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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.

Biogeochemical Processes in Tropical Soils

In recent years science has taken an increased interest in mineralization processes in tropical soils in particular under minimal tillage operations. Plant litter quality and management strongly affect mineralization-nitrification processes in soil and hence the fate of nitrogen in ecosystems and the environment. Plant secondary metabolites like lignin and polyphenols are poorly degradable and interact with proteins (protein binding capacity) and hence protect them from microbial attack. Nitrification, a microbiological process, directly and indirectly influences the efficiency of recovery of N in the vegetation as well as the loss of N (through denitrification and leaching) causing environmental pollution to water bodies and contributes to global warming (e.g. the greenhouse gas N2O is emitted as a by-product of nitrification and denitrification). Nitrifiers comprise a relatively narrow species diversity (at least as known to date) and are generally thought to be sensitive to low soil pH and stress. Despite these properties nitrification occurs in acid tropical soils with high levels of aluminium and manganese. Thus the main objective of the project will be the identification of micro-organisms and mechanisms responsible for mineralization-nitrification processes in acid tropical soils and the influence of long-term litter input of different chemical qualities and minimal tillage options. The project will include the use of stable isotopes (15N, 13C), mass spectrometry, gas chromatography (CO2, N2O), biochemical methods (PLFA) and molecular biology (16s rRNA., PCR, DGGE)

International Surface Ocean - Lower Atmosphere Study (SOLAS)

Since 2004, the International Surface Ocean - Lower Atmosphere Study (SOLAS) project is an international research initiative aiming to understand the key biogeochemical-physical interactions and feedbacks between the ocean and atmosphere. Achievement of this goal is important to understand and quantify the role that ocean-atmosphere interactions play in the regulation of climate and global change. SOLAS celebrated its 10 year anniversary in 2014. In the first decade, the SOLAS community has accomplished a great deal towards the goals of the original Science Plan & Implementation Strategy and Mid-term Strategy (Law et al. 2013) as highlighted by the open access synthesis book on 'Ocean Atmosphere Interactions of Gases and Particles' edited by Liss and Johnson and the synthesis article in Anthropocene from Brévière et al. 2015. However there are still major challenges ahead that require coordinated research by ocean and atmospheric scientists. With this in mind, in 2013, SOLAS has started an effort to define research themes of importance for SOLAS research over the next decade. These themes form the basis of a new science plan for the next phase of SOLAS 2015-2025. SOLAS being a bottom-up organisation, a process in which community consultation play a central role was adopted. After two sets of reviews by our four sponsors (SCOR, Future Earth, WCRP and iCACGP), the SOLAS 2015-2025 Science Plan and Organisation (SPO) was officially approved.

Schwerpunktprogramm (SPP) 1158: Antarctic Research with Comparable Investigations in Arctic Sea Ice Areas; Bereich Infrastruktur - Antarktisforschung mit vergleichenden Untersuchungen in arktischen Eisgebieten, Investigation of mechanism driving glacial/interglacial variability in stratification/mixing and biological productivity of the Pacific Southern Ocean and potential implications on air-sea CO2-exchange: synthesis of climate and ocean biogeochemical modeling with paleoceanographic reconstructions

Atmospheric CO2 concentrations present a repetitive pattern of gradual decline and rapid increase during the last climate cycles, closely related to temperature and sea level change. During the Last Glacial Maximum (LGM; 23-19 kyr BP), when sea level was ca. 120 m below present, the ocean must have stored additionally about 750 Gt carbon. There is consensus that the Southern Ocean represents a key area governing past and present CO2 change. The latter is not only of high scientific but also of socio-economic and political concern since the Southern Ocean provides the potential for an efficient sink of anthropogenic carbon. However, the sensitivity of this carbon sink to climate-change induced reorganizations in wind patterns, ocean circulation, stratification, sea ice extent and biological production remains under debate. Models were not yet able to reproduce the necessary mechanisms involved, potentially due to a lack of the dynamic representation/resolution of atmospheric and oceanic circulation as well as missing carbon cycling. Data on past Southern Ocean hydrography and productivity are mainly from the Atlantic sector, thus do not adequately document conditions in the Pacific sector. This sector is not only the largest part of the Southern Ocean, but it also represents the main drainage area of the marine-based West Antarctic Ice Sheet (WAIS). In the proposed study we aim to generate paleo-data sets with a newly established proxy method from sediment core transects across the Pacific Southern Ocean. This will enhance the baselines for the understanding and modeling of the Southern Ocean's role in carbon cyling, i.e. ocean/atmosphere CO2 exchange and carbon sequestration. It will also allow insight into the response of the WAIS to past warmer than present conditions. Paired isotope measurements (oxygen, silicon) will be made on purified diatoms and radiolarians to describe glacial/interglacial contrasts in physical and nutrient properties at surface and subsurface water depth. This will be used to test (i) the impact of yet unconsidered dust-borne micronutrient deposition on the glacial South Pacific on shifts of primary productivity, Si-uptake rates and carbon export, (ii) the 'silicic-acid leakage' hypothesis (SALH) and (iii) the formation and extent of surface water stratification. Diatom and radiolarian oxygen isotopes will provide information on the timing of surface ocean salinity anomalies resulting from WAIS melt water. Climate model simulations using a complex coupled atmosphere ocean general circulation model (AOGCM) in combination with a sophisticated ocean biogeochemical model including Si-isotopes will be used for comparison with the paleo records. The analysis will cover spatial as well as temporal variability patterns of Southern Ocean hydrography, nutrient cycling and air-sea CO2-exchange. With the help of the climate model we aim to better separate and statistically analyse the individual impacts of ocean circulation and bio

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.

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.

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.

Dynamic (redox) interfaces in soil - Carbon turnover in microbial biomass and flux into soil organic matter

Existing models of soil organic matter (SOM) formation consider plant material as the main source of SOM. Recent results from nuclear magnetic resonance analyses of SOM and from own incubation studies, however, show that microbial residues also contribute to a large extent to SOM formation. Scanning electron microscopy showed that the soil mineral sur-faces are covered by numerous small patchy fragments (100 - 500 nm) deriving from microbial cell wall residues. We will study the formation and fate of these patchy fragments as continuously produced interfaces in artificial soil systems (quartz, montmorillonite, iron oxides, bacteria and carbon sources). We will quantify the relative contributions of different types of soil organisms to patchy fragment formation and elucidate the effect of redox con-ditions and iron mineralogy on the formation and turnover of patchy fragments. The develop-ment of patchy fragments during pedogenesis will be followed by studying soil samples from a chronosequence in the forefield of the retreating Damma glacier. We will characterize chemical and physical properties of the patchy fragments by nanothermal analysis and microscale condensation experiments in an environmental scanning electron microscope. The results will help understanding the processes at and characteristics of biogeochemical interfaces.

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.

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).

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