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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.
Engineered nanoparticles (ENP) are widely used in different industrial fields and products. In the last years, the risk potential for the release of ENP in the environment has increased as never before. ENP are expected to pass the wastewater-river-topsoil-groundwater pathway. In the terrestrial and aquatic environment ENP can undergo aging and transformation processes which can influence fate, transport and toxicological effects to different living organisms.
The scope of this workshop is to gather researchers, scientists, experts and specialists from nanoparticle and colloid science, soil and environmental chemistry, ecotoxicology or neighbouring disciplines to discuss the latest results and findings in the field of aging, fate, transport and toxicological effects of nanoparticles in the environment.
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.
The decline of biodiversity can be observed worldwide and its consequences are alarming. It is therefore crucial that nature must be protected and, where possible, restored. A wide variety of different project options are possible. Yet in the context of limited availability of resources, the selection of the most efficient measures is increasingly important. For this purpose, there is still a lack of information. This pertains, as outlined in the next paragraph, in particular, to information at different scales of projects.
Firstly, there is a lack of information on the concrete added value of biodiversity protection projects. Secondly, there is a lack of information on the actual impacts of such projects and on the costs and benefits associated with a project. Finally, there is a lack of information on the links between the design of a project, the associated framework conditions and the perception of specific impacts. This paper addresses this knowledge gap by providing more information on the three scales by means of three empirical studies on three different biodiversity protection projects in order to help optimize future projects.
The first study “Assessing the trade-offs in more nature-friendly mosquito control in the Upper Rhine region” examines the added value of a more nature-friendly mosquito control in the Upper Rhine Valley of Germany using a contingent valuation method. Recent studies show that the widely used biocide Bti, which is used as the main mosquito control agent in many parts of the world, has more negative effects on nature than previously expected. However, it is not yet clear whether the population supports a more nature-friendly mosquito control, as such an adaptation could potentially lead to higher nuisance. This study attempts to answer this question by assessing the willingness to pay for an adapted mosquito control strategy that reduces the use of Bti, while maintaining nuisance protection within settlements. The results show that the majority of the surveyed population attaches a high value to a more nature-friendly mosquito control and is willing to accept a higher nuisance outside of the villages.
The second study “Inner city river restoration projects: the role of project components for acceptance” examines the acceptance of a river restoration project in Rhineland-Palatinate, Germany. Despite much effort, many rivers worldwide are still in poor condition. Therefore, a rapid implementation of river restoration projects is of great importance. In this context, acceptance by society plays a fundamental role, however, the factors determining such acceptance are still poorly understood. In particular, the complex interplay between the acceptance or rejection of specific project components and the acceptance of the overall project require further exploration. This study addresses this knowledge gap by assessing the acceptance of the project, its various ecological and social components, and the perception of real and fictitious costs as well as the benefits of the components. Our findings demonstrate that while acceptance of the overall project is generally rather high, many respondents reject one or more of the project's components. Complementary social project components, like a playground, find less support than purely ecological components. Overall, our research shows that complementary components may increase or decrease acceptance of the overall project. We, furthermore, found that differences in the acceptance of the individual components depend on individual concerns, such as perceived flood risk, construction costs, expected noise and littering as well as the quality of communication, attachment to the site, and the age of the respondents.
The third study “What determines preferences for semi-natural habitats in agrarian landscapes? A choice-modelling approach across two countries using attributes characterizing vegetation” investigates people's aesthetic preferences for semi-natural habitats in agricultural landscapes. The EU-Common Agricultural Policy promotes the introduction of woody and grassy semi-natural habitats (SNH) in agricultural landscapes. While the benefits of these structures in terms of regulating ecosystem services are already well understood, the effects of SNH on visual landscape quality is still not clear. This study investigates the factors determining people’s visual preferences in the context of grassy and woody SNH elements in Swiss and Hungarian landscapes using picture-based choice experiments. The results suggest that respondents’ choices strongly depend on specific vegetation characteristics that appear and disappear over the year. In particular, flowers as a source of colours and green vegetation as well as ordered structure and the proportion of uncovered soil in the picture play an important role regarding respondents’ aesthetic perceptions of the pictures.
The three empirical studies can help to make future projects in the study areas of biodiversity protection more efficient. While this thesis highlights the importance of exploring biodiversity protection projects at different scales, further analyses of the different scales of biodiversity protection projects are needed to provide a sound basis to develop guidance on identifying the most efficient biodiversity protection projects.
