Nanoparticles are produced and used in huge amounts increasing their probability to end up in surface waters. There, they are subject to environmentally driven modification processes. Consequently, aquatic life may be exposed to different nanoparticle agglomerate sizes, while after sedimentation benthic organisms are more likely to be affected. However, most ecotoxicity studies with nanoparticles exclusively investigated implications of their characteristics (e.g. size) on pelagic organisms, ignoring environmentally modified nanoparticles. Therefore, a systematic assessment of factors triggering the fate and toxicity of nanoparticles under environmentally relevant conditions is needed. The present thesis, therefore, investigates the implications of nanoparticle related factors (i.e., inherent material-properties and nanoparticle characteristics) as well as environmental conditions towards the pelagic living organism Daphnia magna and the benthic species Gammarus fossarum. In detail, inert titanium dioxide (nTiO2) and ion-releasing silver nanoparticles (nAg), both of varying particle characteristics (e.g. initial size), were tested for their toxicity under different environmental conditions (e.g. ultraviolet-light (UV-light)). The results indicate that the toxicity of nTiO2 and nAg is mainly determined by: their adsorption potential onto biota, and their fate in terms of reactive oxygen species or Ag+ ion release. Thus, inherent material-properties, nanoparticle characteristics and environmental conditions promoting or inhibiting these aspects revealed significant implications in the toxicity of nTiO2 and nAg towards daphnids. Furthermore, the presence of ambient UV-light, for example, adversely affected gammarids at 0.20 mg nTiO2/L, while under darkness no effects occurred even at 5.00 mg nTiO2/L. Hence, the currently associated risk of nanoparticles might be underestimated if disregarding their interaction with environmental parameters

Das Institut für Umweltwissenschaften Landau Stressoren der Umwelt Ökosystemdienstleistungen Genetik und Umwelt Klimagase

The intention of this thesis was to characterise the effect of naturally occurring multivalent cations like Calcium and Aluminium on the structure of Soil Organic Matter (SOM) as well as on the sorption behaviour of SOM for heavy metals such as lead. The first part of this thesis describes the results of experiments in which the Al and Ca cation content was changed for various samples originated from soils and peats of different regions in Germany. The second part focusses on SOM-metal cation precipitates to study rigidity in dependence of the cation content. In the third part the effects of various cation contents in SOM on the binding strength of Pb cations were characterised by using a cation exchange resin as desorption method. It was found for soil and peat samples as well as precipitates that matrix rigidity was affected by both type and content of cation. The influence of Ca on rigidity was less pronounced than the influence of Al and of Pb used in the precipitation experiments. For each sample one cation content was identified where matrix rigidity was most pronounced. This specific cation content is below the cation saturation as expected by cation exchange capacity. These findings resulted in a model describing the relation between cation type, content and the degree of networking in SOM. For all treated soil and precipitate samples a step transition like glass transition was observed, determined by the step transition temperature T*. It is known from literature that this type of step transition is due to bridges between water molecules and organic functional groups in SOM. In contrast to the glass transition temperature this thermal event is slowly reversing after days or weeks depending on the re-conformation of the water molecules. Therefore, changes of T* with different cation compositions in the samples are explained by the formation of water-molecule-cation bridges between SOM-functional groups. No influence on desorption kinetics of lead for different cation compositions in soil samples was observed. Therefore it can be assumed that the observed changes of matrix rigidity are highly reversible by changing the water status, pH or putting agitation energy by shaking in there.

A fundamental understanding of attachment of engineered nanoparticles to environmentalrnsurfaces is essential for the prediction of nanoparticle fate and transport in the environment. The present work investigates the attachment of non-coated silver nanoparticles and citraterncoated silver nanoparticles to different model surfaces and environmental surfaces in thernpresence and absence of humic acid. Batch sorption experiments were used for this investigation. The objective of this thesis was to investigate how silver nanoparticles interactrnwith surfaces having different chemical functional groups. The effect of presence of HA, on the particle-surface interactions was also investigated. In the absence of humic acid, nanoparticle-surface interactions or attachment was influencedrnby the chemical nature of the interacting surfaces. On the other hand, in the presence ofrnhumic acid, nanoparticle-surface attachment was influenced by the specific surface area of the sorbent surfaces. The sorption of non-coated silver nanoparticles and citrate coatedrnnanoparticles to all the surfaces was nonlinear and best described by Langmuir isotherm, indicating monolayer sorption of nanoparticles on to the surfaces. This can be explained as due to the blocking effect generated by the particle-particle repulsion. In the presence of humic acid, sorption of nanoparticles to the surfaces was linear. When the humic acid was present in the interacting medium, both the nanoparticles and surfaces were getting coated with humic acid and this masks the chemical functionalities of the surfaces. This leads to the change in particle-surface interactions, in the presence of humic acid. For the silver nanoparticle sorption from an unstable suspension, the sorption isotherms did not follow any classical sorption models, suggesting interplay between aggregation and sorption. Citrate coated silver nanoparticles and humic acid coated silver nanoparticles showed arndepression in sorption compared to the sorption of non-coated silver nanoparticles. In therncase of citrate coated silver nanoparticles the decrease in sorption can be explained by thernmore negative zeta potential of citrate coated nanoparticles compared to non-coated ones. For humic acid coated nanoparticles the sorption depression can be due to the steric hindrance caused by the free humic acid molecules which may coat the sorbent surface or due to the competition for sorption sites between the nanoparticle and free humic acid molecules present in the suspension. Thus nanoparticle surface chemistry is an important factor that determines the attachment of nanoparticles towards surfaces and it makes the characterization of nanoparticle surface an essential step in the study of their fate in the environment. Another aim of this study was to introduce the potential of chemical force microscopy for nanoparticle surface characterization. With the use of this technique, it was possible to distinguish between bare silver nanoparticles, citrate coated silver nanoparticles, and humic acid coated silver nanoparticles. This was possible by measuring the adhesion forces between the nanoparticles and five different AFM probes having different chemical functionalization.

