The loss of biodiversity is recognised on a global scale and also in the anthropogenic landscapes used for agriculture, now covering almost 50% of the global terrestrial land surface. In agriculture pesticides, biologically active chemicals are deliberately distributed to control pests, disease and weeds in the cropped areas. The quantification of remaining semi-naturals structures such as field margins and hedges is a prerequisite to understand the impact of pesticides on biodiversity, since these structures represent habitats for many organisms in agricultural landscapes. The presence of organisms in these habitats and crops is required to obtain an estimate of their potential pesticide exposure. In this text I provide studies on animal groups so far not addressed in risk assessment procedures for the regulation of pesticides such as amphibians, moths and bats. For all groups it becomes apparent that they are present in agricultural landscapes and potentially coincide with pesticide applications indicating a risk. Risk quantification also requires data on the sensitivity of organisms and here data for plants, amphibians and bees are presented. Effects translating to community level were studied for herbicide, insecticide and fertiliser effects in a natural system. After three years the treatments resulted in simplified plant communities with lower species numbers and a reduction in flowering plants. This reduction of flowers is used as an example for an indirect effect and was especially obvious for the effect of an herbicide on the common buttercup. Sublethal herbicide effects for a plant translated in an impact on feeding caterpillars, indicating a reduction in food quality. Insecticide inputs realistic for field margins also reduced moth pollination of white champion flowers by 30%. These indirect effects by distortions of food web characteristics are playing a critical role to understand declines in organism groups, however so far are not accounted for in pesticide risk assessment schemes. The current intense use of pesticides in agriculture and their inherent toxicity may lead to a chemical landscape fragmentation, where populations may not be connected anymore. Source-sink dynamics are important ecological processes and as a final result not only population size but also genetic population structure might be affected. Including potential pesticide impacts as costs in a model for amphibians migrating to breeding ponds in vineyards in Rhineland-Palatinate indicated the isolation of investigated populations. A first validation by analyzing the population structure of the European common frog confirmed the model prediction for some sites. For the regulation of pesticides in Europe a risk assessment is required and for the organisms of the terrestrial habitat a multitude of guidance documents is in place or is recently developed or improved. The results of the presented research indicate that wild plants and especially their reproductive flower stage are highly sensitive and risks are underestimated. Population recovery of arthropods needs a reevaluation at landscape scale and the addition of amphibian risk assessment in regulation procedures is suggested. However, developing or adopting risk assessment procedures and test systems is a time consuming task and therefore the establishment of risk management options is a pragmatic alternative with immediate effects. Artificial wetlands in the agricultural landscape proved to be important foraging sites for bats and their creation could mitigate negative pesticide effects. The integration of direct and indirect effects in a risk assessment scheme for all organism groups addressing also landscape scale and pesticide mixtures requires a long developing time. The establishment of model landscapes where management options and integrated pest management are applied on a larger scale would allow us to study pesticide effects in a realistic scenario and to develop an approach for the agriculture of the future.

The largest population of the anadromous Allis shad (A. alosa) of the 19th century was found in River Rhine and has to be considered extinct today. To facilitate the return of A. alosa into River Rhine an EU LIFE-project was initiated in 2007. The overall objective of this thesis was to assist aquaculture and stocking-measures at River Rhine, as well as to support restoration and conservation of populations of Allis shad in Europe. By culturing the free-swimming nematode T. aceti in a solution of cider vinegar we developed a cost-effective live food organism for the larviculture of fish. As indicated by experiments with C. maraena, T. aceti cannot be regarded as an alternative to Artemia nauplii. However it has to be considered a suitable supplemental feed in the early rearing of C. maraena by providing essential fatty acids, thereby optimizing growth. Also mass-marking practices with Oxytetracycline, as they are applied in the restocking of Allis shad have been evaluated. In experiments with D. rerio we demonstrated that water hardness can detrimentally affect mortality during marking and has to be considered crucial in the development of marking protocols for freshwater fish. In order to get independent from wild spawners an ex-situ Broodstock-facility for Allis shad was established in 2011. Upon examination of two complete year classes of this broodstock, we found a high prevalence of various malformations, which could be traced back to distinct cysts developing one month post hatch. Despite applying a variety of clinical tests we could not identify any infectious agents causing these malformations. The observed malformations are probably a consequence of suboptimal feeding practices or the properties of the physio-chemical rearing environment. The decline of stocks of A. alosa in Europe has been largely explained with the increase of river temperatures as a consequence of global warming. By investigating the temperature physiology of larval Allis shad we demonstrated that A. alosa ranges among the most thermo-tolerant species in Europe and that correlations between rising temperatures and the disappearance of this species have to be understood in a synecological context and by integrating a variety of stressors other than temperature. By capturing and examining juvenile and adult Allis shad from River Rhine, we demonstrated the first natural reproduction of A. alosa in River Rhine since nearly 100 years and the success of stocking measures within the framework of the LIFE project.

