500 Naturwissenschaften und Mathematik
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Agriculture covers one third of the world land area and has become a major source of water pollution due to its heavy reliance on chemical inputs, namely fertilisers and pesticides. Several thousands of tonnes of these chemicals are applied worldwide annually and partly reach freshwaters. Despite their widespread use and relatively unspecific modes of action, fungicides are the least studied group of pesticides. It remains unclear whether the taxonomic groups used in pesticide risk assessment are protective for non-target freshwater fungi. Fungi and bacteria are the main microbial decomposers converting allochthonous organic matter (litter) into a more nutritious food resource for leaf-shredding macroinvertebrates. This process of litter decomposition (LD) is central for aquatic ecosystem because it fuels local and downstream food webs with energy and nutrients. Effects of fungicides on decomposer communities and LD have been mainly analysed under laboratory conditions with limited representation of the multiple factors that may moderate effects in the field.
In this thesis a field study was conducted in a German vineyard area to characterise recurrent episodic exposure to fungicides in agricultural streams (chapter 2) and its effects on decomposer communities and LD (chapter 3). Additionally, potential interaction effects of nutrient enrichment and fungicides on decomposer communities and LD were analysed in a mesocosm experiment (chapter 4).
In the field study event-driven water sampling (EDS) and passive sampling with EmporeTM styrene-divinylbenzene reverse phase sulfonated disks (SDB disks) were used to assess exposure to 15 fungicides and 4 insecticides. A total of 17 streams were monitored during 4 rainfall events within the local application period of fungicides in 2012. EDS exceeded the time-weighted average concentrations provided by the SDB disks by a factor of 3, though high variability among compounds was observed. Most compounds were detected in more than half of the sites and mean and maximum peak (EDS) concentrations were under 1 and 3 µg/l, respectively. Besides, SDB disk-sampling rates and a free-software solution to derive sampling rates under time-variable exposure were provided.
Several biotic endpoints related to decomposers and LD were measured in the same sampling sites as the fungicide monitoring, coinciding with the major litter input period. Our results suggest that polar organic fungicides in streams change the structure of the fungal community. Causality of this finding was supported by a subsequent microcosm experiment. Whether other effects observed in the field study, such as reduced fungal biomass, increased bacterial density or reduced microbial LD can be attributed to fungicides remains speculative and requires further investigation. By contrast, neither the invertebrate LD nor in-situ measured gammarid feeding rates correlated with water-borne fungicide toxicity, but both were negatively associated with sediment copper concentrations. The mesocosm experiment showed that fungicides and nutrients affect microbial decomposers differently and that they can alter community structure, though longer experiments are needed to determine whether these changes may propagate to invertebrate communities and LD. Overall, further studies should include representative field surveys in terms of fungicide pollution and physical, chemical and biological conditions. This should be combined with experiments under controlled conditions to test for the causality of field observations.
The work presented in this thesis investigated interactions of selected biophysical processes that affect zooplankton ecology at smaller scales. In this endeavour, the extent of changes in swimming behaviour and fluid disturbances produced by swimming Daphnia in response to changing physical environments were quantified. In the first research question addressed within this context, size and energetics of hydrodynamic trails produced by Daphnia swimming in non-stratified still waters were characterized and quantified as a function of organisms’ size and their swimming patterns.
The results revealed that neither size nor the swimming pattern of Daphnia affects the width of induced trails or dissipation rates. Nevertheless, as the size and swimming velocity of the organisms increased, trail volume increased in proportional to the cubic power of Reynolds number, and the biggest trail volume was about 500 times the body volume of the largest daphnids. Larger spatial extent of fluid perturbation and prolonged period to decay caused by bigger trail volumes would play a significant role in zooplankton ecology, e.g. increasing the risk of predation.
The study also found that increased trail volume brought about significantly enhanced total dissipated power at higher Reynolds number, and the magnitudes of total dissipated power observed varied in the range of (1.3-10)X10-9 W.
Furthermore, this study provided strong evidence that swimming speed of Daphnia and total dissipated power in Daphnia trails exceeded those of some other selected zooplankton species.
In recognizing turbulence as an intrinsic environmental perturbation in aquatic habitats, this thesis also examined the response of Daphnia to a range of turbulence flows, which correspond to turbu-lence levels that zooplankton generally encounter in their habitats. Results indicated that within the range of turbulent intensities to which the Daphnia are likely to be exposed in their natural habitats, increasing turbulence compelled the organisms to enhance their swimming activity and swim-ming speed. However, as the turbulence increased to extremely high values (10-4 m2s-3), Daphnia began to withdraw from their active swimming behaviour. Findings of this work also demonstrated that the threshold level of turbulence at which animals start to alleviate from largely active swimming is about 10-6 m2s-3. The study further illustrated that during the intermediate range of turbu-lence; 10-7 - 10-6 m2s-3, kinetic energy dissipation rates in the vicinity of the organisms is consistently one order of magnitude higher than that of the background turbulent flow.
