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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.
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.
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 bio-insecticide Bacillus thuringiensis israelensis (Bti) has worldwide become the most commonly used agentin mosquito control programs that pursue two main objectives: the control of vector-borne diseases and the reduction of nuisance, mainly coming frommosquitoes that emerge in large quantities from seasonal wetlands. The Upper Rhine Valley, a biodiversity hotspot in Germany, has been treated withBti for decades to reduce mosquito-borne nuisance and increase human well-being.Although Btiis presumed to be an environmentally safe agent,adverse effects on wetland ecosystems are still a matter of debate especially when it comes to long-term and indirect effects on non-target organisms. In light of the above, this thesis aims at investigating direct and indirect effects of Bti-based mosquito control on non-target organisms within wetland food chains.Effects were examinedin studies with increasingeco(toxico)logical complexity, ranging from laboratory over mesocosm to field approaches with a focus on the non-biting Chironomidae and amphibian larvae (Rana temporaria, Lissotriton sp.).In addition, public acceptance of environmentally less invasive alternative mosquito control methods was evaluated within surveys among the local population.
Chironomids were the most severely affected non-target aquatic invertebrates. Bti substantially reduced larval and adult chironomid abundances and modified their species composition. Repeated exposures to commonly used Bti formulations induced sublethal alterations of enzymatic biomarkers activityin frog tadpoles. Bti-induced reductions of chironomid prey availability indirectly decreased body size of newts at metamorphosis and increased predation on newt larvae in mesocosm experiments. Indirect effects of severe reductions in midge biomassmight equally be passed through aquatic but also terrestrial food chains influencing predators of higher trophic levels. The majority ofaffectedpeople in the Upper Rhine Valley expressed a high willingness to contributefinancially to environmentally less harmful mosquito control.Alternative approaches could still include Bti applications excepting treatment of ecologically valuable areas. Potentially rising mosquito levels could be counteracted with local acting mosquito traps in domestic and urban areas because mosquito presence was experienced as most annoying in the home environment.
As Bti-based mosquito control can adversely affect wetland ecosystems, its large-scale applications, including nature conservation areas, should be considered more carefully to avoid harmful consequences for the environmentat the Upper Rhine Valley.This thesis emphasizesthe importance to reconsiderthe current practice of mosquito control and encourage research on alternative mosquito control concepts that are endorsed by the local population. In the context ofthe ongoing amphibian and insect declinesfurther human-induced effects onwetlands should be avoided to preserve biodiversity in functioning ecosystems.
Recent estimates have confirmed that inland waters emit a considerable amount of CH4 and CO2 to the atmosphere at the regional and global scale. But these estimates are based on extrapolated measured data and lack of data from inland waters in arid and semi-arid regions and carbon sources from wastewater treatment plants (WWTPs) as well insufficient resolution of the spatiotemporal variability of these emissions.
Through this study, we analyzed monthly hydrological, meteorological and water quality data from three irrigation and drinking water reservoirs in the lower Jordan River basin and estimated the atmospheric emission rates of CO2. We investigated the effect of WWTPs on surrounding aquatic systems in term of CH4 and CO2 emission by presenting seasonally resolved data for dissolved concentrations of both gases in the effluents and in the receiving streams at nine WWTPs in Germany.
We investigated spatiotemporal variability of CH4 and CO2 emission from aquatic ecosystems by using of simple low-cost tools for measuring CO2 flux and bubble release rate from freshwater systems. Our estimates showed that reservoirs in semi-arid regions are oversaturated with CO2 and acted as net sources to the atmosphere. The magnitude of observed fluxes at the three water reservoirs in Jordan is comparable to those from tropical reservoirs (3.3 g CO2 m-2 d-1). The CO2 emission rate from these reservoirs is linked to changes of water surface area, which is the result of water management practices. WWTPs have been shown to discharge a considerable amount of CH4 (30.9±40.7 kg yr-1) and CO2 (0.06±0.05 Gg yr-1) to their surrounding streams, and emission rates of CH4 and CO2 from these streams are significantly enhanced by effluents of WWTPs up to 1.2 and 8.6 times, respectively.
