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Release of hexavalent chromium from ore processing residues and the potential of biochar for chromium immobilization in polluted soils

Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.

Immobilisation of arsenic in paddy soil by iron(II)-oxidizing bacteria

Arsenic-contaminated ground- and drinking water is a global environmental problem with about 1-2Prozent of the world's population being affected. The upper drinking water limit for arsenic (10 Micro g/l) recommended by the WHO is often exceeded, even in industrial nations in Europe and the USA. Chronic intake of arsenic causes severe health problems like skin diseases (e.g. blackfoot disease) and cancer. In addition to drinking water, seafood and rice are the main reservoirs for arsenic uptake. Arsenic is oftentimes of geogenic origin and in the environment it is mainly bound to iron(III) minerals. Iron(III)-reducing bacteria are able to dissolve these iron minerals and therefore release the arsenic to the environment. In turn, iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II)- oxidation at neutral pH followed by iron(III) mineral precipitation. This process may reduce arsenic concentrations in the environment drastically, lowering the potential risk for humans dramatically.The main goal of this study therefore is to quantify, identify and isolate anaerobic and aerobic Fe(II)-oxidizing microorganisms in arsenic-containing paddy soil. The co-precipitation and thus removal of arsenic by iron mineral producing bacteria will be determined in batch and microcosm experiments. Finally the influence of rhizosphere redox status on microbial Fe oxidation and arsenic uptake into rice plants will be evaluated in microcosm experiments. The long-term goal of this research is to better understand arsenic-co-precipitation and thus arsenic-immobilization by iron(II)-oxidizing bacteria in rice paddy soil. Potentially these results can lead to an improvement of living conditions in affected countries, e.g. in China or Bangladesh.

The iron-snow regime in Fe-FeS cores: a numerical and experimental approach

In the Earth, the dynamo action is strongly linked to core freezing. There is a solid inner core, the growth of which provides a buoyancy flux that drives the dynamo. The buoyancy in this case derives from a difference in composition between the solid inner core and the fluid outer core. In planetary bodies smaller than the Earth, however, this core differentiation process may differ - Fe may precipitate at the core-mantle boundary (CMB) rather than in the center and may fall as iron snow and initially remelt with greater depth. A chemical stable sedimentation zone develops that comprises with time the entire core - at that time a solid inner core starts to grow. The dynamics of this system is not well understood and also whether it can generate a magnetic field or not. The Jovian moon Ganymede, which shows a present-day magnetic dipole field, is a candidate for which such a scenario has been suggested. We plan to study this Fe-snow regime with both a numerical and experimental approach. In the numerical study, we use a 2D/3D thermo-chemical convection model that considers crystallization and sinking of iron crystals together with the dynamics of the liquid core phase (for the 3D case the influence of the rotation of the Fe snow process is further studied).The numerical calculations will be complemented by two series of experiments: (1) investigations in metal alloys by means of X-ray radioscopy, and (2) measurements in transparent analogues by optical techniques. The experiments will examine typical features of the iron snow regime. On the one hand they will serve as a tool to validate the numerical approach and on the other hand they will yield important insight into sub-processes of the iron snow regime, which cannot be accessed within the numerical approach due to their complexity.

Trophic interactions in the soil of rice-rice and rice-maize cropping systems

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.

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.

Forschergruppe (FOR) 1525: INUIT - Ice Nuclei research UnIT, Heterogende Eisnukleation ausgelöst durch poröse Materialien

Die Nukleation von Eispartikeln spielt eine wichtige Rolle bei der Wolken- und Niederschlagsbildung, mit Konsequenten für die atmosphärische Chemie, die Wolkenphysik und das Erdklima. Für eine Quantifizierung und Vorhersage des Einflusses von Wolken in Wettervorhersage- und Klimamodellen muss die Bildung von Eispartikeln daher in einer realistischen Art und Weise beschrieben werden. Einer der wichtigen Bildungsmechanismen ist dabei die heterogene Eisnukleation im Immersionsmodus, bei dem Eis an der Oberfläche eines in einem wässrigen Tröpfchen suspendierten Eiskeims - zum Beispiel eines Mineralstaub- Partikels - gebildet wird. Wir werden im Rahmen dieses Forschungsprojekts zahlreiche Gefrierexperimente im Immersionsmodus durchführen. So werden eine Reihe verschiedener, als Aerosolpartikel in der Atmosphäre vorkommende Materialien auf ihre Eisnukleationseigenschaften hin untersucht werden. Insbesondere sollen hier die Temperatur- und Zeitabhängigkeit der von diesen Materialien ausgelösten Eisnukleation quantifiziert werden. Dabei werden wir spezielles Augenmerk auf die systematische Untersuchung der von porösen Materialien ausgelösten Eisnukleation legen. Es sollen sowohl synthetische Materialien wie beispielsweise mesoporöse Silikate untersucht werden, als auch natürlich vorkommende Materialien wie etwa mikroporöse Zeolithe.

