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Institute
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.
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.
Modern agriculture is a dominant land use in Europe, although it has been associated with negative effects on biodiversity in agricultural landscapes. One species-rich insect group in agro-ecosystems is the Lepidoptera (moths and butterflies); however, the populations of a number of Lepidoptera species are currently declining. The aims of this thesis were to assess the amount and structure of field margins in agricultural landscapes, study the effects of realistic field margin input rates of agrochemicals (fertilizer and pesticides) on Lepidoptera, and provide information on moth pollination services.
In general, field margins are common semi-natural habitat elements in agro-ecosystems; however, data on the structure, size, and width of field margins is limited. An assessment in two German agricultural landscapes (4,000 ha each) demonstrated that many of the evaluated field margins were less than 3 m wide (Rhineland‐Palatinate: 85% of margin length; Brandenburg: 45% margin length). In Germany, risk mitigation measures (such as buffer zones) to reduce pesticide inputs to terrestrial non-crop habitats do not have to be established by farmers next to narrow field margins. Thus, narrow field margins receive inputs of agrochemicals, especially via overspray and spray drift. These field margins were used as a development habitat for caterpillars, but the mean abundance of caterpillars was 35 – 60% lower compared with that in meadows. Caterpillars were sensitive to realistic field margin input rates of insecticide (pyrethroid, lambda-cyhalothrin) in a field experiment as well as in laboratory experiments. Moreover, 40% fewer Hadena bicruris eggs were observed on Silene latifolia plants treated with this insecticide compared with control plants, and the flowers of these insecticide-treated plants were less likely to be pollinated by moths. In addition, realistic field margin input rates of herbicides can also affect Lepidoptera. Ranunculus acris L. plants treated with sublethal rates of a sulfonylurea herbicide were used as host plants for Mamestra brassicae L. caterpillars, which resulted in significantly lower caterpillar weights, increased time to pupation, and increased overall development time compared with caterpillars feeding on control plants. These results might have been caused by lower nutritional value of the herbicide-treated plants or increased concentrations of secondary metabolites involved in plant defense. Fertilizer applications slightly increased the caterpillar abundance in the field experiment. However, fertilizers reduce plant diversity in the long term and thus, most likely, also reduce caterpillar diversity.
Moths such as Noctuidae and Sphingidae have been observed to act as pollinators for numerous plant species, including a number of Orchidaceae and Caryophyllaceae. Although in temperate agro-ecosystems moths are less likely to act as the main pollinators for crops, they can pollinate non-crop plants in semi-natural habitats. Currently, the role of moths as pollinators appears to be underestimated, and long-term research focusing on ecosystems is necessary to address temporal fluctuations in their abundance and community composition.
Lepidoptera represent a diverse organism group in agricultural landscapes and fulfill essential ecosystem services, such as pollination. To better protect moths and butterflies, agrochemical inputs to (narrow) field margins habitats should be reduced, for example, via risk mitigation measures and agro-environmental schemes.
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.
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.
The intention of this thesis was to characterise the effect of naturally occurring multivalent cations like Calcium and Aluminium on the structure of Soil Organic Matter (SOM) as well as on the sorption behaviour of SOM for heavy metals such as lead.
The first part of this thesis describes the results of experiments in which the Al and Ca cation content was changed for various samples originated from soils and peats of different regions in Germany. The second part focusses on SOM-metal cation precipitates to study rigidity in dependence of the cation content. In the third part the effects of various cation contents in SOM on the binding strength of Pb cations were characterised by using a cation exchange resin as desorption method.
It was found for soil and peat samples as well as precipitates that matrix rigidity was affected by both type and content of cation. The influence of Ca on rigidity was less pronounced than the influence of Al and of Pb used in the precipitation experiments. For each sample one cation content was identified where matrix rigidity was most pronounced. This specific cation content is below the cation saturation as expected by cation exchange capacity. These findings resulted in a model describing the relation between cation type, content and the degree of networking in SOM. For all treated soil and precipitate samples a step transition like glass transition was observed, determined by the step transition temperature T*. It is known from literature that this type of step transition is due to bridges between water molecules and organic functional groups in SOM. In contrast to the glass transition temperature this thermal event is slowly reversing after days or weeks depending on the re-conformation of the water molecules. Therefore, changes of T* with different cation compositions in the samples are explained by the formation of water-molecule-cation bridges between SOM-functional groups. No influence on desorption kinetics of lead for different cation compositions in soil samples was observed. Therefore it can be assumed that the observed changes of matrix rigidity are highly reversible by changing the water status, pH or putting agitation energy by shaking in there.
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.
A fundamental understanding of attachment of engineered nanoparticles to environmentalrnsurfaces is essential for the prediction of nanoparticle fate and transport in the environment.
