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- Fachbereich 7 (99) (remove)
The increase in plastic particles (< 5 mm) in the environment is a global problem, which is in direct correlation to the increasing production quantity and variety. Through direct input (primary) or through the degradation of macroplastics (secondary), particles enter the environmental compartments water and/or soil via conventional material transportation paths. The research and development work on the sustainable removal of microplastic particles (inert organic chemical stressors, IOCS) from wastewater is based on the construction of polymer inclusion compounds. IOCS describe a group of organic chemical molecules, which demonstrate a high level of persistence upon entry in the ecosystem and whose degradation is limited.
Following the principle of Cloud Point Technology, a novel separation technique has been developed which induces particle growth in microplastics and allows easier separation from the water by volume increase according to the state of the art. The concept for the sustainable removal of microplastics from Herbort and Schuhen is based on a three-step synthesis. This concept was further optimized as part of the research and adapted to the criteria of resource efficiency and profitability. The fundamental research is premised on the hypothesis that van der Waals forces with short ranges and localized hydrophobic interactions between precursors and/or material and the IOCS to be connected can induce a fixation through the formation of an inclusion compound with particle growth. Through the addition of silicon-based ecotoxicologically irrelevant coagulation and inclusion units, it is possible to initiate molecular self-organization with the hydrophobic stressors in an aggregation process induced through water. It results in adhesive particle growth around the polymer particles and between particles. Subsequently, the polymer extract can be separated from aquatic media through simple and cost-effective filtration processes (e.g. sand trap, grease trap), due to the 10,000 times larger volume microplastic agglomerates.
The European landscape is dominated by intensive agriculture which leads to widespread impact on the environment. The frequent use of agricultural pesticides is one of the major causes of an ongoing decline in flower-visiting insects (FVIs). The conservation of this ecologically diverse assemblage of mobile, flying insect species is required by international and European policy. To counteract the decrease in species numbers and their abundances, FVIs need to be protected from anthropogenic stressors. European pesticide risk assessment was devised to prevent unacceptable adverse consequences of pesticide use on FVIs. However, there is an ongoing discussion by scientists and policy-makers if the current risk assessment actually provides adequate protection for FVI species.
The first main objective of this thesis was to investigate pesticide impact on FVI species. The scientific literature was reviewed to identify groups of FVIs, summarize their ecology, and determine their habitat. This was followed by a synthesis of studies about the exposure of FVIs in their habitat and subsequent effects. In addition, the acute sensitivity of one FVI group, bee species, to pesticides was studied in laboratory experiments.
The second main objective was to evaluate the European risk assessment for possible deficits and propose improvements to the current framework. Regulatory documents were screened to assess the adequacy of the guidance in place in light of the scientific evidence. The suitability of the honey bee Apis mellifera as the currently only regulatory surrogate species for FVIs was discussed in detail.
The available scientific data show that there are far more groups of FVIs than the usually mentioned bees and butterflies. FVIs include many groups of ecologically different species that live in the entire agricultural landscape. Their habitats in crops and adjacent semi-natural areas can be contaminated by pesticides through multiple pathways. Environmentally realistic exposure of these habitats can lead to severe effects on FVI population parameters. The laboratory studies of acute sensitivity in bee species showed that pesticide effects on FVIs can vary greatly between species and pesticides.
The follow-up critical evaluation of the European FVI risk assessment revealed major shortcomings in exposure and effect assessment. The honey bee proved to be a sufficient surrogate for bee species in lower tier risk assessment. Additional test species may be chosen for higher tier risk assessment to account for ecological differences. This thesis shows that the ecology of FVIs should generally be considered to a greater extent to improve the regulatory process. Data-driven computational approaches could be used as alternative methods to incorporate ecological trait data in spatio-temporal scenarios. Many open questions need to be answered by further research to better understand FVI species and promote necessary changes to risk assessment. In general, other FVI groups than bees need to be investigated. Furthermore, comprehensive data on FVI groups and their ecology need to be collected. Contamination of FVI habitat needs to be linked to exposure of FVI individuals and ecologically complex effects on FVI populations should receive increased attention. In the long term, European FVI risk assessment would benefit from shifting its general principles towards more scientifically informed regulatory decisions. This would require a paradigm shift from arbitrary assumptions and unnecessarily complicated schemes to a substantiated holistic framework.
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.
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.
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.
Die Nachhaltigkeitsberichterstattung kann als ein zentrales Element einer konsequenten Unternehmensstrategie zur Umsetzung der gesellschaftlichen Verantwortung (Corporate Social Responsibility) angesehen werden. Um die Unternehmen bei dieser Aufgabe zu unterstützen stellt die Global Reporting Initiative (GRI) mit ihren G4 Leitlinien einen Orientierungsrahmen bereit, dessen Anwendung sich allerdings für Klein und Mittelunternehmen sehr komplex gestaltet. Ein branchenspezifisches Sector Supplement für den Weinbau existiert derzeit noch nicht.
Ziel der vorliegenden Arbeit ist es, diese Forschungslücke durch die Entwicklung weinbauspezifischer Nachhaltigkeitsaspekte und Indikatoren zu schließen, um den Betrieben eine selbstständige GRI-konforme Berichterstattung zu ermöglichen.
Der Prozess zur Identifikation wesentlicher Nachhaltigkeitsaspekte und -indikatoren erfolgt mittels Erhebungs- und Auswertungsmethoden der qualitativen Sozialforschung in Form
von Workshops, betrieblichen Vorortanalysen und Experteninterviews.
Parallel dazu erfolgt eine umfassende Analyse der weinbaulichen Wertschöpfungskette in Form einer Internet- und Literaturrecherche. Diese umfasst vorrangig die ökologischen Nachhaltigkeitsaspekte als diejenigen Bestandteile weinbaulicher Tätigkeiten, die sich sowohl positiv als auch negativ auf die Umwelt auswirken können. Anschließend erfolgt die zentrale Priorisierung der identifizieren Handlungsfelder und Nachhaltigkeitsthemen durch die Stakeholder. Zur Visualisierung der bewerteten Handlungsfelder dient das Instrument der Wesentlichkeitsanalyse.
Auf dieser Basis erfolgt die Entwicklung eines Handlungsleitfadens zur Erstellung von Nachhaltigkeitsberichten in der Weinwirtschaft. Hiermit erlangen Weingüter die praktische Kompetenz ein eigenes Nachhaltigkeitsreporting anzugehen.
Im Rahmen der Arbeit wurde auch ein elektronisches Tool entwickelt, das den Betrieben die Möglichkeit eröffnet, betriebliche Umweltaspekte zu erfassen und zu bewerten. Gleichzeitig wird den Anwendern damit die Generierung eines überbetrieblichen Vergleichs der Umweltleistung ermöglicht (Benchmarking).
Eine weitere Forschungsfrage der vorliegenden Arbeit beschäftigt sich mit der Biodiversitätserfassung und -bewertung für Rebland. Hintergrund sind die bisher nur geringen Funde auf der durch das Bundesamt für Naturschutz festgelegten Kennartenlisten bzw. den HNV-Stichprobenflächen (High nature value farmland-Indikator) für Rebland.
Hierzu wurde mittels Geoinformationssystemen das Artenvorkommen in rheinland-pfälzischen Weinanbaugebieten analysiert und 30 Pflanzenarten als Indikatorarten für den Weinbau abgeleitet. Ergänzend wurden weinbergstypische, geschützte Tierarten als „Bonusarten“ identifiziert. Die Indikatorarten werden den Winzern als ein Instrument zur eigenständigen Erfassung der Biodiversität in den Weinbergen dienen und im Rahmen einer Nachhaltigkeitsberichterstattung herangezogen werden können.
Groundwater is essential for the provision of drinking water in many areas around the world. The ecosystem services provided by groundwater-related organisms are crucial for the quality of groundwater-bearing aquifers. Therefore, if remediation of contaminated groundwater is necessary, the remediation method has to be carefully selected to avoid risk-risk trade-offs that might impact these valuable ecosystems. In the present thesis, the ecotoxicity of the in situ remediation agent Carbo-Iron (a composite of zero valent nano-iron and active carbon) was investigated, an estimation of its environmental risk was performed, and the risk and benefit of a groundwater remediation with Carbo-Iron were comprehensively analysed.
At the beginning of the work on the present thesis, a sound assessment of the environmental risks of nanomaterials was impeded by a lack of guidance documents, resulting in many uncertainties on selection of suitable test methods and a low comparability of test results from different studies with similar nanomaterials. The reasons for the low comparability were based on methodological aspects of the testing procedures before and during the toxicity testing. Therefore, decision trees were developed as a tool to systematically decide on ecotoxicity test procedures for nanomaterials. Potential effects of Carbo-Iron on embryonic, juvenile and adult life stages of zebrafish (Danio rerio) and the amphipod Hyalella azteca were investigated in acute and chronic tests. These tests were based on existing OECD and EPA test guidelines (OECD, 1992a, 2013a, 2013b; US EPA, 2000) to facilitate the use of the obtained effect data in the risk assessment. Additionally, the uptake of particles into the test organisms was investigated using microscopic methods. In zebrafish embryos, effects of Carbo-Iron on gene expression were investigated. The obtained ecotoxicity data were complemented by studies with the waterflea Daphnia magna, the algae Scenedesmus vacuolatus, larvae of the insect species Chironomus riparius and nitrifying soil microorganisms.
In the fish embryo test, no passage of Carbo-Iron particles into the perivitelline space or the embryo was observed. In D. rerio and H. azteca, Carbo-Iron was detected in the gut at the end of exposure, but no passage into the surrounding tissue was detected. Carbo-Iron had no significant effect on soil microorganisms and on survival and growth of fish. However, it had significant effects on the growth, feeding rate and reproduction of H. azteca and on survival and reproduction in D. magna. Additionally, the development rate of C. riparius and the cell volume of S. vacuolatus were negatively influenced.
A predicted no effect concentration of 0.1 mg/L was derived from the ecotoxicity studies based on the no-effect level determined in the reproduction test with D. magna and an assessment factor of 10. It was compared to measured and modelled environmental concentrations for Carbo-Iron after application to an aquifer contaminated with chlorohydrocarbons in a field study. Based on these concentrations, risk quotients were derived. Additionally, the overall environmental risk before and after Carbo-Iron application was assessed to verify whether the chances for a risk-risk trade-off by the remediation of the contaminated site could be minimized. With the data used in the present study, a reduced environmental risk was identified after the application of Carbo-Iron. Thus, the benefit of remediation with Carbo-Iron outweighs potential negative effects on the environment.
Sediment transport contributes to the movement of inorganic and organic material in rivers. The construction of a dam interrupts the continuity of this sediment transport through rivers, causing sediments to accumulate within the reservoir. Reservoirs can also act as carbon sinks and methane can be released when organic matter in the sediment is degraded under anoxic conditions. Reservoir sedimentation poses a great threat to the sustainability of reservoirs worldwide, and can emit the potent greenhouse gas methane into the atmosphere. Sediment management measures to rehabilitate silted reservoirs are required to achieve both better water quantity and quality, as well as to mitigate greenhouse gas emissions.