In dieser Studie sollte hinsichtlich der Entwicklung eines faunistisch begründeten Monitoringkonzeptes für hydrologische Interaktionen untersucht werden, inwieweit die Meiofauna in Hyporheal und Grundwasser in der Lage ist, Oberflächenwasser-Grundwasser-Interaktionen zu reflektieren und die hydrologischen Verhältnisse einer Uferfiltrationsanlage aufzuzeigen. Dafür wurden hydrochemische und faunistische Analysen bezüglich ihrer Aussagekraft miteinander verglichen. Außerdem wurde die Anwendbarkeit des Grundwasser-Fauna-Index (GFI) zur Beurteilung der Stärke des Oberflächenwassereinflusses auf unterirdisches Wasser überprüft. Für die Untersuchung wurde die Uferfiltrationsanlage Flehe der Stadtwerke Düsseldorf ausgewählt, auf deren Gelände 70 vertikale Entnahmebrunnen über eine Strecke von 1,4 km eine Brunnengalerie bilden, die im Jahr insgesamt 11 Mio. m3 Wasser fördert. Am Untersuchungsstandort wurden insgesamt 15 Observationspegel von Februar 2005 bis Januar 2006 faunistisch und hydrochemisch beprobt. Die physikochemische Untersuchung ergab eine Aufteilung des Untersuchungsgebietes in vier Zonen. Neben dem Oberflächenwasser des Rheins [OW Rhein] konnten das Uferfiltrationswasser zwischen Rhein und den Entnahmebrunnen [Hyporheal], alluviales Grundwasser hinter der Brunnengalerie [Alluv. GW] und bei größerer Entfernung zum Rhein landseitiges Grundwasser [landseitiges GW] differenziert werden. Dabei wies der Rhein die typische Charakteristik eines Fließgewässers auf, gekennzeichnet durch eine große Temperaturamplitude mit einem Sommermaximum, hohen Sauerstoffkonzentrationen mit einem Wintermaximum und erhöhten AOX-, DOC- und SAK254nm-Werten. Am Uferfiltrat der Gruppe [Hyporheal] wurde die Wirksamkeit der mikrobiellen Abbauprozesse während der Uferfiltration mit deutlichen Reduzierungen der DOC- und SAK- und Sauerstoffkonzentrationen ersichtlich. Die Gruppe [Alluv. GW] und verstärkt das [landseitige GW] waren durch eine höhere elektrische Leitfähigkeit und erhöhten Bor- und Sulfatkonzentrationen sowie z. T. geringen Sauerstoffgehalten gekennzeichnet. Anhand dieser hydrochemischen Differenzen konnte die unterschiedliche Herkunft des Wassers im Untersuchungsgebiet ermittelt werden Die faunistischen Untersuchungen zeigten ein differenzierteres Bild von den hydrologischen Verhältnissen als die Hydrochemie. Insgesamt konnten fünf ökologische Gruppen ermittelt werden. Die Gruppe [Hyporheal 1] der A-Pegelreihe wies als einzige euryöke Arten auf, die einen stärkeren Oberflächenwassereinfluss anzeigten. Im [Hyporheal 2] der B-Pegelreihe konnte eine artenreiche ökotonale Fauna nachgewiesen werden, während die Proben des alluvialen Grundwassers der C-Pegelreihe [Alluv. GW (Pumpe)] den Einfluss der Entnahmebrunnen reflektierten. In den Pegeln des alluvialen Grundwassers [Alluv. GW] wurde aufgrund der geringeren Beeinflussung der Pumpen artenreichere Zoozönosen vorgefunden. Das [landseitige GW] wies schließlich eine arten- und abundanzarme Fauna auf, die charakteristisch ist für Grundwasser mit geringem Oberflächenwassereinfluss. Folglich konnte die Fauna nicht nur die Herkunft des Grundwassers anzeigen, sondern auch den Einfluss und die Intensität des Oberflächenwassers auf das Grundwasser sowie anthropogene Störungen wie eine verstärkte Kolmation bzw. die Effekte der Wasserentnahme durch die Brunnen. Die Meiofauna im Grundwasserleiter der Uferfiltrationsanlage dürfte somit als Indikator für hydrologische Verhältnisse gut geeignet sein. Der Grundwasser-Fauna-Index konnte als der wichtigste Faktor aller physikochemischen Parameter ermittelt werden, der die faunistischen Gruppen am stärksten beeinflusst. Außerdem war der GFI in der Lage, die Auswirkung und Intensität des Einflusses von Oberflächenwasser auf die einzelnen Probestandorte anzuzeigen. Die hier dargestellten Ergebnisse zeigen, dass die Grundwasserfauna und der GFI viel versprechende Methoden zur Bewertung der hydrologischen Verhältnisse, insbesondere des Einflusses von Oberflächenwasser auf das Grundwasser sind. Daher sind sie als Ergänzung zur hydrochemischen Analyse zu empfehlen und können auch einen wichtigen Beitrag für die Vulnerabilitätsabschätzung leisten.