The adoption of the EU Water Framework Directive (WFD) in 2000 marked the beginning of a new era of European water policy. However, more than a decade later, the majority of European rivers are still failing to meet one of the main objectives of the WFD: the good ecological status. Pesticides are a major stressor for stream ecosystems. This PhD thesis emphasises the need for WFD managers to consider all main agricultural pesticide sources and influencing landscape parameters when setting up River Basin Management Plans and Programmes of Measures. The findings and recommendations of this thesis can help to successfully tackle the risk of pesticide contamination to achieve the WFD objectives. A total of 663 sites that were situated in the German Federal States of Saxony, Saxony-Anhalt, Thuringia and Hesse were studied (Chapter 3 and 4). In addition to an analysis of the macroinvertebrate data of the governmental WFD monitoring network, a detailed GIS analysis of the main agricultural pesticide sources (arable land and garden allotments as well as wastewater treatment plants (WWTPs)) and landscape elements (riparian buffer strips and forested upstream reaches) was conducted. Based on the results, a screening approach was developed that allows an initial rapid and cost-effective identification of those sites that are potentially affected by pesticide contamination. By using the trait-based bioindicator SPEARpesticides, the insecticidal long-term effects of the WWTP effluents on the structure of the macroinvertebrate community were identified up to at least 1.5 km downstream (in some cases even 3 km) of the WWTPs. The results of the German Saprobic Index revealed that the WWTPs can still be important sources of oxygen-depleting substances. Furthermore, the results indicate that forested upstream reaches and riparian buffer strips at least 5 m in width can be appropriate measures in mitigating the effects and exposure of pesticides. There are concerns that the future expansion of energy crop cultivation will lead to an increased pesticide contamination of ecosystems in agricultural landscapes. Therefore, the potential of energy crops for pesticide contamination was examined based on an analysis of the development of energy crop cultivation in Germany and a literature search on perennial energy crops (Chapter 5). The results indicate that the future large-scale expansion of energy crop cultivation will not necessarily cause an increase or decrease in the amounts of pesticides that are released into the environment. The potential effects will depend on the future design of the agricultural systems. Instead of creating energy monocultures, annual energy crops should be integrated into the existing food production systems. Financial incentives and further education are needed to encourage the use of sustainable crop rotations, innovative cropping systems and perennial energy crops, which may contribute to crop diversity and generate lower pesticide demands than do intensive farming systems.

Biodiversity is not only threatened by habitat loss, climate change and pollution, but also by invasive species. The impact of introduced species is immense and causes substantial ecological and economical costs worldwide. With the start of domestications of the African wildcat (Felis lybica) in the Near East, the transport of house cats (Felis catus) around the world as a commensal and domesticate began. The general aim of my thesis was to investigate the impact of invasive feral cats on native species as well as underlying population genetic structures, diversity and phylogeography. This was studied in the context of the demographic history in Australia and Hawai'i. My studies confirmed that the main introductions of cats to Australia began in the 19th century via ships of European settlers, traders and workers. Similarly, I was able to confirm cat introductions to Hawai'i by European traders and explorers; which has to the present a devastating effect on Hawaiian endemic species. Likewise, cats are widespread across Australia, can be found on most islands and are recognized as one of the major threats to Australian native species. A selective feeding behaviour by invasive predators was found in one of my studies. This study additionally gives an indication for possible population recovery of small Western Australianrnvertebrate species after predator removal. Advancement and the combination of various management techniques allow, if adequately funded, a more efficient planning and implementation of eradication campaigns. Population genetic approaches are able to give insights into population genetic structure, diversity and kinship, thereby enabling management campaigns to be more cost effective and successful. No pattern of isolation by distance between populations of Hawai"i and Australia indicated that trade routes, such as the "Golden Round" of the maritime fur trade, facilitated a link between far off global cat populations. Multiple introductions to Australia and intermixing with domestic breed cats resulted in feral cat populations which showrnno signs of reduced genetic variability. My studies also revealed the advantages of bioproxies in combination with phylogeography, which enable the inference and reconstruction of introduction routes, history and origin of invasive species. Genetic signals of historically introduced genotypesrnare still discernible on islands with low number of introductions over time and thereby low intermixing with domestic fancy breeds. Feral cats' adaptability as an invader was reconfirmed and possible underlying genetic mechanisms enabling their success as a global invader ("global supercat") are discussed. Research into the feralisation process of cats will provide new information regarding the domestication of cats, the genetic basis of feralisation and allow additional insights into cats" adaptive potential.

Engineered nanoparticles (ENP) are widely used in different industrial fields and products. In the last years, the risk potential for the release of ENP in the environment has increased as never before. ENP are expected to pass the wastewater-river-topsoil-groundwater pathway. In the terrestrial and aquatic environment ENP can undergo aging and transformation processes which can influence fate, transport and toxicological effects to different living organisms. The scope of this workshop is to gather researchers, scientists, experts and specialists from nanoparticle and colloid science, soil and environmental chemistry, ecotoxicology or neighbouring disciplines to discuss the latest results and findings in the field of aging, fate, transport and toxicological effects of nanoparticles in the environment.

