The agriculturally dominated region of the Western Cape, South Africa is vulnerable to pesticide pollution. A 2017–2019 pesticide monitoring campaign in the agricultural catchments of Grabouw, Piketberg and Hex River Valley identified year-round detections despite few agricultural applications, making pesticide pollution sources unclear. To better trace pesticide sources in these catchments, our study measured 19 pharmaceutical compounds and one industrial chemical as an indicator for wastewater treatment plant (WWTP) effluent - in addition to 44 pesticides. Passive samplers were deployed monthly in rivers from February 2022 to March 2023 in Grabouw, Hex River Valley, and Piketberg, and one control sample in Jonkershoek Nature Reserve (May 2022). Some pesticides without year-round agricultural applications had high detection frequencies and Groundwater Ubiquity Scores, suggesting leaching of pesticides into groundwater connected to rivers. Cumulative pharmaceutical concentrations correlated strongly with cumulative pesticide concentrations only in the Piketberg catchment, suggesting WWTPs as a possible pesticide source. Herbicide detections in Jonkershoek Nature Reserve (e.g., atrazine) suggest contamination from atmospheric transport, invasive plant control or trail maintenance. The Environmental Quality Standard (EQS) for imidacloprid, chlorpyrifos, terbuthylazine and spiroxamine was exceeded at least once during the 1-year monitoring period, mostly related to expected agricultural applications, indicating high persistence and continuous exposure risk to aquatic organisms. Our study is the first to describe the relevance of WWTPs as a pesticide source in South African agricultural catchments. Drivers of pesticide contamination were area dependent, emphasizing the need for catchment-specific understanding. Future research requires sampling of groundwater and wastewater influent and effluent to improve our understanding of pesticide transport pathways and sources.

Der Bundesrat verabschiedete 2017 den Aktionsplan Pflanzenschutzmittel. Die VSA-Plattform «Wasserqualität» hat im Auftrag des Bundesamts für Umwelt (BAFU) evaluiert, ob die Ziele des Aktionsplans für die Fliessgewässer erreicht werden. Es zeigen sich erste Verbesserungen in der Wasserqualität, aber Pflanzenschutzmittel belasten weiterhin Bäche und Flüsse.

The increasing concern over pesticide pollution in water bodies underscores the need for effective mitigation strategies to support the transition towards sustainable agriculture. This study assesses the effectiveness of landscape mitigation strategies, specifically vegetative buffer strips, in reducing glyphosate loads at the catchment scale under realistic conditions. Conducted over six years (2014–2019) in a small agricultural region in Belgium, our research involved the analysis of 732 water samples from two monitoring stations, differentiated by baseflow and event-driven sampling, and before (baseline) and after the implementation of mitigation measures.
The results indicated a decline in both the number and intensity of point source losses over the years. Additionally, there was a general decrease in load intensity; however, the confluence of varying weather conditions (notably dry years during the mitigation period) and management practices (the introduction of buffer strips) posed challenges for a statistically robust evaluation of each contributing factor. A reduction of loads was measured when comparing mitigation with baseline, although this reduction is not statistically significant. Glyphosate loads during rainfall events correlated with a rainfall index and runoff ratio. Overall, focusing the mitigation strategy on runoff and erosion was a valid approach. Nevertheless, challenges remain, as evidenced by the continuous presence of glyphosate in baseflow conditions, highlighting the complex dynamics of pesticide transport.
The study concludes that while progress has been made towards reducing pesticide pollution, the complexity of interacting factors necessitates further research. Future directions should focus on enhancing farmer engagement in mitigation programs and developing experiments with more intense data collection that help to assess underlying dynamics of pesticide pollution and the impact of mitigation strategies in more detail, contributing towards the goal of reducing pesticide pollution in water bodies.

An inadvertent consequence of pesticide use is aquatic pesticide pollution, which has prompted the implementation of mitigation measures in many countries. Water quality monitoring programs are an important tool to evaluate the efficacy of these mitigation measures. However, large interannual variability of pesticide losses makes it challenging to detect significant improvements in water quality and to attribute these improvements to the application of specific mitigation measures. Thus, there is a gap in the literature that informs researchers and authorities regarding the number of years of aquatic pesticide monitoring or the effect size (e.g., loss reduction) that is required to detect significant trends in water quality. Our research addresses this issue by combining two exceptional empirical data sets with modelling to explore the relationships between the achieved pesticide reduction levels due to mitigation measures and the length of the observation period for establishing statistically significant trends. Our study includes both a large (Rhine at Basel, ∼36,300 km²) and small catchment (Eschibach, 1.2 km²), which represent spatial scales at either end of the spectrum that would be realistic for monitoring programs designed to assess water quality. Our results highlight several requirements in a monitoring program to allow for trend detection. Firstly, sufficient baseline monitoring is required before implementing mitigation measures. Secondly, the availability of pesticide use data helps account for the interannual variability and temporal trends, but such data are usually lacking. Finally, the timing and magnitude of hydrological events relative to pesticide application can obscure the observable effects of mitigation measures (especially in small catchments). Our results indicate that a strong reduction (i.e., 70-90 %) is needed to detect a change within 10 years of monitoring data. The trade-off in applying a more sensitive method for change detection is that it may be more prone to false-positives. Our results suggest that it is important to consider the trade-off between the sensitivity of trend detection and the risk of false positives when selecting an appropriate method and that applying more than one method can provide more confidence in trend detection.