This thesis aims at the improvement of sediment sampling techniques to characterize sediment deposits as a basis for accurate and efficient water jet dredging and to monitor the dredging efficiency by measuring the sediment concentration. To achieve this, we investigated freeze coring as a method to sample (gas-bearing) sediment in situ. The freeze cores from three reservoirs obtained were scanned using a non-destructive X-Ray CT scan technique. This allows the determination of sediment stratification and character-ization of gas bubbles to quantify methane emissions and serve as a basis for the identi-fication of specific (i.e. contaminated) sediment layers to be dredged. The results demon-strate the capability of freeze coring as a method for the characterization of (gas-bearing) sediment and overcomes certain limitations of commonly used gravity cores. Even though the core’s structure showed coring disturbances related to the freezing process, the general core integrity seems to not have been disturbed. For dredging purposes, we analyzed the impact pressure distribution and spray pattern of submerged cavitating wa-ter jets and determined the effects of impinging distances and angles, pump pressures and spray angles. We used an adapted Pressure Measurement Sensing technique to enhance the spatial distribution, which proved to be a comparatively easy-to-use meas-urement method for an improved understanding of the governing factors on the erosional capacity of cavitating water jets. Based on this data, the multiple linear regression model can be used to predict the impact pressure distribution of those water jets to achieve higher dredging accuracy and efficiency. To determine the dredging operational efficien-cy, we developed a semi-continuous automated measurement device to measure the sediment concentration of the slurry. This simple and robust device has lower costs, compared to traditional and surrogate sediment concentration measurement technolo-gies, and can be monitored and controlled remotely under a wide range of concentrations and grain-sizes, unaffected by entrained gas bubbles
Carabids, which are frequently distributed in agricultural landscapes, are natural enemies of different pests including slugs. Semi-natural habitats are known to affect carabids and thus, their potential to support natural pest control.
The impact of semi-natural habitats was investigated on carabids and slugs within different non-crop habitats (chapter 2). Most carabids and Deroceras reticulatum showed preferences for herbaceous semi-natural habitats, while Arion spp. occured mainly in woody habitats. An increase of predatory carabid abundance, which was linked to an inclining amount of semi-natural habitats in the landscape, and a decrease of Arion spp. densities, indicated a high potential for slug control in structural rich landscapes.
Effects of semi-natural habitats were investigated on predatory carabids and slugs in 18 wheat fields (chapter 3). Predatory carabid species richness was positively affected by the increasing amount of semi-natural habitats in the landscape, whereas predatory carabid abundance was neither influenced by adjacent habitat type nor by the proportion of semi-natural habitats in the landscape. The target pest species showed divergent patterns, whereas Arion spp. densities were highest in structural poor landscapes near woody margins. D. reticulatum was not affected by habitat type or landscape, reflecting its adaptation to agriculture. Results indicate an increased control of Arion spp. by carabids in landscapes with a high amount of semi-natural habitats.
Effects of semi-natural habitats and the influence of farming system was tested on carabid distribution within 18 pumpkin fields (chapter 4). Carabid species richness generally increased with decreasing distance to the field margins, whereas carabid abundance responded differently according to the adjacent habitat type. Farming system had no effect on carabids and landscape heterogeneity only affected carabids in organic pumpkin fields.
Slug and slug egg predation of three common carabid species was tested in single and double species treatments in the laboratory (chapter 5). Results show additive and synergistic effects depending on the carabid species. In general, semi-natural habitats can enhance the potential of slug control by carabids. This counts especially for Arionid slugs. Semi-natural habitats can support carabid communities by providing shelter, oviposition and overwintering sites as wells as complementary food sources. Therefore, it is important to provide a certain amount of non-crop habitats in agricultural landscapes.
Grapevine growers have struggled with defending their crops against pests and diseases since the domestication of grapevine over 6000 ears ago. Since then, new growing methods paired with a better nderstanding of the ecological processes in the vineyard ecosystem continue to improve quality and quantity of grape harvests. In this thesis I am describing the effects of two recent innovations in viticulture on pest and beneficial arthropods in vineyards; Fungus-resistant grapevine cultivars (PIWIs) and the pruning system semi-minimal pruned hedge (SMPH). The SMPH pruning system allows for a drastic reduction of manual labor in the vineyard, and PIWIs are resistant to two of the most common fungal diseases of grapevine and therefore allow a drastic reduction of fungicide applications compared to conventional varieties. Heavy use of pesticides is linked to a number of problems, including pollution of waterways, negative effects on human health, and biodiversity loss. Here, I studied the effects of fungicide reduction and minimal pruning on arthropods that are beneficial for natural pest suppression in the vineyard ecosystem such as predatory mites, spiders, ants, earwigs, and lacewings. All of these groups either benefitted from the reduction of fungicide sprayings or were not significantly affected. Structural changes in the canopy of SMPH grapevines altered the microclimate in the canopy which in turn influenced some of the arthropods living in it. Overall, my findings suggest that PIWIs and SMPH, both in combination or separately, improve conditions for natural pest control. This adds to other advantages of these innovative management practices such as a reduction in production cost and a smaller impact on the environment.
Invasive species often have a significant impact on the biodiversity of ecosystems and the species native to it. One of the worst invaders worldwide is Aphanomyces astaci, the causative agent of the crayfish plague, an often fatal disease to crayfish species not native to North America. Aphanomyces astaci originates from North America and was introduced to Europe in the midst of the 19th century. Since then, it spread throughout Europe diminishing the European crayfish populations. The overall aim of this thesis was to evaluate the threat that A. astaci still poses to European crayfish species more than 150 years after its introduction to Europe. In the first part of the thesis, crayfish specimens, which are available in the German pet trade, were tested for infections with A. astaci. Around 13% of the tested crayfish were clearly infected with A. astaci. The study demonstrated the potential danger the pet trade poses for biodiversity through the import of alien species and their potential pathogens, in general. In the second part of the thesis, the A. astaci infection prevalence of crayfish species in wild populations in Europe was tested. While the stone crayfish, Austropotamobius torrentium, showed high susceptibility to different haplogroups of A. astaci, the narrow-clawed crayfish, Astacus leptodactylus, was able to survive infections, even by haplogroup B, which is considered to be highly virulent. In the last part of the thesis, A. astaci was traced back to its original distribution area of North America. While the crayfish plague never had such a devastating effect on crayfish in North America as it had in Europe, the reasons for the success of invasive crayfish within North America are not yet fully understood. It is possible that A. astaci increases the invasion success of some crayfish species. Several populations of the rusty crayfish, Orconectes rusticus, in the Midwest of North America were confirmed to be infected with A. astaci and a new genotype was identified, possibly indicating that each crayfish host is vector of a unique A. astaci genotype, even in North America. Overall, the present thesis provides evidence that A. astaci is still a major threat to the crayfish species indigenous to Europe. Crayfish mass mortalities still occur in susceptible crayfish species like A. torrentium even 150 years after the first introduction of A. astaci. While there are some indications for increased resistances through processes of co-evolution, the continuous introduction of crayfish species to Europe threatens to cause new outbreaks of the crayfish plague through the parallel introduction of new, highly virulent A. astaci strains.
The aquatic environment is exposed to multiple environmental pressures and mixtures of chemical substances, among them petroleum and petrochemicals, metals, and pesticides. Aquatic invertebrate communities are used as bioindicators to reflect long-term and integral effects. Information on the presence of species can be supplemented with information on their traits. SPEAR-type bioindicators integrate such trait information on the community level.
This thesis aimed at enhancing specificity of SPEAR-type bioindicators towards particular groups of chemicals, namely to mixtures of oil sands-derived compounds, hydrocarbons, and metals.
For developing a bioindicator for discontinuous contamination with oil-derived organic toxicants, a field study was conducted in the Canadian oil sands development region in Northern Alberta. The traits ‘physiological sensitivity towards organic chemicals’ and ‘generation time’ were integrated to develop the bioindicator SPEARoil, reflecting the community sensitivity towards oil sands derived contamination in relation to fluctuating hydrological conditions.
According to the SPEARorganic approach, a physiological sensitivity ranking of taxa was developed for hydrocarbon contamination originating from crude oil or petroleum distillates. For this purpose, ecotoxicological information from acute laboratory tests was enriched with rapid and mesocosm test results. The developed Shydrocarbons sensitivity values can be used in SPEAR-type bioindicators.
To specifically reflect metal contamination in streams via bioindicators, Australian field studies were re-evaluated with focus on the traits ‘physiological metal sensitivity’ and ‘feeding type’. Metal sensitivity values, however, explained community effects in the field only weakly. Instead, the trait ‘feeding type’ was strongly related to metal exposure. The fraction of predators in a community can, thus, serve as an indicator for metal contamination in the field.
Furthermore, several metrics reflecting exposure to chemical cocktails in the environment were compared using existing pesticide datasets. Exposure metrics based on the 5% fraction of species sensitivity distributions were found to perform best, however, closely followed by Toxic Unit metrics based on the most sensitive species of a community or Daphnia magna.
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.
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.
Während es eine Vielzahl von Arbeiten zu der technologischen Entwicklung im Bereich der erneuerbaren Energien gibt, fehlt es jedoch bislang an einer mikroökonomischen Analyse
der Verhaltensmuster der Akteure im Umfeld von Anlagen nach dem EEG. Als Akteure kommen hier in erster Linie der Anlagenbetreiber selbst und der Staat in Betracht.
Im Hinblick auf Anlagenbetrieb und Vergütung der erzeugten Energie können beide mit unterschiedlichsten Interessen und Nutzenkalkülen aufeinander treffen. Diese Arbeit untersucht
mikroökonomische Aspekte des EEG-Förderungssystems. Im Mittelpunkt der Betrachtung stehen die Förderungsmechanismen für Biogasanlagen, die im Hinblick auf mögliche Prinzipal-Agenten-Konflikte einer Untersuchung unterzogen werden.
Die Vermeidung von Lebensmittelabfällen als nicht-technische Strategie zur Umsetzung der Bioökonomie
(2018)
Das Konzept der Bioökonomie beruht auf der Vision einer Wirtschaft, die durch die bevorzugte Verwendung biogener Rohstoffe unabhängiger wird von der Nutzung fossiler Quellen und gleichzeitig einen Beitrag zu Klima- und Ressourcenschutz, Ernährungssicherung und Stärkung der heimischen Wirtschaft leisten kann. Da die land- und forstwirtschaftliche Bio-masseproduktion aufgrund knapper Flächen jedoch begrenzt ist und sich bereits heute die negativen Folgen einer verstärkten Nachfrage zeigen, wird bezweifelt, dass sich die Vision in nachhaltiger Weise realisieren lässt. Offizielle Bioökonomie-Strategien setzen auf einen Technik-basierten Umsetzungspfad, in der Hoffnung, mit Hilfe technischer Innovationen Biomasseproduktion und Umweltverbrauch zu entkoppeln. Kritiker aus Wissenschaft und Zivilgesellschaft stehen diesem Weg skeptisch gegenüber. Sie befürchten, dass Effizienzsteigerungen und die Entwicklung neuer, umweltverträglicher Konversionsprozesse nicht ausreichen werden, um potentiell negative Folgen einer verstärkten Biomassenutzung abzuwenden. Angesichts der natürlichen Grenzen der Biosphäre sehen sie vor allem nicht-technische Ansätze zur Veränderung von Produktions- und Konsummustern als unverzichtbare Voraus-setzungen an. Mit der Formulierung eines sozial-ökologischen Umsetzungspfads wird eine Modifizierung des Bioökonomie-Konzepts gefordert, von einem bloßen Wandel der Ressourcenbasis hin zu einer umfassenden gesellschaftlichen Transformation, mit dem Ziel, Ressourcenverbrauch und Rohstoffproduktion neu zu justieren.
