions in ecosystems. Therefore, we propose to establish an integrative project for the evaluation of data obtained and for publication of synergistic work, which will bring the results to a higher level of understanding.

International Collaboration in Chemistry: First Principles Multi-Lattice Kinetic Monte Carlo Simulations of NOx Storage Reduction Catalysts

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.

Modeling Geomagnetic Excursions

Periods of extreme geomagnetic change such as geomagnetic excursions have frequently occurred throughout geological time. Characterizing their behaviour is essential for a full understanding of the geodynamo and the interaction of Earths magnetic field and the space environment. We propose to model the global behaviour of Earths magnetic field between 10 and 50 ka using palaeomagnetic data. During this time the geomagnetic field showed significant variability in direction and intensity, including two well documented excursions: Laschamp and Mono Lake. No model currently exists that spans the total length of this time period, yet this period could provide great insights into the geodynamo. The ultimate goal of the project is to synthesize the results from our empirical modelling with those from numerical dynamo simulations, so that a deeper physical understanding of geodynamo processes can be gained. We will compile all sedimentary and volcanic palaeomagnetic data coupled with geochronological data spanning this period. This data will be added to a community available database along with all rock magnetic and sedimentological metadata. This will allow a detailed assessment of the data used in the modelling. Low quality palaeomagnetic data and erroneous age models may distort geomagnetic field structures generated by our new model and it is a key objective of this study to assess the fidelity of the palaeomagnetic and chronological data included in the modeling. Using this data we will construct a temporally continuous global spherical harmonic geomagnetic field model through a regularized least squares inversion of the data using spherical harmonics in space and cubic B splines in time. This model will enable assessment of the geomagnetic at the core-mantle boundary, the Earths surface and at elevated altitudes. Our key scientific objective is to determine where excursions fit into the spectrum of geomagnetic field variations and how the geodynamo processes that generate excursions differ from those that produce secular variation and reversals.

AsFeP0 - A model concept for in situ investigation or arsenic and phosphate adsorption to predefined iron minerals and to characterize transformation processes of iron minerals

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.

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