Swarming, a common conspicuous behavioural trait observed in many zooplankton species, is considered to play a significant role in defining freshwater ecology of their habitats from food exploitation, mate encountering to avoiding predators through hydrodynamic flow structures produced by them, therefore, this thesis also investigated implications of Daphnia swarms at varied abundance & swarm densities on their swimming kinematics and induced flow field.
The results showed that Daphnia aggregated in swarms with swarm densities of (1.1-2.3)x103 L-1, which exceeded the abundance densities by two orders of magnitude (i.e. 1.7 - 6.7 L-1). The estimated swarm volume decreased from 52 cm3 to 6.5 cm3, and the mean neighbouring distance dropped from 9.9 to 6.4 body lengths. The findings of this work also showed that mean swimming trajectories were primarily horizontal concentric circles around the light source. Mean flow speeds found to be one order of magnitude lower than the corresponding swimming speeds of Daphnia. Furthermore, this study provided evidences that the flow fields produced by swarming Daphnia differed considerably between unidirectional vortex swarming and bidirectional swimming at low and high abundances respectively.
The increasing application of titanium dioxide nanoparticles (nTiO2) entails an increased risk regarding their release to surface water bodies, where they likely co-occur with other anthropogenic stressors, such as heavy metals. Their co-occurrence may lead to an adsorption of the metal ions onto the particles. These nanoparticles often sediment, due to their agglomeration, and thus pose a risk for pelagic or benthic species. The combined toxicity of nTiO2 and heavy metals is likely influenced by the properties of both stressors (since they may alter their interaction) and by environmental parameters (e.g., organic matter, pH, ionic strength) affecting their fate.
These issues were not yet systematically examined by the recent literature. Therefore, this thesis investigated the influence of nTiO2-products with differing crystalline phase composition on the toxicity of copper (as representative for heavy metals) in presence of different organic matters using the pelagic test organism Daphnia magna.
Moreover, the duration of the stressors` interaction (=aging) likely modulates the combined toxicity. Hence, the influence of nTiO2 on copper toxicity after aging as a function of environmental parameters (i.e., organic matter, pH, ionic strength) was additionally investigated.
Finally, the transferability of the major findings to benthic species was examined using Gammarus fossarum. The present thesis discovered a reduction of the copper toxicity facilitated by nTiO2 for all assessed scenarios, while its magnitude was determined by the surface area and structure of nTiO2, the quantity and quality of organic matter as well as the aging of both stressors. The general copper toxicity reduction by nTiO2 was also transferable to benthic species, despite their potentially increased exposure due to the sedimentation of nTiO2 with adsorbed copper. These observations suggest the application of nTiO2 as remediation agent, but potential side effects (e.g., chronic toxicity, reactive oxygen species formation) require further investigations. Moreover, questions regarding the transferability to other stressors (e.g., different heavy metals, organic chemicals) and the fate of stressors adsorbed to nTiO2 in aquatic ecosystems remain open.
The increasing, anthropogenic demand for chemicals has created large environmental problems with repercussions for the health of the environment, especially aquatic ecosystems. As a result, the awareness of the public and decision makers on the risks from chemical pollution has increased over the past half-century, prompting a large number of studies in the field of ecological toxicology (ecotoxicology). However, the majority of ecotoxicological studies are laboratory based, and the few studies extrapolating toxicological effects in the field are limited to local and regional levels. Chemical risk assessment on large spatial scales remains largely unexplored, and therefore, the potential large-scale effects of chemicals may be overlooked.
To answer ecotoxicological questions, multidisciplinary approaches that transcend classical chemical and toxicological concepts are required. For instance, the current models for toxicity predictions - which are mainly based on the prediction of toxicity for a single compound and species - can be expanded to simultaneously predict the toxicity for different species and compounds. This can be done by integrating chemical concepts such as the physicochemical properties of the compounds with evolutionary concepts such as the similarity of species. This thesis introduces new, multidisciplinary tools for chemical risk assessments, and presents for the first time a chemical risk assessment on the continental scale.
After a brief introduction of the main concepts and objectives of the studies, this thesis starts by presenting a new method for assessing the physiological sensitivity of macroinvertebrate species to heavy metals (Chapter 2). To compare the sensitivity of species to different heavy metals, toxicity data were standardized to account for the different laboratory conditions. These rankings were not significantly different for different heavy metals, allowing the aggregation of physiological sensitivity into a single ranking.
Furthermore, the toxicological data for macroinvertebrates were used as input data to develop and validate prediction models for heavy metal toxicity, which are currently lacking for a wide array of species (Chapter 3). Apart from the toxicity data, the phylogenetic information of species (evolutionary relationships among species) and the physicochemical parameters for heavy metals were used. The constructed models had a good explanatory power for the acute sensitivity of species to heavy metals with the majority of the explained variance attributed to phylogeny. Therefore, the integration of evolutionary concepts (relatedness and similarity of species) with the chemical parameters used in ecotoxicology improved prediction models for species lacking experimental toxicity data. The ultimate goal of the prediction models developed in this thesis is to provide accurate predictions of toxicity for a wide range of species and chemicals, which is a crucial prerequisite for conducting chemical risk assessment.