Die Arbeit stellt anhand des Beispiels der Lebensmittelabfälle die Bedeutung nicht-technischer Ansätze für die Realisierung der Bioökonomie heraus. Die Basis bilden fünf Publikationen, von denen sich drei mit dem Aufkommen von Lebensmittelabfällen, den Ursachen ihrer Entstehung und möglichen Vermeidungsstrategien befassen. Die anderen beiden Veröffentlichungen behandeln Flächenkonkurrenzen in der Landwirtschaft sowie Implementierungspfade der Bioökonomie. Die Arbeit kommt zu dem Schluss, dass der Beitrag von Lebensmittelabfällen zur Bioökonomie auf zwei Weisen denkbar ist: Entweder können diese als Ausgangsstoff für die Biogasproduktion oder die Bioraffinerie genutzt werden, was der aktuell vorherrschenden Vorstellung entspricht. Oder es können durch eine Reduktion des Abfallaufkommens Ressourcen, die bisher in die Bereitstellung nicht konsumierter Lebensmittel flossen, für andere Biomassenutzungen freigesetzt werden.
Die Analyse des Abfallaufkommens und der damit verbundenen Umweltwirkungen, aber auch vorhandene Studien über die ökologischen Wirkungen von Abfallvermeidungs- und verwertungsoptionen zeigen, dass die Vermeidung unter dem Gesichtspunkt der Ressourceneffizienz die sinnvollere Option darstellt. Die Arbeit hebt das Potenzial hervor, das sich aus der Berücksichtigung einer Reduktion von Lebensmittelabfällen für die Bioökonomie ergeben könnte. So ist denkbar, dass durch einen effizienteren Umgang mit den bereits produzierten Nahrungsmitteln Ressourcen freigesetzt werden können, die den Spielraum für die Realisierung der Bioökonomie verbessern würden oder aber Perspektiven entstehen für alternative Formen des Landbaus, die eine umweltverträglichere Biomasseproduktion ermöglichen könnten. Da nicht-technische Ansätze in der aktuellen Bioökonomie-Debatte kaum Berücksichtigung finden, besteht Bedarf, diese in das politische Konzept der Bioökonomie einzubeziehen und den wissenschaftlichen Diskurs für diese Aspekte zu öffnen.
Assessment of renewable energy potentials based on GIS. A case study in southwest region of Russia
(2018)
In the present thesis, the initial conditions for the development of RES potentials for the production of wind, solar and biomass energy in the Krasnodar region (southwestern region of the Russian Federation) are examined using a multi-criteria assessment methodology. For the assessment of the RES potentials at regional scale, the prosed multi-criteria methodology based on the geographic information systems (GIS) and has been complemented by the evaluation and analysis of primary and secondary data as well as economic calculations relevant related to economic feasibility of RES projects.
Grundwasser ist eine lebenswichtige Ressource und gleichzeitig ein thermisch stabiler Lebensraum mit einer außergewöhnlichen Fauna. Aufgrund der Klimageschichte der letzten ca. 1,8 Millionen Jahre in Mitteleuropa war die Ausgangshypothese, dass die meisten Grundwasserarten an Temperaturen unterhalb von 14 °C angepasst sind und sich Temperaturerhöhungen daher negativ auf die Grundwasserfauna auswirken.
Um die Folgen einer Klimaerwärmung in situ beurteilen zu können, wurden anthropogen erwärmte Grundwässer als Modelle herangezogen. In ersten Teil dieser Arbeit wurden die Crustaceagemeinschaften natürlich temperierter und anthropogen erwärmter Standorte untersucht. Dazu wurden insgesamt 70 Grundwassermessstellen im Oberrheingraben über ein Jahr (2011 bis 2012) sechsmal beprobt. Ergänzend zu diesem synökologischen Ansatz wurde in einem zweiten Teil die Temperaturpräferenz ausgewählter Arten überprüft. Für diese autökologische Betrachtung wurde ein deutschlandweiter Datensatz herangezogen.
Die ausgewählten Untersuchungsgebiete haben sich als geeignete Modelle für die prognostizierten Temperaturerhöhungen herausgestellt. Die Temperatur erwies sich als einer der wichtigsten Parameter für die Crustaceagemeinschaften. Erwärmungen beeinflussen die Zusammensetzung der Gemeinschaften und die Diversität. Dabei zeigte sich, dass es artspezifisch unterschiedliche Temperaturpräferenzen gibt. Einige vermutlich weniger streng stygobionte Arten scheinen höhere Temperaturen zu tolerieren. Der Großteil der stygobionten Grundwasserarten bevorzugt allerdings Temperaturen unterhalb von 14 °C, wobei wenige Arten als „extrem kalt¬steno-therm“ einzustufen sind. Diese Arten wurden an Standorten nachgewiesen, die aufgrund der hydrologischen Verhältnisse relativ kühl sind und der Fauna auch zukünftig als kalte Refugien Schutz bieten könnten. Einer dieser Standorte ist aufgrund seiner Artenvielalt als „Hot Spot“ einzustufen. Die Ergebnisse legen nahe, dass vor allem kaltstenotherme Arten durch eine Klimaerwärmung und anthropogene Wärmeeinträge gefährdet sind.
Die Untersuchung zeigt, dass Grundwasserlebensräume vor Temperaturerhöhungen zu bewahren sind. Lokale anthropogene Wärmeeinträge sollten keine dauerhafte und großflächige Grundwassererwärmung über 14 °C zur Folge haben. Thermische Ein-träge sollten überwacht und bewertet werden. Es wird empfohlen, die bestehenden rechtlichen Rahmenbedingungen den ökologischen Erfordernissen anzupassen.
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.
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.
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.
For a comprehensive understanding of evolutionary processes and for providing reliable prognoses about the future consequences of environmental change, it is essential to reveal the genetic basis underlying adaptive responses. The importance of this goal increases in light of ongoing climate change, which confronts organisms worldwide with new selection pressures and requires rapid evolutionary change to avoid local extinction. Thereby, freshwater ectotherms like daphnids are particularly threatened. Unraveling the genetic basis of local adaptation is complicated by the interplay of forces affecting patterns of genetic divergence among populations. Due to their key position in freshwater communities, cyclic parthenogenetic mode of reproduction and resting propagules (which form biological archives), daphnids are particularly suited for this purpose.
The aim of this thesis was to assess the impact of local thermal selection on the Daphnia longispina complex and to reveal the underlying genetic loci. Therefore, I compared genetic differentiation among populations containing Daphnia galeata, Daphnia longispina and their interspecific hybrids across time, space, and species boundaries. I revealed strongly contrasting patterns of genetic differentiation between selectively neutral and functional candidate gene markers, between the two species, and among samples from different lakes, suggesting (together with a correlation with habitat temperatures) local thermal selection acting on candidate gene TRY5F and indicating adaptive introgression. To reveal the candidate genes’ impact on fitness, I performed association analyses among data on genotypes and phenotypic traits of D. galeata clones from seven populations. The tests revealed a general temperature effect as well as inter-population differences in phenotypic traits and imply a possible contribution of the candidate genes to life-history traits. Finally, utilizing a combined population transcriptomic and reverse ecology approach, I introduced a methodology with a wide range of applications in evolutionary biology and revealed that local thermal selection was probably a minor force in shaping sequence and gene expression divergence among four D. galeata populations, but contributed to sequence divergence among two populations. I identified many transcripts possibly under selection or contributing strongly to population divergence, a large amount thereof putatively under local thermal selection, and showed that genetic and gene expression variation is not depleted specifically in temperature-related candidate genes.
In conclusion, I detected signs of local adaptation in the D. longispina complex across space, time, and species barriers. Populations and species remained genetically divergent, although increased gene flow possibly contributed, together with genotypes recruited from the resting egg bank, to the maintenance of standing genetic variation. Further work is required to accurately determine the influence of introgression and the effects of candidate genes on individual fitness. While I found no evidence suggesting a response to intense local thermal selection, the high resilience and adaptive potential regarding environmental change I observed suggest positive future prospects for the populations of the D. longispina complex. However, overall, due to the continuing environmental degradation, daphnids and other aquatic invertebrates remain vulnerable and threatened.
Pelagic oxyclines, the transition zone between oxygen rich surface waters and oxygen depleted deep waters, are a common characteristic of eutrophic lakes during summer stratification. They can have tremendous effects on the biodiversity and the ecosystem functioning of lakes and, to add insult to injury, are expected to become more frequent and more pronounced as climate warming progresses. On these grounds, this thesis endeavors to advance the understanding of formation, persistence, and consequences of pelagic oxyclines: We test, whether the formation of metalimnetic oxygen minima is intrinsically tied to a locally enhanced oxygen consuming process, investigate the relative importance of vertical physical oxygen transport and biochemical oxygen consumption for the persistence of pelagic oxyclines, and finally assess their potential consequences for whole lake cycling. To pursue these objectives, the present thesis nearly exclusively resorts to in situ measurements. Field campaigns were conducted at three lakes in Germany featuring different types of oxyclines and resolved either a short (hours to days) or a long (weeks to months) time scale. Measurements comprised temperature, current velocity, and concentrations of oxygen and reduced substances in high temporal and vertical resolution. Additionally, vertical transport was estimated by applying the eddy correlation technique within the pelagic region for the first time. The thesis revealed, that the formation of metalimnetic oxygen minima does not necessarily depend on locally enhanced oxygen depletion, but can solely result from gradients and curvatures of oxygen concentration and depletion and their relative position to each other. Physical oxygen transport was found to be relevant for oxycline persistence when it considerably postponed anoxia on a long time scale. However, its influence on oxygen dynamics was minor on short time scales, although mixing and transport were highly variable. Biochemical consumption always dominated the fate of oxygen in pelagic oxyclines. It was primarily determined by the oxidative breakdown of organic matter originating from the epilimnion, whereas in meromictic lakes, the oxidation of reduced substances dominated. Beyond that, the results of the thesis emphasize that pelagic oxyclines can be a hotspot of mineralization and, hence, short-circuit carbon and nutrient cycling in the upper part of the water column. Overall, the present thesis highlights the importance of considering physical transport as well as biochemical cycling in future studies.
World’s ecosystems are under great pressure satisfying anthropogenic demands, with freshwaters being of central importance. The Millennium Ecosystem Assessment has identified anthropogenic land use and associated stressors as main drivers in jeopardizing stream ecosystem functions and the
biodiversity supported by freshwaters. Adverse effects on the biodiversity of freshwater organisms, such as macroinvertebrates, may propagate to fundamental ecosystem functions, such as organic matter breakdown (OMB) with potentially severe consequences for ecosystem services. In order to adequately protect and preserve freshwater ecosystems, investigations regarding potential and observed as well as direct and indirect effects of anthropogenic land use and associated stressors (e.g. nutrients, pesticides or heavy metals) on ecosystem functioning and stream biodiversity are needed. While greater species diversity most likely benefits ecosystem functions, the direction and magnitude of changes in ecosystem functioning depends primarily on species functional traits. In this context, the functional diversity of stream organisms has been suggested to be a more suitable predictor of changes in ecosystem functions than taxonomic diversity.
The thesis aims at investigating effects of anthropogenic land use on (i) three ecosystem functions by anthropogenic toxicants to identify effect thresholds (chapter 2), (ii) the organic matter breakdown by three land use categories to identify effects on the functional level (chapter 3) and (iii)on the stream community along an established land-use gradient to identify effects on the community level.
