During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.
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.
Das hier vorgeschlagene Projekt, RP6 in INUIT-2, zielt darauf hin, fundamentales Prozessverständnis in Bezug auf heterogene Eisnukleation zu erzielen, und hier besonders auf die Rolle von biogenen Eiskeimen und von Eiskeimen die aus Mischungen von biogenem und mineralischem Material bestehen. Der Leipzig Aerosol Cloud Interaction Simulator (LACIS) wird dazu verwendet werden, das Immersionsgefrierverhalten einer Reihe von verschiedenen Eiskeimen zu untersuchen, darunter biogene (von Pilzen stammende) Eiskeime, solche die aus einer Mischung von biogenem und mineralischem Material bestehen wie Bodenstäube und Proben die innerhalb von INUIT-2 als Test-Materialen verwendet werden. Letztere werden von verschiedenen Gruppen von innerhalb und außerhalb von INUIT vermessen werden, und die Ergebnisse werden Vergleichen unterzogen werden, ähnlich denen, die bereits für einfachere Test-Materialien in INUIT-1 erfolgreich durchgeführt worden sind. Für die Eiskeime, die zur Untersuchung in RP6 vorgeschlagen werden, wird in sinnvollen und machbaren Fallen eine Oberflächenbehandlung durchgeführt werden, mit reaktiven und mit chemisch inerten Substanzen, deren Einfluss auf die Eiskeimfähigkeit dann untersucht wird. Wie bereits in früheren LACISStudien dokumentiert, sind kontrollierte Oberflächenbehandlungen ein ausgezeichnetes Instrument um zu ermitteln, was dazu führt, dass ein Partikel ein effektiver Eiskeim ist. Zusätzlich erhellen diese Untersuchungen den Effekt der Alterung auf die Eiskeime. Es ist auch geplant, die Messungen auszuweiten, hin zu Bedingungen unter denen eine Untersättigung bezüglich Wasserdampf vorliegt. Es soll untersucht werden in wie weit sich die Eiskeimbildung unter diesen Bedingungen verhält wie es im Fall von Immersionsgefrieren in konzentrierten Lösungen zu erwarten wäre. Von all den experimentell erhaltenen Daten werden verschiedene Parametrisierungen abgeleitet, sowohl zeit-abhängige als auch zeit-unabhängige, die dann der Wissenschaftsgemeinschaft für die weitere Verwendung in Modellen zur Verfügung gestellt werden. Die hier vorgeschlagenen Studien werden die bereits erfolgreich an LACIS während INUIT-1 durchgeführten Arbeiten ergänzen, da die Arbeiten in INUIT-1 stärker auf die Untersuchung reiner Mineralstäube und reiner biogener Substanzen hinzielten. Die Untersuchung von komplexeren und entsprechend mehr atmosphärenrelevanten Eiskeimen wird signifikant dazu beisteuern, atmosphärische Eiskeimbildung generell besser zu verstehen, und die entsprechenden Beiträge von mineralischen und biogenen Substanzen zu quantifizieren.
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.
Die Grenzfläche zwischen Ozean und Atmosphäre ist durch einen allgegenwärtigen, < 1 mm dicken marinen Oberflächenfilm, den sogenannten sea-surface microlayer (SML), charakterisiert. Der SML ist nicht nur direkter UV-Strahlung und atmosphärischen Oxidantien ausgesetzt, sondern zeichnet sich im Vergleich zum unterliegenden Wasser auch durch höhere Konzentrationen an organischen Stoffen aus. Bisher ist unklar, welche Bedeutung die dadurch bedingten SML-spezifischen abiotischen Prozesse für die Umsetzung und die Emission organischer Stoffe insgesamt haben und wie man diese Prozesse parametrisieren kann. In diesem Projekt, das eng mit anderen Projekten der interdisziplinären Forschungsgruppe â€ÌBiogeochemische Prozesse und Ozean/Atmosphäre- Austauschprozesse in marinen Oberflächenfilmen (BASS)â€Ì verbunden ist, sollen daher molekulare Details SML-spezifischer Reaktionen (Photochemie, heterogene Oxidation, Radikalchemie) genauer untersucht werden. Ziel ist es, Reaktionsprodukte und -geschwindigkeiten quantitativ zu erfassen und Unterschiede zwischen Reaktionen im SML und in der freien Wassersäule herauszuarbeiten. Basierend auf der Expertise der drei beteiligten Arbeitsgruppen im Bereich Photochemie, Reaktionskinetik, Laserspektroskopie, Analytik und theoretischer Modellierung, soll ein molekulares Verständnis ausgewählter Reaktionen und des Einflusses der komplexen SML-Reaktionsumgebung erreicht werden. Dazu sollen experimentelle Verfahren wie Schwingungs-Summenfrequenzerzeugung, hochempfindliche Chromatographie-Massenspektrometrie und gepulste Laserphotolyse-Langwegabsorption mit Methoden der Quantenchemie und Molekulardynamik kombiniert werden. Arbeitsschwerpunkte bilden die Oxidationskinetik von Halogen- bzw. Hydroxyl-Radikalreaktionen in der flüssigen Phase, die Ozonolyse von Fettsäure-Monoschichten und die durch Photosensibilisatoren verstärkte Bildung von reaktiven Radikalen bzw. Zersetzung von organischen Schichten. Neben wohldefinierten Labor-Modellsystemen werden auch natürliche Proben analysiert werden. Dabei stellt sich z.B. die Frage nach den Einflussfaktoren der während einer Algenblüte zunehmenden Bildung von oberflächenaktiven Stoffen im SML und der Bedeutung der durch die Sonne bedingten Photolyse auf die abiotische Umsetzung organischer Stoffe. Flankierend werden im Projekt auch die eingesetzten Untersuchungsmethoden weiterentwickelt; das beinhaltet sowohl die Ausarbeitung von Messprotokollen zur Quantifizierung bestimmter organischen Substanzklassen (z.B. Carbonyle und Kohlenhydrate) im SML, die Synthese und Charakterisierung von neuartigen oberflächenaktiven Photosensibilisatoren (z.B. Benzoyl-Benzoesäure-funktionalisierte Lipide) sowie die Entwicklung und Erprobung mehrstufiger Modellierungsverfahren zur theoretischen Beschreibung von Struktur-Reaktivitätsbeziehungen der Fettsäure-Ozonolyse (z.B. Beschreibung des Einflusses sterischer und elektronischer Effekte der organischen Matrix).