Our results showed that both diffusive flux and bubble release rate varied in time and space, and both of emission pathways should be included and variability should be resolved adequately in further sampling and measuring strategies. We conclude that future emission measurements and estimates from inland waters may consider water management practices, carbon sources from WWTPs as well spatial and temporal variability of emission.
For decades a worldwide decline of biological diversity has been reported. Landscapes are influenced by several kinds of anthropogenic disturbances. Agricultural land use, application of fertilizers and pesticides and the removal of corridors simplify and homogenize a landscape whereas others like road constructions lead to fragmentation. Both kinds lead to a constraint of habitats, reduce living environment and gene pool, hinder gene flow and change the functional characteristics of species. Furthermore, it facilitates the introduction of alien species. On the other hand, disturbances of different temporal and spatial dimensions lead to a more diverse landscape because they prevent competitive exclusion and create niches where species are able to coexist.
This study focuses on the complexity of disturbance regimes and its influence on phytodiversity. It differs from other studies that mostly select one or few disturbance types in including all identifiable disturbances. Data were derived from three study sites in the north of Bavaria and are subject to different land-use intensities. Two landscapes underlie agriculture and forestry, of which one is intensively used and the second one rather moderate and small-scaled. The third dataset was collected on an actively used military training area. The first part of the study deals with the influence of disturbance regimes on phytodiversity, first with the focus on military disturbances, afterwards in comparison with the agricultural landscapes. The second part examines the influence of disturbance regimes on red-listed species, the distribution of neophytes and generalist plant species and the homogenization of the landscape. All analyses were conducted on landscape and local scale.
A decisive role was played by the variety of disturbance types, especially in different temporal and spatial dimensions and not by single kinds of disturbances, which significantly was proven in the military training area with its multiple and undirected disturbance regime. Homogeneous disturbance regimes that typically are found in agricultural landscapes led to a reduced species number. On local scale, the abiotic heterogeneity which originated of recent and historical disturbances superimposed the positive effects of disturbance regimes, whereas dry and nutrient-poor sites showed a negative effect. Due to a low tree density and moderate treatment species numbers were significantly higher in forest in the training area than in the two agricultural landscapes.
Numbers of red-listed species were positively correlated to the total number of species in all three sites. However, the military training area showed a significantly higher abundance within the area in comparison to the agricultural landscapes where rare species were mostly found on marginal strips. Furthermore, numbers of neophytes and generalist species were lower and consequently homogenization.
In conclusion, the military training area is an ideal landscape from a nature conservation point of view. The moderately used agricultural area showed high species numbers and agricultural productivity. However, yield is too low to withstand either abandonment or land-use intensification.
The role of alternative resources for pollinators and aphid predators in agricultural landscapes
(2021)
The world wide decline of insects is often associated with loss of natural and semi-natural habitat caused by intensified land-use. Many insects provide important ecosystem services to agriculture, such as pest control or pollination. To efficiently promote insects on remaining semi-natural habitat we need precise knowledge of their requirements to non-crop habitat. This thesis focuses on identifying
the most important semi-natural habitats (forest edges, grasslands, and semi-open habitats) for pollinators and natural enemies of crop pests with respect to their food resource requirements. Special
attention is given to floral resources and their spatio-temporal distribution in agricultural landscapes.
Floral resource maps might get closer at characterizing landscapes the way they are experienced by insects compared to classical habitat maps. Performance of the two map types was compared on the prediction of wild bees and natural enemies that consume nectar and pollen, identifying habitats of special importance in the process. In wild bees, influences of spatio-temporal floral resource availability were analysed as well as habitat preferences of specific groups of bees. Understanding dietary needs of natural enemies of crop pests requires additional knowledge on prey use. To this end, ladybird gut contents have been analysed by means of high-throughput sequencing for insight into aphid prey-use.