Systemic neonicotinoids are one of the most widely used insecticide classes worldwide. In addition to their use in agriculture, they are increasingly applied on forest trees as a protective measure against insect pests. However, senescent leaves containing neonicotinoids might, inter alia during autumn leaf fall, enter nearby streams. There, the hydrophilic neonicotinoids may be remobilized from leaves to water resulting in waterborne exposure of aquatic non-target organisms. Despite the insensitivity of the standard test species Daphnia magna (Crustacea, Cladocera) toward neonicotinoids, a potential risk for aquatic organisms is evident as many other aquatic invertebrates (in particular insects and amphipods) display adverse effects when exposed to neonicotinoids in the ng/L- to low µg/L-range. In addition to waterborne exposure, in particular leaf-shredding invertebrates (= shredders) might be adversely affected by the introduction of neonicotinoid-contaminated leaves into the aquatic environment since they heavily rely on leaf litter as food source. However, dietary neonicotinoid exposure of aquatic shredders has hardly received any attention from researchers and is not considered during aquatic environmental risk assessment. The primary aim of this thesis is, therefore, (1) to characterize foliar neonicotinoid residues and exposure pathways relevant for aquatic shredders, (2) to investigate ecotoxicological effects of waterborne and dietary exposure on two model shredders, namely Gammarus fossarum (Crustacea, Amphipoda) and Chaetopteryx villosa (Insecta, Trichoptera), and (3) to identify biotic and abiotic factors potentially modulating exposure under field conditions. During the course of this thesis, ecotoxicologically relevant foliar residues of the neonicotinoids imidacloprid, thiacloprid and acetamiprid were quantified in black alder trees treated at field relevant levels. A worst-case model – developed to simulate imidacloprid water concentrations resulting from an input of contaminated leaves into a stream – predicted only low aqueous imidacloprid concentrations (i.e., ng/L-range). However, the model identified dietary uptake as an additional exposure pathway relevant for shredders up to a few days after the leaves’ introduction into the stream. When test organisms were simultaneously exposed (= combined exposure) to neonicotinoids leaching from leaves into the water and via the consumption of contaminated leaves, adverse effects exceeded those observed under waterborne exposure alone. When exposure pathways were separated using a flow-through system, dietary exposure towards thiacloprid-contaminated leaves caused similar sublethal adverse effects in G. fossarum as observed under waterborne exposure. Moreover, the effect sizes observed under combined exposure were largely predictable using the reference model “independent action”, which assumes different molecular target sites to be affected. Dietary toxicity for shredders might, however, be reduced under field conditions since UV-induced photodegradation and leaching decreased imidacloprid residues in leaves and thereby the toxicity for G. fossarum. In contrast, both shredders were found unable to actively avoid dietary exposure. This thesis thus recommends considering dietary exposure towards systemic insecticides, such as neonicotinoids, already during their registration to safeguard aquatic shredders, associated ecosystem functions (e.g., leaf litter breakdown) and ultimately ecosystem integrity.

Perfluorocarboxylic acids (PFCA) are substances of anthropogenic origin and have been used for several decades. These compounds are a new class of environmental pollutants. Their high surface activity, thermal stability, amphipathicity and weak intermolecular interactions lead to persistence and bioaccumulation. Therefore, there is a great need for reliable analytical methods for detecting the presence and determination of concentration in both environmental samples and everyday products. GC-MS is a cost-effective alternative and supplement to established LC-MS/MS methods. The greatest challenge in the method development is the derivatization reaction. Many of the previously published derivatization reactions for PFCA are time consuming and require high reaction temperatures or toxic reagents. In the present dissertation, two new derivatization reactions for PFCA have been developed and optimized. The first part of the thesis shows the development and optimization of the reaction with triethylsilanol in water. In addition to optimizing the reaction, classical solid-phase extraction was modified to simplify the sample preparation. In the second part of the work, the reaction products of perfluorooctanoic acid (PFOA) with N,N-dimethylformamide dimethyl acetal (DMF-DMA) and -diethyl acetal (DMF-DEA) were identified. From these measurements, it follows that both DMF-DMA and DMF-DEA in the presence of PFOA form an iminium cation, which leads to salt formation. This PFOA salt react further in the GC injector and a corresponding amine is produced. In the last part of the thesis, an analytical method based on the DMF-DMA reaction was developed. The matrix effects have been described in detail. The method has been successfully applied for three different types of samples: dental floss, textiles and sewage sludge. The results were verified by LC-MS/MS analysis in an external laboratory. The differences between the PFCA values for a spiked sample measured by GC-MS and LC-MS/MS were less than 10%.