The present work investigates the attachment of non-coated silver nanoparticles and citraterncoated silver nanoparticles to different model surfaces and environmental surfaces in thernpresence and absence of humic acid. Batch sorption experiments were used for this investigation.
The objective of this thesis was to investigate how silver nanoparticles interactrnwith surfaces having different chemical functional groups. The effect of presence of HA, on the particle-surface interactions was also investigated. In the absence of humic acid, nanoparticle-surface interactions or attachment was influencedrnby the chemical nature of the interacting surfaces. On the other hand, in the presence ofrnhumic acid, nanoparticle-surface attachment was influenced by the specific surface area of the sorbent surfaces. The sorption of non-coated silver nanoparticles and citrate coatedrnnanoparticles to all the surfaces was nonlinear and best described by Langmuir isotherm, indicating monolayer sorption of nanoparticles on to the surfaces. This can be explained as due to the blocking effect generated by the particle-particle repulsion. In the presence of humic acid, sorption of nanoparticles to the surfaces was linear. When the humic acid was present in the interacting medium, both the nanoparticles and surfaces were getting coated with humic acid and this masks the chemical functionalities of the surfaces. This leads to the change in particle-surface interactions, in the presence of humic acid. For the silver nanoparticle sorption from an unstable suspension, the sorption isotherms did not follow any classical sorption models, suggesting interplay between aggregation and sorption. Citrate coated silver nanoparticles and humic acid coated silver nanoparticles showed arndepression in sorption compared to the sorption of non-coated silver nanoparticles. In therncase of citrate coated silver nanoparticles the decrease in sorption can be explained by thernmore negative zeta potential of citrate coated nanoparticles compared to non-coated ones. For humic acid coated nanoparticles the sorption depression can be due to the steric hindrance caused by the free humic acid molecules which may coat the sorbent surface or due to the competition for sorption sites between the nanoparticle and free humic acid molecules present in the suspension. Thus nanoparticle surface chemistry is an important factor that determines the attachment of nanoparticles towards surfaces and it makes the characterization of nanoparticle surface an essential step in the study of their fate in the environment.
Another aim of this study was to introduce the potential of chemical force microscopy for nanoparticle surface characterization. With the use of this technique, it was possible to distinguish between bare silver nanoparticles, citrate coated silver nanoparticles, and humic acid coated silver nanoparticles. This was possible by measuring the adhesion forces between the nanoparticles and five different AFM probes having different chemical functionalization.
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.
The adoption of the EU Water Framework Directive (WFD) in 2000 marked the beginning of a new era of European water policy. However, more than a decade later, the majority of European rivers are still failing to meet one of the main objectives of the WFD: the good ecological status. Pesticides are a major stressor for stream ecosystems. This PhD thesis emphasises the need for WFD managers to consider all main agricultural pesticide sources and influencing landscape parameters when setting up River Basin Management Plans and Programmes of Measures. The findings and recommendations of this thesis can help to successfully tackle the risk of pesticide contamination to achieve the WFD objectives.
A total of 663 sites that were situated in the German Federal States of Saxony, Saxony-Anhalt, Thuringia and Hesse were studied (Chapter 3 and 4). In addition to an analysis of the macroinvertebrate data of the governmental WFD monitoring network, a detailed GIS analysis of the main agricultural pesticide sources (arable land and garden allotments as well as wastewater treatment plants (WWTPs)) and landscape elements (riparian buffer strips and forested upstream reaches) was conducted. Based on the results, a screening approach was developed that allows an initial rapid and cost-effective identification of those sites that are potentially affected by pesticide contamination. By using the trait-based bioindicator SPEARpesticides, the insecticidal long-term effects of the WWTP effluents on the structure of the macroinvertebrate community were identified up to at least 1.5 km downstream (in some cases even 3 km) of the WWTPs. The results of the German Saprobic Index revealed that the WWTPs can still be important sources of oxygen-depleting substances. Furthermore, the results indicate that forested upstream reaches and riparian buffer strips at least 5 m in width can be appropriate measures in mitigating the effects and exposure of pesticides.
There are concerns that the future expansion of energy crop cultivation will lead to an increased pesticide contamination of ecosystems in agricultural landscapes. Therefore, the potential of energy crops for pesticide contamination was examined based on an analysis of the development of energy crop cultivation in Germany and a literature search on perennial energy crops (Chapter 5). The results indicate that the future large-scale expansion of energy crop cultivation will not necessarily cause an increase or decrease in the amounts of pesticides that are released into the environment. The potential effects will depend on the future design of the agricultural systems. Instead of creating energy monocultures, annual energy crops should be integrated into the existing food production systems. Financial incentives and further education are needed to encourage the use of sustainable crop rotations, innovative cropping systems and perennial energy crops, which may contribute to crop diversity and generate lower pesticide demands than do intensive farming systems.