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Effect of diffusive/dispersive processes on stable isotope ratios of organic contaminants in aquifer systems

Groundwater contamination by organic compounds represents a widespread environmental problem. The heterogeneity of geological formations and the complexity of physical and biogeochemical subsurface processes, often hamper a quantitative characterization of contaminated aquifers. Compound specific stable isotope analysis (CSIA) has emerged as a novel approach to investigate contaminant transformation and to relate contaminant sources to downgradient contamination. This method generally assumes that only (bio)chemical transformations are associated with isotope effects. However, recent studies have revealed isotope fractionation of organic contaminants by physical processes, therefore pointing to the need of further research to determine the influence of both transport and reactive processes on the observed overall isotope fractionation. While the effect of gasphase diffusion on isotope ratios has been studied in detail, possible effects of aqueous phase diffusion and dispersion have received little attention so far.The goals of this study are to quantify carbon (13C/12C) and, for chlorinated compounds, chlorine (37Cl/35Cl) isotope fractionation during diffusive/dispersive transport of organic contaminants in groundwater and to determine its consequences for source allocation and assessment of reactive processes using isotopes. The proposed research is based on the combination of high-resolution experimental studies, both at the laboratory (i.e. zero-, one- and two-dimensional systems) and at the field scales, and solute transport modeling. The project combines the expertise in the field of contaminant transport with the expertise on isotope methods in contaminant hydrogeology.

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.

Origin and fate of dissolved organic matter in the subsoil

Dissolved organic matter (DOM) is one major source of subsoil organic matter (OM). P5 aims at quantifying the impact of DOM input, transport, and transformation to the OC storage in the subsoil environment. The central hypotheses of this proposal are that in matric soil the increasing 14C age of organic carbon (OC) with soil depth is due to a cascade effect, thus, leading to old OC in young subsoil, whereas within preferential flowpaths sorptive stabilization is weak, and young and bioa-vailable DOM is translocated to the subsoil at high quantities. These hypotheses will be tested by a combination of DOC flux measurements with the comparative analysis of the composition and the turnover of DOM and mineral-associated OM. The work programme utilizes a DOM monitoring at the Grinderwald subsoil observatory, supplemented by defined experiments under field and labora-tory conditions, and laboratory DOM leaching experiments on soils of regional variability. A central aspect of the experiments is the link of a 13C-leaf litter labelling experiment to the 14C age of DOM and OM. With that P5 contributes to the grand goal of the research unit and addresses the general hypotheses that subsoil OM largely consists of displaced and old OM from overlying horizons, the sorption capacity of DOM and the pool size of mineral-associated OM are controlled by interaction with minerals, and that preferential flowpaths represent 'hot spots' of high substrate availability.

Luftmassenexport aus dem asiatischen Monsun in die außertropische Stratosphäre: Auswirkungen auf Chemie und Strahlung (AirExam)

Der asiatische Sommermonsun ist charakterisiert durch hohe Konvektion über Südasien, die mit der asiatischen Monsun-Antizyklone (AMA) zusammenhängt, der sich von der oberen Troposphäre bis in die untere Stratosphäre (UTLS) erstreckt. Diese Antizyclone ist das ausgeprägteste Zirkulationsmuster in diesen Höhen während des borealen Sommer. Es ist bekannt, dass der Export von Monsunluft quasi-isentropisch aus der AMA sowohl im Osten als auch im Westen, einen großen Einfluss auf die Zusammensetzung der außertropischen unteren Stratosphäre hat. Jedoch sind die relative Stärken der beiden Wege bisher unbekannt. Der Transport von Luftmassen aus der AMA in die nördliche außertropische UTLS wirkt sich entscheidend auf die Chemie der Stratosphäre und ihrenStrahlungshaushalt (z.B. durch Transport von H2O, Aerosol oder ozonschädigende Stoffe) aus. Im Rahmen dieses Projekts AirExam wird der quasi-isentropischer Luftmassenexport aus der AMA durch verschiedene Wegen und seine Auswirkungen auf Chemie und Strahlung der außertropische UTLS quantifiziert durch u.a. HALO-Flugzeugmessungen (insbesondere aus die für Sommer 2023 geplanten PHILEAS-Kampagne), Simulationen mit dem Chemischen Transportmodell CLaMS und Strahlungsberechnungen. Unser Projekt AirExam wird sich mit den folgenden offenen Schlüsselfragen befassen:1) Welchen relativen Beitrag leisten die beiden quasi-horizontalen Transportwege (nach Westen und Osten) aus dem asiatischen Monsun-Antizyklon zur Zusammensetzung der außertropischen unteren Stratosphäre?2) Wie groß ist die jährliche Variabilität des Transports aus der asiatischen Monsun-Antizyklone in die außertropische untere Stratosphäre und was sind die Hauptquellenregionen auf der Erde Oberfläche?3) Was ist die Auswirkung des Wasserdampftransports aus der asiatischen Monsun-Antizyklone zum H2O-Budget der außertropischen UTLS und seine Strahlungswirkung?In unserem Projekt werden wir HALO-Messungen (insbesondere H2O) mit globalen 3-dimensionalen CLaMS-Simulationen kombinieren, die von neuen hochaufgelösten ERA-5-Reanalyse des ECMWF angetrieben werden. CLaMS-Simulationen auf der Grundlage von ERA-5 sind ein neues Instrument zur zuverlässigen Beschreibung von Transportprozessen in der Region des asiatischen Monsuns und seiner globalen Auswirkungen. Die Strahlungswirkung des durch den asiatischen Monsun verursachten H2O-Anstiegs im Sommer und Herbst wird mit Hilfe des Strahlungs-Transfercodes Edwards und Slingo berechnet. H2O ist das wichtigste Treibhausgas, und die Befeuchtung der Stratosphäre ist eine wichtige Triebkraft des Klimawandels. Unser Projekt AirExam wird die Auswirkungen des verstärkten H2O-Transports in die untere Stratosphäre quantifizieren und kann daher dazu beitragen, die potenziellen Risiken des Luftmassentransports aus der asiatischen Monsunregion auf die globale Stratosphäre zu bewerten.