The latter was conducted for the first time on the continental scale (Chapter 4), by making use of a dataset of 4,000 sites distributed throughout 27 European countries and 91 respective river basins. Organic chemicals were likely to exert acute risks for one in seven sites analyzed, while chronic risk was prominent for almost half of the sites. The calculated risks are potentially underestimated by the limited number of chemicals that are routinely analyzed in monitoring programmes, and a series of other uncertainties related with the limit of quantification, the presence of mixtures, or the potential for sublethal effects not covered by direct toxicity.
Furthermore, chemical risk was related to agricultural and urban areas in the upstream catchments. The analysis of ecological data indicated chemical impacts on the ecological status of the river systems; however, it is difficult to discriminate the effects of chemical pollution from other stressors that river systems are exposed to. To test the hypothesis of multiple stressors, and investigate the relative importance of organic toxicants, a dataset for German streams is used in chapter 5. In that study, the risk from abiotic (habitat degradation, organic chemicals, and nutrients enrichment) and biotic stressors (invasive species) was investigated. The results indicated that more than one stressor influenced almost all sites. Stream size and ecoregions influenced the distribution of risks, e.g., the risks for habitat degradation, organic chemicals and invasive species increased with the stream size; whereas organic chemicals and nutrients were more likely to influence lowland streams. In order to successfully mitigate the effects of pollutants in river systems, co-occurrence of stressors has to be considered. Overall, to successfully apply integrated water management strategies, a framework involving multiple environmental stressors on large spatial scales is necessary. Furthermore, to properly address the current research needs in ecotoxicology, a multidisciplinary approach is necessary which integrates fields such as, toxicology, ecology, chemistry and evolutionary biology.
Heat exchangers are used for thickening of various products or desalination of saltwater. Nevertheless, they are used as cooling unit in industries. Thereby, the stainless steel heat transferring elements get in contact with microorganism containing media, such as river water or saltwater, and corrode. After at least two years of utilization the material is covered with bacterial slime called biofilm. This process is called biofouling and causes loss in efficiency and creates huge costs depending on cleaning technique and efficiency. Cleaning a heat exchanger is very expensive and time consuming. It only can be done while the device is out of business.
Changing the surface properties of materials is the best and easiest way to lengthen the initial phase of biofilm formation. This leads to less biofouling (Mogha et al. 2014).
Thin polymer films as novel materials have less costs in production than stainless steel and are easy to handle. Furthermore, they can be functionalzed easily and can be bougth in different sizes all over the world. Because of this, they can reduce the costs of cleaning techniques and lead to a longer high efficiency state of the heat exchanger. If the efficiency of the heat exchanger decreases, the thin polymer films can be replaced.
For a successful investigation of the microbial and the process engineering challenges a cooperation of Technical University of Kaiserslautern (chair of seperation science and technology) and University of Koblenz-Landau (working goup microbiology) was established.
The aim of this work was design engineering and production of a reactor for investigation of biofouling taking place on thin polymeric films and stainless steel. Furthermore, an experimental design has to be established. Several requirements have to be applied for these tasks. Therefore, a real heat exchanger is downscaled, so the process parameters are at least comparable. There are many commercial flow cell kits available. Reducing the costs by selfassembling increased the number of samples, so there is a basis for statistic analysis. In addition, fast and minimal invasive online-in-situ microscopy and Raman spectroscopy can be performed. By creating laminary flow and using a weir we implemented homogenous inflow to the reactors. Reproduceable data on biomass and cell number were created.
The assessment of biomass and cell number is well established for drinking water analysis. Epifluorescense microscopy and gravimetric determination are the basic techniques for this work, too. Differences in cell number and biomass between surface modifications and materials are quantified and statistically analysed.
The wildtype strain Escherichia coli K12 and an inoculum of 500 ml fresh water were used to describe the biofouling of the films. Thereby, we generated data with natural bacterial community in unknown media properties and data with well known media properties, so the technical relevance of the data is given.
Free surface energy and surface roughness are the first attachment hurdles for bacteria. These parameters were measured according to DIN 55660 and DIN EN ISO 4287. The materials science data were correlated with the number of cells and the biomass. This correlation acts as basal link of biofouling as biological induced parameter to the material properties. Material properties for reducing the biofouling can be prospected.
By using Raman spectroscopy as a cutting edge method future investigations could be shortened. If biomass or cell number can be linked with the spectra, new functional materials can be investigated in a short time.
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 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.