In chapter 2, I reviewed the literature regarding pesticide and heavy metal effects on OMB, primary production and community respiration. From each reviewed study that met inclusion criteria, the toxicant concentration resulting in a reduction of at least 20% in an ecosystem function was standardized based on laboratory toxicity data. Effect thresholds were based on the relationship between ecosystem functions and standardized concentration-effect relationships. The analysis revealed that more than one third of pesticide observations indicated reductions in ecosystem functions at concentrations that are assumed being protective in regulation. However, high variation within and between studies hampered the derivation of a concentration-effect relationship and thus effect thresholds.
In chapter 3, I conducted a field study to determine the microbial and invertebrate-mediated OMB by deploying fine and coarse mesh leaf bags in streams with forested, agricultural, vinicultural
and urban riparian land use. Additionally, physicochemical, geographical and habitat parameters were monitored to explain potential differences in OMB among land use types and sites. Regarding results, only microbial OMB differed between land use types. The microbial OMB showed a negative relationship with pH while the invertebrate-mediated OMB was positively related to tree cover. OMB responded to stressor gradients rather than directly to land use.
In chapter 4, macroinvertebrates were sampled in concert with leaf bag deployment and after species identification (i) the taxonomic diversity in terms of Simpson diversity and total taxonomic
richness (TTR) and (ii) the functional diversity in terms of bio-ecological traits and Rao’s quadratic entropy was determined for each community. Additionally, a land-use gradient was established and the response of the taxonomic and functional diversity of invertebrate communities along this gradient was investigated to examine whether these two metrics of biodiversity are predictive for the rate of OMB. Neither bio-ecological traits nor the functional diversity showed a significant relationship with
OMB. Although, TTR decreased with increasing anthropogenic stress and also the community structure and 26 % of bio-ecological traits were significantly related to the stress gradient, any of these shifts propagated to OMB.
Our results show that the complexity of real-world situations in freshwater ecosystems impedes the effect assessment of chemicals and land use for functional endpoints, and consequently our potential to predict changes. We conclude that current safety factors used in chemical risk assessment may not be sufficient for pesticides to protect functional endpoints. Furthermore, simplifying real-world stressor gradients into few land use categories was unsuitable to predict and quantify losses in OMB. Thus, the monitoring of specific stressors may be more relevant than crude land use categories to detect effects on ecosystem functions. This may, however, limit the large scale assessment of the status of OMB. Finally, despite several functional changes in the communities the functional diversity over several trait modalities remained similar. Neither taxonomic nor functional diversity were suitable predictors of OMB. Thus, when understanding anthropogenic impacts on the linkage between biodiversity and ecosystem functioning is of main interest, focusing on diversity metrics that are clearly linked to the stressor in question (Jackson et al. 2016) or integrating taxonomic and functional metrics (Mondy et al., 2012) might enhance our predictive capacity.
Statistical eco(-toxico)logy
(2017)
Freshwaters are of immense importance for human well-being.
Nevertheless, they are currently facing unprecedented levels of threat from habitat loss and degradation, overexploitation, invasive species and
pollution.
To prevent risks to aquatic ecosystems, chemical substances, like agricultural pesticides, have to pass environmental risk assessment (ERA) before entering the market.
Concurrently, large-scale environmental monitoring is used for surveillance of biological and chemical conditions in freshwaters.
This thesis examines statistical methods currently used in ERA.
Moreover, it presents a national-scale compilation of chemical monitoring data, an analysis of drivers and dynamics of chemical pollution in streams and, provides a large-scale risk assessment by combination with results from ERA.
Additionally, software tools have been developed to integrate different datasets used in ERA.
The thesis starts with a brief introduction to ERA and environmental monitoring and gives an overview of the objectives of the thesis.
Chapter 2 addresses experimental setups and their statistical analyses using simulations.
The results show that current designs exhibit unacceptably low statistical power, that statistical methods chosen to fit the type of data provide higher power and that statistical practices in ERA need to be revised.
In chapter 3 we compiled all available pesticide monitoring data from Germany.
Hereby, we focused on small streams, similar to those considered in ERA and used threshold concentrations derived during ERA for a large-scale assessment of threats to freshwaters from pesticides.
This compilation resulted in the most comprehensive dataset on pesticide exposure currently available for Germany.
Using state-of-the-art statistical techniques, that explicitly take the limits of quantification into account, we demonstrate that 25% of small streams are at threat from pesticides.
In particular neonicotinoid pesticides are responsible for these threats.
These are associated with agricultural intensity and can be detected even at low levels of agricultural use.
Moreover, our results indicated that current monitoring underestimates pesticide risks, because of a sampling decoupled from precipitation events.
Additionally, we provide a first large-scale study of annual pesticide exposure dynamics.
Chapters 4 and 5 describe software solutions to simplify and accelerate the integration of data from ERA, environmental monitoring and ecotoxicology that is indispensable for the development of landscape-level risk assessment.
Overall, this thesis contributes to the emerging discipline of statistical ecotoxicology and shows that pesticides pose a large-scale threat to small streams.
Environmental monitoring can provide a post-authorisation feedback to ERA.
However, to protect freshwater ecosystems ERA and environmental monitoring need to be further refined and we provide software solutions to utilise existing data for this purpose.
Agricultural land-use may lead to brief pulse exposures of pesticides in edge-of-field streams, potentially resulting in adverse effects on aquatic macrophytes, invertebrates and ecosystem functions. The higher tier risk assessment is mainly based on pond mesocosms which are not designed to mimic stream-typical conditions. Relatively little is known on exposure and effect assessment using stream mesocosms.
Thus the present thesis evaluates the appliacability of the stream mesocosms to mimic stream-typical pulse exposures, to assess resulting effects on flora and fauna and to evaluate aquatic-terrestrial food web coupling. The first objective was to mimic stream-typical pulse exposure scenarios with different durations (≤ 1 to ≥ 24 hours). These exposure scenarios established using a fluorescence tracer were the methodological basis for the effect assessment of an herbicide and an insecticide. In order to evaluate the applicability of stream mesocosms for regulatory purposes, the second objective was to assess effects on two aquatic macrophytes following a 24-h pulse exposure with the herbicide iofensulfuron-sodium (1, 3, 10 and 30 µg/L; n = 3). Growth inhibition of up to 66 and 45% was observed for the total shoot length of Myriophyllum spicatum and Elodea canadensis, respectively. Recovery of this endpoint could be demonstrated within 42 days for both macrophytes. The third objective was to assess effects on structural and functional endpoints following a 6-h pulse exposure of the pyrethroid ether etofenprox (0.05, 0.5 and 5 µg/L; n = 4). The most sensitive structural (abundance of Cloeon simile) and functional (feeding rates of Asellus aquaticus) endpoint revealed significant effects at 0.05 µg/L etofenprox. This concentration was below field-measured etofenprox concentrations and thus suggests that pulse exposures adversely affect invertebrate populations and ecosystem functions in streams. Such pollutions of streams may also result in decreased emergence of aquatic insects and potentially lead to an insect-mediated transfer of pollutants to adjacent food webs. Test systems capable to assess aquatic-terrestrial effects are not yet integrated in mesocosm approaches but might be of interest for substances with bioaccumulation potential. Here, the fourth part provides an aquatic-terrestrial model ecosystem capable to assess cross-ecosystem effects. Information on the riparian food web such as the contribution of aquatic (up to 71%) and terrestrial (up to 29%) insect prey to the diet of the riparian spider Tetragnatha extensa was assessed via stable isotope ratios (δ13C and δ15N). Thus, the present thesis provides the methodological basis to assess aquatic-terrestrial pollutant transfer and effects on the riparian food web.
Overall the results of this thesis indicate, that stream mesocosms can be used to mimic stream-typical pulse exposures of pesticides, to assess resulting effects on macrophytes and invertebrates within prospective environmental risk assessment (ERA) and to evaluate changes in riparian food webs.
The global problematic issue of the olive oil industry is in its generation of large amounts of olive mill wastewater (OMW). The direct discharge of OMW to the soil is very common which presents environmental problems for olive oil producing countries. Both, positive as well as negative effects on soil have been found in earlier studies. Therefore, the current study hypothesized that whether beneficial effects or negative effects dominate depends on the prevailing conditions before and after OMW discharge to soil. As such, a better understanding of the OMW-soil interaction mechanisms becomes essential for sustainable safe disposal of OMW on soil and sustainable soil quality.
A field experiment was carried out in an olive orchard in Palestine, over a period of 24 months, in which the OMW was applied to the soil as a single application of 14 L m-2 under four different environmental conditions: in winter (WI), spring (SP), and summer with and without irrigation (SUmoist and SUdry). The current study investigated the effects of seasonal conditions on the olive mill wastewater (OMW) soil interaction in the short-term and the long-term. The degree and persistence of soil salinization, acidification, accumulation of phenolic compounds and soil water repellency were investigated as a function of soil depth and time elapsed after the OMW application. Moreover, the OMW impacts on soil organic matter SOM quality and quantity, total organic carbon (SOC), water-extractable soil organic carbon (DOC), as well as specific ultraviolet absorbance analysis (SUVA254) were also investigated for each seasonal application in order to assess the degree of OMW-OM decomposition or accumulation in soil, and therefore, the persisting effects of OMW disposal to soil.
The results of the current study demonstrate that the degree and persistence of relevant effects due to OMW application on soil varied significantly between the different seasonal OMW applications both in the short-term and the long-term. The negative effects of the potentially hazardous OMW residuals in the soil were highly dependent on the dominant transport mechanisms and transformation mechanisms, triggered by the ambient soil moisture and temperature which either intensified or diminished negative effects of OMW in the soil during and after the application season. The negative effects of OMW disposal to the soil decreased by increasing the retention time of OMW in soil under conditions favoring biological activity. The moderate conditions of soil moisture and temperature allowed for a considerable amount of applied OMW to be biologically degraded, while the prolonged application time under dry conditions and high temperature resulted in a less degradable organic fraction of the OMW, causing the OMW constituents to accumulate and polymerize without being degraded. Further, the rainfall during winter season diminished negative effects of OMW in the soil; therefore, the risk of groundwater contamination by non-degraded constituents of OMW can be highly probable during the winter season.
Conversion of natural vegetation into cattle pastures and croplands results in altered emissions of greenhouse gases (GHG), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Their atmospheric concentration increase is attributed the main driver of climate change. Despite of successful private initiatives, e.g. the Soy Moratorium and the Cattle Agreement, Brazil was ranked the worldwide second largest emitter of GHG from land use change and forestry, and the third largest emitter from agriculture in 2012. N2O is the major GHG, in particular for the agricultural sector, as its natural emissions are strongly enhanced by human activities (e.g. fertilization and land use changes). Given denitrification the main process for N2O production and its sensitivity to external changes (e.g. precipitation events) makes Brazil particularly predestined for high soil-derived N2O fluxes.
In this study, we followed a bottom-up approach based on a country-wide literature research, own measurement campaigns, and modeling on the plot and regional scale, in order to quantify the scenario-specific development of GHG emissions from soils in the two Federal States Mato Grosso and Pará. In general, N2O fluxes from Brazilian soils were found to be low and not particularly dynamic. In addition to that, expected reactions to precipitation events stayed away. These findings emphasized elaborate model simulations in daily time steps too sophisticated for regional applications. Hence, an extrapolation approach was used to first estimate the influence of four different land use scenarios (alternative futures) on GHG emissions and then set up mitigation strategies for Southern Amazonia. The results suggested intensification of agricultural areas (mainly cattle pastures) and, consequently, avoided deforestation essential for GHG mitigation.