Human activity is a major driver of ecological and evolutionary change in wild populations and can have diverse effects on eukaryotic organisms as well as on environmental and host-associated microbial communities. Although host–microbiome interactions can be a major determinant of host fitness, few studies consider the joint responses of hosts and their microbiomes to anthropogenic changes. In freshwater ecosystems, wastewater is a widespread anthropogenic stressor that represents a multifarious environmental perturbation. Here, we experimentally tested the impact of treated wastewater on a keystone host (the freshwater isopod Asellus aquaticus) and its gut microbiome. We used a semi-natural flume experiment, in combination with 16S rRNA amplicon sequencing, to assess how different concentrations (0%, 30%, and 80%) of nonfiltered wastewater (i.e. with chemical toxicants, nutrients, organic particles, and microbes) versus ultrafiltered wastewater (i.e. only dissolved pollutants and nutrients) affected host survival, growth, and food consumption as well as mid- and hindgut bacterial community composition and diversity. Our results show that while host survival was not affected by the treatments, host growth increased and host feeding rate decreased with nonfiltered wastewater – potentially indicating that A. aquaticus fed on organic matter and microbes available in nonfiltered wastewater. Furthermore, even though the midgut microbiome (diversity and composition) was not affected by any of our treatments, nonfiltered wastewater influenced bacterial composition (but not diversity) in the hindgut. Ultrafiltered wastewater, on the other hand, affected both community composition and bacterial diversity in the hindgut, an effect that in our system differed between sexes. While the functional consequences of microbiome changes and their sex specificity are yet to be tested, our results indicate that different components of multifactorial stressors (i.e. different constituents of wastewater) can affect hosts and their microbiome in distinct (even opposing) manners and have a substantial impact on eco-evolutionary responses to anthropogenic stressors.

Protected agriculture boosts the production of vegetables, berries and fruits, and it plays a pivotal role in guaranteeing food security globally in the face of climate change. Remote sensing is proven to be useful for identifying the presence of (low-tech) plastic greenhouses and plastic mulches. However, the classification accuracy notoriously decreases in the presence of small-scale farming, heterogeneous land cover and unaccounted seasonal management of protected agriculture. Here, we present the random forest-based pixel-level Open field and Protected Agriculture land cover Classifier (OPAC) developed using Sentinel-2 L2A data. OPAC is trained using tiles from Switzerland over 2 years and the Almeria region in Spain over 1 acquisition day. OPAC classifies eight land covers typical of open field and protected agriculture (plastic mulches, low-tech greenhouses and for the first time high-tech greenhouses). Finally, we assess (1) how the land covers in OPAC are labelled in the Sentinel-2 Scene Classification Layer (SCL) and (2) the correspondence between pixels classified as protected agriculture by OPAC and by the best performing Advanced Plastic Greenhouse Index (APGI). To reduce anthropogenic land covers, we constrain the classification task to agricultural areas retrieved from cadastral data or the Corine Land Cover map. The 5-fold cross-validation reveals an overall accuracy of 92% but other classification scores are moderate when keeping the separation among the three classes of protected agriculture. However, all scores substantially improve upon grouping the three classes into one (with an Intersection Over Union of 0.58 as an average among the scores of the three classes and of 0.98 for one single class). Given the recently acknowledged importance of Sentinel-2 Band 1 (central wavelength of 443 nm), the classification accuracy of OPAC for the Swiss small-scale farming is mostly limited by the band's reduced spatial accuracy (60 m). A careful visual assessment indicates that OPAC achieves satisfactory generalization capabilities also in North European (the Netherlands) and four Mediterranean areas (Spain, Italy, Crete and Turkey) without the need of adding location and temporal specific information. There is good agreement among natural land covers classified by OPAC and the SCL. However, the SCL does not have a class for protected agriculture, the latter being often classified as clouds. APGI achieved similar to lower classification accuracies than OPAC. Importantly, the APGI classification task depends on a user-defined space- and time-specific threshold, whereas OPAC does not. Therefore, OPAC paves the way for rapid mapping of protected agriculture at continental scale.

Pesticides are used throughout the tropics in large amounts to protect crops against pests and weeds. These chemicals may be lost to the aquatic environment and impair its ecological status and the water quality for human consumption. Despite intensive use of pesticides in many developing countries, the knowledge of pesticide levels in aquatic ecosystems is often very limited. In this study, we try to fill this gap for an horticultural catchment of 35.9 km² in Costa Rica, which is intensively used by small-holder farming for potatoes and vegetable production. We continuously monitored pesticides in the Tapezco river during two consecutive rainy seasons with passive sampling systems and screened for a broad set of polar and non-polar pesticides. Spatially distributed measurements revealed high pesticide concentrations of many fungicides, herbicides and insecticides throughout the watershed. Concentration ranges revealed little spatio-temporal variation. From an ecotoxicological point of view, the insecticide levels - notably chlorpyrifos and cypermethrin - were most critical. The observed concentration levels exceeded chronic environmental quality standards more than 100-fold at all sites. These high insecticide levels were partially reflected in the community composition of the macroinvertebrates. Available data revealed a poor status at two upstream locations according to the Costa Rican Biological Monitoring Working Party (BMWP-CR) Index and the SPEAR_pesticides index. However, the indices indicated a good quality at most downstream sites despite their high pesticide levels. The wide-spread occurrence of high pesticide levels demonstrated that the relevant sources and pathways existed throughout the catchment. Field observations and survey data showed the relevance of point sources due to poor pesticide handling as well as diffuse losses from fields, which are strongly enhanced by the steep terrain and linear structures like gullies connecting fields with the stream. Mitigation measures to reduce pesticide losses have to account for these different source-flowpath combinations.