Global crop production increased substantially in recent decades due to agricultural intensification and expansion and today agricultural areas occupy about 38% of Earth’s terrestrial surface - the largest use of land on the planet. However, current high-intensity agricultural practices fostered in the context of the Green Revolution led to serious consequences for the global environment. Pesticides, in particular, are highly biologically active substances that can threaten the ecological integrity of aquatic and terrestrial ecosystems. Although the global pesticide use increases steadily, our field-data based knowledge regarding exposure of non-target ecosystems such as surface waters is very restricted. Available studies have by now been limited to spatially restricted geographical areas or had rather specific objectives rendering the extrapolation to larger spatial scales questionable.
Consequently, this thesis evaluated based on four scientific publications the exposure, effects, and regulatory implications of particularly toxic insecticides` concentrations detected in global agricultural surface waters. FOCUS exposure modelling was used to characterise the highly specific insecticide exposure patterns and to analyse the resulting implications for both monitoring and risk assessment (publication I). Based on more than 200,000 scientific database entries, 838 peer-reviewed studies finally included, and more than 2,500 sites in 73 countries, the risks of agricultural insecticides to global surface waters were analysed by means of a comprehensive meta-analysis (publication II). This meta-analysis evaluated whether insecticide field concentrations exceed legally accepted regulatory threshold levels (RTLs) derived from official EU and US pesticide registration documents and, amongst others, how risks depend on insecticide development over time and stringency of environmental regulation. In addition, an in-depth analysis of the current EU pesticide regulations provided insights into the level of protection and field relevance of highly elaborated environmental regulatory risk assessment schemes (publications III and IV).
The results of this thesis show that insecticide surface water exposure is characterized by infrequent and highly transient concentration peaks of high ecotoxicological relevance. We thus argue in publication I that sampling based on regular intervals is inadequate for the detection of insecticide surface water concentrations and that traditional risk assessment concepts based on all insecticide concentrations including non-detects lead to severely biased results and critical underestimations of risks. Based on these considerations, publication II demonstrates that out of 11,300 measured insecticide concentrations (MICs; i.e., those actually detected and quantified), 52.4% (5,915 cases; 68.5%) exceeded the RTL for either water (RTLSW) or sediments. This indicates a substantial risk for the biological integrity of global water resources as additional analyses on pesticide effects in the field clearly evidence that the regional aquatic biodiversity is reduced by approximately 30% at pesticide concentrations equalling the RTLs. In addition, publication II shows that there is a complete lack of scientific monitoring data for ~90% of global cropland and that both the actual insecticide contamination of surface waters and the resulting ecological risks are most likely even greater due to, for example, inadequate sampling methods employed in the studies and the common occurrence of pesticide mixtures. A linear model analysis identified that RTLSW exceedances depend on the catchment size, sampling regime, sampling date, insecticide substance class, and stringency of countries` environmental regulations, as well as on the interactions of these factors. Importantly, the risks are significantly higher for newer-generation insecticides (i.e., pyrethroids) and are high even in countries with stringent environmental regulations. Regarding the latter, an analysis of the EU pesticide regulations revealed critical deficiencies and the lack of protectiveness and field-relevance for current presumed highly elaborated FOCUS exposure assessment (publication IV) and overall risk assessment schemes (publication III). Based on these findings, essential risk assessment amendments are proposed.
In essence, this thesis analyses the agriculture–environment linkages for pesticides at the global scale and it thereby contributes to a new research frontier in global ecotoxicology. The overall findings substantiate that agricultural insecticides are potential key drivers for the global freshwater biodiversity crisis and that the current regulatory risk assessment approaches for highly toxic anthropogenic chemicals fail to protect the global environment. This thesis provides an integrated view on the environmental side effects of global high-intensity agriculture and alerts that beside worldwide improvements to current pesticide regulations and agricultural pesticide application practices, the fundamental reformation of conventional agricultural systems is urgently needed to meet the twin challenges of providing sufficient food for a growing human population without destroying the ecological integrity of global ecosystems essential to human existence.
Engineered nanoparticles are emerging pollutants. Their increasing use in commercial products suggests a similar increase of their concentrations in the environment. Studying the fate of engineered colloids in the environment is highly challenging due to the complexity of their possible interactions with the main actors present in aquatic systems. Solution chemistry is one of the most central aspects. In particular, the interactions with dissolved organic matter (DOM) and with natural colloids are still weakly understood.
The aim of this work was to further develop the dedicated analytical methods required for investigating the fate of engineered colloids in environmental media as influenced by DOM. Reviewing the literature on DOM interactions with inorganic colloids revealed that a systematic characterization of both colloids and DOM, although essential, lacks in most studies and that further investigations on the fractionation of DOM on the surface of engineered colloids is needed. Another knowledge gap concerns the effects of DOM on the dynamic structure of colloid agglomerates. For this question, analytical techniques dedicated to the characterization of agglomerates in environmental media at low concentrations are required. Such techniques should remain accurate at low concentrations, be specific, widely matrix independent and free of artefact due to sample preparation. Unfortunately, none of the currently available techniques (microscopy, light scattering based methods, separation techniques etc.) fulfills these requirements.
