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Institute
- Fachbereich 7 (78) (remove)
Leaf litter breakdown is a fundamental process in aquatic ecosystems, being mainly mediated by decomposer-detritivore systems that are composed of microbial decomposers and leaf-shredding, detritivorous invertebrates. The ecological integrity of these systems can, however, be disturbed, amongst others, by chemical stressors. Fungicides might pose a particular risk as they can have negative effects on the involved microbial decomposers but may also affect shredders via both waterborne toxicity and their diet; the latter by toxic effects due to dietary exposure as a result of fungicides’ accumulation on leaf material and by negatively affecting fungal leaf decomposers, on which shredders’ nutrition heavily relies. The primary aim of this thesis was therefore to provide an in-depth assessment of the ecotoxicological implications of fungicides in a model decomposer-detritivore system using a tiered experimental approach to investigate (1) waterborne toxicity in a model shredder, i.e., Gammarus fossarum, (2) structural and functional implications in leaf-associated microbial communities, and (3) the relative importance of waterborne and diet-related effects for the model shredder.
Additionally, knowledge gaps were tackled that were related to potential differences in the ecotoxicological impact of inorganic (also authorized for organic farming in large parts of the world) and organic fungicides, the mixture toxicity of these substances, the field-relevance of their effects, and the appropriateness of current environmental risk assessment (ERA).
In the course of this thesis, major differences in the effects of inorganic and organic fungicides on the model decomposer-detritivore system were uncovered; e.g., the palatability of leaves for G. fossarum was increased by inorganic fungicides but deteriorated by organic substances. Furthermore, non-additive action of fungicides was observed, rendering mixture effects of these substances hardly predictable. While the relative importance of the waterborne and diet-related effect pathway for the model shredder seems to depend on the fungicide group and the exposure concentration, it was demonstrated that neither path must be ignored due to additive action. Finally, it was shown that effects can be expected at field-relevant fungicide levels and that current ERA may provide insufficient protection for decomposer-detritivore systems. To safeguard aquatic ecosystem functioning, this thesis thus recommends including leaf-associated microbial communities and long-term feeding studies using detritus feeders in ERA testing schemes, and identifies several knowledge gaps whose filling seems mandatory to develop further reasonable refinements for fungicide ERA.
Agricultural land-use may lead to brief pulse exposures of pesticides in edge-of-field streams, potentially resulting in adverse effects on aquatic macrophytes, invertebrates and ecosystem functions. The higher tier risk assessment is mainly based on pond mesocosms which are not designed to mimic stream-typical conditions. Relatively little is known on exposure and effect assessment using stream mesocosms.
Thus the present thesis evaluates the appliacability of the stream mesocosms to mimic stream-typical pulse exposures, to assess resulting effects on flora and fauna and to evaluate aquatic-terrestrial food web coupling. The first objective was to mimic stream-typical pulse exposure scenarios with different durations (≤ 1 to ≥ 24 hours). These exposure scenarios established using a fluorescence tracer were the methodological basis for the effect assessment of an herbicide and an insecticide. In order to evaluate the applicability of stream mesocosms for regulatory purposes, the second objective was to assess effects on two aquatic macrophytes following a 24-h pulse exposure with the herbicide iofensulfuron-sodium (1, 3, 10 and 30 µg/L; n = 3). Growth inhibition of up to 66 and 45% was observed for the total shoot length of Myriophyllum spicatum and Elodea canadensis, respectively. Recovery of this endpoint could be demonstrated within 42 days for both macrophytes. The third objective was to assess effects on structural and functional endpoints following a 6-h pulse exposure of the pyrethroid ether etofenprox (0.05, 0.5 and 5 µg/L; n = 4). The most sensitive structural (abundance of Cloeon simile) and functional (feeding rates of Asellus aquaticus) endpoint revealed significant effects at 0.05 µg/L etofenprox. This concentration was below field-measured etofenprox concentrations and thus suggests that pulse exposures adversely affect invertebrate populations and ecosystem functions in streams. Such pollutions of streams may also result in decreased emergence of aquatic insects and potentially lead to an insect-mediated transfer of pollutants to adjacent food webs. Test systems capable to assess aquatic-terrestrial effects are not yet integrated in mesocosm approaches but might be of interest for substances with bioaccumulation potential. Here, the fourth part provides an aquatic-terrestrial model ecosystem capable to assess cross-ecosystem effects. Information on the riparian food web such as the contribution of aquatic (up to 71%) and terrestrial (up to 29%) insect prey to the diet of the riparian spider Tetragnatha extensa was assessed via stable isotope ratios (δ13C and δ15N). Thus, the present thesis provides the methodological basis to assess aquatic-terrestrial pollutant transfer and effects on the riparian food web.
Overall the results of this thesis indicate, that stream mesocosms can be used to mimic stream-typical pulse exposures of pesticides, to assess resulting effects on macrophytes and invertebrates within prospective environmental risk assessment (ERA) and to evaluate changes in riparian food webs.
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.
Today’s agriculture heavily relies on pesticides to manage diverse pests and maximise crop yields. Despite elaborate regulation of pesticide use based on a complex environmental risk assessment (ERA) scheme, the widespread use of these biologically active compounds has been shown to be a threat to the environment. For surface waters, pesticide exposure has been observed to exceed safe concentration levels and negatively impact stream ecology leading to the question whether current ERA schemes ensure a sustainable use of pesticides. To answer this, the large-scale “Kleingewässer-Monitoring” (KgM) assessed the occurrence of pesticides and related effects in 124 streams throughout Germany, Central Europe, in 2018 and 2019.
Based on five scientific publications originating from the KgM, this thesis evaluated pesticide exposure in streams, ecological effects and the regulatory implications. More than 1,000 water samples were analysed for over 100 pesticide analytes to characterise occurrence patterns (publication 1). Measured concentrations and effects were used to validate the exposure and effect concentrations predicted in the ERA (publication 2). By jointly analysing real-world pesticide application data and measured pesticide mixtures in streams, the disregard of environmental pesticide mixtures in the ERA was evaluated (publication 3). The toxic potential of mixtures in stream water was additionally investigated using suspect screening for 395 chemicals and a battery of in-vitro bioassays (publication 4). Finally, the results from the KgM stream monitoring were used to assess the capability to identify pesticide risks in governmental monitoring programmes (publication 5).
The results of this thesis reveal the widespread occurrence of pesticides in non-target stream ecosystems. The water samples contained a variety of pesticides occurring in complex mixtures predominantly in short-term peaks after rainfall events (publications 1 & 4). Respective pesticide concentration maxima were linked to declines in vulnerable invertebrate species and exceeded regulatory acceptable concentrations in about 80% of agricultural streams, while these thresholds were still estimated partly insufficient to protect the invertebrate community (publication 2). The co-occurrence of pesticides in streams led to a risk underestimated in the single substance-oriented ERA by a factor of about 3.2 in realistic worst-case scenarios, which is further exacerbated by a high frequency at which non-target organism are exposed to pesticides (publication 3). Stream water samples taken after rainfall caused distinct effects in bioassays which were only explainable to a minor extent by the many analytes, indicating the relevance of unknown chemical or biological mixture components (publication 4). Finally, the regulatory monitoring of surface waters under the Water Framework Directive (WFD) was found to significantly underestimate pesticide risks, as about three quarters of critical pesticides and more than half of streams at risk were overlooked (publication 5).
Essentially, this thesis involves a new level of validation of the ERA of pesticides in aquatic ecosystems by assessing pesticide occurrence and environmental impacts at a scale so far unique. The overall results demonstrate that the current agricultural use of pesticides leads to significant impacts on stream ecology that go beyond the level tolerated under the ERA. This thesis identified the underestimation of pesticide exposure, the potential insufficiency of regulatory thresholds and the general inertia of the authorisation process as the main causes why the ERA fails to meet its objectives. To achieve a sustainable use of pesticides, the thesis proposes substantial refinements of the ERA. Adequate monitoring programmes such as the KgM, which go beyond current government monitoring efforts, will continue to be needed to keep pesticide regulators constantly informed of the validity of their prospective ERA, which will always be subject to uncertainty.
Groundwater is essential for the provision of drinking water in many areas around the world. The ecosystem services provided by groundwater-related organisms are crucial for the quality of groundwater-bearing aquifers. Therefore, if remediation of contaminated groundwater is necessary, the remediation method has to be carefully selected to avoid risk-risk trade-offs that might impact these valuable ecosystems. In the present thesis, the ecotoxicity of the in situ remediation agent Carbo-Iron (a composite of zero valent nano-iron and active carbon) was investigated, an estimation of its environmental risk was performed, and the risk and benefit of a groundwater remediation with Carbo-Iron were comprehensively analysed.
At the beginning of the work on the present thesis, a sound assessment of the environmental risks of nanomaterials was impeded by a lack of guidance documents, resulting in many uncertainties on selection of suitable test methods and a low comparability of test results from different studies with similar nanomaterials. The reasons for the low comparability were based on methodological aspects of the testing procedures before and during the toxicity testing. Therefore, decision trees were developed as a tool to systematically decide on ecotoxicity test procedures for nanomaterials. Potential effects of Carbo-Iron on embryonic, juvenile and adult life stages of zebrafish (Danio rerio) and the amphipod Hyalella azteca were investigated in acute and chronic tests. These tests were based on existing OECD and EPA test guidelines (OECD, 1992a, 2013a, 2013b; US EPA, 2000) to facilitate the use of the obtained effect data in the risk assessment. Additionally, the uptake of particles into the test organisms was investigated using microscopic methods. In zebrafish embryos, effects of Carbo-Iron on gene expression were investigated. The obtained ecotoxicity data were complemented by studies with the waterflea Daphnia magna, the algae Scenedesmus vacuolatus, larvae of the insect species Chironomus riparius and nitrifying soil microorganisms.