In den 50 Jahren ihres Bestehens ermöglichte die Nationale Daueruntersuchung der Fliessgewässer (NADUF), zahlreiche Erfolge von Gewässerschutzmassnahmen in der Schweiz quantitativ zu belegen und Zustandsänderungen aufzuzeigen. Dazu gehören reduzierte Einträge von Phosphat, Schwermetallen oder Stickstoffverbindungen in die Gewässer. In der Zukunft stellen sich beim Monitoring neue Herausforderungen wie die Ermittlung der Einträge von organischen Mikroverunreinigungen oder die durch den Klimawandel induzierten Änderungen im aquatischen Ökosystem.

Global change assessments have typically ignored synthetic chemical pollution, despite the rapid increase of pharmaceuticals, pesticides and industrial chemicals in the environment. Part of the problem reflects the multifarious origins of these micropollutants, which can derive from urban and agricultural sources. Understanding how micropollutants harm ecosystems is a major scientific challenge due to asymmetries of stress across trophic levels and ecological surprises generated by multiple drivers interacting in human-impacted landscapes. We used field assays above and below municipal wastewater treatment plants (WWTPs) in 60 sampling locations across 20 Swiss streams to test how micropollutants and nutrients originating from WWTPs affect two trophic levels (microbes and detritivores) and their role in leaf litter processing. Wastewater impacts were asymmetric across trophic levels, with the detritivore contribution declining relative to microbial-driven decomposition. The strength of negative impacts were context dependent, peaking at sites with the highest upstream abundances of detritivorous invertebrates. Diffuse pollution from intensive agriculture and wastewater-born micropollutants contributed to reduced litter processing rates, including indirect effects apparently mediated through negative influences of insecticides on detritivores. Asymmetries in stress responses across trophic levels can introduce quantitative changes in consumer–resource dynamics and leaf litter processing. This means functional redundancies at different trophic levels are insufficient to compensate for biodiversity losses, causing environmental stressors such as chemical pollutants to have pervasive ecosystem-level impacts.

Calls for supporting sustainability through more and better research rest on an incomplete understanding of scientific evidence use. We argue that a variety of barriers to a transformative impact of evidence arises from diverse actor motivations within different stages of evidence use. We abductively specify this variety in policy and practice arenas for three actor motivations (truth-seeking, sense-making, and utility-maximizing) and five stages (evidence production, uptake, influence on decisions, effects on sustainability outcomes, and feedback from outcome evaluations). Our interdisciplinary synthesis focuses on the sustainability challenge of reducing environmental and human health risks of agricultural pesticides. It identifies barriers resulting from (1) truth-seekers’ desire to reduce uncertainty that is complicated by evidence gaps, (2) sense-makers’ evidence needs that differ from the type of evidence available, and (3) utility-maximizers’ interests that guide strategic evidence use. We outline context-specific research–policy–practice measures to increase evidence use for sustainable transformation in pesticides and beyond.

The Western Cape in South Africa has a Mediterranean climate, which has in part led to an abundance of agriculturally productive land supporting the wheat, deciduous fruit, wine, and citrus industries. South Africa is the leading pesticide user in Sub-Saharan Africa. There is limited data on the pesticide pollution of surface water over different seasons in low- and middle-income countries. We evaluated the seasonal drivers of aquatic pesticide pollution in three river catchments (Berg, Krom, and Hex Rivers) from July 2017 to June 2018 and April to July 2019, using 48 passive samplers. Our sampling followed the most severe drought (2015-2018) since recordings in 1960. Thus, our analyses focus on how drought and post-drought conditions may affect in-stream pesticide concentrations and loads. Samples were analyzed for 101 pesticide compounds using liquid chromatography - high-resolution mass spectrometry. Environmental Quality Standards (EQS) were used to assess the risks. We detected 60 pesticide compounds across the sampling periods. Our results indicate that all samples across all three catchments contained at least three pesticides and that the majority (83%) contained five or more pesticides. Approximately half the number of pesticides were detected after the drought in 2018. High concentration sums of pesticides (>1 μg/L) were detected over long time periods in the Hex River Valley (22 weeks) and in Piketberg (four weeks). Terbuthylazine, imidacloprid, and metsulfuron-methyl were detected in the highest concentrations, making up most of the detected mass, and were frequently above EQS. The occurrence of some pesticides in water generally correlated with their application and rainfall events. However, those of imidacloprid and terbuthylazine did not, suggesting that non-rainfall-driven transport processes are important drivers of aquatic pesticide pollution. The implementation of specific, scientifically sound, mitigation measures against aquatic pesticide pollution would require comprehensive pesticide application data as well as a targeted study identifying sources and transport processes for environmentally persistent pesticides.