Comprehension of belowground competition between plant species is a central part in understanding the complex interactions in intercropped agricultural systems, between crops and weeds as well as in natural ecosystems. So far, no simple and rapid method for species discrimination of roots in the soil exists. We will be developing a method for root discrimination of various species based on Fourier Transform Infrared (FTIR)-Attenuated Total Reflexion (ATR) Spectroscopy and expanding its application to the field. The absorbance patterns of FTIR-ATR spectra represent the chemical sample composition like an individual fingerprint. By means of multivariate methods, spectra will be grouped according to spectral and chemical similarity in order to achieve species discrimination. We will investigate pea and oat roots as well as maize and barnyard grass roots using various cultivars/proveniences grown in the greenhouse. Pea and oat are recommendable species for intercropping to achieve superior grain and protein yields in an environmentally sustainable manner. To evaluate the effects of intercropping on root distribution in the field, root segments will be measured directly at the soil profile wall using a mobile FTIR spectrometer. By extracting the main root compounds (lipids, proteins, carbohydrates) and recording their FTIR-ATR spectra as references, we will elucidate the chemical basis of species-specific differences.
Barley (Hordeum vulgare) is an important cereal grain which serves as major animal fodder crop as well as basis for malt beverages or staple food. Currently barley is ranked fourth in terms of quantity of cereal crops produced worldwide. In times of a constantly growing world population in conjunction with an unforeseeable climate change and groundwater depletion, the accumulation of knowledge concerning cereal growth and rate of yield gain is important. The Nordic Genetic Resource Center holds a major collection of barley mutants produced by irradiation or chemical treatment. One phenotypic group of barley varieties are dwarf mutants (erectoides, brachytic, semidwarf, uzu). They are characterized by a compact spike and high rate of yield while the straw is short and stiff, enhancing the lodging resistance of the plant. Obviously they are of applied interest, but they are also of scientific interest as virtually nothing is known about the genes behind the development of plant dwarfism. The aim of this project is to identify and isolate the genes carrying the mutations by using state of the art techniques for gene cloning at the Carlsberg Laboratory. The identified genes will be connected with the mutant phenotype to reveal the gene function in general. One or two genes will be overexpressed and the resulting recombinant proteins will be biochemically and structurally characterized. The insights how the mutation effects the protein will display the protein function in particular. Identified genes and their mutant alleles will be tested in the barley breeding program of the Carlsberg brewery.
Fusarium species of the Gibberella fujikuroi species complex cause serious diseases on different crops such as rice, wheat and maize. An important group of plant pathogens is the Gibberella fujikuroi species complex (GFC) of closely related Fusarium species which are associated with specific hosts; F. verticillioides and F. proliferatum are particularly associated with maize where they can cause serious ear-, root-, and stalk rot diseases. Two other closely related species of the GFC, F. mangiferae and F. fujikuroi, which share about 90Prozent sequence identity with F. verticillioides, are pathogens on mango and rice, respectively. All of these species produce a broad spectrum of secondary metabolites such as phytohormones (gibberellins, auxins, and cytokinins), and harmful mycotoxins, such as fumonisin, fusarin C, or fusaric acid in large quantities. However, the spectrum of those mycotoxins might differ between closely related species suggesting that secondary metabolites might be determinants for host specificity. In this project, we will study the potential impact of secondary metabolites (i.e. phytohormones and certain mycotoxins) and some other species-specific factors (e.g. species-specific transcription factors) on host specificity. The recently sequenced genomes of F. mangiferae and F. fujikuroi by our groups and the planned sequencing of F. proliferatum will help to identify such determinants by genetic manipulation of the appropriate metabolic pathway(s).
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.
Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.