In the fish embryo test, no passage of Carbo-Iron particles into the perivitelline space or the embryo was observed. In D. rerio and H. azteca, Carbo-Iron was detected in the gut at the end of exposure, but no passage into the surrounding tissue was detected. Carbo-Iron had no significant effect on soil microorganisms and on survival and growth of fish. However, it had significant effects on the growth, feeding rate and reproduction of H. azteca and on survival and reproduction in D. magna. Additionally, the development rate of C. riparius and the cell volume of S. vacuolatus were negatively influenced.
A predicted no effect concentration of 0.1 mg/L was derived from the ecotoxicity studies based on the no-effect level determined in the reproduction test with D. magna and an assessment factor of 10. It was compared to measured and modelled environmental concentrations for Carbo-Iron after application to an aquifer contaminated with chlorohydrocarbons in a field study. Based on these concentrations, risk quotients were derived. Additionally, the overall environmental risk before and after Carbo-Iron application was assessed to verify whether the chances for a risk-risk trade-off by the remediation of the contaminated site could be minimized. With the data used in the present study, a reduced environmental risk was identified after the application of Carbo-Iron. Thus, the benefit of remediation with Carbo-Iron outweighs potential negative effects on the environment.
Pelagic oxyclines, the transition zone between oxygen rich surface waters and oxygen depleted deep waters, are a common characteristic of eutrophic lakes during summer stratification. They can have tremendous effects on the biodiversity and the ecosystem functioning of lakes and, to add insult to injury, are expected to become more frequent and more pronounced as climate warming progresses. On these grounds, this thesis endeavors to advance the understanding of formation, persistence, and consequences of pelagic oxyclines: We test, whether the formation of metalimnetic oxygen minima is intrinsically tied to a locally enhanced oxygen consuming process, investigate the relative importance of vertical physical oxygen transport and biochemical oxygen consumption for the persistence of pelagic oxyclines, and finally assess their potential consequences for whole lake cycling. To pursue these objectives, the present thesis nearly exclusively resorts to in situ measurements. Field campaigns were conducted at three lakes in Germany featuring different types of oxyclines and resolved either a short (hours to days) or a long (weeks to months) time scale. Measurements comprised temperature, current velocity, and concentrations of oxygen and reduced substances in high temporal and vertical resolution. Additionally, vertical transport was estimated by applying the eddy correlation technique within the pelagic region for the first time. The thesis revealed, that the formation of metalimnetic oxygen minima does not necessarily depend on locally enhanced oxygen depletion, but can solely result from gradients and curvatures of oxygen concentration and depletion and their relative position to each other. Physical oxygen transport was found to be relevant for oxycline persistence when it considerably postponed anoxia on a long time scale. However, its influence on oxygen dynamics was minor on short time scales, although mixing and transport were highly variable. Biochemical consumption always dominated the fate of oxygen in pelagic oxyclines. It was primarily determined by the oxidative breakdown of organic matter originating from the epilimnion, whereas in meromictic lakes, the oxidation of reduced substances dominated. Beyond that, the results of the thesis emphasize that pelagic oxyclines can be a hotspot of mineralization and, hence, short-circuit carbon and nutrient cycling in the upper part of the water column. Overall, the present thesis highlights the importance of considering physical transport as well as biochemical cycling in future studies.
World’s ecosystems are under great pressure satisfying anthropogenic demands, with freshwaters being of central importance. The Millennium Ecosystem Assessment has identified anthropogenic land use and associated stressors as main drivers in jeopardizing stream ecosystem functions and the
biodiversity supported by freshwaters. Adverse effects on the biodiversity of freshwater organisms, such as macroinvertebrates, may propagate to fundamental ecosystem functions, such as organic matter breakdown (OMB) with potentially severe consequences for ecosystem services. In order to adequately protect and preserve freshwater ecosystems, investigations regarding potential and observed as well as direct and indirect effects of anthropogenic land use and associated stressors (e.g. nutrients, pesticides or heavy metals) on ecosystem functioning and stream biodiversity are needed. While greater species diversity most likely benefits ecosystem functions, the direction and magnitude of changes in ecosystem functioning depends primarily on species functional traits. In this context, the functional diversity of stream organisms has been suggested to be a more suitable predictor of changes in ecosystem functions than taxonomic diversity.
The thesis aims at investigating effects of anthropogenic land use on (i) three ecosystem functions by anthropogenic toxicants to identify effect thresholds (chapter 2), (ii) the organic matter breakdown by three land use categories to identify effects on the functional level (chapter 3) and (iii)on the stream community along an established land-use gradient to identify effects on the community level.
In chapter 2, I reviewed the literature regarding pesticide and heavy metal effects on OMB, primary production and community respiration. From each reviewed study that met inclusion criteria, the toxicant concentration resulting in a reduction of at least 20% in an ecosystem function was standardized based on laboratory toxicity data. Effect thresholds were based on the relationship between ecosystem functions and standardized concentration-effect relationships. The analysis revealed that more than one third of pesticide observations indicated reductions in ecosystem functions at concentrations that are assumed being protective in regulation. However, high variation within and between studies hampered the derivation of a concentration-effect relationship and thus effect thresholds.
In chapter 3, I conducted a field study to determine the microbial and invertebrate-mediated OMB by deploying fine and coarse mesh leaf bags in streams with forested, agricultural, vinicultural
and urban riparian land use. Additionally, physicochemical, geographical and habitat parameters were monitored to explain potential differences in OMB among land use types and sites. Regarding results, only microbial OMB differed between land use types. The microbial OMB showed a negative relationship with pH while the invertebrate-mediated OMB was positively related to tree cover. OMB responded to stressor gradients rather than directly to land use.
In chapter 4, macroinvertebrates were sampled in concert with leaf bag deployment and after species identification (i) the taxonomic diversity in terms of Simpson diversity and total taxonomic
richness (TTR) and (ii) the functional diversity in terms of bio-ecological traits and Rao’s quadratic entropy was determined for each community. Additionally, a land-use gradient was established and the response of the taxonomic and functional diversity of invertebrate communities along this gradient was investigated to examine whether these two metrics of biodiversity are predictive for the rate of OMB. Neither bio-ecological traits nor the functional diversity showed a significant relationship with
OMB. Although, TTR decreased with increasing anthropogenic stress and also the community structure and 26 % of bio-ecological traits were significantly related to the stress gradient, any of these shifts propagated to OMB.
Our results show that the complexity of real-world situations in freshwater ecosystems impedes the effect assessment of chemicals and land use for functional endpoints, and consequently our potential to predict changes. We conclude that current safety factors used in chemical risk assessment may not be sufficient for pesticides to protect functional endpoints. Furthermore, simplifying real-world stressor gradients into few land use categories was unsuitable to predict and quantify losses in OMB. Thus, the monitoring of specific stressors may be more relevant than crude land use categories to detect effects on ecosystem functions. This may, however, limit the large scale assessment of the status of OMB. Finally, despite several functional changes in the communities the functional diversity over several trait modalities remained similar. Neither taxonomic nor functional diversity were suitable predictors of OMB. Thus, when understanding anthropogenic impacts on the linkage between biodiversity and ecosystem functioning is of main interest, focusing on diversity metrics that are clearly linked to the stressor in question (Jackson et al. 2016) or integrating taxonomic and functional metrics (Mondy et al., 2012) might enhance our predictive capacity.
The European landscape is dominated by intensive agriculture which leads to widespread impact on the environment. The frequent use of agricultural pesticides is one of the major causes of an ongoing decline in flower-visiting insects (FVIs). The conservation of this ecologically diverse assemblage of mobile, flying insect species is required by international and European policy. To counteract the decrease in species numbers and their abundances, FVIs need to be protected from anthropogenic stressors. European pesticide risk assessment was devised to prevent unacceptable adverse consequences of pesticide use on FVIs. However, there is an ongoing discussion by scientists and policy-makers if the current risk assessment actually provides adequate protection for FVI species.
The first main objective of this thesis was to investigate pesticide impact on FVI species. The scientific literature was reviewed to identify groups of FVIs, summarize their ecology, and determine their habitat. This was followed by a synthesis of studies about the exposure of FVIs in their habitat and subsequent effects. In addition, the acute sensitivity of one FVI group, bee species, to pesticides was studied in laboratory experiments.
The second main objective was to evaluate the European risk assessment for possible deficits and propose improvements to the current framework. Regulatory documents were screened to assess the adequacy of the guidance in place in light of the scientific evidence. The suitability of the honey bee Apis mellifera as the currently only regulatory surrogate species for FVIs was discussed in detail.
The available scientific data show that there are far more groups of FVIs than the usually mentioned bees and butterflies. FVIs include many groups of ecologically different species that live in the entire agricultural landscape. Their habitats in crops and adjacent semi-natural areas can be contaminated by pesticides through multiple pathways. Environmentally realistic exposure of these habitats can lead to severe effects on FVI population parameters. The laboratory studies of acute sensitivity in bee species showed that pesticide effects on FVIs can vary greatly between species and pesticides.
The follow-up critical evaluation of the European FVI risk assessment revealed major shortcomings in exposure and effect assessment. The honey bee proved to be a sufficient surrogate for bee species in lower tier risk assessment. Additional test species may be chosen for higher tier risk assessment to account for ecological differences. This thesis shows that the ecology of FVIs should generally be considered to a greater extent to improve the regulatory process. Data-driven computational approaches could be used as alternative methods to incorporate ecological trait data in spatio-temporal scenarios. Many open questions need to be answered by further research to better understand FVI species and promote necessary changes to risk assessment. In general, other FVI groups than bees need to be investigated. Furthermore, comprehensive data on FVI groups and their ecology need to be collected. Contamination of FVI habitat needs to be linked to exposure of FVI individuals and ecologically complex effects on FVI populations should receive increased attention. In the long term, European FVI risk assessment would benefit from shifting its general principles towards more scientifically informed regulatory decisions. This would require a paradigm shift from arbitrary assumptions and unnecessarily complicated schemes to a substantiated holistic framework.