Effluents of wastewater treatment plants can impact microbial communities in the receiving streams. However, little is known about the role of microorganisms in wastewater as opposed to other wastewater constituents, such as nutrients and micropollutants. We aimed therefore at determining the impact of wastewater microorganisms on the microbial diversity and function of periphyton, key microbial communities in streams. We used a flow-through channel system to grow periphyton upon exposure to a mixture of stream water and unfiltered or ultra-filtered wastewater. Impacts were assessed on periphyton biomass, activities and tolerance to micropollutants, as well as on microbial diversity. Our results showed that wastewater microorganisms colonized periphyton and modified its community composition, resulting for instance in an increased abundance of Chloroflexi and a decreased abundance of diatoms and green algae. This led to shifts towards heterotrophy, as suggested by the changes in nutrient stoichiometry and the increased mineralization potential of carbon substrates. An increased tolerance towards micropollutants was only found for periphyton exposed to unfiltered wastewater but not to ultra-filtered wastewater, suggesting that wastewater microorganisms were responsible for this increased tolerance. Overall, our results highlight the need to consider the role of wastewater microorganisms when studying potential impacts of wastewater on the receiving water body.

Convolutional Neural Networks (CNNs) offer an alternative to the image cross-correlation methods used in Particle Image Velocimetry (PIV) to reconstruct the fluid velocity field from the experimental recording. Despite the flexibility of CNNs, the accuracy and robustness of the standard image processing remains unsurpassed for general PIV data. As CNNs are non-linear and typically entail up to millions of trainable parameters, they require large and carefully designed training datasets to avoid over-fitting and to obtain results that are accurate for a wide range of flow conditions and length scales. Most training datasets consist of PIV-like data that are generated from displacement fields resulting from numerical flow simulations, which, in addition of being computationally expensive, may be able to inform the network only about relatively few classes of flow problems. To overcome this issue and improve the accuracy of the velocity reconstructed by CNNs, we propose to train the networks with synthetic PIV-like data generated from random displacement fields. The underlying idea is that the training dataset simply needs to teach the network about the kinematic relationship between position and velocity. These kinematic training datasets are computationally inexpensive and may allow a much richer variability in terms of length scales by varying the generation parameters. By training a state-of-the-art CNN, we investigate the accuracy of the reconstructed displacement and velocity with synthetic and experimental test cases, such as a sinusoidal flow and wind-tunnel data from a turbulent-boundary-layer and a cylinder-wake experiment. We demonstrate that kinematic training can drastically improve the accuracy of the CNN and allows the network to outperform conventional cross-correlation methods, being more robust with respect to data noise and providing reconstructed velocity fields that have considerably higher spatial resolution (at pixel level).

Over the past three decades, the Vietnamese Mekong Delta has experienced a significant increase in agricultural productivity, partly achieved through increased agrochemical use. To abate negative effects on human and environmental health, several national programs were launched to enhance safer pesticide use. This study aimed to assess the patterns and relationships of official sustainable agriculture educational programs, pesticide safety knowledge, and practices of smallholder farmers in the Mekong Delta. A cross-sectional survey was conducted with 400 smallholder farmers from three communes in Thoi Lai district (Can Tho province) from March to May 2020. Twenty-four questions on pesticide safety knowledge and practices were used to identify traits using latent class analysis. Adjusted generalized linear regression was used to assess determinants of pesticide safety knowledge and estimate associations of pesticide safety knowledge with pesticide practices. 96.2% of participants have used at least one WHO class II pesticide during the past year while the use of specific personal protective equipment was limited mainly due to unavailability (37.0%) or discomfort (83.0%). High education (Odds Ratio (OR), 95% Confidence Interval; 3.84, 1.70-9.45), exposure to official educational programs (1.87, 1.13-3.12), peer-to-peer knowledge exchange (3.58, 2.18-6.00), and learning from governmental extension services (2.31, 1.14-4.98) were positively associated with increased pesticide safety knowledge. Compared to poor practices, pesticide safety knowledge was increasingly positively associated with intermediate (1.65, 1.02-2.66) and good pesticide practices (8.96, 2.58-31.12). These findings highlight the importance of school education and educational programs, access to PPE, and addressing discomforts of PPE to improve the protection of farmers from pesticide exposures. Simultaneously, pesticide market authorization processes should be reconsidered to promote the authorization of less toxic products. Further in-depth studies on the nature of pesticides used, nonuse of personal protective equipment, and effectiveness of educational programs will further define leverage points for safer pesticide use.