Results showed, that wild bees were predicted better by floral resource maps compared to classical habitat maps. Forest edge area, as well as floral resources in forest edges had positive effects on abundance and diversity of rare bees and important crop pollinators. Similar patterns were retained for grassland diversity. Especially early floral resources seemed to have positive effects on wild bees. Crops and fruit trees produced a resource pulse in April that exceeded floral resource availability in May and June by tenfold. Most floral resources in forest edges appeared early in the season, with the highest floral density per area. Grasslands provided the lowest amount of floral resources but highest diversity, which was evenly distributed over the season.
Despite natural enemies need for floral resources, classical habitat maps performed better at predicting natural enemies of crop pests compared to floral resource maps. Classical habitat maps revealed a positive effect of forest edge habitat on the abundance of pest enemies, which translated into improved aphid control. Results from gut content analysis reveal high portions of pest aphid species and nettle aphids as well as a broader insight into prey spectra retained from ladybirds collected from sticky traps compared to individuals collected by hand. The aphid specific primer designed for this purpose will be helpful for identifying aphid consumption by ladybirds in future studies.
Findings of this thesis show the potential of floral resource maps for understanding interactions of wild bees and the landscape but also indicate that natural enemies are limited by other resources. I would like to highlight the positive effects of forest edges for different groups of bees as well as natural enemies and their performance on pest control.
Fate and effects of insecticides in vegetated agricultural drainage ditches and constructed wetlands
(2006)
Studies have shown that runoff and spray-drift are important sources of nonpoint-source pesticide pollution of surface waters. Owing to this, public concern over the presence of pesticides in surface and ground water has resulted in intensive scientific efforts to find economical, yet environmentally sound solutions to the problem. The primary objective of this research was to assess the effectiveness of vegetated aquatic systems in providing buffering between natural aquatic ecosystems and agricultural landscape following insecticide associated runoff and spray-drift events. The first set of studies were implemented using vegetated agricultural ditches, one in Mississippi, USA, using pyrethroids (bifenthrin, lambda-cyhalothrin) under simulated runoff conditions and the other in the Western Cape, South Africa using the organophosphate insecticide, azinphos-methyl (AZP), under natural runoff and spray-drift conditions. The second set of studies were implemented using constructed wetlands, one in the Western Cape using AZP under natural spray-drift conditions and the other in Mississippi, USA using the organophosphate MeP under simulated runoff conditions. Results from the Mississippi-ditch study indicated that ditch lengths of less than 300 m would be sufficient to mitigate bifenthrin and lambda-cyhalothrin. In addition, data from mass balance calculations determined that the ditch plants were the major sink (generally > 90%) and/or sorption site for the rapid dissipation of the above pyrethroids from the water column. Similarly, results from the ditch study in South Africa showed that a 180 m vegetated system was effective in mitigating AZP after natural spray drift and low flow runoff events. Analytical results from the first wetland study show that the vegetated wetland was more effective than the non-vegetated wetland in reducing loadings of MeP. Mass balance calculations indicated approximately 90% of MeP mass was associated with the plant compartment. Ninety-six hours after the contamination, a significant negative acute effect of contamination on abundances was found in 8 out of the 15 macroinvertebrate species in both wetland systems. Even with these toxic effects, the overall reaction of macroinvertebrates clearly demonstrated that the impact of MeP in the vegetated wetland was considerably lower than in the non-vegetated wetland. Results from the constructed wetland study in South Africa revealed that concentrations of AZP at the inlet of the 134 m wetland system were reduced by 90% at the outlet. Overall, results from all of the studies in this thesis indicate that the presence of the plant compartment was essential for the effective mitigation of insecticide contamination introduced after both simulated and natural runoff or spray-drift events. Finally, both the vegetated agricultural drainage ditch and vegetated constructed wetland systems studied would be effective in mitigating pesticide loadings introduced from either runoff or spray-drift, in turn lowering or eliminating potential pesticide associated toxic effects in receiving aquatic ecosystems. Data produced in this research provide important information to reduce insecticide risk in exposure assessment scenarios. It should be noted that incorporating these types of best management practices (BMPs) will decrease the risk of acute toxicity, but chronic exposure may still be an apparent overall risk.
