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.