1. Freshwater is vital to much life on Earth and is an essential resource for humans. Climate change, however, dramatically changes freshwater systems and reduces water quality, poses a risk to drinking water availability and has severe impacts on aquatic ecosystems and their biodiversity.
2. The direct effects of climate change, such as increased temperatures and higher frequency of extreme meteorological events, interact with human responses to climate change, which we refer to here as 'indirect effects'. The latter possibly have even greater impact than the direct effects of climate change. Specifically, changes in land-use practices as responses to climate change, such as adjusted cropping regimes or a shift to renewable hydroelectricity to mitigate climate change, can very strongly affect freshwater ecosystems.
3. Hitherto, these indirect effects and the possibility of idiosyncratic outcomes are under-recognized. Here, we synthesize knowledge and identify threats to freshwater environments in alpine and pre-alpine regions, which are particularly affected by climate change.
4. We focus on the effects of adapted agriculture and hydropower production on freshwater quality and ecological status, as these examples have strong indirect effects that interact with direct effects of climate change (e.g., water temperature, droughts, isolation of populations).
5. We outline how failure to effectively account for indirect effects associated with human responses to climate change may exacerbate direct climate change impacts on aquatic ecosystems. If managed properly, however, human responses to indirect effects offer potential for rapid and implementable leverage to mitigate some of the direct climate change effects on aquatic ecosystems. To better address looming risks, policy- and decisionmakers must account for indirect effects and incorporate them into restoration planning and the respective sectorial policies.

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.

Microbial life in natural biofilms is dominated by prokaryotes and microscopic eukaryotes living in dense association. In stream ecosystems, microbial biofilms influence primary production, elemental cycles, food web interactions as well as water quality. Understanding how biofilm communities respond to anthropogenic impacts, such as wastewater treatment plant (WWTP) effluent, is important given the key role of biofilms in stream ecosystem function. Here, we implemented 16S and 18S rRNA gene sequencing of stream biofilms upstream (US) and downstream (DS) of WWTP effluents in four Swiss streams to test how bacterial and eukaryotic communities respond to wastewater constituents. Stream biofilm composition was strongly affected by geographic location – particularly for bacteria. However, the abundance of certain microbial community members was related to micropollutants in the wastewater – among bacteria, micropollutant-associated members were found e.g. in Alphaproteobacteria, and among eukaryotes e.g. in Bacillariophyta (algal diatoms). This study corroborates several previously characterized responses (e.g. as seen in diatoms), but also reveals previously unknown community responses – such as seen in Alphaproteobacteria. This study advances our understanding of the ecological impact of the current wastewater treatment practices and provides information about potential new marker organisms to assess ecological change in stream biofilms.

Wicked problems exceed traditional sectoral and jurisdictional boundaries and involve multiple actors as stakeholders, victims, and culprits. Wicked problems inherently feature uncertainty and knowledge gaps. Science plays a crucial role in generating evidence for solving these problems and contributing to societal transformation. However, researchers may perceive and study problems detached from practitioners' perceptions of the world. We use the example of smallholder pesticide management in Uganda and the three types of knowledge approach, a framework borrowed from transdisciplinary research, to disentangle knowledge gaps. To identify these gaps, we integrated and co-produce knowledge in a two-day participatory workshop applying design thinking. Our results show, that a transition towards safe pesticide management depends on changes in the system, such as a revision and implementation of exiting regulation or professionalization of agro-dealers. Furthermore, this transition is only possible if interventions address target groups beyond the individual farmers (e.g. agro-dealers or district government officials). Compared to existing academic knowledge, co-produced knowledge provides a broader systemic perspective and yields more fine grained insights about potential new pathways. This investigation confirms, that practitioners’ knowledge is more fine-grained and detailed, thus exemplifying how knowledge integration is essential to avoid a gap between what researchers investigate and what practitioners need.

Synthetic Plant Protection Products (PPPs) are a key element for a large part of today's global food systems. However, the transport of PPPs and their transformation products (TPs) to water bodies has serious negative effects on aquatic ecosystems. Small streams in agricultural catchments may experience pronounced concentration peaks given the proximity to fields and poor dilution capacity. Traditional sampling approaches often prevent a comprehensive understanding of PPPs and TPs concentration patterns being limited by trade-offs between temporal resolution and duration of the observation period. These limitations result in a knowledge gap for accurate ecotoxicological risk assessment and the achievement of optimal monitoring strategies for risk mitigation. We present here high-frequency PPPs and TPs concentration time-series measured with the autonomous MS²Field platform that combines continuous sampling and on-site measurements with a high-resolution mass spectrometer, which allows for overcoming temporal trade-offs. In a small agricultural catchment, we continuously measured 60 compounds at 20 minutes resolution for 41 days during the growing season. This observation period included 8 large and 15 small rain events and provided 2560 concentration values per compound.
To identify similarities and differences among the compound-specific concentration time-series, we analysed the entire dataset with positive matrix factorisation. Six factors sufficiently captured the overall complexity in concentration dynamics. While one factor reflected dilution during rainfall, five factors identified PPPs groups that seemed to share a common history of recent applications. The investigation per event of the concentration time-series revealed a surprising complexity of dynamic patterns; physico-chemical properties of the compounds did not influence the (dis)similarity of chemographs. Some PPPs concentration peaks led while others lagged by several hours the water level peaks during large events. During small events, water level peaks always preceded concentration peaks, which were generally only observed when the water levels had almost receded to pre-event levels. Thus, monitoring schemes relying on rainfall or water level as proxies for triggering sampling may lead to systematic biases.
The high temporal resolution revealed that the Swiss national monitoring integrating over 3.5 days underestimated critical concentration peaks by a factor of eight to more than 32, captured 3 out of 11 exceedances of legal acute quality standards (the relevant values in the Swiss Water Protection Law) and recorded 1 out of 9 exceedances of regulatory acceptable concentrations (the relevant values for the PPPs registration process).
MS²Field allowed for observing unexpected and overlooked pesticide dynamics with consequences for further research but also for monitoring. The large variability in timing of concentration peaks relative to water level calls for more in-depth analyses regarding the respective transport mechanisms. To perform these analyses, spatially distributed sampling and time-series of geo-referenced PPPs application data are needed.