Flowering habitats to enhance biodiversity and pest control services in agricultural landscapes
(2015)
Meeting growing demands for agricultural products requires management solutions that enhance food production, whilst minimizing negative environmental impacts. Conventional agricultural intensification jeopardizes farmland biodiversity and associated ecosystem services through excessive anthropogenic inputs and landscape simplification. Agri-environment schemes (AES) are commonly implemented to mitigate the adverse effects of conventional intensification on biodiversity. However the moderate success of such schemes thus far would strongly benefit from more explicit goals regarding ecosystem service provisioning. Providing key resources to beneficial organisms may improve their abundance, fitness, diversity and the ecosystem services they provide. With targeted habitat management, AES may synergistically enhance biodiversity and agricultural production and thus contribute to ecological intensification. We demonstrate that sown perennial wildflower strips, as implemented in current AES focusing on biodiversity conservation also benefit biological pest control in nearby crops (Chapter 2).
Comparing winter wheat fields adjacent to wildflower strips with fields without wildflower strips we found strongly reduced cereal leaf beetle (Oulema sp.) density and plant damage near wildflower strips. In addition, winter wheat yield was 10 % higher when fields adjoined wildflower strips. This confirms previous assumptions that wildflower strips, known for positive effects on farmland biodiversity, can also enhance ecosystem services such as pest control and the positive correlation of yield with flower abundance and diversity suggests that floral resources are key. Refining sown flower strips for enhanced service provision requires mechanistic understanding of how organisms benefit from floral resources. In climate chamber experiments investigating the impact of single and multiple flowering plant species on fitness components of three key arthropod natural enemies of aphids, we demonstrate that different natural enemies benefit differently from the offered resources (Chapter 3).
Some flower species were hereby more valuable to natural enemies than others overall. Additionally, the mixture with all flowers generally performed better than monocultures, yet with no transgressive overyielding. By explicitly tailoring flower strips to the requirements of key natural enemies of crop pests we aimed to maximise natural enemy mediated pest control in winter wheat (Chapter 4)and potato (Chapter 5) crops.
Respecting the manifold requirements of diverse natural enemies but not pests, in terms of temporal and spatial provisioning of floral, extra floral and structural resources, we designed targeted annual flower strips that can be included in crop rotation to support key arthropods at the place and time they are needed. Indeed, field experiments revealed that cereal leaf beetle density and plant damage in winter wheat can be reduced by 40 % to 61 % and aphid densities in potatoes even by 77 %, if a targeted flower strip is sown into the field. These effects were not restricted to the vicinity of flower strips and, in contrast to fields without flower strip, often prevented action thresholds from being reached. This suggests that targeted flower strips could replace insecticides. All adult natural enemies were enhanced inside targeted flower strips when compared to control strips. Yet, spillover to the field was restricted to key natural enemies such as ground beetles (winter wheat), hoverflies (potato) and lacewings (winter wheat and potato), suggesting their dominant role in biological control. In potatoes, targeted flower strips also enhanced hoverfly species richness in strips and crop, highlighting their additional benefits for diversity.
The present results provide more insights into the mechanisms underlying conservation biological control and highlight the potential of tailored habitat management for ecological intensification.
Although most plastic pollution originates on land, current research largely remains focused on aquatic ecosystems. Studies pioneering terrestrial microplastic research have adapted analytical methods from aquatic research without acknowledging the complex nature of soil. Meanwhile, novel methods have been developed and further refined. However, methodical inconsistencies still challenge a comprehensive understanding of microplastic occurrence and fate in and on soil. This review aims to disentangle the variety of state-of-the-art sample preparation techniques for heterogeneous solid matrices to identify and discuss best-practice methods for soil-focused microplastic analyses. We show that soil sampling, homogenization, and aggregate dispersion are often neglected or incompletely documented. Microplastic preconcentration is typically performed by separating inorganic soil constituents with high-density salt solutions. Not yet standardized but currently most used separation setups involve overflowing beakers to retrieve supernatant plastics, although closed-design separation funnels probably reduce the risk of contamination. Fenton reagent may be particularly useful to digest soil organic matter if suspected to interfere with subsequent microplastic quantification. A promising new approach is extraction of target polymers with organic solvents. However, insufficiently characterized soils still impede an informed decision on optimal sample preparation. Further research and method development thus requires thorough validation and quality control with well-characterized matrices to enable robust routine analyses for terrestrial microplastics.
Population genetic structure in European Hyalodaphnia species: Monopolization versus gene flow
(2012)
Cyclic parthenogens displays an alternation of asexual and sexual reproduction which has consequences for the genetic structure of these organisms. The clonal diversity of cyclic parthenogenetic zooplankton populations is influenced by the size of the dormant egg bank, i.e., the amount of sexually produced dormant eggs that assembled in the sediment, as these dormant eggs contribute new genetic variants to the populations. Further, the clonal diversity is impacted by clonal erosion over time, which reduces the number of different clones through stochastic and selective processes. Although freshwater invertebrates are good dispersers through their dormant stages, the influence of gene flow is assumed to be negligible, as the local population successfully monopolizes the available resources. As these populations reach carrying capacity fast due to the asexual reproduction, the first colonizing individuals are able to successfully establish in the habitat, resulting in a priority effect which hinders the invasion of new genotypes. Due to clonal selection and sexual reproduction a population will locally adapt over time and will establish a dormant egg bank which facilitates the fast re-colonization after a hostile period. This thesis evaluates the processes altering the population genetic structure of cyclic parthenogenetic zooplankton with a special focus on the concepts of monopolization as well as the counteracting effects of gene flow, using large-lake Daphnia species. Thirty-two variable microsatellite DNA markers were developed and a subset of twelve markers was evaluated regarding their suitability for species assignment and hybrid class detection. With this marker set and an additional mitochondrial DNA marker forty-four natural European populations of the species D. cucullata, D. galeata and D. longispina were studied. In D. galeata, most populations were characterized by low clonal diversities which suggest high influence from clonal erosion over the growing season and a low contribution from the dormant egg bank. Further, recent expansions as well as gene flow were detected, probably caused by the anthropogenic alteration of freshwater habitats, in particular eutrophication of many European lakes. D. longispina and D. cucullata revealed a different genetic structure compared to D. galeata, with high genetic differentiation among populations. This indicates low levels of effective gene flow which is in line with the predictions of monopolization. Further, high clonal diversities were found in populations of the two taxa, suggesting a high contribution from the dormant egg bank while clonal erosion was often not detectable. In D. longispina, mitochondrial data revealed an ancient expansion which was probably initiated by the formation of glacial lakes after the last ice age.
In addition, in D. longispina not only clonal diversity but also genetic diversity was high, indicating that during the build-up of the studied populations the influence from gene flow was probably high. To better understand the processes that act on early populations the population build-up in regard to the temporal advantage of clones during invasion succession was experimentally studied and revealed that priority effects shape population structure of Daphnia species. However, in certain cases the highly superior clones resulted in the extinction of inferior clones independent of the temporal advantage the single clones had.
This clearly shows that not only the time of succession is important but also the competitive strength. rnIn conclusion, the results obtained show that the population genetic structure in cyclic parthenogenetic zooplankton species is impacted by various processes. In addition to earlier studies, which mainly focus on local adaptation, clonal erosion and the size of the dormant egg bank to understand population genetic structure, this thesis could show that gene flow may be effective as well. During population build-up the advantage of early arriving individuals does not necessarily predict the outcome of population assembly, as additional genotypes may contribute to the population. Finally, the genetic structure of established populations may be severely impacted by effective gene flow, if severe environmental changes alter the habitat of the locally adapted population.
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 global problematic issue of the olive oil industry is in its generation of large amounts of olive mill wastewater (OMW). The direct discharge of OMW to the soil is very common which presents environmental problems for olive oil producing countries. Both, positive as well as negative effects on soil have been found in earlier studies. Therefore, the current study hypothesized that whether beneficial effects or negative effects dominate depends on the prevailing conditions before and after OMW discharge to soil. As such, a better understanding of the OMW-soil interaction mechanisms becomes essential for sustainable safe disposal of OMW on soil and sustainable soil quality.
A field experiment was carried out in an olive orchard in Palestine, over a period of 24 months, in which the OMW was applied to the soil as a single application of 14 L m-2 under four different environmental conditions: in winter (WI), spring (SP), and summer with and without irrigation (SUmoist and SUdry). The current study investigated the effects of seasonal conditions on the olive mill wastewater (OMW) soil interaction in the short-term and the long-term. The degree and persistence of soil salinization, acidification, accumulation of phenolic compounds and soil water repellency were investigated as a function of soil depth and time elapsed after the OMW application. Moreover, the OMW impacts on soil organic matter SOM quality and quantity, total organic carbon (SOC), water-extractable soil organic carbon (DOC), as well as specific ultraviolet absorbance analysis (SUVA254) were also investigated for each seasonal application in order to assess the degree of OMW-OM decomposition or accumulation in soil, and therefore, the persisting effects of OMW disposal to soil.
The results of the current study demonstrate that the degree and persistence of relevant effects due to OMW application on soil varied significantly between the different seasonal OMW applications both in the short-term and the long-term. The negative effects of the potentially hazardous OMW residuals in the soil were highly dependent on the dominant transport mechanisms and transformation mechanisms, triggered by the ambient soil moisture and temperature which either intensified or diminished negative effects of OMW in the soil during and after the application season. The negative effects of OMW disposal to the soil decreased by increasing the retention time of OMW in soil under conditions favoring biological activity. The moderate conditions of soil moisture and temperature allowed for a considerable amount of applied OMW to be biologically degraded, while the prolonged application time under dry conditions and high temperature resulted in a less degradable organic fraction of the OMW, causing the OMW constituents to accumulate and polymerize without being degraded. Further, the rainfall during winter season diminished negative effects of OMW in the soil; therefore, the risk of groundwater contamination by non-degraded constituents of OMW can be highly probable during the winter season.
Statistical eco(-toxico)logy
(2017)
Freshwaters are of immense importance for human well-being.
Nevertheless, they are currently facing unprecedented levels of threat from habitat loss and degradation, overexploitation, invasive species and
pollution.
To prevent risks to aquatic ecosystems, chemical substances, like agricultural pesticides, have to pass environmental risk assessment (ERA) before entering the market.