This PhD thesis is situated within the framework of the Research-Group Learning and Neurosciences (ReGLaN)-Health and Logistics project. The goal of this project is the optimisation of health service delivery in the rural areas of South Africa. Cooperation takes place between ReGLaN-Health and Logistics and the South African Council for Scientific and Industrial Research (CSIR) Meraka Institute, with Prof Dr Dr Marlien Herselman of Pretoria, South Africa, as the central contact person. This thesis deals with the mathematical modelling of Geographic Information System (GIS)-tailoredrnGraphical User Interface (GUI) design with the application of spatial fuzzy logic. This thesis considers the mathematical visualisation of risk and resource maps for epidemiological issues using GIS and adaptive GUI design for an Open Source (OS) application for digital devices. The intention ofrnthis thesis is to provide spatial decision support tailored to different user groups. In order for the GUI elements to be evaluated and initialised, empirical teaching-learning-research on dealing with geomedia and GUI elements was conducted.

Structure of soil organic matter (SOM) is a hot topic of discussion among scientific community for several decades. The mostly discussed models, among many, are polymer model and supramolecular model. While the former considers SOM as macromolecules consisting of amorphous and crystalline domains, the latter explains SOM as a physicochemical entity dominated by weak hydrophobic and H-bond interactions in the secondary level, which holds individual molecules of primary structure together. The weak forces in secondary level impart characteristic mobility of SOM. Very important consequence of this multidimensional formulation is that physicochemical structure plays a crucial role in most biogeochemical functions of SOM, apart from the chemical composition. Recently introduced concept of cation and water molecule mediated bridges between OM molecular segments (CaB and WaMB, respectively) evolved from physicochemical understanding of SOM structure. Even though several indirect evidences were produced for CaB and WaMB during last years, no clear-cut understanding of these processes has been achieved yet. Experimental difficulty due to overlapping effects of equally important CaB-governing parameters such a pH and competing cations raises huge challenge in investigating CaB-related influences. This thesis, therefore, aims to validate an experimental set-up for inducing CaB within OM structures and assessing it from various chemical and physicochemical aspects. The method involved removal of omnipresent cations and adjustment of pH before cation addition. This helped to separate pH effects and cation effects. Based on results obtained on two different types of organic matter, it can be deduced that multivalent cations can cross-link SOM, given that functional group density of the SOM material is enough for the functional groups to be arranged in sufficient spatial proximity to each other. Physicochemical structural reorganisation during aging causes formation of more and/or stronger CaB and WaMB. As for inducing CaB directly after cation treatment, cationic size and valency were found determinant also for aging effect. A strongly cross-linked system in the beginning is less vulnerable to structural changes and undergoes aging with lower intensity, than an initially weakly cross-linked system. Responsible for the structural changes is, the inherent mobility of SOM within its physicochemical assemblage. Thus the information on structural requirement of CaB and its consequences on OM matrix rigidity will help to obtain insight into the physicochemical SOM structure. Additionally, organic matter quality (assessed by thermal analysis) and pore structure of SOM formed in a set of artificial soils showed that mineral materials are important for the chemical nature of SOM molecules, but not for the physical structure of organo-mineral associations, at least after several months of SOM development. Furthermore, nanothermal analysis using atomic force microscopy (AFM-nTA) was implemented in soils for the first time to reveal nanoscale thermal properties and their spatial distribution in nano- and micrometer scales. This helped to identify physicochemical processes, such as disruption of WaMB, in low-organic soils, in which bulk methods fail due to their low sensitivity. Further, various types of materials constituting in soils were distinguished with high resolution by advanced application of the method, in combination with other AFM parameters. Attempts were done to identify various materials, with the usage of defined test materials. Above all, the method is potent to reveal microspatial heterogeneity on sample surfaces, which could help understanding process-relevant hotspots, for example. This thesis thus contributes to the scientific understanding on physicochemical structural dynamics via cross-linking by cations and via nanoscale thermal properties. Direct investigation on CaB demonstrated here will potentially help making a big leap in knowledge about the interaction. The observed aging effects add well to the understanding of supramolecular consideration of SOM. By introducing nanothermal analysis to the field of soil science, it is made possible to face the problem of heterogeneity and spatial distribution of thermal characteristics. Another important achievement of AFM-nTA is that it can be used to detect physicochemical processes, which are of low intensity.

