Recent EU-frameworks enforce the implementation of risk mitigation measures for nonpoint-source pesticide pollution in surface waters. Vegetated surface flow treatments systems (VTS) can be a way to mitigate risk of adverse effects in the aquatic ecosystems following unavoidable pollution after rainfall-related runoff events. Studies in experimental wetland cells and vegetated ditch mesocosms with common fungicides, herbicides and insecticides were performed to assess efficiency of VTS. Comprehensive monitoring of fungicide exposure after rainfall-related runoff events and reduction of pesticide concentrations within partially optimised VTS was performed from 2006-2009 at five vegetated detention ponds and two vegetated ditches in the wine growing region of the Southern Palatinate (SW-Germany). Influence of plant density, size related parameters and pesticide properties in the performance of the experimental devices, and the monitored systems were the focus of the analysis. A spatial tool for prediction of pesticide pollution of surface waters after rainfall-related runoff events was programmed in a geographic information system (GIS). A sophisticated and high resolution database on European scale was built for simulation. With the results of the experiments, the monitoring campaign and further results of the EU-Life Project ArtWET mitigation measures were implemented in a georeferenced spatial decision support system. The database for the GIS tools was built with open data. The REXTOX (ratio of exposure to toxicity) Risk Indicator, which was proposed by the OECD (Organisation for Economic Co-operation and Development), was extended, and used for modeling the risk of rainfall-related runoff exposure to pesticides, for all agricultural waterbodies on European scale. Results show good performance of VTS. The vegetated ditches and wetland cells of the experimental systems showed a very high reduction of more than 90% of pesticide concentrations and potential adverse effects. Vegetated ditches and wetland cells performed significantly better than devices without vegetation. Plant density and sorptivity of the pesticide were the variables with the highest explanatory power regarding the response variable reduction of concentrations. In the experimental vegetated ditches 65% of the reduction of peak concentrations was explained with plant density and KOC. The monitoring campaign showed that concentrations of the fungicides and potential adverse effects of the mixtures were reduced significantly within vegetated ditches (Median 56%) and detention ponds (Median 38%) systems. Regression analysis with data from the monitoring campaign identified plant density and size related properties as explanatory variables for mitigation efficiency (DP: R²=0.57, p<0.001; VD: R²=0.19, p<0.001). Results of risk model runs are the input for the second tool, simulating three risk mitigation measures. VTS as risk mitigation measures are implemented using the results for plant density and size related performance of the experimental and monitoring studies, supported by additional data from the ArtWET project. Based on the risk tool, simulations can be performed for single crops, selected regions, different pesticide compounds and rainfall events. Costs for implementation of the mitigation measures are estimated. Experiments and monitoring, with focus on the whole range of pesticides, provide novel information on VTS for pesticide pollution. The monitoring campaign also shows that fungicide pollution may affect surface waters. Tools developed for this study are easy to use and are not only a good base for further spatial analysis but are also useful as decision support of the non-scientific community. On a large scale, the tools on the one hand can help to compute external costs of pesticide use with simulation of mitigation costs on three levels, on the other hand feasible measures mitigating or remediating the effects of nonpoint-source pollution can be identified for implementation. Further study of risk of adverse effects caused by fungicide pollution and long-time performance of optimised VTS is needed.

Today’s agriculture heavily relies on pesticides to manage diverse pests and maximise crop yields. Despite elaborate regulation of pesticide use based on a complex environmental risk assessment (ERA) scheme, the widespread use of these biologically active compounds has been shown to be a threat to the environment. For surface waters, pesticide exposure has been observed to exceed safe concentration levels and negatively impact stream ecology leading to the question whether current ERA schemes ensure a sustainable use of pesticides. To answer this, the large-scale “Kleingewässer-Monitoring” (KgM) assessed the occurrence of pesticides and related effects in 124 streams throughout Germany, Central Europe, in 2018 and 2019. Based on five scientific publications originating from the KgM, this thesis evaluated pesticide exposure in streams, ecological effects and the regulatory implications. More than 1,000 water samples were analysed for over 100 pesticide analytes to characterise occurrence patterns (publication 1). Measured concentrations and effects were used to validate the exposure and effect concentrations predicted in the ERA (publication 2). By jointly analysing real-world pesticide application data and measured pesticide mixtures in streams, the disregard of environmental pesticide mixtures in the ERA was evaluated (publication 3). The toxic potential of mixtures in stream water was additionally investigated using suspect screening for 395 chemicals and a battery of in-vitro bioassays (publication 4). Finally, the results from the KgM stream monitoring were used to assess the capability to identify pesticide risks in governmental monitoring programmes (publication 5). The results of this thesis reveal the widespread occurrence of pesticides in non-target stream ecosystems. The water samples contained a variety of pesticides occurring in complex mixtures predominantly in short-term peaks after rainfall events (publications 1 & 4). Respective pesticide concentration maxima were linked to declines in vulnerable invertebrate species and exceeded regulatory acceptable concentrations in about 80% of agricultural streams, while these thresholds were still estimated partly insufficient to protect the invertebrate community (publication 2). The co-occurrence of pesticides in streams led to a risk underestimated in the single substance-oriented ERA by a factor of about 3.2 in realistic worst-case scenarios, which is further exacerbated by a high frequency at which non-target organism are exposed to pesticides (publication 3). Stream water samples taken after rainfall caused distinct effects in bioassays which were only explainable to a minor extent by the many analytes, indicating the relevance of unknown chemical or biological mixture components (publication 4). Finally, the regulatory monitoring of surface waters under the Water Framework Directive (WFD) was found to significantly underestimate pesticide risks, as about three quarters of critical pesticides and more than half of streams at risk were overlooked (publication 5). Essentially, this thesis involves a new level of validation of the ERA of pesticides in aquatic ecosystems by assessing pesticide occurrence and environmental impacts at a scale so far unique. The overall results demonstrate that the current agricultural use of pesticides leads to significant impacts on stream ecology that go beyond the level tolerated under the ERA. This thesis identified the underestimation of pesticide exposure, the potential insufficiency of regulatory thresholds and the general inertia of the authorisation process as the main causes why the ERA fails to meet its objectives. To achieve a sustainable use of pesticides, the thesis proposes substantial refinements of the ERA. Adequate monitoring programmes such as the KgM, which go beyond current government monitoring efforts, will continue to be needed to keep pesticide regulators constantly informed of the validity of their prospective ERA, which will always be subject to uncertainty.