Concurrently, large-scale environmental monitoring is used for surveillance of biological and chemical conditions in freshwaters.
This thesis examines statistical methods currently used in ERA.
Moreover, it presents a national-scale compilation of chemical monitoring data, an analysis of drivers and dynamics of chemical pollution in streams and, provides a large-scale risk assessment by combination with results from ERA.
Additionally, software tools have been developed to integrate different datasets used in ERA.
The thesis starts with a brief introduction to ERA and environmental monitoring and gives an overview of the objectives of the thesis.
Chapter 2 addresses experimental setups and their statistical analyses using simulations.
The results show that current designs exhibit unacceptably low statistical power, that statistical methods chosen to fit the type of data provide higher power and that statistical practices in ERA need to be revised.
In chapter 3 we compiled all available pesticide monitoring data from Germany.
Hereby, we focused on small streams, similar to those considered in ERA and used threshold concentrations derived during ERA for a large-scale assessment of threats to freshwaters from pesticides.
This compilation resulted in the most comprehensive dataset on pesticide exposure currently available for Germany.
Using state-of-the-art statistical techniques, that explicitly take the limits of quantification into account, we demonstrate that 25% of small streams are at threat from pesticides.
In particular neonicotinoid pesticides are responsible for these threats.
These are associated with agricultural intensity and can be detected even at low levels of agricultural use.
Moreover, our results indicated that current monitoring underestimates pesticide risks, because of a sampling decoupled from precipitation events.
Additionally, we provide a first large-scale study of annual pesticide exposure dynamics.
Chapters 4 and 5 describe software solutions to simplify and accelerate the integration of data from ERA, environmental monitoring and ecotoxicology that is indispensable for the development of landscape-level risk assessment.
Overall, this thesis contributes to the emerging discipline of statistical ecotoxicology and shows that pesticides pose a large-scale threat to small streams.
Environmental monitoring can provide a post-authorisation feedback to ERA.
However, to protect freshwater ecosystems ERA and environmental monitoring need to be further refined and we provide software solutions to utilise existing data for this purpose.
During olive oil production, large amounts of olive mill wastewater (OMW) are generated within a short period of time. OMW has a high nutrient content and could serve as fertilizer when applied on land. However, its fatty and phenolic constituents have adverse effects on soil properties. It is still unknown how seasonal fluctuations in temperature and precipitation influence the fate and effect of OMW components on soil properties in a long-term perspective. An appropriate application season could mitigate negative consequences of OMW while preserving its beneficial effects. In order to investigate this, 14 L OMW m-2 were applied to different plots of an olive plantation in winter, spring, and summer respectively. Hydrological soil properties (water drop penetration time, hydraulic conductivity, dynamic contact angle), physicochemical parameters (pH, EC, soluble ions, phenolic compounds, organic matter), and biological degradation (bait-lamina test) were measured to assess the soil state after OMW application. After one rainy season following OMW application, the soil quality of summer treatments significantly decreased compared to the control. This was particularly apparent in a three-times lower biodegradation performance, ten-fold higher soil water repellency, and a four-fold higher content of phenolic compounds. The soil properties of winter treatments were comparable to the control, which demonstrated the recovery potential of the soil ecosystem. Spring treatments resulted in an intermediate response compared to summer and winter treatments, but without any precipitation following OMW application. Significant accumulation or leaching effects to deeper soil were not observed. Therefore, the direct application of legally restricted OMW amounts to soil is considered acceptable during the moist seasons. Further research is needed to quantify the effect of spring treatments and to gain further insight into the composition and kinetics of organic OMW constituents in the soil.
The use of agricultural plastic covers has become common practice for its agronomic benefits such as improving yields and crop quality, managing harvest times better, and increasing pesticide and water use efficiency. However, plastic covers are suspected of partially breaking down into smaller debris and thereby contributing to soil pollution with microplastics. A better understanding of the sources and fate of plastic debris in terrestrial systems has so far been hindered by the lack of adequate analytical techniques for the mass-based and polymer-selective quantification of plastic debris in soil. The aim of this dissertation was thus to assess, develop, and validate thermoanalytical methods for the mass-based quantification of relevant polymers in and around agricultural fields previously covered with fleeces, perforated foils, and plastic mulches. Thermogravimetry/mass spectrometry (TGA/MS) enabled direct plastic analyses of 50 mg of soil without any sample preparation. With polyethylene terephthalate (PET) as a preliminary model, the method limit of detection (LOD) was 0.7 g kg−1. But the missing chromatographic separation complicated the quantification of polymer mixtures. Therefore, a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method was developed that additionally exploited the selective solubility of polymers in specific solvents prior to analysis. By dissolving polyethylene (PE), polypropylene (PP), and polystyrene (PS) in a mixture of 1,2,4-trichlorobenzene and p-xylene after density separation, up to 50 g soil became amenable to routine plastic analysis. Method LODs were 0.7–3.3 mg kg−1, and the recovery of 20 mg kg−1 PE, PP, and PS from a reference loamy sand was 86–105%. In the reference silty clay, however, poor PS recoveries, potentially induced by the additional separation step, suggested a qualitative evaluation of PS. Yet, the new solvent-based Py-GC/MS method enabled a first exploratory screening of plastic-covered soil. It revealed PE, PP, and PS contents above LOD in six of eight fields (6% of all samples). In three fields, PE levels of 3–35 mg kg−1 were associated with the use of 40 μm thin perforated foils. By contrast, 50 μm PE films were not shown to induce plastic levels above LOD. PP and PS contents of 5–19 mg kg−1 were restricted to single observations in four fields and potentially originated from littering. The results suggest that the short-term use of thicker and more durable plastic covers should be preferred to limit plastic emissions and accumulation in soil. By providing mass-based information on the distribution of the three most common plastics in agricultural soil, this work may facilitate comparisons with modeling and effect data and thus contribute to a better risk assessment and regulation of plastics. However, the fate of plastic debris in the terrestrial environment remains incompletely understood and needs to be scrutinized in future, more systematic research. This should include the study of aging processes, the interaction of plastics with other organic and inorganic compounds, and the environmental impact of biodegradable plastics and nanoplastics.
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.
Aquatic macrophytes can contribute to the retention of organic contaminants in streams, whereas knowledge on the dynamics and the interaction of the determining processes is very limited. The objective of the present study was thus to assess how aquatic macrophytes influence the distribution and the fate of organic contaminants in small vegetated streams. In a first study that was performed in vegetated stream mesocosms, the peak reductions of five compounds were significantly higher in four vegetated stream mesocosms compared to a stream mesocosm without vegetation. Compound specific sorption to macrophytes was determined, the mass retention in the vegetated streams, however, did not explain the relationship between the mitigation of contaminant peaks and macrophyte coverage. A subsequent mesocosm study revealed that the mitigation of peak concentrations in the stream mesocosms was governed by two fundamentally different processes: dispersion and sorption. Again, the reductions of the peak concentrations of three different compounds were in the same order of magnitude in a sparsely and a densely vegetated stream mesocosm, respectively, but higher compared to an unvegetated stream mesocosm. The mitigation of the peak reduction in the sparsely vegetated stream mesocosm was found to be fostered by longitudinal dispersion as a result of the spatial distribution of the macrophytes in the aqueous phase. The peak reduction attributable to longitudinal dispersion was, however, reduced in the densely vegetated stream mesocosm, which was compensated by compound-specific but time-limited and reversible sorption to macrophytes. The observations on the reversibility of sorption processes were subsequently confirmed by laboratory experiments. The experiments revealed that sorption to macrophytes lead to compound specific elimination from the aqueous phase during the presence of transient contaminant peaks in streams. After all, these sorption processes were found to be fully reversible, which results in the release of the primarily adsorbed compounds, once the concentrations in the aqueous phase starts to decrease. Nevertheless, the results of the present thesis demonstrate that the processes governing the mitigation of contaminant loads in streams are fundamentally different to those already described for non-flowing systems. In addition, the present thesis provides knowledge on how the interaction of macrophyte-induced processes in streams contributes to mitigate loads of organic contaminants and the related risk for aquatic environments.
Assessment of bat activity in agricultural environments and the evaluation of the risk of pesticides
(2013)
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.
Factors triggering the ecotoxicity of metal-based nanoparticles towards aquatic invertebrates
(2015)
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
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.
Worldwide one third to one half of the freshwater crayfish species are threatened with population decline or extinction. Besides habitat deterioration, pollution, and other man-made environmental changes, invasive species and pathogens are major threats to the survival of European crayfish species. Freshwater crayfish are the largest freshwater invertebrates and strongly influence the structure of food webs. The disappearance of crayfish from a water body may change the food web and could have dramatic consequences for an ecosystem.rnOne goal in modern species conservation strategies is the conservation of genetic diversity, since genetic diversity is an advantage for the long-term survival of a species. The main aim of my thesis was to reveal the genetic structure and to identify genetic hotspots of the endangered noble crayfish (Astacus astacus) throughout Europe (part 1 of my thesis). Since the most significant threat to biodiversity of European crayfish species is the crayfish plague pathogen Aphanomyces astaci I studied new aspects in the distribution of A. astaci (part two of my thesis). The results serve as a basis for future conservation programs for freshwater crayfish. In the first part of my thesis I conducted a phylogeographic analysis of noble crayfish using mitochondrial DNA and nuclear microsatellite data. With these methods I aimed to identify its genetic hotspots and to reconstruct the recolonization history of central Europe by this species. I detected high genetic diversities in southestern Europe indicating that noble crayfish outlasted the cold climate phases during the Pleistocene in this region (Appendix 1). Because of the high genetic diversity found there, southeastern Europe is of particular importance for the conservation of noble crayfish. The mitochondrial DNA analysis points to a bifurcated colonization process from the eastern Black Sea basin to a) the North Sea and to b) the Baltic Sea basin (Appendix 2). A second independent refugium that was localized on the Western Balkans did not contribute to the colonization of central Europe. Furthermore, I found that the natural genetic structure is dissolved, probably due to the high human impact on the distribution of noble crayfish (e.g. artificial translocation). In the second part of this thesis using real-time PCR I identified calico crayfish (Orconectes immunis) as the fourth North American crayfish species to be carrier of the agent of the crayfish plague (Appendix 3). Furthermore I detected the crayfish plague pathogen in American spiny-cheek crayfish (Orconectes limosus) and native narrow-clawed crayfish (Astacus leptodactylus) in the lower Danube in Romania (Appendix 4). The distribution of infected spiny-cheek crayfish poses a threat to the native biodiversity in southeastern Europe and shows the high invasion potential of this crayfish species. Moreover, I found that even the native narrow-clawed crayfish in the Danube Delta, about 970 km downstream of the current invasion front of American crayfish, is a carrier of A. astaci (Appendix 5). This finding is of high importance, as the native species do not seem to suffer from the infection. In Appendix 6 I elucidate demonstrate that the absence of the crayfish plague agent is the most likely explanation for the coexistence of populations of European and American crayfish in central Europe. In my thesis I show that the common assumption that all North American crayfish are carrier of A. astaci and that all native crayfish species die when infected with A. astaci does not hold true. The studies presented in my thesis reveal new aspects that are crucial for native crayfish conservation: 1) The genetic diversity of noble crayfish is highest in southeastern Europe where noble crayfish outlasted the last glacial maximum in at least two different refugia. 2) Not all American crayfish populations are carrier of A. astaci and 3) not all Europen crayish populations die shortly after being infected with the crayfish plague pathogen.rnTo conserve native crayfish species and their (genetic) diversity in the long term, further introductions of American crayfish into European waters must be avoided. However, the introduction will only decrease if the commercial trade with non-indigenous crayfish species is prohibited.