Chemical plant protection is an essential element in integrated pest management and hence, in current crop production. The use of Plant Protection Products (PPPs) potentially involves ecological risk. This risk has to be characterised, assessed and managed. For the coming years, an increasing need for agricultural products is expected. At the same time, preserving our natural resources and biodiversity per se is of equally fundamental importance. The relationship of our economic success and cultural progress to protecting the environment has been made plain in the Ecosystem Service concept. These distinct 'services' provide the foundation for defining ecological protection goals (Specific Protection Goals, SPGs) which can serve in the development of methods for ecological risk characterisation, assessment and management. Ecological risk management (RM) of PPPs is a comprehensive process that includes different aspects and levels. RM is an implicit part of tiered risk assessment (RA) schemes and scenarios, yet RM also explicitly occurs as risk mitigation measures. At higher decision levels, RM takes further risks, besides ecological risk, into account (e.g., economic). Therefore, ecological risk characterisation can include RM (mitigation measures) and can be part of higher level RM decision-making in a broader Ecosystem Service context. The aim of this thesis is to contribute to improved quantification of ecological risk as a basis for RA and RM. The initial general objective had been entitled as "… to estimate the spatial and temporal extent of exposure and effects…" and was found to be closely related to forthcoming SPGs with their defined 'Risk Dimension'. An initial exploration of the regulatory framework of ecological RA and RM of PPPs and their use, carried out in the present thesis, emphasised the value of risk characterisation at landscape-scale. The landscape-scale provides the necessary and sufficient context, including abiotic and biotic processes, their interaction at different scales, as well as human activities. In particular, spatially (and temporally) explicit landscape-scale risk characterisation and RA can provide a direct basis for PPP-specific or generic RM. From the general need for tiered landscape-scale context in risk characterisation, specific requirements relevant to a landscape-scale model were developed in the present thesis, guided by the key objective of improved ecological risk quantification. In principle, for an adverse effect (Impact) to happen requires a sensitive species and life stage to co-occur with a significant exposure extent in space and time. Therefore, the quantification of the Probability of an Impact occurring is the basic requirement of the model. In a landscape-scale context, this means assessing the spatiotemporal distribution of species sensitivity and their potential exposure to the chemical. The core functionality of the model should reflect the main problem structures in ecological risk characterisation, RA and RM, with particular relationship to SPGs, while being adaptable to specific RA problems. This resulted in the development of a modelling framework (Xplicit-Framework), realised in the present thesis. The Xplicit-Framework provides the core functionality for spatiotemporally explicit and probabilistic risk characterisation, together with interfaces to external models and services which are linked to the framework using specific adaptors (Associated-Models, e.g., exposure, eFate and effect models, or geodata services). From the Xplicit-Framework, and using Associated-Models, specific models are derived, adapted to RA problems (Xplicit-Models). Xplicit-Models are capable of propagating variability (and uncertainty) of real-world agricultural and environmental conditions to exposure and effects using Monte Carlo methods and, hence, to introduce landscape-scale context to risk characterisation. Scale-dependencies play a key role in landscape-scale processes and were taken into account, e.g., in defining and sampling Probability Density Functions (PDFs). Likewise, evaluation of model outcome for risk characterisation is done at ecologically meaningful scales. Xplicit-Models can be designed to explicitly address risk dimensions of SPGs. Their definition depends on the RA problem and tier. Thus, the Xplicit approach allows for stepwise introduction of landscape-scale context (factors and processes), e.g., starting at the definitions of current standard RA (lower-tier) levels by centring on a specific PPP use, while introducing real-world landscape factors driving risk. With its generic and modular design, the Xplicit-Framework can also be employed by taking an ecological entity-centric perspective. As the predictive power of landscape-scale risk characterisation increases, it is possible that Xplicit-Models become part of an explicit Ecosystem Services-oriented RM (e.g., cost/benefit level).

The polysaccharide hydration phenomenon is nowadays the subject of intense research. The interaction of native and modified polysaccharides and polysaccharides-based bioconjugates with water has an important influence on their functional behaviour. Notwithstanding that the hydration phenomenon has been studied for decades, there is still a lack of awareness about the influence of hydration water on the polysaccharide´s structure and consequences for industrial or medicinal applications. The hydration of polysaccharides is often described by the existence of water layers differing in their physical properties depending on the distance from the polysaccharide. Using the differential scanning calorimetry (DSC) such water layers were categorized according their properties upon cooling in hyaluronan (HYA, sodium salt of ß-1,4-linked units of ß-1,3-linked D-glucuronic acid and N-acetyl-D-glucosamine), a model polysaccharide in the present work. The amount of non-freezing water, i.e. water in close proximity of HYA chain which does not freeze et all, was determined around 0.74gH2O/gHYA for HYA with molecular weight from 100 to 740kDa and 0.84gH2O/gHYA for molecular weight of 1390kDa. The amount of freezing-bound water, the water pool which is affected by presence of HYA but freezes, was determined in the range from 0.74 to 2gH2O/gHYA. Above this value only non-freezing and bulk water are present since melting enthalpy measured above this concentration reached the same value as for pure water. Since this approach suffers from several experimental problems, a new approach, based on the evaporation enthalpy determination, was suggested. The analysis of the evaporation enthalpies revealed an additional process associated with apparent energy release taking part below the water content of 0.34gH2O/gHYA. Existence of this phenomenon was observed also for protonated form of HYA. The existence of energy compensating process was confirmed with the Kissinger-Akahira-Sunose method which allowed determination of actual water evaporation/desorption enthalpies in all stages of the evaporation process. In fact, the apparent evaporation enthalpy value increased until water content of 0.34gH2O/gHYA, and then dropped down to lower values which were, still higher than the value of the pure water evaporation enthalpy. By the use of time domain nuclear magnetic resonance (TD-NMR) technique it was revealed that this phenomenon is the plasticisation of HYA. Further, it was revealed that the non-freezing water determined by the use of DSC consists of two water fractions, i.e. 15% of water structurally integrated, interacting directly with polar sites, and 85% of water structurally restricted, embedded in-between the HYA chains. The occurrence of plasticisation concentration close to equilibrium moisture content provided the possibility to influence the HYA physical structure during the drying. In this way three samples of native HYA, dried under various conditions were prepared and their physical properties were analyzed. The samples differed in kinetics of rehydration, plasticisation concentration, glass transitions, and morphology. The properties of water pool were studied in solutions of 10"25mg HYA/mL as well. The fast filed cycling (FFC) NMR relaxometry showed the existence of three water fractions which correlation times spanned from 10"6 to 10"10 seconds, progressively decreasing in dependency on its distance from HYA chain. The formation of a weak and transient intramolecular water bridge between HYA chains was observed. It was shown that, unlike the inorganic electrolytes, polyelectrolytes hydration is a dynamic process which reflects not only the technique used for the analysis, experimental conditions but also the conformation of the polysaccharide and its "thermal" and "hydration" history. It was demonstrated that some native polysaccharide structures can be easily modified by manipulation of preparation conditions, giving fractions with specific physicochemical properties without necessity of any chemical modification.