The outcomes of this study provide a very good basis for (a) further research on the understanding of underlying processes causing low N2O fluxes from Brazilian soils and (b) political attempts to avoid new deforestation and keep GHG emissions low.
The work presented in this thesis investigated interactions of selected biophysical processes that affect zooplankton ecology at smaller scales. In this endeavour, the extent of changes in swimming behaviour and fluid disturbances produced by swimming Daphnia in response to changing physical environments were quantified. In the first research question addressed within this context, size and energetics of hydrodynamic trails produced by Daphnia swimming in non-stratified still waters were characterized and quantified as a function of organisms’ size and their swimming patterns.
The results revealed that neither size nor the swimming pattern of Daphnia affects the width of induced trails or dissipation rates. Nevertheless, as the size and swimming velocity of the organisms increased, trail volume increased in proportional to the cubic power of Reynolds number, and the biggest trail volume was about 500 times the body volume of the largest daphnids. Larger spatial extent of fluid perturbation and prolonged period to decay caused by bigger trail volumes would play a significant role in zooplankton ecology, e.g. increasing the risk of predation.
The study also found that increased trail volume brought about significantly enhanced total dissipated power at higher Reynolds number, and the magnitudes of total dissipated power observed varied in the range of (1.3-10)X10-9 W.
Furthermore, this study provided strong evidence that swimming speed of Daphnia and total dissipated power in Daphnia trails exceeded those of some other selected zooplankton species.
In recognizing turbulence as an intrinsic environmental perturbation in aquatic habitats, this thesis also examined the response of Daphnia to a range of turbulence flows, which correspond to turbu-lence levels that zooplankton generally encounter in their habitats. Results indicated that within the range of turbulent intensities to which the Daphnia are likely to be exposed in their natural habitats, increasing turbulence compelled the organisms to enhance their swimming activity and swim-ming speed. However, as the turbulence increased to extremely high values (10-4 m2s-3), Daphnia began to withdraw from their active swimming behaviour. Findings of this work also demonstrated that the threshold level of turbulence at which animals start to alleviate from largely active swimming is about 10-6 m2s-3. The study further illustrated that during the intermediate range of turbu-lence; 10-7 - 10-6 m2s-3, kinetic energy dissipation rates in the vicinity of the organisms is consistently one order of magnitude higher than that of the background turbulent flow.
Swarming, a common conspicuous behavioural trait observed in many zooplankton species, is considered to play a significant role in defining freshwater ecology of their habitats from food exploitation, mate encountering to avoiding predators through hydrodynamic flow structures produced by them, therefore, this thesis also investigated implications of Daphnia swarms at varied abundance & swarm densities on their swimming kinematics and induced flow field.
The results showed that Daphnia aggregated in swarms with swarm densities of (1.1-2.3)x103 L-1, which exceeded the abundance densities by two orders of magnitude (i.e. 1.7 - 6.7 L-1). The estimated swarm volume decreased from 52 cm3 to 6.5 cm3, and the mean neighbouring distance dropped from 9.9 to 6.4 body lengths. The findings of this work also showed that mean swimming trajectories were primarily horizontal concentric circles around the light source. Mean flow speeds found to be one order of magnitude lower than the corresponding swimming speeds of Daphnia. Furthermore, this study provided evidences that the flow fields produced by swarming Daphnia differed considerably between unidirectional vortex swarming and bidirectional swimming at low and high abundances respectively.
Agriculture covers one third of the world land area and has become a major source of water pollution due to its heavy reliance on chemical inputs, namely fertilisers and pesticides. Several thousands of tonnes of these chemicals are applied worldwide annually and partly reach freshwaters. Despite their widespread use and relatively unspecific modes of action, fungicides are the least studied group of pesticides. It remains unclear whether the taxonomic groups used in pesticide risk assessment are protective for non-target freshwater fungi. Fungi and bacteria are the main microbial decomposers converting allochthonous organic matter (litter) into a more nutritious food resource for leaf-shredding macroinvertebrates. This process of litter decomposition (LD) is central for aquatic ecosystem because it fuels local and downstream food webs with energy and nutrients. Effects of fungicides on decomposer communities and LD have been mainly analysed under laboratory conditions with limited representation of the multiple factors that may moderate effects in the field.
In this thesis a field study was conducted in a German vineyard area to characterise recurrent episodic exposure to fungicides in agricultural streams (chapter 2) and its effects on decomposer communities and LD (chapter 3). Additionally, potential interaction effects of nutrient enrichment and fungicides on decomposer communities and LD were analysed in a mesocosm experiment (chapter 4).
In the field study event-driven water sampling (EDS) and passive sampling with EmporeTM styrene-divinylbenzene reverse phase sulfonated disks (SDB disks) were used to assess exposure to 15 fungicides and 4 insecticides. A total of 17 streams were monitored during 4 rainfall events within the local application period of fungicides in 2012. EDS exceeded the time-weighted average concentrations provided by the SDB disks by a factor of 3, though high variability among compounds was observed. Most compounds were detected in more than half of the sites and mean and maximum peak (EDS) concentrations were under 1 and 3 µg/l, respectively. Besides, SDB disk-sampling rates and a free-software solution to derive sampling rates under time-variable exposure were provided.
Several biotic endpoints related to decomposers and LD were measured in the same sampling sites as the fungicide monitoring, coinciding with the major litter input period. Our results suggest that polar organic fungicides in streams change the structure of the fungal community. Causality of this finding was supported by a subsequent microcosm experiment. Whether other effects observed in the field study, such as reduced fungal biomass, increased bacterial density or reduced microbial LD can be attributed to fungicides remains speculative and requires further investigation. By contrast, neither the invertebrate LD nor in-situ measured gammarid feeding rates correlated with water-borne fungicide toxicity, but both were negatively associated with sediment copper concentrations. The mesocosm experiment showed that fungicides and nutrients affect microbial decomposers differently and that they can alter community structure, though longer experiments are needed to determine whether these changes may propagate to invertebrate communities and LD. Overall, further studies should include representative field surveys in terms of fungicide pollution and physical, chemical and biological conditions. This should be combined with experiments under controlled conditions to test for the causality of field observations.
Leaf litter breakdown is a fundamental process in aquatic ecosystems, being mainly mediated by decomposer-detritivore systems that are composed of microbial decomposers and leaf-shredding, detritivorous invertebrates. The ecological integrity of these systems can, however, be disturbed, amongst others, by chemical stressors. Fungicides might pose a particular risk as they can have negative effects on the involved microbial decomposers but may also affect shredders via both waterborne toxicity and their diet; the latter by toxic effects due to dietary exposure as a result of fungicides’ accumulation on leaf material and by negatively affecting fungal leaf decomposers, on which shredders’ nutrition heavily relies. The primary aim of this thesis was therefore to provide an in-depth assessment of the ecotoxicological implications of fungicides in a model decomposer-detritivore system using a tiered experimental approach to investigate (1) waterborne toxicity in a model shredder, i.e., Gammarus fossarum, (2) structural and functional implications in leaf-associated microbial communities, and (3) the relative importance of waterborne and diet-related effects for the model shredder.
Additionally, knowledge gaps were tackled that were related to potential differences in the ecotoxicological impact of inorganic (also authorized for organic farming in large parts of the world) and organic fungicides, the mixture toxicity of these substances, the field-relevance of their effects, and the appropriateness of current environmental risk assessment (ERA).
In the course of this thesis, major differences in the effects of inorganic and organic fungicides on the model decomposer-detritivore system were uncovered; e.g., the palatability of leaves for G. fossarum was increased by inorganic fungicides but deteriorated by organic substances. Furthermore, non-additive action of fungicides was observed, rendering mixture effects of these substances hardly predictable. While the relative importance of the waterborne and diet-related effect pathway for the model shredder seems to depend on the fungicide group and the exposure concentration, it was demonstrated that neither path must be ignored due to additive action. Finally, it was shown that effects can be expected at field-relevant fungicide levels and that current ERA may provide insufficient protection for decomposer-detritivore systems. To safeguard aquatic ecosystem functioning, this thesis thus recommends including leaf-associated microbial communities and long-term feeding studies using detritus feeders in ERA testing schemes, and identifies several knowledge gaps whose filling seems mandatory to develop further reasonable refinements for fungicide ERA.
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.
Die vorliegende Arbeit beschäftigt sich mit der Fragestellung, wie eine repräsentative und aussagekräftige Vergleichbarkeit hinsichtlich der Nachhaltigkeitsleistung (Ökoeffizienz) von Unternehmen branchenunabhängig gewährleistet werden kann trotz der Problematik der Definition repräsentativer Bewertungskriterien der Nachhaltigkeit, sowie der Heterogenität der zu bewertenden Branchen. Bisherige Konzepte zu Umwelt- und Nachhaltigkeitsmanagementsystemen (z.B. EMAS, ISO 14000, ISO 26000, EMASplus), zur Umweltleistungsmessung sowie zur Nachhaltigkeitsbewertung und -berichterstattung (z.B. DNK, GRI) sind mit ihren branchenunabhängigen Formulierung zu allgemein gehalten, um für eine konkrete effizienzorientierte Messung nachhaltigen Wirtschaftens von Unternehmen geeignet zu sein.
Folglich besteht kein System zur Messung der Umweltleistung, um den Forschungsbedarf der Herstellung einer aussagekräftigen Vergleichbarkeit der Ressourcen- und Energieverbräuche der Betriebe einer heterogenen Branche zu begegnen. Angesichts dessen wurde im Rahmen der Arbeit eine allgemeine und branchenunabhängig anwendbare aber dennoch –spezifische Methodik zur Herstellung der Vergleichbarkeit von Unternehmen einer Branche hinsichtlich der Ressourcen- und Energieeffizienz entwickelt. Dabei stellt der Kern der Methodik die Generierung eines betriebsindividuellen Gesamtgewichtungsfaktors dar (GGF-Konzept), welcher als Operationalisierung der Vergleichbarkeit angesehen werden kann und damit der Problematik der Heterogenität begegnet. Die Ermittlung von Kriteriengewichtungen im Rahmen des GGF-Konzeptes kann in Analogie zu einem Entscheidungsproblem bei Mehrfachzielsetzung (Multi Criteria Decision Making – MCDM) gesehen werden, da mehrere Kriterien und Sub-Kriterien zueinander in Relation gesetzt werden mussten. Infolgedessen stellte sich der Analytische-Hierarchie-Prozess als das geeignete Verfahren im Rahmen der Methodikentwicklung heraus. Anwendung fand die Methodik in einem ersten empirischen Test anhand einer ausgewählten Stichprobe von 40 Wäschereibetrieben. Dabei zeigten die Ergebnisse auf, dass repräsentatives sowie aussagekräftiges betriebsindividuelles Benchmarking der Ressourcen- und Energieverbräuche völlig unterschiedlicher und bislang nicht vergleichbarer Betriebe möglich wurde. Hierfür mussten zunächst branchenspezifische repräsentative Bewertungskriterien der Ressourcen- und Energieeffizienz bestimmt werden. Abschließend konnten betriebsspezifische Brennpunkte identifiziert und somit Handlungsempfehlungen zur Optimierung der Ressourcen- und Energieeffizienz der Wäschereibetriebe abgeleitet werden, sodass eine zielorientierte Reduzierung des Ressourcen- und Energieverbrauchs folgen kann.