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
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.
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 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 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.
Mathematical Modelling of GIS Tailored GUI Design with the Application of Spatial Fuzzy Logic
(2014)
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.
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.
Natural pest control and pollination are important ecosystem services for agriculture. They can be supported by organic farming and by seminatural habitats at the local and landscape scale.
The potential of seminatural habitats to support predatory flies (chapters 2 and 3) and bees(chapter 7) at the local and landscape scale was investigated in seminatural habitats. Predatory flies were more abundant in woody habitats and positively related to landscape complexity. The diversity and the abundance of honey and wild bees were positively related to the supply of flowers offered in the seminatural habitats.
The influence of organic farming, adjacent seminatural habitats and landscape complexity on pest control (chapter 4) and pollination (chapter 6) was investigated in 18 pumpkin fields. Organic farming lacked strong effects both on the pest control and on the pollination of pumpkin.
Pest control is best supported at the local scale by the flower abundance in the adjacent habitat. The flower supply positively affected the density of natural enemies and tended to reduce aphid densities in pumpkin fields.
Pumpkin provides a striking example for a dominant role of wild pollinators for pollination success, because bumble bees are the key pollinators of pumpkin in Germany, despite a higher visitation frequency of honey bees. Pollination is best supported by landscape complexity. Bumble bee visits and as a result pollen delivery in pumpkin were negatively related to the dominance of agricultural land in the surrounding landscape.
The influence of aphid density (chapter 8) and pollination (chapter 5) on pumpkin yield was evaluated. Pumpkin yields were not affected by aphid densities observed in the pumpkin fields and not limited by pollination at the current levels of bee visitation.
In conclusion, especially seminatural habitats, that provide diverse, continuous floral resources, are important for natural enemies and pollinators. A sufficient proportion of different seminatural habitat types in agricultural landscapes should be maintained and restored. Thereby natural enemies such as predatory flies, wild pollinators such as bumble bees, and the pest control and pollination provided by them can be supported.
Grapevine growers have struggled with defending their crops against pests and diseases since the domestication of grapevine over 6000 ears ago. Since then, new growing methods paired with a better nderstanding of the ecological processes in the vineyard ecosystem continue to improve quality and quantity of grape harvests. In this thesis I am describing the effects of two recent innovations in viticulture on pest and beneficial arthropods in vineyards; Fungus-resistant grapevine cultivars (PIWIs) and the pruning system semi-minimal pruned hedge (SMPH). The SMPH pruning system allows for a drastic reduction of manual labor in the vineyard, and PIWIs are resistant to two of the most common fungal diseases of grapevine and therefore allow a drastic reduction of fungicide applications compared to conventional varieties. Heavy use of pesticides is linked to a number of problems, including pollution of waterways, negative effects on human health, and biodiversity loss. Here, I studied the effects of fungicide reduction and minimal pruning on arthropods that are beneficial for natural pest suppression in the vineyard ecosystem such as predatory mites, spiders, ants, earwigs, and lacewings. All of these groups either benefitted from the reduction of fungicide sprayings or were not significantly affected. Structural changes in the canopy of SMPH grapevines altered the microclimate in the canopy which in turn influenced some of the arthropods living in it. Overall, my findings suggest that PIWIs and SMPH, both in combination or separately, improve conditions for natural pest control. This adds to other advantages of these innovative management practices such as a reduction in production cost and a smaller impact on the environment.
Invasive species often have a significant impact on the biodiversity of ecosystems and the species native to it. One of the worst invaders worldwide is Aphanomyces astaci, the causative agent of the crayfish plague, an often fatal disease to crayfish species not native to North America. Aphanomyces astaci originates from North America and was introduced to Europe in the midst of the 19th century. Since then, it spread throughout Europe diminishing the European crayfish populations. The overall aim of this thesis was to evaluate the threat that A. astaci still poses to European crayfish species more than 150 years after its introduction to Europe. In the first part of the thesis, crayfish specimens, which are available in the German pet trade, were tested for infections with A. astaci. Around 13% of the tested crayfish were clearly infected with A. astaci. The study demonstrated the potential danger the pet trade poses for biodiversity through the import of alien species and their potential pathogens, in general. In the second part of the thesis, the A. astaci infection prevalence of crayfish species in wild populations in Europe was tested. While the stone crayfish, Austropotamobius torrentium, showed high susceptibility to different haplogroups of A. astaci, the narrow-clawed crayfish, Astacus leptodactylus, was able to survive infections, even by haplogroup B, which is considered to be highly virulent. In the last part of the thesis, A. astaci was traced back to its original distribution area of North America. While the crayfish plague never had such a devastating effect on crayfish in North America as it had in Europe, the reasons for the success of invasive crayfish within North America are not yet fully understood. It is possible that A. astaci increases the invasion success of some crayfish species. Several populations of the rusty crayfish, Orconectes rusticus, in the Midwest of North America were confirmed to be infected with A. astaci and a new genotype was identified, possibly indicating that each crayfish host is vector of a unique A. astaci genotype, even in North America. Overall, the present thesis provides evidence that A. astaci is still a major threat to the crayfish species indigenous to Europe. Crayfish mass mortalities still occur in susceptible crayfish species like A. torrentium even 150 years after the first introduction of A. astaci. While there are some indications for increased resistances through processes of co-evolution, the continuous introduction of crayfish species to Europe threatens to cause new outbreaks of the crayfish plague through the parallel introduction of new, highly virulent A. astaci strains.
Soil organic matter (SOM) is a key component responsible for sequestration of organic molecules in soil and regulation of their mobility in the environment. The basic structure of SOM is a supramolecular assembly responding dynamically to the environmental factors and the presence of interacting molecules. Despite of the advances in the understanding of sorption processes, the relation between sorbate molecules, SOM supramolecular structure and its dynamics is limited. An example of a dynamic nature of SOM is a physicochemical matrix aging that is responsible for SOM structural arrangement. The underlying process of the physicochemical aging is the formation of water molecule bridges (WaMB) between functional groups of molecular segments. Since WaMB influence the stiffness of SOM structure, it was hypothesized that formation of WaMB contributes to the sequestration of organic molecules. However, this hypothesis has not been tested experimentally until now. Furthermore, the knowledge about the influence of organic molecules on WAMB is based solely on computer modeling studies. In addition, the influence of organic molecules on some physical phases forming SOM is not well understood. Especially, the interactions between organic molecules and crystalline phases represented by aliphatic crystallites, are only presumed. Thus, the investigation of those interactions in unfractioned SOM is of high importance.
In order to evaluate the involvement of WaMB in the sequestration of organic molecules and to increase our understanding about interactions of organic chemicals with WaMB or aliphatic crystallites, the following hypotheses were tested experimentally. 1) Similarly to crystalline phases in synthetic polymers, aliphatic crystallites, as a part of SOM, cannot be penetrated by organic molecules. 2) The stability of WaMB is determined by the ability of surrounding molecules to interact with water forming WaMB. 3) WaMB prevent organic molecules to leave the SOM matrix and contribute thus to their immobilization. In order to test the hypotheses 1 and 2, a set of experiments including treatment of soils with chosen chemicals was prepared. Interaction abilities of these chemicals were characterized using interaction parameters from the Linear Solvation Energy Relationship theory. WaMB characteristics were monitored using Differential Scanning Calorimetry (DSC) allowing to measure the WaMB thermal stability and the rigidity of SOM matrix; which in turn was determined by the heat capacity change. In addition, DSC and 13C NMR spectroscopy assessed thermal properties and the structure of aliphatic crystallites. The spiking of samples with a model compound, phenol, and measurements of its desorption allowed to link parameters of the desorption kinetics with WaMB characteristics.
The investigation showed that the WaMB stability is significantly reduced by the presence of molecules with H-donor/acceptor interaction abilities. The matrix rigidity associated with WaMB was mainly influenced by the McGowan’s volume of surrounding molecules, suggesting the importance of dispersion forces. The desorption kinetics of phenol followed a first order model with two time constants. Both of them showed a relation with WaMB stability, which supports the hypothesis that WaMB contribute to the physical immobilization of organic molecules. The experiments targeted to the crystallites revealed their structural change from the ordered to the disordered state, when in contact with organic chemicals. This manifested in their melting point depression and the decrease of overall crystallinity. Described structural changes were caused by molecules interacting with specific as well as non-specific forces, which suggests that aliphatic crystallites can be penetrated and modified by molecules with a broad range of interaction abilities.
