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Ecotoxicology of Organotin compounds

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.

DFG Trilateral collaboration Deutschland-Israel-Palestine: Wastewater from Olive Oil Mills in Israel and Palestine: Interactions with Soil, Organic Contaminants and Mechanisms of Incorporation into Soil

Due to the often practised uncontrolled disposal into the environment, olive oil production wastewater (OPWW) is presently a serious environmental problem in Palestine and Israel. The objectives of this interdisciplinary trilateral research project are (i) to understand the mechanisms of influence of the olive oil production wastewater on soil wettability, water storage, interaction with organic agrochemicals and pollutants; (ii) monitor short-term and long-term effects of OPWW land application in model laboratory and field experiments; (iii) identify the components responsible for unwanted changes in soil properties and (iv) analyse the mechanisms of association of OPWW OM with soil, the interplay between climatic conditions, pH, presence of multivalent cations and the resulting effects of land application. Laboratory incubation experiments, field experiments and new experiments to study heat-induced water repellency will be conducted to identify responsible OPWW compounds and mechanisms of interaction. Samples from field experiments and laboratory experiments are investigated using 3D excitation-emission fluorescence spectroscopy, thermogravimetry-differential thermal analysis-mass spectrometry (TGA-DSC-MS), LC-MS and GC-MS analyses. We will combine thermal decomposition profiles from OPWW and OPWW-treated soils in dependence of the incubation status using TGA-DSC-MS, contact angle measurements, sorption isotherms and the newly developed time dependent sessile drop method (TISED). The resulting process understanding will open a perspective for OPWW wastewater reuse in small-scale and family-scale olive oil production busi-nesses in the Mediterranean area and will further help to comprehend the until now not fully un-ravelled effects of wastewater irrigation on soil water repellency.

Rehabilitation of Degraded Forests in Yunnan (German-Chinese Cooperation for Agrarian Research)

Background: An increasing frequency of massive flooding along the lower Yangtse River in China ended in a disastrous catastrophe in summer 1998 leaving several thousand people homeless, more than 3.600 dead and causing enormous economic damage. Inappropriate land-use techniques and large scale timber felling in the water catchment of the upper Yangtse and its feeder streams were stated to be the main causes. Immediate timber cutting bans were imposed and investigations on land use patterns were initiated by the Chinese Government. The Institute for World Forestry of the Federal Research Centre for Forestry and Forest Products was approached by the Yunnan Academy of Forestry in Kunming to exchange experiences and to cooperate scientifically in the design and application of appropriate afforestation and silvicultural management techniques in the water catchment area of the Yangtse. This cooperation was initiated in 1999 and is based on formal agreements in the fields of agrarian research between the German and Chinese Governments. Objectives: The cooperation was in the first step focussing on the identification of factors which caused the enormous floodings. After their identification measures of prevention were determined and put into practice. In this context experiences made in past centuries in the alpine region of central Europe served as an incentive and example for similar environmental problems and solutions under comparable conditions. Relevant key questions of the cooperation project were: - Analysis of forest related factors influencing the recent floodings of the Yangtse, - Analysis and evaluation of silvicultural management experiences from central Europe for know-how transfer, - Evaluation of rehabilitation measures for successful application in Yunnan, - Dissemination of knowledge through vocational training. Results: - Frequent wild grazing of husbandry is a key factor for forest degeneration beyond unsustainable timber harvests, forest fires and insect calamities leading to increased water run-off in the mountainous region of Yunnan; - Browsing of cattle interrupts succession thus avoiding natural regeneration and leaving a logging ban ineffective; - Mountain pasture in the Alps had similar effects in the past in central Europe. The introduction of controlled grazing has led to an ecologically compatible coexistence of pasture and ecology. Close-to-nature forestry can have positive effects in this sensitive environment. - Afforestation with site adopted broadleaves and coniferous tree species was implemented on demonstration level using advanced techniques in Yunnan.

Tierexperimentelle Untersuchungen zum Verhalten von PCB, HCB und HCH-Isomeren in der Nahrungskette Pflanze - Milchtier - Milch - Mensch

Im Rahmen des Forschungsvorhabens werden Untersuchungen zum Vorkommen der genannten Verbindungen und ihr Verhalten in der Nahrungskette (Carry Over von Futtermitteln fuer Milchtiere in die Milch u.ae.) durchgefuehrt.

REFOPLAN 2025 - Ressortforschungsplan 2025, Fiskalische und sozio-ökonomische Effekte von Maßnahmen nachhaltiger Stadtentwicklung