During olive oil production, large amounts of olive mill wastewater (OMW) are generated within a short period of time. OMW has a high nutrient content and could serve as fertilizer when applied on land. However, its fatty and phenolic constituents have adverse effects on soil properties. It is still unknown how seasonal fluctuations in temperature and precipitation influence the fate and effect of OMW components on soil properties in a long-term perspective. An appropriate application season could mitigate negative consequences of OMW while preserving its beneficial effects. In order to investigate this, 14 L OMW m-2 were applied to different plots of an olive plantation in winter, spring, and summer respectively. Hydrological soil properties (water drop penetration time, hydraulic conductivity, dynamic contact angle), physicochemical parameters (pH, EC, soluble ions, phenolic compounds, organic matter), and biological degradation (bait-lamina test) were measured to assess the soil state after OMW application. After one rainy season following OMW application, the soil quality of summer treatments significantly decreased compared to the control. This was particularly apparent in a three-times lower biodegradation performance, ten-fold higher soil water repellency, and a four-fold higher content of phenolic compounds. The soil properties of winter treatments were comparable to the control, which demonstrated the recovery potential of the soil ecosystem. Spring treatments resulted in an intermediate response compared to summer and winter treatments, but without any precipitation following OMW application. Significant accumulation or leaching effects to deeper soil were not observed. Therefore, the direct application of legally restricted OMW amounts to soil is considered acceptable during the moist seasons. Further research is needed to quantify the effect of spring treatments and to gain further insight into the composition and kinetics of organic OMW constituents in the soil.
The (un-)controlled application of olive oil mill wastewater (OMW) has positive and negative effects on soil quality. On the one hand it can be used as fertilizer, on the other hand especially the occurrence of soil water repellency is problematic. Due to this fact the objective of this study was to characterize the effects of OMW application on soil and to investigate the mechanisms that are in combination with changes of soil organic matter quality responsible for soil water repellency depending on the climatic conditions.
At first several locations of uncontrolled OMW disposal were screened for positive and negative im-pacts. Then, laboratory incubation experiments and finally a field experiment in Israel were conducted in order to determine the influence of climatic conditions. Besides standard soil parameters (pH, elec-tric conductivity, total carbon, dissolved organic carbon , specific UV-Absorption) it was focused on the determination of phenolic compounds, the carbon isotope ratio, the water drop penetration time and the contact angle as well as the thermal analysis.
This thesis shows that soil water repellency of OMW-polluted soils depends on the climatic conditions, i.e. the application season. In the laboratory as well as in the field the wettability of the soil was strongly reduced under hot and dry conditions. It was observed, that the stable carbon fraction characterized by a high calorific value is responsible for soil water repellency. In particular, amphiphilic substances, e.g. fatty acids, may interact with soil particles as a consequence of drying. On the contrary, no reduc-tion of the wettability of the soil was determined under moist conditions and degradation of organic matter of the OMW was enhanced. Nevertheless, too strong irrigation or rainfall, e.g. in winter, may leach phenolic ingredients of the OMW into the groundwater.
At the same time the application led to an increase of organic and inorganic nutrients, which should be emphasized as a positive effect. Due to these results, a controlled application of olive oil mill wastewater as alternative, low-cost and sustainable treatment option is recommended. But, instead of the current application season winter, the olive mill wastewater should be stored and not be spread before spring in order to avoid negative impacts on the soil.
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.
Global crop production increased substantially in recent decades due to agricultural intensification and expansion and today agricultural areas occupy about 38% of Earth’s terrestrial surface - the largest use of land on the planet. However, current high-intensity agricultural practices fostered in the context of the Green Revolution led to serious consequences for the global environment. Pesticides, in particular, are highly biologically active substances that can threaten the ecological integrity of aquatic and terrestrial ecosystems. Although the global pesticide use increases steadily, our field-data based knowledge regarding exposure of non-target ecosystems such as surface waters is very restricted. Available studies have by now been limited to spatially restricted geographical areas or had rather specific objectives rendering the extrapolation to larger spatial scales questionable.
Consequently, this thesis evaluated based on four scientific publications the exposure, effects, and regulatory implications of particularly toxic insecticides` concentrations detected in global agricultural surface waters. FOCUS exposure modelling was used to characterise the highly specific insecticide exposure patterns and to analyse the resulting implications for both monitoring and risk assessment (publication I). Based on more than 200,000 scientific database entries, 838 peer-reviewed studies finally included, and more than 2,500 sites in 73 countries, the risks of agricultural insecticides to global surface waters were analysed by means of a comprehensive meta-analysis (publication II). This meta-analysis evaluated whether insecticide field concentrations exceed legally accepted regulatory threshold levels (RTLs) derived from official EU and US pesticide registration documents and, amongst others, how risks depend on insecticide development over time and stringency of environmental regulation. In addition, an in-depth analysis of the current EU pesticide regulations provided insights into the level of protection and field relevance of highly elaborated environmental regulatory risk assessment schemes (publications III and IV).
The results of this thesis show that insecticide surface water exposure is characterized by infrequent and highly transient concentration peaks of high ecotoxicological relevance. We thus argue in publication I that sampling based on regular intervals is inadequate for the detection of insecticide surface water concentrations and that traditional risk assessment concepts based on all insecticide concentrations including non-detects lead to severely biased results and critical underestimations of risks. Based on these considerations, publication II demonstrates that out of 11,300 measured insecticide concentrations (MICs; i.e., those actually detected and quantified), 52.4% (5,915 cases; 68.5%) exceeded the RTL for either water (RTLSW) or sediments. This indicates a substantial risk for the biological integrity of global water resources as additional analyses on pesticide effects in the field clearly evidence that the regional aquatic biodiversity is reduced by approximately 30% at pesticide concentrations equalling the RTLs. In addition, publication II shows that there is a complete lack of scientific monitoring data for ~90% of global cropland and that both the actual insecticide contamination of surface waters and the resulting ecological risks are most likely even greater due to, for example, inadequate sampling methods employed in the studies and the common occurrence of pesticide mixtures. A linear model analysis identified that RTLSW exceedances depend on the catchment size, sampling regime, sampling date, insecticide substance class, and stringency of countries` environmental regulations, as well as on the interactions of these factors. Importantly, the risks are significantly higher for newer-generation insecticides (i.e., pyrethroids) and are high even in countries with stringent environmental regulations. Regarding the latter, an analysis of the EU pesticide regulations revealed critical deficiencies and the lack of protectiveness and field-relevance for current presumed highly elaborated FOCUS exposure assessment (publication IV) and overall risk assessment schemes (publication III). Based on these findings, essential risk assessment amendments are proposed.
In essence, this thesis analyses the agriculture–environment linkages for pesticides at the global scale and it thereby contributes to a new research frontier in global ecotoxicology. The overall findings substantiate that agricultural insecticides are potential key drivers for the global freshwater biodiversity crisis and that the current regulatory risk assessment approaches for highly toxic anthropogenic chemicals fail to protect the global environment. This thesis provides an integrated view on the environmental side effects of global high-intensity agriculture and alerts that beside worldwide improvements to current pesticide regulations and agricultural pesticide application practices, the fundamental reformation of conventional agricultural systems is urgently needed to meet the twin challenges of providing sufficient food for a growing human population without destroying the ecological integrity of global ecosystems essential to human existence.
Aquatic macrophytes can contribute to the retention of organic contaminants in streams, whereas knowledge on the dynamics and the interaction of the determining processes is very limited. The objective of the present study was thus to assess how aquatic macrophytes influence the distribution and the fate of organic contaminants in small vegetated streams. In a first study that was performed in vegetated stream mesocosms, the peak reductions of five compounds were significantly higher in four vegetated stream mesocosms compared to a stream mesocosm without vegetation. Compound specific sorption to macrophytes was determined, the mass retention in the vegetated streams, however, did not explain the relationship between the mitigation of contaminant peaks and macrophyte coverage. A subsequent mesocosm study revealed that the mitigation of peak concentrations in the stream mesocosms was governed by two fundamentally different processes: dispersion and sorption. Again, the reductions of the peak concentrations of three different compounds were in the same order of magnitude in a sparsely and a densely vegetated stream mesocosm, respectively, but higher compared to an unvegetated stream mesocosm. The mitigation of the peak reduction in the sparsely vegetated stream mesocosm was found to be fostered by longitudinal dispersion as a result of the spatial distribution of the macrophytes in the aqueous phase. The peak reduction attributable to longitudinal dispersion was, however, reduced in the densely vegetated stream mesocosm, which was compensated by compound-specific but time-limited and reversible sorption to macrophytes. The observations on the reversibility of sorption processes were subsequently confirmed by laboratory experiments. The experiments revealed that sorption to macrophytes lead to compound specific elimination from the aqueous phase during the presence of transient contaminant peaks in streams. After all, these sorption processes were found to be fully reversible, which results in the release of the primarily adsorbed compounds, once the concentrations in the aqueous phase starts to decrease. Nevertheless, the results of the present thesis demonstrate that the processes governing the mitigation of contaminant loads in streams are fundamentally different to those already described for non-flowing systems. In addition, the present thesis provides knowledge on how the interaction of macrophyte-induced processes in streams contributes to mitigate loads of organic contaminants and the related risk for aquatic environments.
Flowering habitats to enhance biodiversity and pest control services in agricultural landscapes
(2015)
Meeting growing demands for agricultural products requires management solutions that enhance food production, whilst minimizing negative environmental impacts. Conventional agricultural intensification jeopardizes farmland biodiversity and associated ecosystem services through excessive anthropogenic inputs and landscape simplification. Agri-environment schemes (AES) are commonly implemented to mitigate the adverse effects of conventional intensification on biodiversity. However the moderate success of such schemes thus far would strongly benefit from more explicit goals regarding ecosystem service provisioning. Providing key resources to beneficial organisms may improve their abundance, fitness, diversity and the ecosystem services they provide. With targeted habitat management, AES may synergistically enhance biodiversity and agricultural production and thus contribute to ecological intensification. We demonstrate that sown perennial wildflower strips, as implemented in current AES focusing on biodiversity conservation also benefit biological pest control in nearby crops (Chapter 2).
Comparing winter wheat fields adjacent to wildflower strips with fields without wildflower strips we found strongly reduced cereal leaf beetle (Oulema sp.) density and plant damage near wildflower strips. In addition, winter wheat yield was 10 % higher when fields adjoined wildflower strips. This confirms previous assumptions that wildflower strips, known for positive effects on farmland biodiversity, can also enhance ecosystem services such as pest control and the positive correlation of yield with flower abundance and diversity suggests that floral resources are key. Refining sown flower strips for enhanced service provision requires mechanistic understanding of how organisms benefit from floral resources. In climate chamber experiments investigating the impact of single and multiple flowering plant species on fitness components of three key arthropod natural enemies of aphids, we demonstrate that different natural enemies benefit differently from the offered resources (Chapter 3).
Some flower species were hereby more valuable to natural enemies than others overall. Additionally, the mixture with all flowers generally performed better than monocultures, yet with no transgressive overyielding. By explicitly tailoring flower strips to the requirements of key natural enemies of crop pests we aimed to maximise natural enemy mediated pest control in winter wheat (Chapter 4)and potato (Chapter 5) crops.