Formation of mega-glendonites in the aftermath of the Paleocene-Eocene thermal maximum

Glendonites are pseudomorphs after the mineral ikaite (CaCO3 x 6H2O) and composed of calcite (CaCO3). In the past, they have been used as a paleo-thermometer because the primary mineral ikaite, according to observations and experiments, seems to be formed at temperatures near freezing, high alkalinity and high phosphate concentrations in marine sediments. An enigmatic occurrence of the largest glendonites known world-wide, in the Early Eocene Fur Formation of northwestern Denmark offers the unique possibility to shed more light on the actual mechanism and controlling parameters of ikaite formation. Right in the aftermath of the Paleocene-Eocene thermal maximum, a time known for its global pertubation in the global carbon cycle, the formation of authigenic calcium carbonate concretions start in the Fur Formation. In a specific stratigraphic interval inbetween these concretions, the glendonites can be found. We will investigate if termperature changes or changes in geochemical parameters of the Danish Basin caused the sudden formation of ikaite during a time interval that was based on known paleoclimatic reconstructions (semi tropic) not favorable for ikaite formation.

Community-mediated mechanisms to stabilize pollination of agricultural production highly dependent on shrinking honey bee populations under global change

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.

Einfluss von Ionen auf das atmosphärische Partikelwachstum - Studien an einem Flussreaktor und einer Aerosolkammer

Sekundäre Partikelneubildung ist eine Hauptquelle für atmosphärische Partikel mit wichtigen Folgen für das Klima und die menschliche Gesundheit. Dieses Vorhaben untersucht die Rolle von Luft Ionen bei der sekundären Partikelneubildung in Flussreaktor- und Aerosolkammer-Experimenten unter kontrollierten Laborbedingungen. Trotz beträchtlicher Fortschritte in der Messtechnik zur Untersuchung der atmosphärischen Nukleation und des Partikelwachstums bestehen weiterhin Verständnislücken hinsichtlich der grundlegenden physikalischen und chemischen Prozesse. Insbesondere die möglichen Effekte von Ionen-Partikel-Wechselwirkungen und von Ionenchemie auf die Partikelneubildung werden kontrovers diskutiert. In Ergänzung zu bestehenden Forschungsprogrammen hinsichtlich der Rolle von Ionen im initialen Nukleationsschritt wird vorgeschlagen, Ionen-Partikel-Wechselwirkungen während des anschließenden Partikelwachstums zu untersuchen und sich dabei auf direkte Messungen des Ladungszustands, der Wachstumsraten und der chemischen Zusammensetzung von sekundärem organischem Aerosol zu konzentrieren. Hierzu werden der Ladungszustand und die Wachstumsraten von Partikelpopulationen mit einem modifizierten Mobilitätspartikelspektrometer unter wohldefinierten Randbedingungen in Laborexperimenten quantifiziert. In einem nächsten Schritt werden die neuartigen Messmöglichkeiten unseres Aerosol-Massenspektrometers CAChUP voll ausgeschöpft, um den Beitrag verschiedener organischer Vorläufergase zur chemischen Zusammensetzung von sekundärem organischen Aerosol bei variierenden Ladungszuständen zu quantifizieren. Schließlich werden die Ergebnisse dieser Experimente durch Messungen zur sekundären organischen Partikelbildung bei wohldefinierten Ionenkonzentrationen an einer Aerosolkammer überprüft. Die vorgeschlagene Forschungsagenda ist somit darauf abgestimmt, mögliche ladungs-katalysierte chemische Mechanismen bei der sekundären Aerosolbildung besser einzuordnen.

Forscherguppe (FOR) 1536: INTERNANO: Mobility, aging and functioning of engineered inorganic nanoparticles at the aquatic-terrestrial interface, Aging of engineered inorganic nanoparticles in surface waters

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.

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