However, a compromise was found with hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry (HDC-ICP-MS). This method has the potential to size inorganic particles in complex media in concentration ranges below ppb and is element specific; however, its limitations were not systematically explored. In this work, the potential of this method has been further explored. The simple size separation mechanism ensures a high flexibility of the elution parameters and universal calibration can be accurately applied to particles of different compositions and surface chemistries. The most important limitations of the method are its low size resolution and the effect of the particle shape on the retention factor. The implementation of HDC coupled to single particle ICP-MS (HDC-SP-ICP-MS) offers new possibilities for the recognition of particle shape and hence the differentiation between primary particles and homoagglomerates. Therefore, this coupling technique is highly attractive for monitoring the effects of DOM on the stability of colloids in complex media. The versatility of HDC ICP MS is demonstrated by its successful applications to diverse samples. In particular, it has been used to investigate the stability of citrate stabilized silver colloids in reconstituted natural water in the presence of different types of natural organic matter. These particles were stable for at least one hour independently of the type of DOM used and the pH, in accordance with a coauthored publication addressing the stability of silver colloids in the River Rhine. Direct monitoring of DOM adsorption on colloids was not possible using UV and fluorescence detectors. Preliminary attempts to investigate the adsorption mechanism of humic acids on silver colloids using fluorescence spectroscopy suggest that fluorescent molecules are not adsorbed on silver particles. Several solutions for overcoming the encountered difficulties in the analysis of DOM interactions are proposed and the numerous perspectives offered by further developments and applications of HDC-(SP)-ICP-MS in environmental sciences are discussed in detail.
Field margins are often the only remaining habitats of various wild plant species in agricultural landscapes. However, due to their proximity to agricultural fields, the vegetation of field margins can be affected by agrochemicals applied to the crop fields. The aim of this thesis was to investigate the individual and combined effects of herbicide, insecticide and fertilizer inputs on the plant community of a field margin. Therefore, a 3-year field experiment with a randomized block design including seven treatments (H: herbicide, I: insecticide, F: fertilizer, H+I, F+I, F+H and F+H+I) and one control was conducted on a low-production meadow. Each treatment was replicated 8 times in 8 m x 8 m plots with a distance of 2 m between each plot. The fertilizer rates (25 % of the field rate) and pesticide rates (30 % of the field rate) used for the plot applications were consistent with realistic average input rates (overspray + drift) in the first meter of a field margin directly adjacent to a wheat field.
The study revealed that fertilizer and herbicide misplacements in field margins are major factors that affect the natural plant communities of these habitats. In total, 20 of the 26 abundant species on the study site were significantly affected by the fertilizer and herbicide treatment. The fertilizer promoted plants with high nutrient uptake and decreased the frequencies of small species. The herbicide caused a nearly complete disappearance of three species directly after the first application, whereas sublethal effects (e.g., phytotoxic effects and reduced seed productions of up to 100 %) were observed for the other affected species. However, if field margins are exposed to repeated agrochemical applications over several years, then such sublethal effects (particularly reproduction effects) also reduce the population size of plant species significantly, as observed in this study.
Significant herbicide-fertilizer interaction effects were also detected and could not be extrapolated from individual effects. The fertilizer and herbicide effects became stronger over time, leading to shifts in plant community compositions after three years and to a 15 % lower species diversity than in the control. The insecticide significantly affected the frequencies of two plant species (1 positively and 1 negatively). The results of the experiment suggest that a continuous annual agrochemical application on the study site would cause further plant community shifts and would likely lead to the disappearance of certain affected plants. A clear trend of increasing grass dominance at the expense of flowering herbs was detected. This finding corresponds well with monitoring data from field margins near the study site.
Although herbicide risk assessment aims to protect non-target plants in off-field habitats from adverse effects, reproduction effects and combined effects are currently not considered. Furthermore, no regulations for fertilizer applications next to field margins exist and thus, fertilizer misplacements in field margins are likely to occur and to interact with herbicide effects.
Adaptations of the current risk assessment, a development of risk mitigation measures (e.g., in-field buffers) for the application of herbicides and fertilizers, and general management measures for field margins are needed to restore and conserve plant diversity in field margins in agricultural landscapes.
This study explored the question whether greenhouse gas mitigation projects in Namibia could be initiated through local economic development programmes. In particular, research was done on whether the Clean Development Mechanism (CDM) of the Kyoto Protocol could play an essential role in the promotion of such mitigation projects.