Although agriculture dominates with around 50% area much of Europe- landscape, there is virtually no information on how bats use this farmed environment for foraging. Consequently, little is known about effective conservation measures to compensate potential negative effects of agrarian management practice on the food availability for bats in this habitat. Moreover, there are currently no specific regulatory requirements to include bats in European Union risk assessments for the registration of pesticides since no information about pesticide exposure on this mammal group is available. To evaluate the potential pesticide exposure of bats via ingestion of contaminated insects, information about bat presence and activity in agricultural habitats is required. In order to examine bat activity on a landscape scale it was necessary to establish a suitable survey method. Contrary to capture methods, telemetry, and direct observations, acoustic surveys of bat activity are a logistically feasible and cost-effective way of obtaining bat activity data. However, concerns regarding the methodological designs of many acoustic surveys are expressed in the scientific literature. The reasons are the failing of addressing temporal and spatial variation in bat activity patterns and the limitations of the suitability of the used acoustic detector systems. By comparing different methods and detector systems it was found that the set up of several stationary calibrated detector systems which automatically trigger the ultrasonic recording has the highest potential to produce reliable, unbiased and comparable data sets on the relative activity of bats. By using the proposed survey method, bat diversity and activity was recorded in different crops and semi-natural habitats in southern Rhineland-Palatinate. Simultaneously, the availability of aerial prey insects was studied by using light and sticky traps. In more than 500 sampling nights about 110,000 call sequences were acoustically recorded and almost 120,000 nocturnal insects were sampled. A total of 14 bat species were recorded, among them the locally rare and critically endangered northern bat (Eptesicus nilssonii) and the barbastelle (Barbastella barbastellum), all of them also occurring over agricultural fields. The agricultural landscape of southern Palatinate is dominated by vineyards, a habitat that was shown to be of low quality for most bat species because of the demonstrated low availability of small aerial insects. By surveying bat activity and food availably in a pair-wise design on several rain water retention ponds and neighbouring vineyards it was demonstrated that aquatic insect emergence in artificial wetlands can provide an important resource subsidy for bats. The creation of artificial wetlands would be a possibility to create important foraging habitats for bats and mitigate negative effects of management practice in the agricultural landscape. In several other agricultural crops, however, high abundances of suitable prey insects and high bat activity levels, comparable or even higher than in the nearby forests and meadows known to be used as foraging habitats were demonstrated. Especially high bat activity levels were recorded over several fruit orchards and vegetable fields where insects were also present. Both crops are known for high pesticide inputs, and, therefore, a pesticide exposure through ingestion of contaminated insects can not be excluded. To follow the current risk assessment approach for birds and mammals pesticide residues were measured on bat-specific food items in an apple orchard following insecticide applications and bat activity was recorded in parallel. The highest residue values were measured on foliage-dwelling arthropods which may results in a reproductive risk for all bat species that, even to a small extent, include this prey group in their diet. The presence of bats in agricultural landscapes that form a majority of the land area in Europe but also on a global scale leads to exposure of bats by contaminated food and depletion of their food resources by pesticide use. So far conservation efforts for bats focussed on securing hibernation sites and the creation of artificial roost sites since especially the latter were thought to be limiting population growth. However the potential pesticide effects might be also crucial for the population persistence in agricultural landscapes of bats and need to be addressed adequately, especially in risk assessment procedures for the regulation of pesticides.

Agricultural pesticides, especially insecticides, are an integral part of modern farming. However, these may often leave their target ecosystems and cause adverse effects in non- target, especially freshwater ecosystems, leading to their deterioration. In this thesis, the focus will be on Insect Growth Regulators (IGRs) that can in many ways cause disruption of the endocrine system of invertebrates. Freshwater invertebrates play important ecological, economic and medical roles, and disruption of their endocrine systems may be crucial, considering the important role hormones play in the developmental and reproductive processes in organisms. Although Endocrine Disruption Chemicals (EDCs) can affect moulting, behaviour, morphology, sexual maturity, time to first brood, egg development time, brood size (fecundity), and sex determination in invertebrates, there is currently no agreement upon how to characterize and assess endocrine disruption (ED). Current traditional ecotoxicity tests for Ecological Risk Assessment (ERA) show limitations on generating data at the population level that may be relevant for the assessment of EDCs, which effects may be sublethal, latent and persist for several generations of species (transgenerational). It is therefore the primary objective of this thesis to use a test method to investigate adverse effects of EDCs on endpoints concerning development and reproduction in freshwater invertebrates. The full life-cycle test over two generations that includes all sensitive life stages of C. riparius (a sexual reproductive organism) allows an assessment of its reproduction and should be suitable for the investigation of long-term toxicity of EDCs in freshwater invertebrates. C. riparius is appropriate for this purpose because of its short life cycle that enables the assessment of functional endpoints of the organism over several generations. Moreover, the chironomid life cycle consists of a complete metamorphosis controlled by a well-known endocrine mechanism and the endocrine system of insects has been most investigated in great detail among invertebrates. Hence, the full life-cycle test with C. riparius provides an approach to assess functional endpoints (e.g. reproduction, sex ratio) that are population-relevant as a useful amendment to the ERA of EDCs. In the laboratory, C. riparius was exposed to environmentally-relevant concentrations of the selected IGRs in either spiked water or spiked sediment scenario over two subsequent generations. The results reported in this thesis revealed significant effects of the IGRs on the development and the reproduction of C. riparius with the second (F1) generation showing greater sensitivity. These findings indicated for the first time the suitability of multigenerational testing for various groups of EDCs and strongly suggested considering the full life-cycle of C. riparius as an appropriate test method for a better assessment of EDCs in the freshwater environment. In conclusion, this thesis helps to detect additional information that can be extrapolated at population level and, thus, might contribute to better protection of freshwater ecosystems against the risks of Endocrine Disrupting Chemicals (EDCs.) It may furthermore contribute to changes in the ERA process that are necessary for a real implementation of the new European chemical legislation, REACH (Registration, Evaluation Authorization and Restriction of Chemicals). Finally, significant interactions between temperature, chemical exposure and generation were reported for the first time and, may help predict impacts that may occur in the future, in the field, under predicted climate change scenarios.