Spray drift is considered a major pesticide transport pathway to surface waters. Current research and legislation usually only considers direct spray drift. However, also spray drift on roads and subsequent wash-off to surface waters was identified as a possible transport pathway. Hydraulic shortcuts (storm drainage inlets, channel drains, ditches) have been shown to connect roads to surface waters, thus increasing the risk of drift wash-off to surface waters. However, the importance of this pathway has never been assessed on larger scales. To address this knowledge gap, we studied 26 agricultural catchments with a predominance of arable cropping (n = 17) and vineyards (n = 9). In these study sites, we assessed the occurrence of shortcuts by field mapping. Afterwards, we modelled the areas of roads drained to surface waters using a high-resolution digital elevation model (0.5 m resolution) and a multiple flow algorithm. Finally, we modelled drift deposition to drained roads and surface waters using a spatially explicit, georeferenced spray drift model. Our results show that for most sites, the drift to drained roads is much larger than the direct drift to surface waters. In arable land sites, drift to roads exceeds the direct drift by a factor of 4.5 to 18, and in vineyard sites by 35 to 140. In arable land sites, drift to drained roads is rather small (0.0015% to 0.0049% of applied amount) compared to typical total pesticide losses to surface waters. However, substantial drift to drained roads in vineyard sites was found (0.063% to 0.20% of applied amount). Current literature suggests that major fractions of the drift deposited on roads can be washed off during rain events, especially for pesticides with low soil adsorption coefficients. For such pesticides and particularly in vineyards, spray drift wash-off from drained roads is therefore expected to be a major transport pathway to surface waters.

Wastewater treatment plants (WWTPs) play an important role in retaining organic matter and nutrients but to a lesser extent micropollutants. Therefore, treated wastewater is recognized as a major source of multiple stressors, including complex mixtures of micropollutants. These can potentially affect microbial communities in the receiving water bodies and the ecological functions they provide. In this study, we evaluated in flow-through channels the consequences of an exposure to a mixture of stream water and different percentages of urban WWTP effluent, ranging from 0% to 80%, on the microbial diversity and function of periphyton communities. Assuming that micropollutants exert a selective pressure for tolerant microorganisms within communities, we further examined the periphyton sensitivity to a micropollutant mixture extracted from passive samplers that were immersed in the wastewater effluent. As well, micropollutants in water and in periphyton were comprehensively quantified. Our results show that micropollutants detected in periphyton differed from those found in water, both in term of concentration and composition. Especially photosystem II inhibitors accumulated in periphyton more than other pesticides. Although effects of other substances cannot be excluded, this accumulation may have contributed to the observed higher tolerance of phototrophic communities to micropollutants upon exposure to 30% and 80% of wastewater. On the contrary, no difference in tolerance was observed for heterotrophic communities. Exposure to the gradient of wastewater led to structural differences in both prokaryotic and eukaryotic communities. For instance, the relative abundance of cyanobacteria was higher with increasing percentage of wastewater effluent, whereas the opposite was observed for diatoms. Such results could indicate that differences in community structure do not necessarily lead to higher tolerance. This highlights the need to consider other wastewater constituents such as nutrients and wastewater-derived microorganisms that can modulate community structure and tolerance. By using engineered flow-through channels that mimic to some extent the required field conditions for the development of tolerance in periphyton, our study constitutes a base to investigate the mechanisms underlying the increased tolerance, such as the potential role of microorganisms originating from wastewater effluents, and different treatment options to reduce the micropollutant load in effluents.

Background: Pesticides can have negative effects on human and environmental health, especially when not handled as intended. In many countries, agro-input dealers sell pesticides to smallholder farmers and are supposed to provide recommendations on application and handling. This study investigates the role of agro-input dealers in transmitting safety information from chemical manufacturers to smallholder farmers, assesses the safety of their shops, what products they sell, and how agro-input dealers abide by laws and recommendations on best practices for preventing pesticide risk situations.
Methods: Applying a mixed-methods approach, we studied agro-input dealers in Central and Western Uganda. Structured questionnaires were applied to understand agro-input dealers' knowledge, attitude and practices on pesticides (n = 402). Shop layout (n = 392) and sales interaction (n = 236) were assessed through observations. Actual behavior of agro-input dealers when selling pesticides was revealed through mystery shopping with local farmers buying pesticides (n = 94).
Results: While 97.0% of agro-input dealers considered advising customers their responsibility, only 26.6% of mystery shoppers received any advice from agro-input dealers when buying pesticides. 53.2% of products purchased were officially recommended. Sales interactions focused mainly on product choice and price. Agro-input dealers showed limited understanding of labels and active ingredients. Moreover, 25.0% of shops were selling repackaged products, while 10.5% sold unmarked or unlabeled products. 90.1% of shops were lacking safety equipment. Pesticides of World Health Organization toxicity class I and II were sold most frequently. Awareness of health effects seemed to be high, although agro-input dealers showed incomplete hygiene practices and were lacking infrastructure. One reason for these findings might be that only 55.7% of agro-input dealers held a certificate of competency on safe handling of pesticides and even fewer (5.7%) were able to provide a government-approved up-to-date license.
Conclusion: The combination of interviews, mystery shopping and observations proved to be useful, allowing the comparison of stated and actual behavior. While agro-input dealers want to sell pesticides and provide the corresponding risk advice, their customers might receive neither the appropriate product nor sufficient advice on proper handling. In light of the expected increase in pesticide use, affordable, accessible and repeated pesticide training and shop inspections are indispensable.