In a first step supporting and inhibiting factors (potential for mitigation projects, business and investment climate, institutions, etc.) were discussed, which have a negative or positive influence on mitigation projects. In a second step the mind-set of climate and energy experts as well as of local economic development experts and practitioners was analysed with regard to the research questions. To this end, 229 questionnaires, 28 interviews and the output of a focus group discussion with 20 participants were evaluated. Additionally, the author conducted a real life case study to investigate the practicability of initiating greenhouse gas mitigation projects through local economic development efforts. Parallel to the development of an economic development strategy in the Namibian region of Otjozondjupa, the potential for greenhouse gas mitigation projects was explored. Based on the outcome of this investigation project ideas were developed and their potential socio-economic impact was evaluated. Promising projects were then included into the development strategy.
Due to various factors such as the complexity of CDM, low greenhouse gas emissions in Namibia, the low price of emission rights and insufficient financial means it is unlikely that CDM projects can be initiated through local economic development initiatives in Namibia. However, many stakeholders consider the idea of interlinking mitigation projects and local economic development initiatives favourably as long as such projects support the broader objectives of those initiatives. This research has shown that locally initiated mitigation projects do not contribute much to employment or income generation at the local level in Namibia. Thus, national strategic objectives should be considered, such as improving access to electricity to all strata of society or becoming less dependent on electricity imports. This requires, however, that local economic development strategies also cover the energy sector, that local governments are willing and capacitated to initiate mitigation projects, that national and local public institutions work together more closely, that national and local economic framework conditions are improved so as to attract private investments, and that the experiences and interests of the relevant stakeholders are considered throughout the project development process.
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.
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.
The transport of pesticides from agricultural land into surface waters via diffuse entry pathways such as runoff is a major threat to aquatic ecosystems and their communities. Although certain risk mitigation measures are currently stipulated during pesticide product authorisation, further approaches might be needed to manage hot spots of pesticide exposure. Such a management is, for example, required by the European Union- directive for the sustainable use pesticides (2009/128/EC).
The need for mitigation measures was investigated within the present thesis at stream sites draining an arable and a vineyard region in Germany by characterising pesticide exposure following edge-of-field runoff and (expected) effects on the aquatic macroinvertebrates. The results of these field studies showed, that streams in both regions were exposed to pesticide concentrations suggesting effects on the macroinvertebrate community. In the arable region the observed toxicity was mainly attributed to the insecticides lambda-cyhalothrin (in the water-phase samples) and alpha-cypermethrin (in the suspended particle samples), whereas in the vineyard region fungicides were most important. Furthermore stream water and suspended particles sampled in the vineyard region showed critical copper concentrations, which might cause ecotoxicological effects in the field. In addition to pesticide exposure, in the arable region also the effects on aquatic macroinvertebrates were assessed in the field. Generally, invertebrate fauna was dominated by pesticide-tolerant species, which suggested a high pesticide exposure at almost all sites. The elevated levels of suspended particle contamination in terms of maximum toxic units per sample (logTUMax > -2) reflect also this result. At two sites that received high aqueous-phase entries of the insecticide lambda-cyhalothrin (logTUMax > -0.6), the abundance and number of sensitive species (indicated by the SPEcies At Risk index) decreased during the pesticide application period. In contrast, at sites characterised by low water-phase toxicity (logTUMax < -3.5), no acute significant negative effects on macroinvertebrates were observed. In conclusion these data showed that in both regions the implementation of risk mitigation measures is needed to protect the aquatic communities.
To mitigate runoff-related pesticide entries, riparian buffer strips are often recommended. However, the mitigating influence with increasing buffer strip width could not be demonstrated for riparian buffers which were already present in the arable and vineyard region. This result was attributed in the vineyard region to the high number of paved field paths associated with artificial erosion rills, which concentrate and rapidly transport receiving edge-of-field runoff in stream direction. Consequently the pesticide reduction efficiency of buffer strips is considerably reduced. We assumed that a similar process occurred in the arable region, due to a high number of erosion rills, which complicate a laminar sheet flow of edge-of-field runoff through the riparian buffer strip. Additionally also the presence of ephemeral drainage ditches, which led surface runoff from the agricultural fields to the streams may have contributed to observed pesticide entries despite wide buffers.
Effective risk mitigation measures should address these identified most important input pathways in the study areas. As possible measures the implementation of grassed field paths and vegetated ditches or wetlands were suggested. In general also the improvement of currently present riparian buffer strips regarding their efficiency to reduce pesticide runoff entries should be taken into account. In conclusion the results of the field studies underline the importance that risk mitigation measures are identified specifically for the respective pollution situation in stream catchments. To facilitate this process, a user guide was developed within the present thesis for identifying appropriate mitigation measures at high-risk sites. Based on a survey of exposure relevant landscape parameter a set of risk mitigation measures is suggested that focus on the specific pollution situation. Currently the guide includes 12 landscape- and six application-related measures and presents an overview of these measures" efficiency to reduce pesticide entries via runoff and spray drift, their feasibility and expected acceptability to farmers. Based on this information the user can finally choose the mitigation measures for implementation. The present guide promotes the practical implementation of appropriate risk mitigation measures in pesticide-polluted streams, and thus the protection of aquatic stream communities against pesticide entries.