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.

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.

Transport of EINP through soil affected by the dynamics of infiltration flux and particle properties

In this project we experimentally explore the transport of engineered inorganic nanoparticles (EINP) through soils. This is done for original EINPs and some pre-aged form. Transport of NPs in soil is expected to be different from that of reactive solutes, in that hydrodynamic drag, inertial and shear forces as well as the affinity to water-gas interfaces are expected to be more relevant. Hence, the mobility of EINPs in soil is highly sensitive to the morphology of the porous structure and the dynamics of water saturation.This project provides the pore network structure for natural soils using X-ray micro-tomography to allow for an up-scaling of pore-scale interactions explored by project partners to the scale of soil horizons. The pore structure is represented by a network model suitable for pore scale simulations including the dynamics of water-gas interfaces.Pore network simulations will be compared to column experiments for conservative tracers as well as for unaltered and pre-aged EINPs (obtained from INTERFACE). This includes steady state flow scenarios for saturated (ponding) and unsaturated conditions as well as for transient flow to explore the impact of moving water-gas interfaces. The final goal is to arrive at a consistent interpretation of experimental findings and numerical simulations to develop a module for modelling EINP transfer through soil as a function of particle properties, soil structural characteristics and external forcing in terms of flux boundary conditions.

Schwerpunktprogramm (SPP) 1315: Biogeochemische Grenzflächen in Böden; Biogeochemical Interfaces in Soil, Quantification of active interfaces with respect to dissolved chemicals in unsaturated structured soil

During the first project period we developed a general approach to quantify soil pore structure based on X-ray micro-tomography Vogel et al. (2010) which is applicable at various scales to cover soil pores larger that 0.05 mm in a representative way. Based on this method we generated equivalent network models to numerically simulate flow and transport of dissolved chemicals. The existing network model was extended to handle reactive transport and infiltration processes which are especially critical for matter flux in soil. The results were compared to experimental findings. The original research question 'what does a particle see on its way through soil' could be answered quantitatively for various boundary conditions including steady state flux and infiltration. However, we identified various critical aspects of the proposed modeling concept which will be in the focus of the second period. This includes 1) the spatial arrangement of interfaces having different quality which is crucial for chemical interactions and pore scale water dynamics, 2) the realistic multiphase dynamics at the pore scale which need to reflect the dynamic pressure and movement of trapped non-wetting phase and 3) the parametrization of structural complexity which need to be developed beyond the measurement of continuous Minkowski functions to allow the development of quantitative relations between structure and function. These aspects will be explored in a joint experiments in cooperation with partners within the SPP.

Schwerpunktprogramm (SPP) 1144: Vom Mantel zum Ozean: Energie-, Stoff- und Lebenszyklen an Spreizungsachsen, Methane transport to the ocean from the Mid-Atlantic Ridge, 2°S to 11°S

Schwerpunktprogramm (SPP) 1315: Biogeochemische Grenzflächen in Böden; Biogeochemical Interfaces in Soil, The detritusphere as the biogeochemical interface for bacterial and fungal degradation of MCPA

The detritusphere is an excellent model to study microbial-physicochemical interactions during degradation of the herbicide MCPA. Whereas during the first phase of SPP 1315 we focused on bacterial and fungal abundance at the soil litter interface and carbon flow between different compartments, the second phase will be devoted to elucidating complex regulation mechanisms of MCPA degradation in the detritusphere: (1) At the cellular level, co-substrate availability and laccase abundance might be important regulators, (2) at the community level, bacteria harbouring different classes of tfdA genes might control degradation of MCPA and (3) at the microhabitat level, interaction between MCPA degraders and organo-mineral surfaces as well as transport processes might be important regulators. The concept of hierarchical regulation of MCPA degradation will be included into the modelling of small-scale microbial growth, MCPA transport and MCPA degradation near the soil-litter interface.

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