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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.

Der Einfluss der SML auf die Spurengasbiogeochemie und den Ozean-Atmosphäre-Gasaustausch

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.

Identification of groundwater nitrogen point source contribution through combined distribute temperature sensing and in-situ UV photometry

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.

Forschergruppe (FOR) 861: Cross-scale Monitoring: Biodiversity and Ecosystem Functions, Quantification of functional hydro-biogeochemical indicators in Ecuadorian ecosystems and their reaction on global change

Water is an intrinsic component of ecosystems acting as a key agent of lateral transport for particulate and dissolved nutrients, forcing energy transfers, triggering erosion, and driving biodiversity patterns. Given the drastic impact of land use and climate change on any of these components and the vulnerability of Ecuadorian ecosystems with regard to this global change, indicators are required that not merely describe the structural condition of ecosystems, but rather capture the functional relations and processes. This project aims at investigating a set of such functional indicators from the fields of hydrology and biogeochemistry. In particular we will investigate (1) flow regime and timing, (2) nutrient cycling and flux rates, and (3) sediment fluxes as likely indicators. For assessing flow regime and timing we will concentrate on studying stable water isotopes to estimate mean transit time distributions that are likely to be impacted by changes in rainfall patterns and land use. Hysteresis loops of nitrate concentrations and calculated flux rates will be used as functional indicators for nutrient fluxes, most likely to be altered by changes in temperature as well as by land use and management. Finally, sediment fluxes will be measured to indicate surface runoff contribution to total discharge, mainly influenced by intensity of rainfall as well as land use. Monitoring of (1) will be based on intensive sampling campaigns of stable water isotopes in stream water and precipitation, while for (2) and (3) we plan to install automatic, high temporal-resolution field analytical instruments. Based on the data obtained by this intensive, bust cost effective monitoring, we will develop the functional indicators. This also provides a solid database for process-based model development. Models that are able to simulate these indicators are needed to enable projections into the future and to investigate the resilience of Ecuadorian landscape to global change. For the intended model set up we will couple the Catchment Modeling Framework, the biogeochemical LandscapeDNDC model and semi-empirical models for aquatic diversity. Global change scenarios will then be analyzed to capture the likely reaction of functional indicators. Finally, we will contribute to the written guidelines for developing a comprehensive monitoring program for biodiversity and ecosystem functions. Right from the beginning we will cooperate with four SENESCYT companion projects and three local non-university partners to ensure that the developed monitoring program will be appreciated by locals and stakeholders. Monitoring and modelling will focus on all three research areas in the Páramo (Cajas National Park), the dry forest (Reserva Laipuna) and the tropical montane cloud forest (Reserva Biologica San Francisco).

Ecosystem Engineering: Sediment entrainment and flocculation mediated by microbial produced extracellular polymeric substances (EPS)

Sediment erosion and transport is critical to the ecological and commercial health of aquatic habitats from watershed to sea. There is now a consensus that microorganisms inhabiting the system mediate the erosive response of natural sediments ('ecosystem engineers') along with physicochemical properties. The biological mechanism is through secretion of a microbial organic glue (EPS: extracellular polymeric substances) that enhances binding forces between sediment grains to impact sediment stability and post-entrainment flocculation. The proposed work will elucidate the functional capability of heterotrophic bacteria, cyanobacteria and eukaryotic microalgae for mediating freshwater sediments to influence sediment erosion and transport. The potential and relevance of natural biofilms to provide this important 'ecosystem service' will be investigated for different niches in a freshwater habitat. Thereby, variations of the EPS 'quality' and 'quantity' to influence cohesion within sediments and flocs will be related to shifts in biofilm composition, sediment characteristics (e.g. organic background) and varying abiotic conditions (e.g. light, hydrodynamic regime) in the water body. Thus, the proposed interdisciplinary work will contribute to a conceptual understanding of microbial sediment engineering that represents an important ecosystem function in freshwater habitats. The research has wide implications for the water framework directive and sediment management strategies.

Forschergruppe (FOR) 1806: The Forgotten Part of Carbon Cycling: Organic Matter Storage and Turnover in Subsoils (SUBSOM), Biological Regulation of Subsoil C-cycling under Field Conditions

The nature of the microbial communities inhabiting the deeper soil horizons is largely unknown. It is also not clear why subsurface microorganisms do not make faster use of organic compounds under field conditions. The answer could be provided by a reciprocal soil transfer experiment studying the response of transferred soils to fluctuations in microclimate, organic inputs, and soil biota. The subproject P9 will be responsible for the establishment of reciprocal transfer experiments offering a strong link between subgroups interested in organic matter quality, transport of organic substances, as well as functions of the soil microbial community. A single, high molecular weight substrate (13C labelled cellulose) will be applied at two different levels in the pre-experiment to understand the dose-dependent reaction of soil microorganisms in transferred surface and sub-soils. Uniformly 13C labelled beech roots - representing complex substrates - will be used for the main reciprocal soil transfer experiment. We hypothesize that transferring soil cores between subsoil and surface soil as well as addition of labelled cellulose or roots will allow us to evaluate the relative impact of surface/subsurface habitat conditions and resource availability on abundance, function, and diversity of the soil microbial community. The second objective of the subproject is to understand whether minerals buried within different soil compartments (topsoil vs. subsoil) in the field contribute to creation of hot spots of microbial abundance and activity within a period of two to five years. We hypothesize that soil microorganisms colonize organo-mineral complexes depending on their nutritional composition and substrate availability. The existence of micro-habitat specific microbial communities could be important for short term carbon storage (1 to 6 years). The third objective is to understand the biogeography and function of soil microorganisms in different subsoils. Parent material as well as mineral composition might control niche differentiation during soil development. Depending on size and interconnectedness of niches, colonization and survival of soil microbial communities might be different in soils derived from loess, sand, terra fusca, or sandstone. From the methodological point of view, our specific interest is to place community composition into context with soil microbial functions in subsoils. Our subgroup will be responsible for determining the abundance, diversity, und function of soil microorganisms (13C microbial biomass, 13C PLFA, enzyme activities, DNA extraction followed by quantitative PCR). Quantitative PCR will be used to estimate total abundances of bacteria, archaea and fungi as well as abundances of specific groups of bacteria at high taxonomic levels. We will apply taxa specific bacterial primers because classes or phyla might be differentiated into ecological categories on the basis of their life strategies.