By the work presented in this thesis, the CH4 emissions of the River Saar were quantified in space and time continuously and all relevant processes leading to the observed pattern were identified. The direct comparison between reservoir zones and free-flowing intermediate reaches revealed, that the reservoir zones are CH4 emission hot spots and emitted over 90% of the total CH4. On average, the reservoir zones emitted over 80 times more CH4 per square meter than the intermediate reaches between dams (0.23 vs. 19.7 mol CH4 m-2 d-1). The high emission rates measured in the reservoir zones fall into the range of emissions observed in tropical reservoirs. The main reason for this is the accumulation of thick organic rich sediments and we showed that the net sedimentation rate is an excellent proxy for estimating ebullitive emissions. Within the hot spot zones, the ebullitive flux enhanced also the diffusive surface emissions as well as the degassing emissions at dams.
To resolve the high temporal variability, we developed an autonomous instrument for continuous measurements of the ebullition rate over long periods (> 4 weeks). With this instrument we could quantify the variability and identify the relevant trigger mechanisms. At the Saar, ship-lock induces surges and ship waves were responsible for over 85% of all large ebullition events. This dataset was also used to determine the error associated with short sampling periods and we found that with sampling periods of 24 hours as used in other studies, the ebullition rates were systematically underestimated by ~50%. Measuring the temporal variability enabled us to build up a conceptual framework for estimating the temporal pattern of ebullition in other aquatic systems. With respect to the contribution of freshwater systems to the global CH4 emissions, hot spot emission sites in impounded rivers have the potential to increase the current global estimate by up to 7%.
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.
The conservation of groundwater ecosystems requires an assessment and evaluation scheme that shows the state of the ecosystem. Consequently, faunal and microbial criteria are required for groundwater monitoring, in addition to physico-chemical analyses. To proof the adequacy of the application of groundwater organisms for the biological assessment of groundwater quality, an extensive sampling collection of various groundwater systems was accomplished between 2002 and 2009 in Germany. Key aspects were the examination of the indicator potential of groundwater communities towards surface-groundwater interactions and anthropogenic impacts, as well as the analysis of stygofaunal distribution patterns, as a base and reference for a faunal assessment scheme of groundwater systems. The sampling design considered local, regional, and biogeographic conditions. To test the indicator potential of groundwater organisms on a local and regional scale, groundwater systems in Nordrhein-Westfalen (NRW) and Baden-Württemberg (BW) were examined. The faunal and microbial data from unconsolidated aquifers (Erftgebiet, NRW) show the sensitivity of groundwater organisms against land use effects, e.g. extensive agriculture. Data analyses revealed positive correlations of organic material (estimated amount of detritus, TOC) and nitrate with faunal abundance, species richness, diversity and the proportions of stygoxene species. Moreover, the bacterial abundance and diversity in the groundwater of the Erftgebiet was high compared to oligotrophic groundwater systems, indicating an effect of surface influence due to agricultural land use. The groundwater colonization in the Alb-Donau-Kreis (BW) was analyzed for regional effects (landscape, type of aquifer, hydrogeology) and local effects (comparing single wells). The results show that the fauna reflects the strength of the hydrological exchange on different spatial scales. Furthermore, the fauna reflects the interaction of regional and local conditions. Accordingly, the diversity and abundance of groundwater organisms was influenced by the high connectivity of the karst and unconsolidated alluvial aquifers, the type of land use, covering layers of soil, the age of groundwater, and the sampling depths. In general, faunal and microbial data of the Alb-Donau-Kreis are characteristic for oligotrophic, oligoalimonic groundwaters. The large scale analyses of stygofaunal distribution patterns revealed significant biogeographical differences of the communities. These community patterns of the groundwater fauna do not coincide with existing classification schemes defined for surface landscapes or freshwater systems. The largest differences between faunal surface and subsurface distribution patterns were found between the groundwater of northern and southern Germany and the foothills of the central mountain ranges - all of them regions shaped by the last ice ages.
In accordance with the faunal data assessed in groundwater, four different stygoregions were defined that are populated by distinct faunal assemblages. These are 1) the "Northern lowlands", 2) the "Central mountain ranges", 3) the "South-western mountain ranges", and 4) the "Southern mountain ranges and northern alps". The study corroborates that stygofaunal and microbial communities are an adequate tool for the qualitative assessment and monitoring of groundwater ecosystems. The best indicators to detect anthropogenic impacts on groundwater ecosystems are the faunal diversity, abundance, the proportions of stygobitic (obligate groundwater species) and stygoxene species (species not obligate for groundwater), and the bacterial abundance. The development of an ecologically based groundwater assessment and management, is crucial for the conservation of our groundwater ecosystems and thus, healthy drinking water. The defintion of "stygoregions" is an important base for the development of an assessment and reference scheme for groundwater ecosystems. The assessment of the ecological state of groundwater systems must be conducted on local scale, because the strength of the local hydrological influence determines the amount of food and oxygen as well as stygoxene animals within the aquifer, and thus shapes the local groundwater communities. Nevertheless, information of the biogeographic and regional conditions is needed as a reference for the type of species and abundances that potentially can occur in certain groundwater systems.