Small streams in catchments with agricultural land use are at high risk of diffuse pollution by herbicides. Fast transport processes can cause concentration peaks that exceed regulatory requirements. These processes have a high spatio-temporal variability and data characterizing their occurrence is often sparse. For this reason, such systems show a stochastic behavior at the resolution we observe them (same input and initial conditions lead to different output). Realistic model representations should acknowledge this pronounced apparent intrinsic stochasticity. However, a deterministic description of the physical and chemical processes at the catchment scale is state of the art in research and practice. We explore the potential of stochastic process formulations in combination with the Bayesian learning paradigm to (a) improve the quantification of the uncertainty of conceptual catchment-scale pesticide transport models and (b) gain new mechanistic insights about the system by interpreting the temporal evolution of the stochastic processes. This is done with the help of a framework for time-varying stochastic parameters. Thereby, we find that (a) the stochastic process formulation can lead to a more realistic characterization of the uncertainty of internal states and model output compared to the deterministic one, and that (b) the temporal dynamics of parameters resulting from the inference can highlight model deficits (and inspire improvements) such as a better sustained baseflow in dry periods. We also identify two key challenges: numerical difficulties in sampling the posterior and the question of where to introduce and how to constrain the additional degrees of freedom such that they are not misused.

The role of diffuse phosphorus (P) losses from agricultural land gained importance since technical and constructional measures in urban areas and industry have reached their potential in temperate regions. Phytoremediation strategies are a new suggestion to effectively reduce soil legacy P but until now, there is a lack of estimates on the time such strategies should take. With a rainfall-runoff model, spatial information on the hydrological risk of the catchment of Lake Baldegg (Switzerland) was generated and combined with a soil test P (CO₂-saturated water extraction) map. Based on these results, two potential soil target test P values (2.0 mg P (kg soil)^-1 target-P 1 and 1.6 mg P (kg soil)^-1 target-P 2) were set. A simple nonlinear mixed effects model was used to compare different balance and cropping scenarios to decrease soil test P. The relationship between P-balance (input - output) and soil test P was found to be exponential. The confidence interval for the predicted time necessary to reach target-P 2 after a cessation of P-fertilization on intensively managed grassland was 2 to 9 years depending on the initial soil test P. If fertilization is completely ceased, the predicted P-decline times were longer (8 to 32 years). The decline-time for the balance that is recommended for farmers in the catchment of a P-fertilization that covers 80% of the demand was predicted to be 11 to 47 years. The study emphasizes that P phytoextraction can be an effective and time and resource efficient mitigation strategy for catchments with high legacy P.

Phosphorus (P) is an essential element to all living beings but also a finite resource. P-related problems center around broken P cycles from local to global scales. This paper presents outcomes from the 9th International Phosphorus Workshop (IPW9) held 2019 on how to move towards a sustainable P management. It is based on two sequential discussion rounds with all participants. Important progress was reported regarding the awareness of P as finite mineable resource, technologies to recycle P, and legislation towards a circular P economy. Yet, critical deficits were identified such as how to handle legacy P, how climate change may affect ecosystem P cycling, or working business models to up-scale existing recycling models. Workshop participants argued for more transdisciplinary networks to narrow a perceived science-practice/policy gap. While this gap may be smaller in reality as illustrated with a Swiss example, we formulate recommendations how to bridge this gap more effectively.

Tracking the occurrence of a broad variety of chemicals in the aquatic environment at a high temporal resolution over extended time periods is challenging. Here, we present a transportable platform integrating sample preparation, liquid chromatography-high-resolution mass spectrometry measurement, automated data processing, and remote control and surveillance. The system is capable of quantifying pollutants at 20 min intervals with high sensitivity (limit of quantification down to 10 ng/L) and operated stably on-site over prolonged periods (<3 ppm mass drift over two weeks, <0.3 min retention time drift over six weeks). Field campaigns under different conditions demonstrated unprecedented insights into pollutant dynamics. Time-resolved measurements in a small creek revealed concentration peaks with up to 10-fold exceedances of environmental quality standards. The quantification of illicit drugs and their metabolites in raw wastewater distinguished fractions of consumed and discarded cocaine. Frequency analyses and data mining showed clusters of diurnal, episodic, and possibly industry-related pollutants, including newly identified substances. With this enabling technology the potential for researching and managing chemicals in natural and technical environments can be significantly expanded beyond our current capabilities, for example, real-time control in process engineering and sewer operation (water management and environmental toxicology), industrial surveillance, and wastewater-based epidemiology.