This work shows that chosen organic molecules interact with constituents of SOM as exemplified on WaMB and aliphatic crystallites, and cause measurable changes of their structure and properties. These findings show that the relevance of aliphatic crystallites for sorption in soil may have been underestimated. The results support the hypothesis that physicochemical matrix aging significantly contributes to the immobilization of organic chemicals in SOM.
Despite the significant presence of neuroactive substances in the environment, bioassays that allow to detect diverse groups of neuroactive mechanisms of action are not well developed and not properly integrated into environmental monitoring and chemical regulation. Therefore, there is a need to develop testing methods which are amenable for fast and high-throughput neurotoxicity testing. The overall goal of this thesis work is to develop a test method for the toxicological characterization and screening of neuroactive substances and their mixtures which could be used for prospective and diagnostic hazard assessment.
In this thesis, the behavior of zebrafish embryos was explored as a promising tool to distinguish between different neuroactive mechanisms of action. Recently, new behavioral tests have been developed including photomotor response (PMR), locomotor response (LMR) and spontaneous tail coiling (STC) tests. However, the experimental parameters of these tests lack consistency in protocols such as exposure time, imaging time, age of exposure, endpoint parameter etc. To understand how experimental parameters may influence the toxicological interpretation of behavior tests, a systematic review of existing behavioral assays was conducted in Chapter 2. Results show that exposure concentration and exposure duration highly influenced the comparability between different test methods and the spontaneous tail coiling (STC) test was selected for further testing based on its relative higher sensitivity and capacity to detect neuroactive substances (Chapter 2).
STC is the first observable motor activity generated by the developing neural network of the embryo which is assumed to occur as a result of the innervation of the muscle by the primary motor neurons. Therefore, STC could be a useful endpoint to detect effect on the muscle innervation and also the on the whole nervous system. Consequently, important parameters of the STC test were optimized and an automated workflow to evaluate the STC with the open access software KNIME® was developed (Chapter 3).
To appropriately interpret the observed effect of a single chemical and especially mixture effects, requires the understanding of toxicokinetics and biotransformation. Most importantly, the biotransformation capacity of zebrafish embryos might be limited and this could be a challenge for assessment of chemicals such as organophosphates which require a bioactivation step to effectively inhibit the acetylcholinesterase (AChE) enzyme. Therefore, the influence of the potential limited biotransformation on the toxicity pathway of a typical organophosphate, chlorpyrifos, was investigated in Chapter 5. Chlorpyrifos could not inhibit AChE and this was attributed to possible lack of biotransformation in 24 hpf embryos (Chapter 5).
Since neuroactive substances occur in the environment as mixtures, it is therefore more realistic to assess their combined effect rather than individually. Therefore, mixture toxicity was predicted using the concentration addition and independent action models. Result shows that mixtures of neuroactive substances with different mechanisms of action but similar effects can be predicted with concentration addition and independent action (Chapter 4). Apart
from being able to predict the combined effect of neuroactive substances for prospective risk assessment, it is also important to assess in retrospect the combined neurotoxic effect of environmental samples since neuroactive substances are the largest group of chemicals occurring in the environment. In Chapter 6, the STC test was found to be capable of detecting neurotoxic effects of a wastewater effluent sample. Hence, the STC test is proposed as an effect based tool for monitoring environmental acute and neurotoxic effects.
Overall, this thesis shows the utility and versatility of zebrafish embryo behavior testing for screening neuroactive substances and this allows to propose its use for prospective and diagnostic hazard assessment. This will enhance the move away from expensive and demanding animal testing. The information contained in this thesis is of great potential to provide precautionary solutions, not only for the exposure of humans to neuroactive chemicals but for the environment at large.
Invasive species play increasing roles worldwide. Invasions are considered successful when species establish and spread in their exotic range. Subsequently, dispersal is a major determinant of species’ range dynamics. Mermessus trilobatus, native to North America, has rapidly spread in Europe via aerial dispersal. Here we investigated the interplay of ecological and evolutionary processes behind its colonisation success.
First, we examined two possible ecological mechanisms. Similar to other invasive invertebrates, the colonisation success of Mermessus trilobatus might be related to human-induced habitat disturbance. Opposite to this expectation, our results showed that densities of Mermessus trilobatus decreased with soil disturbance in grasslands suggesting that its invasion success was not connected to a ruderal strategy. Further, invasive species often escape the ecological pressures from novel enemies in their exotic ranges. Unexpectedly, invasive Mermessus trilobatus was more sensitive to a native predator than native Erigone dentipalpis during our predator susceptibility trials. This indicates that the relation between the invasive spider and its native predator is dominated by prey naïveté rather than enemy release.
The remaining three chapters of the thesis investigated the dispersal behaviour of this invasive species. Hitherto, studies of passive aerial dispersal used wind as the primary dispersal-initiating factor despite a recent demonstration of the effects of the atmospheric electric fields on spiders’ pre-dispersal behaviour. During our experiments, only the wind facilitated the flight, although electric fields induced pre-dispersal behaviour in spiders. Consequently, studies around passive aerial dispersal should control electric fields but use wind as a stimulating factor.
Rapidly expanding species might be disproportionately distributed in their exotic range, with an accumulation of dispersive genotypes at the leading edge of their range. Such imbalanced spatial segregation is possible when the dispersal behaviour of expanding species is heritable. Our results showed that the dispersal traits of Mermessus trilobatus were heritable through both parents and for both sexes with recessive inheritance of high dispersal ability in this species.
Following the heritability experiments, we documented an accelerated spread of Mermessus trilobatus in Europe and tested whether dispersal, reproduction or competing ability was at the source of this pattern. Our results showed that the accumulation of more mobile but not reproductive or competitive genotypes at the expansion front of this invasive species gave rise to an accelerated range expansion by more than 1350 km in under 45 years.
Invasive Mermessus trilobatus is inferior to native sympatric species with respect to competing ability (Eichenberger et al., 2009), disturbance tolerance and predation pressure. Nevertheless, the species successfully established in its exotic range and spread by accelerating its expansion rate. Rapid reproduction that balances the high ecological pressures might be the other potential mechanism behind its colonisation success in Europe and deserves further investigation.
Grassland management has been increasingly intensified throughout centuries since mankind started to control and modify the landscape. Species communities were always shaped alongside management changes leading to huge alterations in species richness and diversity up to the point where land use intensity exceeded the threshold. Since then biodiversity became increasingly lost. Today, global biodiversity and especially grassland biodiversity is pushed beyond its boundaries. Policymakers and conservationists seek for management options which fulfill the requirements of agronomic interests as well as biodiversity conservation alongside with the maintenance of ecosystem processes. However, there is and will always be a trade-off.
Earlier in history, natural circumstances in a landscape mainly determined regionally adapted land use. These regional adaptions shaped islands for many specialist species, and thus diverse species communities, favoring the establishment of a high β-diversity. With the raising food demand, these regional and traditional management regimes became widely unprofitable, and the invention of mineral fertilizers ultimately led to a wide homogenization of grassland management and, as follows, the loss of biotic heterogeneity. In the course of the green revolution, this immediate coherence and the dependency between grassland biodiversity and traditional land use practices becomes increasingly noticed. Indeed, some traditional forms of management such as meadow irrigation have been preserved in a few regions and thus give us the opportunity to directly investigate their long-term relevance for the species communities and ecosystem processes. Traditional meadow irrigation was a common management practice to improve productivity in lowland, but also alpine hay meadows throughout Europe until the 20th century. Nowadays, meadow irrigation is only practiced as a relic in a few remnant areas. In parts of the Queichwiesen meadows flood irrigation goes back to the Middle Ages, which makes them a predestined as a model region to study the long- and short-term effects of lowland meadow irrigation on the biodiversity and ecosystem processes.
Our study pointed out the conservation value of traditional meadow irrigation for the preservation of local species communities as well as the plant diversity at the landscape scale. The structurally more complex irrigated meadows lead to the assumption of a higher arthropod diversity (Orthodoptera, Carabidae, Araneae), which could not be detected. However, irrigated meadows are a significant habitat for moisture dependent arthropod species. In the light of the agronomic potential, flood irrigation could be a way to at least reduce fertilizer costs to a certain degree and possibly prevent overfertilization pulses which are necessarily hazardous to non-target ecosystems. Still, the reestablishment of flood irrigation in formerly irrigated meadows, or even the establishment of new irrigation systems needs ecological and economic evaluation dependent on regional circumstances and specific species communities, at which this study could serve as a reference point.
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%.
Agriculture requires a sustainable intensification to feed the growing world population without exacer-bating soil degradation and threatening soil quality. Globally, plastic mulching (PM) is increasingly used to improve crop growth and yields and consequently agronomic productivity. However, recent literature reported also critical aspects of PM for soil quality and showed contradictory outcomes. This might result from the numerous applications of PM in different climates across various crops, soils and agri-cultural techniques. Thus, a closer look is necessary on how PM influences soil processes under certain climate and cultivation conditions to obtain a comprehensive understanding of its effects, which is im-portant to evaluate PM in terms of a sustainable agriculture.
The aim of this PhD thesis was to understand how multiannual PM influences soil properties and pro-cesses under the temperate, humid Central European cultivation conditions and to evaluate the resulting consequences for soil quality. I designed a three-year field study to investigate the influence of PM (black polyethylene, 50 μm) on microclimate, structural stability, soil organic matter (SOM) and the concentrations of selected fungicides and mycotoxins in three soil layers (0–10, 10–30 and 30–60 cm) compared to straw mulching (SM). Both mulching types were applied in a drip-irrigated ridge-furrow system in strawberry cultivation.