The role of turgor in rain-cracking of sweet cherry fruit

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.

Schwerpunktprogramm (SPP) 1488: Planetary Magnetism (PlanetMag), Structure and electronic transport properties of metallic liquids at conditions of planetary cores

Electrical conductivity is a key parameter in models of magnetic field generation in planetary interiors through magneto-hydrodynamic convection. Measurements of this key material parameter of liquid metals is not possible to date by experiments at relevant conditions, and dynamo models rely on extrapolations from low pressure/temperature experiments, or more recently on ab-initio calculations combining molecular dynamics and linear response calculations, using the Kubo-Greenwood formulation of transport coefficients. Such calculations have been performed for Fe, Fe-alloys, H, He and H-He mixtures to cover the interior of terrestrial and giant gas planets. These simulations are computationally expensive, and an efficient accurate scheme to determine electrical conductivities is desirable. Here we propose a model that can, at much lower computational costs, provide this information. It is based on Ziman theory of electrical conductivity that uses information on the liquid structure, combined with an internally consistent model of potentials for the electron-electron, electron-atom, and atom-atom interactions. In the proposal we formulate the theory and expand it to multi-component systems. We point out that fitting the liquid structure factor is the critical component in the process, and devise strategies on how this can be done efficiently. Fitting the structure factor in a thermodynamically consistent way and having a transferable electron-atom potential we can then relatively cheaply predict the electrical conductivity for a wide range of conditions. Only limited molecular dynamics simulations to obtain the structure factors are required.In the proposed project we will test and advance this model for liquid aluminum, a free-electron like metal, that we have studied with the Kubo-Greenwood method previously. We will then be able to predict the conductivities of Fe, Fe-light elements and H, He, as well as the H-He system that are relevant to the planetary interiors of terrestrial and giant gas planets, respectively.

Hydraulic activation of stomata (HAS) - development; impact on nutrient and water balance; application

The 'hydraulic activation of stomata' (HAS) describes the establishment of continuous liquid water connections along stomatal walls, which affects individual stomata. It enables the efficient bidirectional transport of water, solutes, and hydraulic signals between the leaf interior and leaf surface and makes stomatal transpiration partly independent of stomatal aperture. While in our earlier work we postulated the existence of these connections and contributed substantially to their final approval, this research proposal focusses on the fundamental significance of HAS for the water and nutrient relations of plants, for atmosphere/plant interaction, and for the modelling of gas exchange. The planned experimental investigations aim to describe HAS formation by hygroscopic salts, to examine new concepts of the plant humidity sensor, nocturnal transpiration, stomatal water uptake, and the 'extended apoplast', as well as the significance of epicuticle waxes for atmospheric particle capture. Together, this should lead both to the further development of new theoretical concepts describing plant adaptations to aerosol regimes, and to practical applications in foliar fertilization, plant protection, and improvement of salt stress tolerance.

Redox processes along gradients

The relevance of biogeochemical gradients for turnover of organic matter and contaminants is yet poorly understood. This study aims at the identification and quantification of the interaction of different redox processes along gradients. The interaction of iron-, and sulfate reduction and methanogenesis will be studied in controlled batch and column experiments. Factors constraining the accessibility and the energy yield from the use of these electron acceptors will be evaluated, such as passivation of iron oxides, re-oxidation of hydrogen sulfide on iron oxides. The impact of these constraints on the competitiveness of the particular process will then be described. Special focus will be put on the evolution of methanogenic conditions in systems formerly characterized by iron and sulfate reducing condition. As methanogenic conditions mostly evolve from micro-niches, methods to study the existence, evolution and stability of such micro-niches will be established. To this end, a combination of Gibbs free energy calculations, isotope fractionation and tracer measurements, and mass balances of metabolic intermediates (small pool sizes) and end products (large pool sizes) will be used. Measurements of these parameters on different scales using microelectrodes (mm scale), micro sampling devices for solutes and gases (cm scale) and mass flow balancing (column/reactor scale) will be compared to characterize unit volumes for organic matter degradation pathways and electron flow. Of particular interest will be the impact of redox active humic substances on the competitiveness of involved terminal electron accepting processes, either acting as electron shuttles or directly providing electron accepting capacity. This will be studied using fluorescence spectroscopy and parallel factor analysis (PARAFAC) of the gained spectra. We expect that the results will provide a basis for improving reactive transport models of anaerobic processes in aquifers and sediments.

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