In the new epoch of Anthropocene, global freshwater resources are experiencing extensive degradation from a multitude of stressors. Consequently, freshwater ecosystems are threatened by a considerable loss of biodiversity as well as substantial decrease in adequate and secured freshwater supply for human usage, not only on local scales, but also on regional to global scales. Large scale assessments of human and ecological impacts of freshwater degradation enable an integrated freshwater management as well as complement small scale approaches. Geographic information systems (GIS) and spatial statistics (SS) have shown considerable potential in ecological and ecotoxicological research to quantify stressor impacts on humans and ecological entitles, and disentangle the relationships between drivers and ecological entities on large scales through an integrated spatial-ecological approach. However, integration of GIS and SS with ecological and ecotoxicological models are scarce and hence the large scale spatial picture of the extent and magnitude of freshwater stressors as well as their human and ecological impacts is still opaque. This Ph.D. thesis contributes novel GIS and SS tools as well as adapts and advances available spatial models and integrates them with ecological models to enable large scale human and ecological impacts identification from freshwater degradation. The main aim was to identify and quantify the effects of stressors, i.e climate change and trace metals, on the freshwater assemblage structure and trait composition, and human health, respectively, on large scales, i.e. European and Asian freshwater networks. The thesis starts with an introduction to the conceptual framework and objectives (chapter 1). It proceeds with outlining two novel open-source algorithms for quantification of the magnitude and effects of catchment scale stressors (chapter 2). The algorithms, i.e. jointly called ATRIC, automatically select an accumulation threshold for stream network extraction from digital elevation models (DEM) by assuring the highest concordance between DEM-derived and traditionally mapped stream networks. Moreover, they delineate catchments and upstream riparian corridors for given stream sampling points after snapping them to the DEM-derived stream network. ATRIC showed similar or better performance than the available comparable algorithms, and is capable of processing large scale datasets. It enables an integrated and transboundary management of freshwater resources by quantifying the magnitude of effects of catchment scale stressors. Spatially shifting temporal points (SSTP), outlined in chapter 3, estimates pooled within-time series (PTS) variograms by spatializing temporal data points and shifting them. Data were pooled by ensuring consistency of spatial structure and temporal stationarity within a time series, while pooling sufficient number of data points and increasing data density for a reliable variogram estimation. SSTP estimated PTS variograms showed higher precision than the available method. The method enables regional scale stressors quantification by filling spatial data gaps integrating temporal information in data scarce regions. In chapter 4, responses of the assumed climate-associated traits from six grouping features to 35 bioclimatic indices for five insect orders were compared, their potential for changing distribution pattern under future climate change was evaluated and the most influential climatic aspects were identified (chapter 4). Traits of temperature preference grouping feature and the insect order Ephemeroptera exhibited the strongest response to climate as well as the highest potential for changing distribution pattern, while seasonal radiation and moisture were the most influential climatic aspects that may drive a change in insect distribution pattern. The results contribute to the trait based freshwater monitoring and change prediction. In chapter 5, the concentrations of 10 trace metals in the drinking water sources were predicted and were compared with guideline values. In more than 53% of the total area of Pakistan, inhabited by more than 74 million people, the drinking water was predicted to be at risk from multiple trace metal contamination. The results inform freshwater management by identifying potential hot spots. The last chapter (6) synthesizes the results and provides a comprehensive discussion on the four studies and on their relevance for freshwater resources conservation and management.