New media are continually gaining importance in society. This process also has an increasing influence on developments in the field of education. Due to the use of computers as an integral part of schooling, new possibilities with regard to the organisation of learning processes arise. In this context, it is of great significance that appropriate computer applications for the respective learning group be prepared, so that justifiable use of computers in lessons can take place. Furthermore, efficient integration of computers requires changes in spatial organisation, in teaching methodology and in the role of the teacher. Such reflection and re-orientation are the essential basis for meaningful usage of new media in teaching and learning processes. An initial aim of this thesis is an empirical analysis of the situation regarding the usage of computers in geometry lessons in primary schools, based on a regional survey. The evaluation gives information as to how intensively the computer is used in the learning process and shows us which factors determine the use of computers in geometry lessons. The results are an empirical foundation for the development of a computer-based learning environment called "Geolizi" (the second aim of my study). Within this learning environment, the pupils should work independently on the topics "mirror-imaged figures" and "the construction of rectangles and squares", with the help of the computer. During this process, hands-on media, traditional drawing instruments and interactive worksheets are available to the pupils. The computer (with its appropriate applications) takes over different functions in this learning process. Testing of this learning environment ("Geolizi") took place in several primary school classes, within the scope of formative and summative evaluation. With the help of questionnaires filled in by the pupils, the usability of the individual elements was tested. Based on a pre-post-investigation design, an attempt has been made to discover possible changes in the attitude of teachers regarding the usage of computers in the teaching of elementary geometry. The results of this test phase, together with the evaluation of the questionnaires, lead to the founded presumption that usage of the multimedia-based learning environment " Geolizi " could result in greater use of computers in geometry lessons. All in all, the developed learning environment demonstrates an interesting possibility of how to use computers in the teaching of geometry at primary schools, thus making an important contribution to an independent, individualised learning process.

To assess the effect of organic compounds on the aquatic environment, organisms are typically exposed to toxicant solutions and the adverse effects observed are linked to the concentration in the surrounding media. As compounds generally need to be taken up into the organism and distributed to the respective target sites for the induction of effects, the internal exposure is postulated to best represent the observed effects. The aim of this work is to contribute to an improved effect assessment of organic compounds by describing experimental and modelling methods to obtain information on the internal exposure of contaminants in organisms. Chapter 2 details a protocol for the determination of bioconcentration parameter for uptake (k1) and elimination (k2) of organic compounds in zebrafish (Danio rerio) eggs. This enables the simulation of the internal exposure in zebrafish eggs from an ambient exposure concentration over time. The accumulated contaminant amount in zebrafish eggs was also determined, using a biomimetic extraction method. Different bioconc-entration estimation models for the determination of internal steady-state concentrat-ion of pharmaceutical compounds in fish to an environmental exposure are presented in Chapter 3. Bioconcentration factors were estimated from the compounds octanol: water partition coefficient (KOW) to determine the internal exposure to an ambient concentration. To assess the integral bioavailable fraction from the water and sediment phase of environmental contaminants for rooted aquatic plants, the internal exposure in river-living Myriophyllum aquaticum plants were determined over time, presented in Chapter 4. The plants were collected at different time points, with the accumulated organic contaminants determined using a liquid extraction method. In Chapter 5 a protocol was established to enable the non-invasive observation of effects in M. aquaticum plants exposed to contaminated sediments over time. Since the toxicant effects are a result of all uptake and distribution processes to the target site and the toxico-dynamic process leading to an observed effect during static exposure, information on the internal exposure could thus be gained from the temporal effect expression.rn

Studies have shown that wastewater treatment plant (WWTP) effluents are the major pathways of organic and inorganic chemicals of anthropogenic use (=micropollutants) into aquatic environments. There, micropollutants can be transferred to ground water bodies - and may finally end up in drinking water - or cause various effects in aquatic organisms like multiple resistances of bacteria. Hence, the upgrading of WWTPs with the aim to reduce the load of those micropollutants is currently under discussion. Therefore, the primary objective of this thesis was to assess ecotoxicological effects of wastewater ozonation, a tertiary treatment method, using specifically developed toxicity tests with Gammarus fossarum (Koch) at various levels of ecological complexity. Several studies were designed in the laboratory and under semi-field conditions to cope with this primary objective. Prior to the investigations with ozone treated wastewater, the ecotoxicity of secondary treated (=non-ozone treated) wastewater from WWTP Wüeri, Switzerland, for the test species was assessed by a four-week experiment. This experiment displayed statistically significant impairments in feeding, assimilation and physiological endpoints related to population development and reproduction. The first experiment investigating ecotoxicological implications of ozone application in wastewater from the same WWTP displayed a preference of G. fossarum for leaf discs conditioned in ozone treated wastewater when offered together with leaf discs conditioned in non-ozone treated wastewater. This effect seems to be mainly driven by an alteration in the leaf associated microbial community. Another series of laboratory experiments conducted also with wastewater from WWTP Wüeri treated with ozone at the lab- or full-scale, revealed significantly increased feeding rates of G. fossarum exposed to ozone treated wastewater compared to non-ozone treated wastewater. These laboratory experiments also indicated that any alteration in the organic matrix potentially caused by ozone treatment is not related to the effects in feeding as this endpoint showed only negligible deviation in secondary treated wastewater, which contained hardly any (micro)pollutants (i.e. pharmaceuticals), from the same wastewater additionally treated with ozone. Moreover, it was shown that shifts in the dissolved organic carbon (DOC) profile do not affect the feeding rate of gammarids. In situ bioassays conducted in the receiving stream of the WWTP Wüeri confirmed the results of the laboratory experiments by displaying significantly reduced feeding rates of G. fossarum exposed below the WWTP effluent if non-ozone treated wastewater was released. However, at the time the ozonation was operating, no adverse effects in feeding rates were observed below the effluent compared to the unaffected upstream sites. Also population studies in on-site flow-through stream microcosms displayed an increased feeding and a statistically significantly higher population size after ten weeks when exposed to ozone treated wastewater compared to non-ozone treated wastewater. In conclusion, the present thesis documents that ozonation might be a suitable tool to reduce both the load of micropollutants as well as the ecotoxicity of wastewaters. Thus, this technology may help to meet the requirements of the Water Framework Directive also under predicted climate change scenarios, which may lead to elevated proportions of wastewater in the receiving stream during summer discharge. However, as ozone application may also produce by-products with a higher toxicity than their parent compounds, the implementation of this technique should be assessed further both via chemical analysis and ecotoxicological bioassays.