Fresh water resources like rivers and reservoirs are exposed to a drastically changing world. In order to safeguard these lentic ecosystems, they need stronger protection in times of global change and population growth. In the last years, the exploitation pressure on drinking water reservoirs has increased steadily worldwide. Besides securing the demands of safe drinking water supply, international laws especially in Europe (EU Water Framework Directive) stipulate to minimize the impact of dams on downstream rivers. In this study we investigate the potential of a smart withdrawal strategy at Grosse Dhuenn Reservoir to improve the temperature and discharge regime downstream without jeopardizing drinking water production. Our aim is to improve the existing withdrawal strategy for operating the reservoir in a sustainable way in terms of water quality and quantity. First, we set-up and calibrated a 1D numerical model for Grosse Dhuenn Reservoir with the open-source community model “General Lake Model” (GLM) together with its water quality module “Aquatic Ecodynamics” library (AED2). The reservoir model reproduced water temperatures and hypolimnetic dissolved oxygen concentrations accurately over a 5 year period. Second, we extended the model source code with a selective withdrawal functionality (adaptive offtake) and added operational rules for a realistic reservoir management. Now the model is able to autonomously determine the best withdrawal height according to the temperature and flow requirements of the downstream river and the raw water quality objectives. Criteria for the determination of the withdrawal regime are selective withdrawal, development of stratification and oxygen content in the deep hypolimnion. This functionality is not available in current reservoir models, where withdrawal heights are generally provided a priori to the model and kept fixed during the simulation. Third, we ran scenario simulations identifying an improved reservoir withdrawal strategy to balance the demands for downstream river and raw water supply. Therefore we aimed at finding an optimal parallel withdrawal ratio between cold hypolimnetic water and warm epilimnetic or metalimnetic water in order to provide a pre-defined temperature in the downstream river. The reservoir model and the proposed withdrawal strategy provide a simple and efficient tool to optimize reservoir management in a multi-objective view for mastering future reservoir management challenges.
Vertebrate biodiversity is rapidly decreasing worldwide with amphibians being the most endangered vertebrate group. In the EU, 21 of 89 amphibian species are recognized as being endangered. The intensively used European agricultural landscape is one of the major causes for these declines. As agriculture represents an essential habitat for amphibians, exposure to pesticides can have adverse effects on amphibian populations. Currently, the European risk assessment of pesticides for vertebrates requires specific approaches for fish regarding aquatic vertebrate toxicity and birds as well as mammals for terrestrial vertebrate toxicity but does not address the unique characteristics of amphibians. Therefore, the overall goal of this thesis was to investigate the ecotoxicological effects of pesticides on Central European anuran amphibians. For this, effects on aquatic and terrestrial amphibian life stages as well as on reproduction were investigated. Then, in anticipation of a risk assessment of pesticides for amphibians, this thesis discussed potential regulatory risk assessment approaches.
For the investigated pesticides and amphibian species, it was observed that the acute aquatic toxicity of pesticides can be addressed using the existing aquatic risk assessment approach based on fish toxicity data. However, lethal as well as sublethal effects were observed in terrestrial juveniles after dermal exposure to environmentally realistic pesticide concentrations, which cannot be covered using an existing risk assessment approach. Therefore, pesticides should also be evaluated for potential terrestrial toxicity using risk assessment tools before approval. Additionally, effects of co-formulants and adjuvants of pesticides need specific consideration in a future risk assessment as they can increase toxicity of pesticides to aquatic and terrestrial amphibian stages. The chronic duration of combined aquatic and terrestrial exposure was shown to affect amphibian reproduction. Currently, such effects cannot be captured by the existing risk assessment as data involving field scenarios analysing effects of multiple pesticides on amphibian reproduction are too rare to allow comparison to data of other terrestrial vertebrates such as birds and mammals. In the light of these findings, future research should not only address acute and lethal effects, but also chronic and sublethal effects on a population level. As pesticide exposure can adversely affect amphibian populations, their application should be considered even more carefully to avoid further amphibian declines. Overall, this thesis emphasizes the urgent need for a protective pesticide risk assessment for amphibians to preserve and promote stable amphibian populations in agricultural landscapes.
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.
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.
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.
The research described in this thesis was designed to yield information on the impact of particle-bound pesticides on organisms living in the interface between sediment and water column in a temporarily open estuary (TOCEs). It was hypothesized that natural variables such as salinity and temperature and anthropogenic stressors such as particle-bound pesticides contribute to the variability of the system. A multiple line of evidence approach is necessary due to the variability in sediment type, contaminant distribution and spatial and temporal variability within the ecosystem in particular within TOCEs. The first aim of this thesis was to identify which particle-bound pesticides are important to the contamination of the Lourens River estuary (Western Cape, South Africa), taking into account their environmental concentrations, physico-chemical and toxicological properties (Exposure assessment). The second aim was to identify spatial and temporal variations in particle bound pesticide contamination, natural environmental variables and benthic community structure (effect assessment). The third aim was to test the hypothesis: "does adaptation to fluctuating salinities lead to enhanced survival of the harpacticoid copepod Mesochra parva when exposed to a combination of particle associated chlorpyrifos exposure and hypo-osmotic stress during a 96 h sediment toxicity test?" The last aim was to identify the driving environmental variables (including natural and anthropogenic stressors) in a "natural" (Rooiels River) compared to a "disturbed" (Lourens River) estuary and to identify if and how these variables change the benthic community structure in both estuaries. Data produced in this research thus provide important information to understand the impact of pesticides and its interaction with natural variables in a temporarily open estuary. To summarise, this study indicated, by the use of the multi-evidence approach, that the pesticides endosulfan and chlorpyrifos posed a risk towards benthic organisms in a temporarily open estuary in particular during spring season. Furthermore an important link between pesticide exposure/ toxicity and salinity was identified, which has important implications for the management of temporarily open estuaries.