Gel effect induced by mucilage in the pore space and consequences on soil physical properties
(2020)
Water uptake, respiration and exudation are some of the biological functions fulfilled by plant roots. They drive plant growth and alter the biogeochemical parameters of soil in the vicinity of roots, the rhizosphere. As a result, soil processes such as water fluxes, carbon and nitrogen exchanges or microbial activity are enhanced in the rhizosphere in comparison to the bulk soil. In particularly, the exudation of mucilage as a gel-like substance by plant roots seems to be a strategy for plants to overcome drought stress by increasing soil water content and soil unsaturated hydraulic conductivity at negative water potentials. Although the variations of soil properties due to mucilage are increasingly understood, a comprehensive understanding of the mechanisms in the pore space leading to such variations is lacking.
The aim of this work was to elucidate the gel properties of mucilage in the pore space, i.e. interparticulate mucilage, in order to link changes of the physico-chemical properties in the rhizosphere to mucilage. The fulfilment of this goal was confronted to the three following challenges: The lack of methods for in situ detection of mucilage in soil; The lack of knowledge concerning the properties of interparticulate mucilage; The unknown relationship between the composition and the properties of model substances and root mucilage produced by various species. These challenges are addressed in several chapters.
In a first instance, a literature review picked information from various scientific fields about methods enabling the characterization of gels and gel phases in soil. The variation of soil properties resulting from biohydrogel swelling in soil was named the gel effect. The combined study of water entrapment of gels and gel phases in soil and soil structural properties in terms of mechanical stability or visual structures proved promising to disentangle the gel effect in soil.
The acquired methodical knowledge was used in the next experiments to detect and characterize the properties of interparticulate gel. 1H NMR relaxometry allows the non-invasive measure of water mobility in porous media. A conceptual model based on the equations describing the relaxation of water protons in porous media was developed to integrate the several gel effects into the NMR parameters and quantify the influence of mucilage on proton relaxation. Rheometry was additionally used to assess mucilage viscosity and soil microstructural stability and ESEM images to visualize the network of interparticulate gel. Combination of the results enabled to identify three main interparticulate gel properties: The spider-web effect restricts the elongation of the polymer chains due to the grip of the polymer network to the surface of soil particles. The polymer network effect illustrates the organization of the polymer network in the pore space according to the environment. The microviscosity effect describes the increased viscosity of interparticulate gel in contrast to free gel. The impact of these properties on soil water mobility and microstructural stability were investigated. Consequences on soil hydraulic and soil mechanical properties found in the literature are further discussed.
The influence of the chemical properties of polymers on gel formation mechanism and gel properties was also investigated. For this, model substances with various uronic acid content, degree of esterification and amount of calcium were tested and their amount of high molecular weight substances was measured. The substances investigated included pectic polysaccharides and chia seed mucilage as model polymers and wheat and maize root mucilage. Polygalacturonic acid and low-methoxy pectin proved as non-suitable model polymers for seed and root mucilage as ionic interactions with calcium control their properties. Mucilage properties rather seem to be governed by weak electrostatic interactions between the entangled polymer chains. The amount of high molecular weight material varies considerably depending on mucilage´s origin and seems to be a straight factor for mucilage’s gel effect in soil. Additionally to the chemical characterization of the high molecular weight compounds, determination of their molecular weight and of their conformation in several mucilages types is needed to draw composition-property profiles. The variations measured between the various mucilages also highlight the necessity to study how the specific properties of the various mucilages fulfill the needs of the plant from which they are exuded.
Finally, the integration of molecular interactions in gel and interparticulate gel properties to explain the physical properties of the rhizosphere was discussed. This approach offers numerous perspectives to clarify for example how water content or hydraulic conductivity in the rhizosphere vary according to the properties of the exuded mucilage. The hypothesis that the gel effect is general for all soil-born exudates showing gel properties was considered. As a result, a classification of soil-born gel phases including roots, seeds, bacteria, hyphae and earthworm’s exuded gel-like material according to their common gel physico-chemical properties is recommended for future research. An outcome could be that the physico-chemical properties of such gels are linked with the extent of the gel effect, with their impact on soil properties and with the functions of the gels in soil.