In Zeiten angespannter öffentlicher Haushalte wird verstärkt geprüft, ob Maßnahmen einer nachhaltigen Stadtentwicklungspolitik noch finanziell darstellbar oder aufschiebbar sind. Bei diesen Abwägungen gerät oftmals aus dem Blick, welche finanziellen Einsparungen sich aus Investitionen in z.B. einen verbesserten Zugang zu Grün- und Wasserflächen, nachhaltige Mobilität, eine Reduzierung der Luft- und Lärmverschmutzung, des Wasserverbrauchs, der Abfallproduktion sowie eine bessere Anpassung an die Folgen des Klimawandels ergeben. Maßnahmen nachhaltiger Stadtentwicklungspolitik werden oft als Kostenfaktor missverstanden und entsprechend depriorisiert. Dabei wird nicht ausreichend berücksichtigt, dass z.B. die Verfügbarkeit von Grünflächen einen erheblichen positiven Effekt auf die körperliche und mentale Gesundheit der Bevölkerung hat und damit erhebliche Kosten im Gesundheitssystem spart (vgl. dazu die BfN-Studie von Rittel et al., 2014). Das BMBF-gefördete Projekt 'Stadtgrün wertschätzen' hat bereits eine Reihe der Ökosystemleistungen von Stadtgrün quantifiziert, dessen Erkenntnisse einbezogen und um zusätzliche Aspekte wie Gesundheits- und Infrastrukturkosten erweitert werden sollten. Internationale Modellvorhaben (z.B. Barcelona) und Untersuchungen sollen ebenfalls Eingang finden mit dem Ziel, Politik und Verwaltung eine evidenz-basierte Grundlage für Investitionen in Maßnahmen nachhaltiger Stadtentwicklung zu verschaffen. Vor diesem Hintergrund verfolgt dieses Forschungsvorhaben das Ziel, die positiven Effekte unterschiedlicher Maßnahmen nachhaltiger Stadtentwicklungspolitik, national wie international, zu identifizieren und fiskalisch zu quantifizieren. Hierzu zählen z.B. Einsparungen aufgrund positiver mentaler und körperlicher Gesundheitseffekte, Kühlungseffekte durch Verschattung, CO2-Einsparungen durch Stadtgrün, Prävention von Schäden durch Extremwetter sowie Entlastungen öffentlicher Infrastruktur (z.B. der Kanalisation) durch Stadtgrün.

Biopores in the subsoil: Formation, nutrient turnover and effects on crops with distinct rooting systems (BioFoNT)

Perennial fodder cropping potentially increases subsoil biopore density by formation of extensive root systems and temporary soil rest. We will quantify root length density, earthworm abundance and biopore size classes after Medicago sativa, Cichorium intybus and Festuca arundinacea grown for 1, 2 and 3 years respectively in the applied research unit's Central Field Trial (CeFiT) which is established and maintained by our working group. Shoot parameters including transpiration, gas exchange and chlorophyll fluorescence will frequently be recorded. Precrop effects on oilseed rape and cereals will be quantified with regard to crop yield, nutrient transfer and H2-release. The soil associated with biopores (i.e. the driloshpere) is generally rich in nutrients as compared to the bulk soil and is therefore supposed to be a potential hot spot for nutrient acquisition. However, contact areas between roots and the pore wall have been reported to be low. It is still unclear to which extent the nutrients present in the drilosphere are used and which potential relevance subsoil biopores may have for the nutrient supply of crops. We will use a flexible videoscope to determine the root-soil contact in biopores. Nitrogen input into the drilosphere by earthworms and potential re-uptake of nitrogen from the drilosphere by subsequent crops with different rooting systems (oilseed rape vs. cereals) will be quantified using 15N as a tracer.

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.

Quantification of the influence of current use fungicides and climate change on allochthonous Organic MATer decomposition in streams (QUANTOMAT)

The decomposition of terrestrial organic material such as leaf litter represents a fundamental ecosystem function in streams that delivers energy for local and downstream food webs. Although agriculture dominates most regions in Europe and fungicides are applied widely, effects of currently used fungicides on the aquatic decomposer community and consequently the leaf decomposition rate are largely unknown. Also potential compensation of such hypothesised adverse effects due to nutrients or higher average water temperatures associated with climate change are not considered. Moreover, climate change is predicted to alter the community of aquatic decomposers and an open question is, whether this alteration impacts the leaf decomposition rate. The current projects follows a tripartite design to answer these research questions. Firstly, a field study in a vine growing region where fungicides are applied in large amounts will be conducted to whether there is a dose-response relationship between the exposure to fungicides and the leaf decomposition rate. Secondly, experiments in artificial streams with field communities will be carried out to assess potential compensatory mechanisms of nutrients and temperature for effects of fungicides. Thirdly, field experiments with communities exhibiting a gradient of taxa sensitive to climate change will be used to investigate potential climate-related effects on the leaf decomposition rate.

Barley dwarfs acting big in agronomy. Identification of genes and characterization of proteins involved in dwarfism, lodging resistance and crop yield

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.

Dissolved organic matter driven changes in minerals and organic-mineral interactions during paddy soil development

Previous studies indicated that the development and biogeochemistry of paddy soils relates to the parent material, thus the original soil paddies derive from. The proposed research focuses on redox-mediated changes in mineral composition and mineral-associated organic matter (OM) during paddy transformation of different soils. We plan to subject soil samples to a series of redox cycles, in order to mimic paddy soil formation and development. Soils with strongly different properties and mineral composition as well as at different states of paddy transformation; ranging from unchanged soils to fully developed paddy soils, are to be included. We hypothesize that dissolved organic matter is one key driver in redox-mediated transformations, serving as an electron donator as well as interacting with dissolved metals and minerals. The extent of effects shall depend on the parent soil's original mineral assemblage and organic matter and their mutual interactions. The experimental paddy soil transformation will tracked by analyses of soil solutions, of the (re-)distribution of carbon (by addition of 13C-labelled rice straw), of indicative biomolecules (sugars, amino sugars, fatty acids, lignin) and of minerals (including the redox state of Fe). For analyses of organic matter as well as of mineral characteristics we plan to utilize EXAFS and XPS, for Fe-bearing minerals also Mößbauer spectroscopy. This approach of experimental pedology seems appropriate to give insight into the major factors during paddy soil formation and development.

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