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.

The application of pesticides to agricultural areas can result in transport to adjacent non-target environments. In particular, surface water systems are likely to receive agricultural pesticide input. When pesticides enter aquatic environments, they may pose a substantial threat to the ecological integrity of surface water systems. To minimize the risk to non-target ecosystems the European Union prescribes an ecotoxicological risk assessment within the registration procedure of pesticides, which consists of an effect and an exposure assessment. This thesis focuses on the evaluation of the exposure assessment and the implications to the complete regulatory risk assessment, and is based on four scientific publications. The main part of the thesis focuses on evaluation of the FOCUS modelling approach, which is used in regulatory risk assessment to predict pesticide surface water concentrations. This was done by comparing measured field concentrations (MFC) of agricultural insecticides (n = 466) and fungicides (n = 417) in surface water to respective predicted environmental concentrations (PEC) calculated with FOCUS step 1 to step 4 at two different levels of field relevance. MFCs were extracted from the scientific literature and were measured in field studies conducted primarily in Europe (publications 1 and 3). In addition, an alternative fugacity-based multimedia mass-balance model, which needs fewer input parameters and less computing effort, was used to calculate PECs for the same insecticide MFC dataset and compared to the FOCUS predictions (publication 3). Furthermore, FOCUS predictions were also conducted for veterinary pharmaceuticals in runoff from an experimental plot study, to assess the FOCUS predictions for a different class of chemicals with a different relevant entry pathway (publication 2). In publication 4, the FOCUS step-3 approach was used to determine relevant insecticide exposure patterns. These patterns were analysed for different monitoring strategies and the implications for the environmental risk assessment (publication 4). The outcome of this thesis showed that the FOCUS modelling approach is neither protective nor appropriate in predicting insecticide and fungicide field concentrations. Up to one third of the MFCs were underpredicted by the model calculations, which means that the actual risk might be underestimated. Furthermore, the results show that a higher degree of realism even reduces the protectiveness of model results and that the model predictions are worse for highly hydrophobic and toxic pyrethroids. In addition, the absence of any relationship between measured and predicted concentrations questions the general model performance quality (publication 1 and 3). Further analyses revealed that deficiencies in protectiveness and predictiveness of the environmental exposure assessment might even be higher than shown in this thesis, because actual short-term peak concentrations are only detectable with an event-related sampling strategy (publication 4). However, it was shown that the PECs of a much simpler modelling approach are much more appropriate for the prediction of insecticide MFC, especially for calculations with a higher field relevance (publication 3). The FOCUS approach also failed to predict concentrations of veterinary pharmaceuticals in runoff water (publication 2). In conclusion, the findings of this thesis showed that there is an urgent need for the improvement of exposure predictions conducted in the environmental risk assessment of pesticides as a group of highly relevant environmental chemicals, to ensure that the increasing use of those chemicals does not lead to further harmful effects in aquatic ecosystems.