Respecting the manifold requirements of diverse natural enemies but not pests, in terms of temporal and spatial provisioning of floral, extra floral and structural resources, we designed targeted annual flower strips that can be included in crop rotation to support key arthropods at the place and time they are needed. Indeed, field experiments revealed that cereal leaf beetle density and plant damage in winter wheat can be reduced by 40 % to 61 % and aphid densities in potatoes even by 77 %, if a targeted flower strip is sown into the field. These effects were not restricted to the vicinity of flower strips and, in contrast to fields without flower strip, often prevented action thresholds from being reached. This suggests that targeted flower strips could replace insecticides. All adult natural enemies were enhanced inside targeted flower strips when compared to control strips. Yet, spillover to the field was restricted to key natural enemies such as ground beetles (winter wheat), hoverflies (potato) and lacewings (winter wheat and potato), suggesting their dominant role in biological control. In potatoes, targeted flower strips also enhanced hoverfly species richness in strips and crop, highlighting their additional benefits for diversity.
The present results provide more insights into the mechanisms underlying conservation biological control and highlight the potential of tailored habitat management for ecological intensification.
Change of ecosystems and the associated loss of biodiversity is among the most important environmental issues. Climate change, pollution, and impoundments are considered as major drivers of biodiversity loss. Organism traits are an appealing tool for the assessment of these three stressors, due to their ability to provide mechanistic links between organism responses and stressors, and consistency over wide geographical areas.
Additionally, traits such as feeding habits influence organismal performance and ecosystem processes. Although the response of traits of specific taxonomic groups to stressors is known, little is known about the response of traits of different taxonomic groups to stressors. Additionally, little is known about the effects of small impoundments on stream ecosystem processes, such as leaf litter decomposition, and food webs.
After briefly introducing the theoretical background and objectives of the studies, this thesis begins by synthesizing the responses of traits of different taxonomic groups to climate change and pollution. Based on 558 peer-reviewed studies, the uniformity (i.e., convergence) in trait response across taxonomic groups was evaluated through meta-analysis (Chapter 2). Convergence was primarily limited to traits related to tolerance.
In Chapter 3, the hypothesis that small impoundments would modify leaf litter decomposition rates at the sites located within the vicinity of impoundments, by altering habitat variables and invertebrate functional feeding groups (FFGs) (i.e., shredders), was tested. Leaf litter decomposition rates were significantly reduced at the study sites located immediately upstream (IU) of impoundments, and were significantly related to the abundance of invertebrate shredders.
In Chapter 4, the invertebrate FFGs were used to evaluate the effect of small impoundments on stream ecosystem attributes. The results showed that heterotrophic production was significantly reduced at the sites IU. With regard to food webs, the contribution of methane gas derived carbon to the biomass of chironomid larvae was evaluated through correlation of stable carbon isotope values of chironomid larvae and methane gas concentrations.
The results indicated that the contribution of methane gas derived carbon into stream benthic food web is low. In conclusion, traits are a useful tool in detecting ecological responses to stressors across taxonomic groups, and the effects of small impoundments on stream ecological integrity and food web are limited.
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.
Modern agriculture is a dominant land use in Europe, although it has been associated with negative effects on biodiversity in agricultural landscapes. One species-rich insect group in agro-ecosystems is the Lepidoptera (moths and butterflies); however, the populations of a number of Lepidoptera species are currently declining. The aims of this thesis were to assess the amount and structure of field margins in agricultural landscapes, study the effects of realistic field margin input rates of agrochemicals (fertilizer and pesticides) on Lepidoptera, and provide information on moth pollination services.
In general, field margins are common semi-natural habitat elements in agro-ecosystems; however, data on the structure, size, and width of field margins is limited. An assessment in two German agricultural landscapes (4,000 ha each) demonstrated that many of the evaluated field margins were less than 3 m wide (Rhineland‐Palatinate: 85% of margin length; Brandenburg: 45% margin length). In Germany, risk mitigation measures (such as buffer zones) to reduce pesticide inputs to terrestrial non-crop habitats do not have to be established by farmers next to narrow field margins. Thus, narrow field margins receive inputs of agrochemicals, especially via overspray and spray drift. These field margins were used as a development habitat for caterpillars, but the mean abundance of caterpillars was 35 – 60% lower compared with that in meadows. Caterpillars were sensitive to realistic field margin input rates of insecticide (pyrethroid, lambda-cyhalothrin) in a field experiment as well as in laboratory experiments. Moreover, 40% fewer Hadena bicruris eggs were observed on Silene latifolia plants treated with this insecticide compared with control plants, and the flowers of these insecticide-treated plants were less likely to be pollinated by moths. In addition, realistic field margin input rates of herbicides can also affect Lepidoptera. Ranunculus acris L. plants treated with sublethal rates of a sulfonylurea herbicide were used as host plants for Mamestra brassicae L. caterpillars, which resulted in significantly lower caterpillar weights, increased time to pupation, and increased overall development time compared with caterpillars feeding on control plants. These results might have been caused by lower nutritional value of the herbicide-treated plants or increased concentrations of secondary metabolites involved in plant defense. Fertilizer applications slightly increased the caterpillar abundance in the field experiment. However, fertilizers reduce plant diversity in the long term and thus, most likely, also reduce caterpillar diversity.
Moths such as Noctuidae and Sphingidae have been observed to act as pollinators for numerous plant species, including a number of Orchidaceae and Caryophyllaceae. Although in temperate agro-ecosystems moths are less likely to act as the main pollinators for crops, they can pollinate non-crop plants in semi-natural habitats. Currently, the role of moths as pollinators appears to be underestimated, and long-term research focusing on ecosystems is necessary to address temporal fluctuations in their abundance and community composition.
Lepidoptera represent a diverse organism group in agricultural landscapes and fulfill essential ecosystem services, such as pollination. To better protect moths and butterflies, agrochemical inputs to (narrow) field margins habitats should be reduced, for example, via risk mitigation measures and agro-environmental schemes.
Factors triggering the ecotoxicity of metal-based nanoparticles towards aquatic invertebrates
(2015)
Nanoparticles are produced and used in huge amounts increasing their probability to end up in surface waters. There, they are subject to environmentally driven modification processes. Consequently, aquatic life may be exposed to different nanoparticle agglomerate sizes, while after sedimentation benthic organisms are more likely to be affected.
However, most ecotoxicity studies with nanoparticles exclusively investigated implications of their characteristics (e.g. size) on pelagic organisms, ignoring environmentally modified nanoparticles. Therefore, a systematic assessment of factors triggering the fate and toxicity of nanoparticles under environmentally relevant conditions is needed. The present thesis, therefore, investigates the implications of nanoparticle related factors (i.e., inherent material-properties and nanoparticle characteristics) as well as environmental conditions towards the pelagic living organism Daphnia magna and the benthic species Gammarus fossarum. In detail, inert titanium dioxide (nTiO2) and ion-releasing silver nanoparticles (nAg), both of varying particle characteristics (e.g. initial size), were tested for their toxicity under different environmental conditions (e.g. ultraviolet-light (UV-light)).
The results indicate that the toxicity of nTiO2 and nAg is mainly determined by: their adsorption potential onto biota, and their fate in terms of reactive oxygen species or Ag+ ion release. Thus, inherent material-properties, nanoparticle characteristics and environmental conditions promoting or inhibiting these aspects revealed significant implications in the toxicity of nTiO2 and nAg towards daphnids.
Furthermore, the presence of ambient UV-light, for example, adversely affected gammarids at 0.20 mg nTiO2/L, while under darkness no effects occurred even at 5.00 mg nTiO2/L. Hence, the currently associated risk of nanoparticles might be underestimated if disregarding their interaction with environmental parameters
The increasing application of titanium dioxide nanoparticles (nTiO2) entails an increased risk regarding their release to surface water bodies, where they likely co-occur with other anthropogenic stressors, such as heavy metals. Their co-occurrence may lead to an adsorption of the metal ions onto the particles. These nanoparticles often sediment, due to their agglomeration, and thus pose a risk for pelagic or benthic species. The combined toxicity of nTiO2 and heavy metals is likely influenced by the properties of both stressors (since they may alter their interaction) and by environmental parameters (e.g., organic matter, pH, ionic strength) affecting their fate.
These issues were not yet systematically examined by the recent literature. Therefore, this thesis investigated the influence of nTiO2-products with differing crystalline phase composition on the toxicity of copper (as representative for heavy metals) in presence of different organic matters using the pelagic test organism Daphnia magna.
Moreover, the duration of the stressors` interaction (=aging) likely modulates the combined toxicity. Hence, the influence of nTiO2 on copper toxicity after aging as a function of environmental parameters (i.e., organic matter, pH, ionic strength) was additionally investigated.
Finally, the transferability of the major findings to benthic species was examined using Gammarus fossarum. The present thesis discovered a reduction of the copper toxicity facilitated by nTiO2 for all assessed scenarios, while its magnitude was determined by the surface area and structure of nTiO2, the quantity and quality of organic matter as well as the aging of both stressors. The general copper toxicity reduction by nTiO2 was also transferable to benthic species, despite their potentially increased exposure due to the sedimentation of nTiO2 with adsorbed copper. These observations suggest the application of nTiO2 as remediation agent, but potential side effects (e.g., chronic toxicity, reactive oxygen species formation) require further investigations. Moreover, questions regarding the transferability to other stressors (e.g., different heavy metals, organic chemicals) and the fate of stressors adsorbed to nTiO2 in aquatic ecosystems remain open.
Engineered nanoparticles are emerging pollutants. Their increasing use in commercial products suggests a similar increase of their concentrations in the environment. Studying the fate of engineered colloids in the environment is highly challenging due to the complexity of their possible interactions with the main actors present in aquatic systems. Solution chemistry is one of the most central aspects. In particular, the interactions with dissolved organic matter (DOM) and with natural colloids are still weakly understood.
The aim of this work was to further develop the dedicated analytical methods required for investigating the fate of engineered colloids in environmental media as influenced by DOM. Reviewing the literature on DOM interactions with inorganic colloids revealed that a systematic characterization of both colloids and DOM, although essential, lacks in most studies and that further investigations on the fractionation of DOM on the surface of engineered colloids is needed. Another knowledge gap concerns the effects of DOM on the dynamic structure of colloid agglomerates. For this question, analytical techniques dedicated to the characterization of agglomerates in environmental media at low concentrations are required. Such techniques should remain accurate at low concentrations, be specific, widely matrix independent and free of artefact due to sample preparation. Unfortunately, none of the currently available techniques (microscopy, light scattering based methods, separation techniques etc.) fulfills these requirements.