Galerucinae, Latreille 1802 is the second largest subgroup of chrysomelidae. 1837 Chervrolat described the taxon Ootheca, which has originally only one listed species. Nearly 200 years all galerucinae with a "compact" bodyshape, a broad pronotum, a convex dorsum , short antennae and short legs were assigned to Ootheca. When I started a revision of Ootheca, this taxon included 38 species. Comparing morphological characters of the exoskeleton combined with the depiction/description of characteristic structures of the male genitalia allowed a detailed description of the genus Ootheca and its species. After the revision 9 valid species remained in Ootheca, 4 are described to be new, 13 species were transferred to other valid described genera and 10 species remained, because of a lack of unambiguous assignment. The examination of the median lobe additionally enables me to describe three sister taxa: Oothecoides (6 species), Ootibia (5 species ) und Oosagitta (6 species).
This habilitation thesis deals with the effects of toxicants on freshwater ecosystems and considers different toxicant classes (pesticides, organic toxicants, salinity) and biotic endpoints (taxonomic community structure, trait community structure, ecosystem functions).
The thesis comprises 12 peer-reviewed international publications on these topics. All of the related studies rely on mesocosm or field investigations, or the analysis of field biomonitoring or chemical monitoring data. Publications I and II are devoted to passive sampling of a neonicotinoid insecticide and polycyclic aromatic hydrocarbons (PAHs), respectively. They show that biofouling and a diffusion-limiting membrane can reduce the sampling rate of the pulsed insecticide exposure and that receiving phases of different thicknesses can be used to assess the kinetic regime during field deployment of passive samplers. Publications III to VI mainly focus on trait-based approaches to reveal toxicant effects on invertebrates in streams. An overview on the framework and several applications of a trait-based approach to detect effects of pesticides (SPEARpesticides index) are given in publication III. Publication IV describes the development of a trait database for South-East Australian stream invertebrates and its successful application in the adaptation of SPEARpesticides as well as the development of a salinity index. Moreover, a conceptual model for the future development of trait-based biomonitoring indices is proposed. Publication V reports a mesocom study on the effects of a neonicotinoid insecticide on field-realistic invertebrate communities. The insecticide had long-term effects on the invertebrate communities, which were only detected when grouping the taxa according to their life-history traits. A comprehensive field study employing different pesticide sampling methods including passive sampling and biomonitoring of the invertebrate and microbial communities is presented in publication VI. The study did not find pesticide-induced changes in the microbial communities, but detected adverse effects of current-use pesticides on the invertebrate communities using the trait-based SPEARpesticides index. This index is also applied in a meta-analysis on thresholds for the effects of pesticides on invertebrate communities in publication VII. It is shown that there is a similar dose-response relationship between SPEARpesticides and pesticide toxicity over different biogeographical regions and continents. In addition, the thresholds for effects of pesticides are lower than derived from most mesocosm studies and than considered in regulatory pesticide risk assessment. The publications VIII to X use statistical data analysis approaches to examine effects of toxicants in freshwater ecosystems. Using governmental monitoring data on 331 organic toxicants monitored monthly in 4 rivers over 11 years, publication VIII finds that organic toxicants frequently occurred in concentrations envisaging acute toxic effects on invertebrates and algae even in large rivers. Insecticides and herbicides were the chemical groups mainly contributing to the ecotoxicological risk. Publication IX introduces a novel statistical method based on a similarity index to estimate thresholds for the effects of toxicants or other stressors on ecological communities. The application of the method for deriving thresholds for salinity, heavy metals and pesticides in streams is presented in three case studies. Publication X tackles the question of interactive effects between different toxicants using data from a field study on stream invertebrates in 24 sites of South-East Australia. Both salinity and pesticides exhibited statistically significant effects on the invertebrate communities, but no interaction between the stressors was found. Moreover, salinity acted on a higher taxonomical level than pesticides suggesting evolutionary adaptation of stream invertebrates compared to pesticide stress. Publications XI and XII concentrate on the effects of toxicants on biodiversity, ecosystem functions and ecosystem services, with publication XI summarising different studies related to the ecological risk assessment for these endpoints. A field study on the effects of pesticides and salinity on the ecosystem functions of allochthonous organic matter decomposition, gross primary production and ecosystem respiration is presented in publication XII. Both pesticides and salinity reduced the breakdown of allochthonous organic matter, whereas no effects on the other ecosystem functions were detected. A chapter following these publications synoptically discusses all studies of this habilitation thesis and draws general conclusions. It is stressed that in order to advance the understanding of effects of toxicants on freshwater ecosystems more ecological realism is needed in ecotoxicological approaches and that the spatiotemporal extent of toxicant effects needs more scrutiny.