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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.
Lakes and reservoirs are important sources of methane, a potent greenhouse gas. Although freshwaters cover only a small fraction of the global surface, their contribution to global methane emission is significant and this is expected to increase, as a positive feedback to climate warming and exacerbated eutrophication. Yet, global estimates of methane emission from freshwaters are often based on point measurements that are spatio-temporally biased. To better constrain the uncertainties in quantifying methane fluxes from inland waters, a closer examination of the processes transporting methane from sediment to atmosphere is necessary. Among these processes, ebullition (bubbling) is an important transport pathway and is a primary source of uncertainty in quantifying methane emissions from freshwaters. This thesis aims to improve our understanding of ebullition in freshwaters by studying the processes of methane bubble formation, storage and release in aquatic sediments. The laboratory experiments demonstrate that aquatic sediments can store up to ~20% (volumetric content) gas and the storage capacity varies with sediment properties. The methane produced is stored as gas bubbles in sediment with minimal ebullition until the storage capacity is reached. Once the sediment void spaces are created by gas bubble formation, they are stable and available for future bubble storage and transport. Controlled water level drawdown experiments showed that the amounts of gas released from the sediment scaled with the total volume of sediment gas storage and correlated linearly to the drop in hydrostatic pressure. It was hypothesized that not only the timing of ebullition is controlled by sediment gas storage, but also the spatial distribution of ebullition. A newly developed freeze corer, capable of characterizing sediment gas content under in situ environments, enabled the possibility to test the hypothesis in a large subtropical lake (Lake Kinneret, Israel). The results showed that gas content was variable both vertically and horizontally in the lake sediment. Sediment methane production rate and sediment characteristics could explain these variabilities. The spatial distribution of ebullition generally was in a good agreement with the horizontal distribution of depth-averaged (surface 1 m) sediment gas content. While discrepancies were found between sediment depth-integrated methane production and the snapshot ebullition rate, they were consistent in a long term (multiyear average). These findings provide a solid basis for the future development of a process-based ebullition model. By coupling a sediment transport model with a sediment diagenetic model, general patterns of ebullition hotspots can be predicted at a system level and the uncertainties in ebullition flux measurements can be better constrained both on long-term (months to years) and short-term (minutes to hours) scales.
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.
The physical-biological interactions that affect the temporal variability of benthic oxygen fluxes were investigated to gain improved understanding of the factors that control these processes. This study, for the first time is able to resolve benthic diffusive boundary layer (DBL) dynamics using the newly developed lifetime-based laser induced fluorescence (τLIF) oxygen imaging system, which enables study of the role of small-scale fluid mechanics generated by benthic organism activity, and hence a more detailed analysis of oxygen transport mechanisms across the sediment-water interface (SWI).
The net benthic oxygen flux across the sediment-water interface is controlled by sediment oxygen uptake and oxygen transport. While the oxygen transport is largely influenced by turbulence driven by large-scale flows, sediment oxygen uptake is mainly affected by oxygen production and biological- and chemical-oxygen degradation of organic matter. Both processes can be enhanced by the presence of fauna and are intimately coupled. The benthic oxygen flux can be influenced by fauna in two ways, i.e. by modulating the availability of oxygen, which enhances the sediment oxygen uptake, and by enhancing the transport of oxygen.
In-situ and a series of laboratory measurements were conducted to estimate the short- and seasonal variability of benthic fluxes including the effects of burrow ventilation activity by tube-dwelling animals using eddy correlation (EC) and τLIF oxygen imaging techniques, respectively.
The in-situ benthic oxygen fluxes showed high variability at hourly and seasonal timescales, where statistical analysis indicated that current velocity and water depth were the most significant predictors of benthic oxygen flux at the waterside, which co-varied with the discharge, temperature, and oxygen concentration. The range of variability of seasonal fluxes corresponded to the friction velocities which were driven by large-scale flows. Application of a simplified analytical model that couples the effect of hydrodynamic forcing of the diffusive boundary layer with a temperature-dependent oxygen consumption rate within the sediment showed that friction velocity and temperature cause similar variability of the steady-state benthic oxygen flux.
The application of τLIF oxygen imaging system in bioturbation experiments enabled the investigation and discovery of insights into oxygen transport mechanisms across the sediment-water interface. Distinct oxygen structures above burrow openings were revealed, these were associated with burrow ventilation. The DBL was degraded in the presence of burrow ventilation. Advective transport generated by the energetic plumes released at burrow outlets was the dominant transport driving mechanism. The contribution of diffusive flux to the total estimated decreased with increasing larval density. For a range of larvae densities, commonly observed in ponds and lakes, sediment oxygen uptake rates increased up to 2.5-fold in the presence of tube-dwelling animals, and the oxygen transport rate exceeded chironomid respiration by up to a factor of 4.
The coupled physical-biological factors affecting net benthic oxygen flux can be represented by temperature, which is a prominent factor that accounts for both oxygen transport and sediment oxygen uptake. Low oxygen transport by flow coincided with high summer temperatures, amplified by a reduction of benthic population density and pupation. It can also, however, be offset by increased ventilation activity. In contrast, low temperature coincided with high oxygen concentrations, an abundance of larvae, and higher flow is offset by less burrow ventilation activity. Investigation of the effect of hydrodynamics on oxygen transport alone suggested that the expected increase of benthic oxygen flux under global warming can be offset by a reduction in flow velocity, which could ultimately lead to increasing carbon burial rates, and in a growing importance of anaerobic mineralization pathways with increasing emission rates of methane.