Die Arbeit stellt die Frage nach den Effekten einer tertiären Präventionsmaßnahme in Bezug auf Schmerzbewältigung und Schmerzveränderung bei chronischen Lumbalgiepatienten. Im Rahmen der Überprüfung werden ausdifferenzierte psychophysische Interventionsmaßnahmen aus den Bereichen der Physiotherapie/Krankengymnastik und Psychologie eingesetzt. Die Gruppenunterteilung erfolgt in eine behandelte Versuchsgruppe und eine unbehandelte Warte-Kontrollgruppe mit jeweils 100 Probanden (N=200). Die Ergebnisse der tertiären Präventionsmaßnahme zeigen statistisch und klinisch relevante sowie positive Veränderungen in den Bereichen der Schmerzbewältigung und Schmerzveränderung.

Studies have shown that runoff and spray-drift are important sources of nonpoint-source pesticide pollution of surface waters. Owing to this, public concern over the presence of pesticides in surface and ground water has resulted in intensive scientific efforts to find economical, yet environmentally sound solutions to the problem. The primary objective of this research was to assess the effectiveness of vegetated aquatic systems in providing buffering between natural aquatic ecosystems and agricultural landscape following insecticide associated runoff and spray-drift events. The first set of studies were implemented using vegetated agricultural ditches, one in Mississippi, USA, using pyrethroids (bifenthrin, lambda-cyhalothrin) under simulated runoff conditions and the other in the Western Cape, South Africa using the organophosphate insecticide, azinphos-methyl (AZP), under natural runoff and spray-drift conditions. The second set of studies were implemented using constructed wetlands, one in the Western Cape using AZP under natural spray-drift conditions and the other in Mississippi, USA using the organophosphate MeP under simulated runoff conditions. Results from the Mississippi-ditch study indicated that ditch lengths of less than 300 m would be sufficient to mitigate bifenthrin and lambda-cyhalothrin. In addition, data from mass balance calculations determined that the ditch plants were the major sink (generally > 90%) and/or sorption site for the rapid dissipation of the above pyrethroids from the water column. Similarly, results from the ditch study in South Africa showed that a 180 m vegetated system was effective in mitigating AZP after natural spray drift and low flow runoff events. Analytical results from the first wetland study show that the vegetated wetland was more effective than the non-vegetated wetland in reducing loadings of MeP. Mass balance calculations indicated approximately 90% of MeP mass was associated with the plant compartment. Ninety-six hours after the contamination, a significant negative acute effect of contamination on abundances was found in 8 out of the 15 macroinvertebrate species in both wetland systems. Even with these toxic effects, the overall reaction of macroinvertebrates clearly demonstrated that the impact of MeP in the vegetated wetland was considerably lower than in the non-vegetated wetland. Results from the constructed wetland study in South Africa revealed that concentrations of AZP at the inlet of the 134 m wetland system were reduced by 90% at the outlet. Overall, results from all of the studies in this thesis indicate that the presence of the plant compartment was essential for the effective mitigation of insecticide contamination introduced after both simulated and natural runoff or spray-drift events. Finally, both the vegetated agricultural drainage ditch and vegetated constructed wetland systems studied would be effective in mitigating pesticide loadings introduced from either runoff or spray-drift, in turn lowering or eliminating potential pesticide associated toxic effects in receiving aquatic ecosystems. Data produced in this research provide important information to reduce insecticide risk in exposure assessment scenarios. It should be noted that incorporating these types of best management practices (BMPs) will decrease the risk of acute toxicity, but chronic exposure may still be an apparent overall risk.