PM shifted the soil microclimate to higher soil temperatures and lower soil moistures. The higher soil temperature seems thus to be the key factor for the increased crop growth and yields under the present humid climate. The reduced soil moisture under PM indicated that under PM the impeded rainfall infil-tration had a stronger effect on the water balance than the reduced evaporation. This indicate an ineffi-cient rainwater use in contrast to arid climates. PM changed the water cycling in the ridges from down-ward directed water flows to lateral water flows from furrows to ridges. This reduced nitrogen leaching in the topsoil (0–10 cm) in the strawberry establishment period. The plastic mulches avoided aggregate breakdown due to rapid soil wetting and excess water during rainfalls and thus maintained a loose and stable soil structure in the surface soil, which prevents soil compaction and made soil less prone to erosion. PM changed carbon fluxes and transformation so that a larger total and more stable SOM was observed. Thus, the higher belowground biomass productivity under PM compensated the impeded aboveground biomass input and the temperature-induced SOM decomposition. However, SM increased the labile and total SOM in the topsoil after the first experiment year and promoted microbial growth due to the aboveground biomass incorporation. PM reduced fungicide entry into soil compared to SM and reduced consequently the fungal biomass reduction and the biosynthesis of the mycotoxin deoxyni-valenol. The modified microclimate under PM did not increase mycotoxin occurrence. In this context, PM poses no risk for an increased soil contamination, impairing soil quality. This PhD thesis demon-strated that the PM effects on soil can vary depending on time, season and soil depth, which emphasizes the importance to include soil depth and time in future studies.
Compared to semiarid and arid regions, the PM effects found in this PhD thesis were small, absent or in another way. I attributed this to the fact that PM under humid climate reduced instead of increased soil moisture and that SM had due to straw und strawberry canopy a similar ‘covering effect’ as PM. Thus, generalizing the PM effects on soil across different climates seems hardly possible as they differ in type and extent depending on climate. A differentiated consideration is hence necessary to evaluate the PM effects on soil quality. I conclude that PM under temperate, humid climate might contribute to reduce soil degradation (e.g., SOM depletion, erosion, nutrient leaching, soil compaction and soil contamina-tion), which sustains soil quality and helps to enable a sustainable agricultural intensification. However, further research is necessary (1) to support my findings on a larger scale, longer time periods and across various soil and crop types, (2) to address remaining open questions and (3) to develop optimization to overcome the critical aspects of PM (e.g. macro- and microplastic waste in soil, mulch disposal).
Conversion of natural vegetation into cattle pastures and croplands results in altered emissions of greenhouse gases (GHG), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Their atmospheric concentration increase is attributed the main driver of climate change. Despite of successful private initiatives, e.g. the Soy Moratorium and the Cattle Agreement, Brazil was ranked the worldwide second largest emitter of GHG from land use change and forestry, and the third largest emitter from agriculture in 2012. N2O is the major GHG, in particular for the agricultural sector, as its natural emissions are strongly enhanced by human activities (e.g. fertilization and land use changes). Given denitrification the main process for N2O production and its sensitivity to external changes (e.g. precipitation events) makes Brazil particularly predestined for high soil-derived N2O fluxes.
In this study, we followed a bottom-up approach based on a country-wide literature research, own measurement campaigns, and modeling on the plot and regional scale, in order to quantify the scenario-specific development of GHG emissions from soils in the two Federal States Mato Grosso and Pará. In general, N2O fluxes from Brazilian soils were found to be low and not particularly dynamic. In addition to that, expected reactions to precipitation events stayed away. These findings emphasized elaborate model simulations in daily time steps too sophisticated for regional applications. Hence, an extrapolation approach was used to first estimate the influence of four different land use scenarios (alternative futures) on GHG emissions and then set up mitigation strategies for Southern Amazonia. The results suggested intensification of agricultural areas (mainly cattle pastures) and, consequently, avoided deforestation essential for GHG mitigation.
The outcomes of this study provide a very good basis for (a) further research on the understanding of underlying processes causing low N2O fluxes from Brazilian soils and (b) political attempts to avoid new deforestation and keep GHG emissions low.
Assessment of renewable energy potentials based on GIS. A case study in southwest region of Russia
(2018)
In the present thesis, the initial conditions for the development of RES potentials for the production of wind, solar and biomass energy in the Krasnodar region (southwestern region of the Russian Federation) are examined using a multi-criteria assessment methodology. For the assessment of the RES potentials at regional scale, the prosed multi-criteria methodology based on the geographic information systems (GIS) and has been complemented by the evaluation and analysis of primary and secondary data as well as economic calculations relevant related to economic feasibility of RES projects.
Change of ecosystems and the associated loss of biodiversity is among the most important environmental issues. Climate change, pollution, and impoundments are considered as major drivers of biodiversity loss. Organism traits are an appealing tool for the assessment of these three stressors, due to their ability to provide mechanistic links between organism responses and stressors, and consistency over wide geographical areas.
Additionally, traits such as feeding habits influence organismal performance and ecosystem processes. Although the response of traits of specific taxonomic groups to stressors is known, little is known about the response of traits of different taxonomic groups to stressors. Additionally, little is known about the effects of small impoundments on stream ecosystem processes, such as leaf litter decomposition, and food webs.
After briefly introducing the theoretical background and objectives of the studies, this thesis begins by synthesizing the responses of traits of different taxonomic groups to climate change and pollution. Based on 558 peer-reviewed studies, the uniformity (i.e., convergence) in trait response across taxonomic groups was evaluated through meta-analysis (Chapter 2). Convergence was primarily limited to traits related to tolerance.
In Chapter 3, the hypothesis that small impoundments would modify leaf litter decomposition rates at the sites located within the vicinity of impoundments, by altering habitat variables and invertebrate functional feeding groups (FFGs) (i.e., shredders), was tested. Leaf litter decomposition rates were significantly reduced at the study sites located immediately upstream (IU) of impoundments, and were significantly related to the abundance of invertebrate shredders.
In Chapter 4, the invertebrate FFGs were used to evaluate the effect of small impoundments on stream ecosystem attributes. The results showed that heterotrophic production was significantly reduced at the sites IU. With regard to food webs, the contribution of methane gas derived carbon to the biomass of chironomid larvae was evaluated through correlation of stable carbon isotope values of chironomid larvae and methane gas concentrations.
The results indicated that the contribution of methane gas derived carbon into stream benthic food web is low. In conclusion, traits are a useful tool in detecting ecological responses to stressors across taxonomic groups, and the effects of small impoundments on stream ecological integrity and food web are limited.
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.
Environmental processes transforming inorganic nanoparticles: implications on aquatic invertebrates
(2020)
Engineered inorganic nanoparticles (EINPs) are produced and utilized on a large scale and will end up in surface waters. Once in surface waters, EINPs are subjected to transformations induced by environmental processes altering the particles’ fate and inherent toxicity. UV irradiation of photoactive EINPs is defined as one effect-inducing pathway, leading to the formation of reactive oxygen species (ROS), increasing EINP toxicity by exerting oxidative stress in aquatic life. Simultaneously, UV irradiation of photoactive EINP alters the toxicity of co-occurring micropollutants (e.g. pesticides) by affecting their degradation. The presence of natural organic matter (NOM) reduces the agglomeration and sedimentation of EINPs, extending the exposure of pelagic species, while delaying the exposure of benthic species living in and on the sediment, which is suggested as final sink for EINPs. However, the joint impact of NOM and UV irradiation on EINP-induced toxicity, but also EINP-induced degradation of micropollutants, and the resulting risk for aquatic biota, is poorly understood. Although potential effects of EINPs on benthic species are increasingly investigated, the importance of exposure pathways (waterborne or dietary) is unclear, along with the reciprocal pathway of EINPs, i.e. the transport back from aquatic to terrestrial ecosystems. Therefore, this thesis investigates: (i) how the presence of NOM affects the UV-induced toxicity of the model EINP titanium dioxide (nTiO2) on the pelagic organism Daphnia magna, (ii) to which extent UV irradiation of nTiO2 in the presence and absence of NOM modifies the toxicity of six selected pesticides in D. magna, (iii) potential exposure pathway dependent effects of nTiO2 and silver (nAg) EINPs on the benthic organism Gammarus fossarum, and (iv) the transport of nTiO2 and gold EINPs (nAu) via the merolimnic aquatic insect Chaetopteryx villosa back to terrestrial ecosystems. nTiO2 toxicity in D. magna increased up to 280-fold in the presence of UV light, and was mitigated by NOM up to 12-fold. Depending on the pesticide, UV irradiation of nTiO2 reduced but also enhanced pesticide toxicity, by (i) more efficient pesticide degradation, and presumably (ii) formation of toxic by-products, respectively. Likewise, NOM reduced and increased pesticide toxicity, induced by (i) protection of D. magna against locally acting ROS, and (ii) mitigation of pesticide degradation, respectively. Gammarus’ energy assimilation was significantly affected by both EINPs, however, with distinct variation in direction and pathway dependence between nTiO2 and nAg. EINP presence delayed C. villosa emergence by up to 30 days, and revealed up to 40% reduced lipid reserves, while the organisms carried substantial amounts of nAu (~1.5 ng/mg), and nTiO2 (up to 2.7 ng/mg). This thesis shows, that moving test conditions of EINPs towards a more field-relevant approach, meaningfully modifies the risk of EINPs for aquatic organisms. Thereby, more efforts need to be made to understand the relative importance of EINP exposure pathways, especially since a transferability between different types of EINPs may not be given. When considering typically applied risk assessment factors, adverse effects on aquatic systems might already be expected at currently predicted environmental EINP concentrations in the low ng-µg/L range.