This study suggests a significant contribution of biological induced benthic oxygen flux to physical transport driven by large-scale flow-fields contributing to bottom-boundary layer turbulence.
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.
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.
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.
Die deutsche Holzhausbranche wächst seit Jahren, allerdings beschäftigen sich die Unternehmen nicht strategisch mit dem Thema Marketing. Diese Dissertation bildet durch qualitative und quantitative Bewohnerbefragungen die Basis für die Entwicklung eines strategischen Marketingansatzes im Holzhausbereich.
The European weatherfish (Misgurnus fossilis) is a benthic freshwater fish species belonging to the family Cobitidae, that is subjected to a considerable decline in many regions across its original distribution range. Due to its cryptic behavior and low economic value, the causes of threat to weatherfish remained partly unknown and the species is rarely at the center of conservation efforts. In order to address these concerns, the overall aim of the present thesis was to provide a comprehensive approach for weatherfish conservation, including the development of stocking measures, investigations on the species autecology and the evaluation of potential threats. The first objective was to devise and implement a regional reintroduction and stock enhancement program with hatchery-reared weatherfish in Germany. Within this program (2014-2016), a total number of 168,500 juvenile weatherfish were stocked to seven water systems. Recaptures of 45 individuals at two reintroduction sites supported the conclusion that the developed stocking strategy was appropriate. In order to broaden the knowledge about weatherfish autecology and thereby refining the rearing conditions and the selection of appropriate stocking waters, the second objective was to investigate the thermal requirements of weatherfish larvae. Here, the obtained results revealed that temperatures higher than previously suggested were tolerated by larvae, whereas low temperatures within the range of likely habitat conditions increased mortality rates. As weatherfish can be frequently found in agriculturally impacted waters (e.g. ditch systems), they are assumed to have an increased probability to be exposed to chemical stress. Since the resulting risk has not yet been investigated with a focus on weatherfish, the third objective was to provide a methodical foundation for toxicity testing that additionally complies with the requirements of alternative test methods. For this purpose, the acute fish embryo toxicity test was successfully transferred to weatherfish and first results exhibited that sensitivity of weatherfish towards a tested reference substance (3,4-dichloroaniline) was highest compared to other species. On the basis of these findings, the fourth objective was to apply weatherfish embryos for multiple sediment bioassays in order to investigate teratogenic effects derived from sediment-associated contaminants. In this context, weatherfish revealed particular sensitivity to water extractable substances, indicating that sediment contamination might pose a considerable risk. Moreover, as an endangered benthic fish species with high ecological relevance for European waters that are specifically exposed to hazardous contaminants, the weatherfish might be a prospective species for an ecological risk assessment of sediment toxicity. Overall, the present thesis contributed to the conservation of weatherfish by considering a variety of aspects that interact and reinforce one another in order to achieve improvements for the species situation.
Stream ecosystems are one of the most threatened ecosystems worldwide due to their exposure to diverse anthropogenic stressors. Pesticides appear to be the most relevant stressor for agricultural streams. Due to the current mismatch of modelled and measured pesticide concentrations, monitoring is necessary to inform risk assessment or improve future pesticide approvals. Knowing if biotic stress responses are similar across large scales and long time frames could ultimately help in estimating protective stressor thresholds.
This thesis starts with an overview of entry pathways of pesticides to streams as well as the framework of current pesticide monitoring and gives an outline of the objectives of the thesis. In chapter 2, routine monitoring data based on grab sampling from several countries is analysed to identify the most frequently occurring pesticide mixtures. These mixtures are comprised of relatively low numbers of pesticides, of which herbicides are dominating. The detected pesticide mixtures differ between regions and countries, due to differences in the spectrum of analysed compounds and limits of quantification. Current routine monitoring does not include sampling during pesticide peaks associated with heavy rainfall events which likely influences the detected pesticide mixtures. In chapter 3, sampling rates of 42 organic pesticides for passive sampling are provided together with recommendations for the monitoring of field-relevant peaks. Using this information, in chapter 4 a pesticide gradient is established in an Eastern European region where agricultural intensity adjacent to sampled streams ranges from low to high. In contrast to current routine monitoring, rainfall events were sampled and a magnitude of pesticides were analysed. This led to the simultaneous detection of numerous pesticides of which one to three drive the pesticide toxicity. The toxicity, however, showed no relationship to the agricultural intensity. Using microcosms, the stress responses of fungal communities, the hyphomycetes, and the related ecosystem function of leaf decomposition, is investigated in chapter 5. Effects of a field-relevant fungicide mixture are examined across three biogeographical regions for three consecutive cycles of microbial leaf colonisation and decomposition. Despite different initial communities, stress responses as well as recoveries were similar across biogeographical regions, indicating a general pattern.
Overall, this thesis contributes to an improved understanding of occurrence and concentrations of pesticides mixtures in streams, their monitoring and impact on an ecosystem function. We showed that estimated pesticide toxicities reach levels that affect non-target organisms and thereby potentially whole ecosystems. Routine monitoring, however, likely underestimates the threat by pesticides. Effects leading to a loss in biodiversity or functions in streams ecosystems can be reduced by reassessing approved pesticides with ongoing targeted monitoring and increased knowledge of effects caused by these pesticides.