However, a compromise was found with hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry (HDC-ICP-MS). This method has the potential to size inorganic particles in complex media in concentration ranges below ppb and is element specific; however, its limitations were not systematically explored. In this work, the potential of this method has been further explored. The simple size separation mechanism ensures a high flexibility of the elution parameters and universal calibration can be accurately applied to particles of different compositions and surface chemistries. The most important limitations of the method are its low size resolution and the effect of the particle shape on the retention factor. The implementation of HDC coupled to single particle ICP-MS (HDC-SP-ICP-MS) offers new possibilities for the recognition of particle shape and hence the differentiation between primary particles and homoagglomerates. Therefore, this coupling technique is highly attractive for monitoring the effects of DOM on the stability of colloids in complex media. The versatility of HDC ICP MS is demonstrated by its successful applications to diverse samples. In particular, it has been used to investigate the stability of citrate stabilized silver colloids in reconstituted natural water in the presence of different types of natural organic matter. These particles were stable for at least one hour independently of the type of DOM used and the pH, in accordance with a coauthored publication addressing the stability of silver colloids in the River Rhine. Direct monitoring of DOM adsorption on colloids was not possible using UV and fluorescence detectors. Preliminary attempts to investigate the adsorption mechanism of humic acids on silver colloids using fluorescence spectroscopy suggest that fluorescent molecules are not adsorbed on silver particles. Several solutions for overcoming the encountered difficulties in the analysis of DOM interactions are proposed and the numerous perspectives offered by further developments and applications of HDC-(SP)-ICP-MS in environmental sciences are discussed in detail.
The intention of this thesis was to characterise the effect of naturally occurring multivalent cations like Calcium and Aluminium on the structure of Soil Organic Matter (SOM) as well as on the sorption behaviour of SOM for heavy metals such as lead.
The first part of this thesis describes the results of experiments in which the Al and Ca cation content was changed for various samples originated from soils and peats of different regions in Germany. The second part focusses on SOM-metal cation precipitates to study rigidity in dependence of the cation content. In the third part the effects of various cation contents in SOM on the binding strength of Pb cations were characterised by using a cation exchange resin as desorption method.
It was found for soil and peat samples as well as precipitates that matrix rigidity was affected by both type and content of cation. The influence of Ca on rigidity was less pronounced than the influence of Al and of Pb used in the precipitation experiments. For each sample one cation content was identified where matrix rigidity was most pronounced. This specific cation content is below the cation saturation as expected by cation exchange capacity. These findings resulted in a model describing the relation between cation type, content and the degree of networking in SOM. For all treated soil and precipitate samples a step transition like glass transition was observed, determined by the step transition temperature T*. It is known from literature that this type of step transition is due to bridges between water molecules and organic functional groups in SOM. In contrast to the glass transition temperature this thermal event is slowly reversing after days or weeks depending on the re-conformation of the water molecules. Therefore, changes of T* with different cation compositions in the samples are explained by the formation of water-molecule-cation bridges between SOM-functional groups. No influence on desorption kinetics of lead for different cation compositions in soil samples was observed. Therefore it can be assumed that the observed changes of matrix rigidity are highly reversible by changing the water status, pH or putting agitation energy by shaking in there.
The increasing, anthropogenic demand for chemicals has created large environmental problems with repercussions for the health of the environment, especially aquatic ecosystems. As a result, the awareness of the public and decision makers on the risks from chemical pollution has increased over the past half-century, prompting a large number of studies in the field of ecological toxicology (ecotoxicology). However, the majority of ecotoxicological studies are laboratory based, and the few studies extrapolating toxicological effects in the field are limited to local and regional levels. Chemical risk assessment on large spatial scales remains largely unexplored, and therefore, the potential large-scale effects of chemicals may be overlooked.
To answer ecotoxicological questions, multidisciplinary approaches that transcend classical chemical and toxicological concepts are required. For instance, the current models for toxicity predictions - which are mainly based on the prediction of toxicity for a single compound and species - can be expanded to simultaneously predict the toxicity for different species and compounds. This can be done by integrating chemical concepts such as the physicochemical properties of the compounds with evolutionary concepts such as the similarity of species. This thesis introduces new, multidisciplinary tools for chemical risk assessments, and presents for the first time a chemical risk assessment on the continental scale.
After a brief introduction of the main concepts and objectives of the studies, this thesis starts by presenting a new method for assessing the physiological sensitivity of macroinvertebrate species to heavy metals (Chapter 2). To compare the sensitivity of species to different heavy metals, toxicity data were standardized to account for the different laboratory conditions. These rankings were not significantly different for different heavy metals, allowing the aggregation of physiological sensitivity into a single ranking.
Furthermore, the toxicological data for macroinvertebrates were used as input data to develop and validate prediction models for heavy metal toxicity, which are currently lacking for a wide array of species (Chapter 3). Apart from the toxicity data, the phylogenetic information of species (evolutionary relationships among species) and the physicochemical parameters for heavy metals were used. The constructed models had a good explanatory power for the acute sensitivity of species to heavy metals with the majority of the explained variance attributed to phylogeny. Therefore, the integration of evolutionary concepts (relatedness and similarity of species) with the chemical parameters used in ecotoxicology improved prediction models for species lacking experimental toxicity data. The ultimate goal of the prediction models developed in this thesis is to provide accurate predictions of toxicity for a wide range of species and chemicals, which is a crucial prerequisite for conducting chemical risk assessment.
The latter was conducted for the first time on the continental scale (Chapter 4), by making use of a dataset of 4,000 sites distributed throughout 27 European countries and 91 respective river basins. Organic chemicals were likely to exert acute risks for one in seven sites analyzed, while chronic risk was prominent for almost half of the sites. The calculated risks are potentially underestimated by the limited number of chemicals that are routinely analyzed in monitoring programmes, and a series of other uncertainties related with the limit of quantification, the presence of mixtures, or the potential for sublethal effects not covered by direct toxicity.
Furthermore, chemical risk was related to agricultural and urban areas in the upstream catchments. The analysis of ecological data indicated chemical impacts on the ecological status of the river systems; however, it is difficult to discriminate the effects of chemical pollution from other stressors that river systems are exposed to. To test the hypothesis of multiple stressors, and investigate the relative importance of organic toxicants, a dataset for German streams is used in chapter 5. In that study, the risk from abiotic (habitat degradation, organic chemicals, and nutrients enrichment) and biotic stressors (invasive species) was investigated. The results indicated that more than one stressor influenced almost all sites. Stream size and ecoregions influenced the distribution of risks, e.g., the risks for habitat degradation, organic chemicals and invasive species increased with the stream size; whereas organic chemicals and nutrients were more likely to influence lowland streams. In order to successfully mitigate the effects of pollutants in river systems, co-occurrence of stressors has to be considered. Overall, to successfully apply integrated water management strategies, a framework involving multiple environmental stressors on large spatial scales is necessary. Furthermore, to properly address the current research needs in ecotoxicology, a multidisciplinary approach is necessary which integrates fields such as, toxicology, ecology, chemistry and evolutionary biology.
A fundamental understanding of attachment of engineered nanoparticles to environmentalrnsurfaces is essential for the prediction of nanoparticle fate and transport in the environment.
The present work investigates the attachment of non-coated silver nanoparticles and citraterncoated silver nanoparticles to different model surfaces and environmental surfaces in thernpresence and absence of humic acid. Batch sorption experiments were used for this investigation.
The objective of this thesis was to investigate how silver nanoparticles interactrnwith surfaces having different chemical functional groups. The effect of presence of HA, on the particle-surface interactions was also investigated. In the absence of humic acid, nanoparticle-surface interactions or attachment was influencedrnby the chemical nature of the interacting surfaces. On the other hand, in the presence ofrnhumic acid, nanoparticle-surface attachment was influenced by the specific surface area of the sorbent surfaces. The sorption of non-coated silver nanoparticles and citrate coatedrnnanoparticles to all the surfaces was nonlinear and best described by Langmuir isotherm, indicating monolayer sorption of nanoparticles on to the surfaces. This can be explained as due to the blocking effect generated by the particle-particle repulsion. In the presence of humic acid, sorption of nanoparticles to the surfaces was linear. When the humic acid was present in the interacting medium, both the nanoparticles and surfaces were getting coated with humic acid and this masks the chemical functionalities of the surfaces. This leads to the change in particle-surface interactions, in the presence of humic acid. For the silver nanoparticle sorption from an unstable suspension, the sorption isotherms did not follow any classical sorption models, suggesting interplay between aggregation and sorption. Citrate coated silver nanoparticles and humic acid coated silver nanoparticles showed arndepression in sorption compared to the sorption of non-coated silver nanoparticles. In therncase of citrate coated silver nanoparticles the decrease in sorption can be explained by thernmore negative zeta potential of citrate coated nanoparticles compared to non-coated ones. For humic acid coated nanoparticles the sorption depression can be due to the steric hindrance caused by the free humic acid molecules which may coat the sorbent surface or due to the competition for sorption sites between the nanoparticle and free humic acid molecules present in the suspension. Thus nanoparticle surface chemistry is an important factor that determines the attachment of nanoparticles towards surfaces and it makes the characterization of nanoparticle surface an essential step in the study of their fate in the environment.
Another aim of this study was to introduce the potential of chemical force microscopy for nanoparticle surface characterization. With the use of this technique, it was possible to distinguish between bare silver nanoparticles, citrate coated silver nanoparticles, and humic acid coated silver nanoparticles. This was possible by measuring the adhesion forces between the nanoparticles and five different AFM probes having different chemical functionalization.
Field margins are often the only remaining habitats of various wild plant species in agricultural landscapes. However, due to their proximity to agricultural fields, the vegetation of field margins can be affected by agrochemicals applied to the crop fields. The aim of this thesis was to investigate the individual and combined effects of herbicide, insecticide and fertilizer inputs on the plant community of a field margin. Therefore, a 3-year field experiment with a randomized block design including seven treatments (H: herbicide, I: insecticide, F: fertilizer, H+I, F+I, F+H and F+H+I) and one control was conducted on a low-production meadow. Each treatment was replicated 8 times in 8 m x 8 m plots with a distance of 2 m between each plot. The fertilizer rates (25 % of the field rate) and pesticide rates (30 % of the field rate) used for the plot applications were consistent with realistic average input rates (overspray + drift) in the first meter of a field margin directly adjacent to a wheat field.
The study revealed that fertilizer and herbicide misplacements in field margins are major factors that affect the natural plant communities of these habitats. In total, 20 of the 26 abundant species on the study site were significantly affected by the fertilizer and herbicide treatment. The fertilizer promoted plants with high nutrient uptake and decreased the frequencies of small species. The herbicide caused a nearly complete disappearance of three species directly after the first application, whereas sublethal effects (e.g., phytotoxic effects and reduced seed productions of up to 100 %) were observed for the other affected species. However, if field margins are exposed to repeated agrochemical applications over several years, then such sublethal effects (particularly reproduction effects) also reduce the population size of plant species significantly, as observed in this study.
Significant herbicide-fertilizer interaction effects were also detected and could not be extrapolated from individual effects. The fertilizer and herbicide effects became stronger over time, leading to shifts in plant community compositions after three years and to a 15 % lower species diversity than in the control. The insecticide significantly affected the frequencies of two plant species (1 positively and 1 negatively). The results of the experiment suggest that a continuous annual agrochemical application on the study site would cause further plant community shifts and would likely lead to the disappearance of certain affected plants. A clear trend of increasing grass dominance at the expense of flowering herbs was detected. This finding corresponds well with monitoring data from field margins near the study site.
Although herbicide risk assessment aims to protect non-target plants in off-field habitats from adverse effects, reproduction effects and combined effects are currently not considered. Furthermore, no regulations for fertilizer applications next to field margins exist and thus, fertilizer misplacements in field margins are likely to occur and to interact with herbicide effects.
Adaptations of the current risk assessment, a development of risk mitigation measures (e.g., in-field buffers) for the application of herbicides and fertilizers, and general management measures for field margins are needed to restore and conserve plant diversity in field margins in agricultural landscapes.