Rivers play an important role in the global water cycle, support biodiversity and ecological integrity. However, river flow and thermal regimes are heavily altered in dammed rivers. These impacts are being exacerbated and become more apparent in rivers fragmented by multiple dams. Recent studies mainly focused on evaluating the cumulative impact of cascade reservoirs on flow or thermal regimes, but the role of upstream reservoirs in shaping the hydrology and hydrodynamics of downstream reservoirs remains poorly understood. To improve the understanding of the hydrodynamics in cascade reservoirs, long-term observational data are used in combination with numerical modeling to investigate the changes in flow and thermal regime in three cascade reservoirs at the upper reach of the Yangtze River. The three studied reservoirs are Xiluodu (XLD), Xiangjiaba (XJB) and Three Gorges Reservoir (TGR). In addition, the effects of single reservoir operation (at seasonal/daily time scale) on hydrodynamics are examined in a large tributary of TGR. The results show that the inflow of TGR has been substantially altered by the two upstream reservoirs with a higher discharge in spring and winter and a reduced peak flow in summer. XJB had no obvious contribution to the variations in inflow of TGR. The seasonal water temperature of TGR was also widely affected by the upstream two reservoirs, i.e., an increase in winter and decrease in spring, associated with a delay in water temperature rise and fall. These effects will probably be intensified in the coming years due to the construction of new reservoirs. The study also underlines the importance of reservoir operation in shaping the hydrodynamics of TGR. The seasonal dynamics of density currents in a tributary bay of TGR are closely related to seasonal reservoir operations. In addition, high-frequency water level fluctuations and flow velocity variations were observed in response to periodic tributary bay oscillations, which are driven by the diurnal discharge variations caused by the operation of TGR. As another consequence of operation of cascade reservoirs, the changes in TGR inflow weakened spring thermal stratification and caused warming in spring, autumn and winter. In response to this change, the intrusions from TGR occurred more frequently as overflow and earlier in spring, which caused a sharp reduction in biomass and frequency of phytoplankton blooms in tributary bays of TGR. This study suggests that high-frequency bay oscillations can potentially be used as an efficient management strategy for controlling algal blooms, which can be included in future multi-objective ecological conservation strategies.
With 47% land coverage in 2016, agricultural land was one of the largest terrestrial biomes in Germany. About 70% of the agricultural land was cropped area with associated pesticide applications. Agricultural land also represents an essential habitat for amphibians. Therefore, exposure of amphibians to agrochemicals, such as fertilizers and pesticides, seems likely. Pesticides can be highly toxic for amphibians, even a fraction of the original application rate may result in high amphibian mortality.
To evaluate the potential risk of pesticide exposure for amphibians, the temporal coincidence of amphibian presence on agricultural land and pesticide applications (N = 331) was analyzed for the fire-bellied toad (Bombina bombina), moor frog (Rana arvalis), spadefoot toad (Pelobates fuscus) and crested newt (Triturus cristatus) during spring migration. In 2007 and 2008, up to 80% of the migrating amphibians temporally coincided with pesticide applications in the study area of Müncheberg, about 50 km east of Berlin. Pesticide interception by plants ranged between 50 to 90% in winter cereals and 80 to 90% in winter rape. The highest coincidence was observed for the spadefoot toad, where 86.6% of the reproducing population was affected by a single pesticide in winter rape during stem elongation with 80% pesticide interception by plants. Late migrating species, such as the fire-bellied toad and the spadefoot toad, overlapped more with pesticide applications than early migrating species, such as the moor frog, did. Under favorable circumstances, the majority of early migrants may not coincide with the pesticide applications of arable fields during spring migration.
To evaluate the potential effect of pesticide applications on populations of the common frog (Rana temporaria), a landscape genetic study was conducted in the vinicultural area of Southern Palatinate. Due to small sample sizes at breeding sites within viniculture, several DNA sampling methods were tested. Furthermore, the novel repeated randomized selection of genotypes approach was developed to utilize genetic data from siblings for more reliable estimates of genetic parameters. Genetic analyses highlighted three of the breeding site populations located in viniculture as isolated from the meta-population. Genetic differentiation among breeding site populations in the viniculture (median pairwise FST=0.0215 at 2.34 km to 0.0987 at 2.39 km distance) was higher compared to genetic differentiation among breeding site populations in the Palatinate Forest (median pairwise FST=0.0041 at 5.39 km to 0.0159 at 9.40 km distance).
The presented studies add valuable information about the risk of pesticide exposure for amphibians in the terrestrial life stage and possible effects of agricultural land on amphibian meta-populations. To conserve endemic amphibian species and their (genetic) diversity in the long run, the risk assessment of pesticides and applied agricultural management measures need to be adjusted to protect amphibians adequately. In addition, other conservation measures such as the creation of new suitable breeding site should be considered to improve connectivity between breeding site populations and ensure the persistence of amphibians in the agricultural land.
Ponds in agricultural landscapes are often used by amphibians as breeding habitat. However, the characteristics of agricultural ponds and especially the surrounding area are usually said to be suboptimal for many amphibian species. Using suboptimal habitats might allow a species’ survival and reproduction, but can have negative consequences at the individual and population level. In the present study, we investigated Palmate Newt (Lissotriton helveticus) populations from an intensive wine-growing region in southern Germany and compared them with populations located in a nearby forested area in terms of biometric traits, age and genetic structure. By analyzing over 900 adult newts from 11 ponds, we could show that newts reproducing in forest ponds were larger than newts reproducing in agricultural ponds. We did not find differences in the newt age and growth rate between habitat types. Therefore, differences in the body size of newts might already existed in larvae and/or juveniles, what might be related to a lower habitat quality for larvae and/or juveniles in the agricultural landscape. Body mass, body condition and sexual dimorphic traits (length of the caudal filament and max. height of the tail) correlated with body size, but no additional effect of the habitat type was found. The analysis of microsatellites revealed a higher genetic diversity in forest ponds. However, no clear sign of inbreeding was observed in any agricultural population, suggesting some degree of gene flow between them. We conclude, that agricultural ponds can be suitable habitats for the Palmate Newt and that conservation effort should aim to preserve them. The observed effects on body size indicate the need to increase the quality of the aquatic and terrestrial habitat for early life stages of this newt species in agricultural landscapes.
In the last decades, it became evident that the world is facing an unprecedented, human-induced global biodiversity crisis with amphibians being one of the most threatened species groups. About 41% of the amphibian species are classified as endangered by the IUCN, but even in amphibian species that are listed as "least concern", population declines can be observed on a local level. With land-use change and agrochemicals (i.e. pesticides), two of the main drivers for this amphibian decline are directly linked to intensive agriculture, which is the dominant landscape type in large parts of Europe. Thus, understanding the situation of amphibians in the agricultural landscape is crucial for conservation measures. In the present thesis, I investigated the effects of viticulture on amphibian populations around Landau in der Pfalz (Germany) in terms of habitat use, pesticide exposure, biometric traits as well as genetic and age structure. From the perspective of amphibians, land-use change means usually the destruction of habitats in agricultural landscapes, which often leads to landscape fragmentation. Thus, I followed the question if also vineyards lead to the fragmentation of the landscape and if pesticides that are frequently used in viticulture have to be considered as a factor too, so if there is a chemical landscape fragmentation. Using telemetry, I could show that common toads (Bufo bufo) can be found directly in vineyards, but that they tend to avoid them as habitat. Analysing the genetic structure of common frogs (Rana temporaria) revealed that vineyards have to be considered as a barrier for amphibians. To identify if pesticides contribute to the resulting landscape fragmentation, I conducted an arena choice experiment in the laboratory in which I found evidence for an avoidance of pesticide-contaminated soil. Such an avoidance could be one of the underlying reasons for a potential chemical landscape fragmentation. By combining telemetry data with information about pesticide applications from local wine growers, I could show that a large part of the common toads is likely to come in contact with pesticides. Further, I demonstrated that the agricultural landscape, probably due to the application of pesticides, can have negative effects on the reproduction capacity of common toads. By studying palmate newts (Lissotriton helveticus) I found that adult newts from agricultural ponds are smaller than those from forest ponds. As I did not find differences in the age structure and growth, these differences might be carry-over effects from earlier life stages. While agricultural ponds might be suitable habitats for adult palmate newts, the potential carry-over effect indicates suboptimal conditions for larvae and/or juveniles. I conclude that the best management measure for sustaining amphibians in the agricultural landscape would be a heterogeneous cultural landscape with a mosaic of different habitat patches that work without or at least a reduced amount of pesticides. Green corridors between populations and different habitats would allow migrating individuals to avoid agricultural and thus pesticide-contaminated areas. This would reduce the pesticide exposure risk of amphibians, while preventing the fragmentation of the landscape and thus the isolation of populations.
This thesis examined two specific cases of point and diffuse pollution, pesticides and salinisation, which are two of the most concerning stressors of Germany’s freshwater bodies. The findings of this thesis were organized into three major components, of which the first component presents the contribution of WWTPs to pesticide toxicity (Chapter 2). The second component focuses on the current and future background salt ion concentrations under climate change with the absence of anthropogenic activities (Chapter 3). Finally, the third major component shows the response of invertebrate communities in terms of species turnover to levels of salinity change, considered as a proxy for human-driven salinisation (Chapter 4).
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.
Larvae of Cx.pipiens coocurred with Cladocera, but the latter established delayed in time. Biotope structure influenced time of species occurrence with ponds at reed-covered wetlands favouring crustacean development, while ponds at grassland biotopes favoured colonization by mosquito larvae. The mechanisms driving the negative effect of crustaceans on mosquito larvae were investigated within an experiment under artificial conditions. Crustacean communities were found to reduce both oviposition and larval development of Cx.pipiens. Crustacean communities of high taxa diversity, including both predatory and competing crustaceans, were more effective compared with crustacean communities dominated by single taxa. Presence of crustacean communities characterised by high taxa diversity increased the sensitivity of Cx.pipiens larvae towards Bti and prolonged the time of recolonization. In a final step the combined approach, using Bti and crustaceans, was evaluated under field conditions. The joint application of Bti and crustaceans was found to reduce mosquito larval populations over the whole observation period, while single application of Bti caused only short-term reduction of mosquito larvae. Single application of crustaceans had no significant effect, because high abundances of prior established mosquito larvae impeded propagation of crustaceans. At combined treatment, mosquito larvae were reduced by Bti application and hence crustaceans were able to proliferate without disturbance by interspecific competition. In conclusion, natural competitors were found to have a strong negative impact on mosquito larval populations. However, a time span of about 2 weeks has to be bridged, before crustacean communities reached a level sufficient for mosquito control. Results of a combined approach, complementing the short-term effect of the biological insecticide Bti with the long-term effect of crustaceans, were promising. Using natural competitors within an integrated control strategy could be an important tool for an effective, environmentally friendly and sustainable mosquito management.