Quellen sind hochdiverse Lebensräume mit einer stark spezialisierten Fauna, wobei noch Lücken im Verständnis der besiedlungsrelevanten Faktoren für die aquatische Makrofauna bestehen, so dass die Arbeit einen klärenden Beitrag hinsichtlich anthropogener Veränderungen und ihrer Auswirkungen auf die Besied-lung leisten will. Basierend auf Daten von 334 Quellen aller Grundwasserlandschaften von Rheinland-Pfalz wurden die Quellen morphologisch und faunistisch bewertet. Außerdem wurden die Quellen des Landes morphologisch typisiert, Referenzquellen analysiert und ein Ansatz für die morphologische und faunistische Leitbildentwicklung gegeben. Außerdem wird ein selbst entwickeltes, kompaktes Kartier- und Bewertungsverfahren zur Quellstruktur vorgestellt, wo bislang noch ein Defizit bestand. Das Verfahren erfasst in einem Erfassungsbogen alle ökologisch bedeutsamen Strukturparameter und bewertet in einem 5-stufigen System. Quellen sind hochdiverse Lebensräume mit kleinen Populationen in isolierter Lage. Bei der Untersuchung der 310 Quellen wurden insgesamt 292 Arten bzw. höhere Taxa des Makrozoobenthos nachgewiesen. Es wurden 89 quellassoziierte Taxa gezählt, hiervon waren 24 krenobiont und 65 krenophil. Der Anteil der quellassoziierten Fauna an der Gesamtfauna lag bei über 30%. Es fanden sich 19 Erstnachweise für Rheinland-Pfalz, 9 besondere Nachweise (seltene Arten) und 19 Rote-Liste-Arten. Erstnachweise fanden sich in wenig bearbeiteten Dipterengruppen, vor allem den Psychodidae (13), Limoniidae (5) und ferner den Simu-liidae (1). Bei den Köcherfliegen wurden etliche seltene Arten gefunden, welche bisher in Rheinland-Pfalz kaum gefunden wurden. Häufigere krenobionte Taxa waren Crunoecia irrorata, Bythinella dunkeri, Niphar-gus sp., Pisidium personatum, Salamandra salamandra, Thaumalea sp., Agabus guttatus, Crenobia alpina, Oxycera sp. und Beraea maura. Die durchschnittliche Taxazahl pro Quelle betrug 11, die maximale 62 Taxa. Schüttung und Morphologie der Quellen waren von Naturraum und Grundwasserlandschaft abhängig, so schütteten etwa Buntsandsteinquellen ergiebiger und konstanter als Tonschieferquellen. Quellen spiegeln die Hydrologie ihrer Einzugsgebiete wider, so dass in verschiedenen hydrogeologischen Einheiten die chemischen Parameter differierten. In einzelnen Quellen schwankte die Hydrochemie jahreszeitlich aber nur gering. Der pH-Wert etwa war im Quellwasser versauerungsgefährdeter Gebiete niedrig (Hunsrück, Pfälzer-wald), der Nitratgehalt anthropogen bedingt hoch in intensiv landwirtschaftlich genutzten Räumen. Die morphologische Quelltypologie, welche sich in erster Linie auf gängige Quelltypen stützte, ergab in elf hydrogeologischen Quelltypenräumen vier Basisquelltypen und fünf geochemische Sondertypen. Die Wan-derquelle wurde neu hinzu genommen. Die landesweite Verteilung der Quelltypen ergab bei ungefassten Quellen 57 % Sicker-, 32 % Sturz-, 9 % Tümpel- und über 2 % Wanderquellen. Wanderquellen dürften aber noch öfter vorkommen. Relief und Substrateigenschaften waren entscheidende Faktoren für die Typologie, so dass etwa Sturzquellen vor allem im Buntsandstein häufig waren, während Sickerquellen im Tonschiefer des rheinischen Schiefergebirges dominierten. Es wurden 85 Strukturreferenzquellen als typische, naturnahe Beispiele für einzelne Quelltypenräume genannt. Etwa zwei Drittel aller Quellen waren strukturell beein-trächtigt bis stark geschädigt, 59 % gefasst. Fassungen, Verrohrungen und Betonverbau waren ökologisch besonders bedeutsam. In Regionen mit intensiver Landwirtschaft lagen generell die stärksten Schädigungen vor. Im Forst waren Quellen durch Nadelholzmonokulturen und in den Hochlagen pufferarmer Mittelgebirge durch Versauerung geschädigt. Hinsichtlich der Besiedlung ergaben sich Unterschiede zwischen den Naturräumen, beeinflusst durch die Faktoren Geologie, Hydrochemie, Schüttungsverhältnisse, Landnutzung im Einzugsgebiet sowie die Struk-turvielfalt an der Quelle. Strukturell unveränderte und unversauerte Quellen besaßen im Schnitt höhere Ta-xazahlen. Einzelne Faktoren mit Einfluss auf die Besiedlung wurden in ihrer Auswirkung getestet. In Quel-len ist die Versauerung grundsätzlich besiedlungsbeschränkend und überlagert strukturelle Faktoren. Bei niedrigen pH-Werten kommt es zu verminderten Taxazahlen, allerdings sind viele Quellorganismen offen-sichtlich an eine leichte Versauerung angepasst, da in sauren Quellen der Anteil der Quellfauna höher war. Außerdem ergab die Untersuchung, dass neue und intakte Fassungen weniger Taxa und Quelltaxa aufwiesen, während bei alten und verfallenen Fassungen oft eine hohe Quelltaxazahl vorlag, so dass diese als sekundär ökologisch wertvoll zu bezeichnen sind. Die Umfeldnutzung und die Größe des Quellbereichs sind ebenfalls wichtig, so dass Quellen in Laub- und Mischwald sowie in extensivem Grünland am besten besiedelt waren. Die stärksten statistischen Zusammenhänge mit der faunistischen Besiedlung ergaben sich bei den Bewer-tungsergebnissen des Strukturverfahrens, was zeigt, dass das Verfahren realistisch bewertet. Multivariate statistische Methoden dienten der Ermittlung von Besiedlungsfaktoren und der Leitbildentwick-lung. Es ergab sich eine unterschiedliche Besiedlung bei verschiedener Hydrogeologie und Hydrochemie sowie bei verschiedenen Quelltypen. Allerdings waren die Ergebnisse nicht eindeutig, so dass die Trennung der Quelltypen nur teilweise gelang und die Quelltypen von den Grundwasserlandschaften überlagert waren. Die Faunenunterschiede verschiedener Regionen waren größer als die einer Region, so dass morphologische Quelltypen faunistisch nur innerhalb einer hydrogeologischen Einheit von Bedeutung sind. Es wurden regionale faunistische Leitarten für vier Grundwasserlandschaften genannt, wobei sich auf wenige hochstete Quellarten beschränkt wurde. Die Arbeit zeigt, dass faunistisch orientierte Leitbilder nur unter Schwierigkeiten anzugeben sind und vollständige Typuszönosen für größere Gebiete grundsätzlich in Frage zu stellen sind. Sehr häufige grundsätzliche Leitarten für Quellen silikatischer Mittelgebirge in Rheinland-Pfalz sind Crunoecia irrorata und Bythinella dunkeri.