Surface runoff represents a major pathway for pesticide transport from agricultural areas to surface waters. The influence of artificial structures (e.g. roads, hedges, and ditches) on surface runoff connectivity has been shown in various studies. In Switzerland, so-called hydraulic shortcuts (e.g. inlet and maintenance shafts of road or field storm drainage systems) have been shown to influence surface runoff connectivity and related pesticide transport. Their occurrence and their influence on surface runoff and pesticide connectivity have, however, not been studied systematically.
To address that deficit, we randomly selected 20 study areas (average size of 3.5 km²) throughout the Swiss plateau, representing arable cropping systems. We assessed shortcut occurrence in these study areas using three mapping methods, namely field mapping, drainage plans, and high-resolution aerial images. Surface runoff connectivity in the study areas was analysed using a 2×2 m digital elevation model and a multiple-flow algorithm. Parameter uncertainty affecting this analysis was addressed by a Monte Carlo simulation. With our approach, agricultural areas were divided into areas that are either directly, indirectly (i.e. via hydraulic shortcuts), or not at all connected to surface waters. Finally, the results of this connectivity analysis were scaled up to the national level, using a regression model based on topographic descriptors, and were then compared to an existing national connectivity model.
Inlet shafts of the road storm drainage system were identified as the main shortcuts. On average, we found 0.84 inlet shafts and a total of 2.0 shafts per hectare of agricultural land. In the study catchments, between 43 % and 74 % of the agricultural area is connected to surface waters via hydraulic shortcuts. On the national level, this fraction is similar and lies between 47 % and 60 %. Considering our empirical observations led to shifts in estimated fractions of connected areas compared to the previous connectivity model. The differences were most pronounced in flat areas of river valleys.
These numbers suggest that transport through hydraulic shortcuts is an important pesticide flow path in a landscape where many engineered structures exist to drain excess water from fields and roads. However, this transport process is currently not considered in Swiss pesticide legislation and authorization. Therefore, current regulations may fall short in addressing the full extent of the pesticide problem. However, independent measurements of water flow and pesticide transport to quantify the contribution of shortcuts and validating the model results are lacking. Overall, the findings highlight the relevance of better understanding the connectivity between fields and receiving waters and the underlying factors and physical structures in the landscape.

River networks are one of the main routes by which the public could be exposed to environmental sources of antibiotic resistance, that may be introduced e.g. via treated wastewater. In this study, we applied a comprehensive integrated analysis encompassing mass-flow concepts, chemistry, bacterial plate counts, resistance gene quantification and shotgun metagenomics to track the fate of the resistome (collective antibiotic resistance genes (ARGs) in a microbial community) of treated wastewater in two Swiss rivers at the kilometer scale. The levels of certain ARGs and the class 1 integron integrase gene (intI1) commonly associated with anthropogenic sources of ARGs decreased quickly over short distances (2-2.5 km) downstream of wastewater discharge points. Mass-flow analysis based on conservative tracers suggested this decrease was attributable mainly to dilution but ARG loadings frequently also decreased (e.g., 55.0-98.5 % for ermB and tetW) over the longest studied distances (6.8 and 13.7 km downstream). Metagenomic analysis confirmed that ARG of wastewater-origin did not persist in rivers after 5 ∼ 6.8 km downstream distance. sul1 and intI1 levels and loadings were more variable and even increased sharply at 5 ∼ 6.8 km downstream distance on one occasion. While input from agriculture and in-situ positive selection pressure for organisms carrying ARGs cannot be excluded, in-system growth of biomass is a more probable explanation. The potential for direct human exposure to the resistome of wastewater-origin thus appeared to typically abate rapidly in the studied rivers. However, the riverine aquatic resistome was also dynamic, as evidenced by the increase of certain gene markers downstream, without obvious sources of anthropogenic contamination. This study provides new insight into drivers of riverine resistomes and pinpoints key monitoring targets indicative of where human sources and exposures are likely to be most acute.

Pesticides are used globally in agriculture and pose a threat to the health of farmers, communities, and the environment. Smallholder farmers in low- and middle-income countries have generally a low socio-economic status and educational level. Consequently, they are particularly vulnerable to negative impacts of pesticides on their health, yields, or land. In a Knowledge, Attitude, and Practices study, we compared the pest management practices between a market-oriented farming system in Zarcero County, Costa Rica, and a subsistence-based farming system in Wakiso District, Uganda. We conducted a cross-sectional survey among smallholder farmers from Costa Rica (n = 300) in 2016 and from Uganda (n = 302) in 2017. We enrolled conventional and organic farmers, but also farmers with mixed practices and non-applicators of any pest management strategy. We found that the majority of pesticides used in both case studies are classified as highly hazardous by the World Health Organization. While more than 90% of smallholder farmers from both countries were aware of the negative health effects of pesticide exposure, <11% in Costa Rica and <2% in Uganda reported using personal protective equipment every time they handled or applied pesticides. Hygiene and other safe use practices were not adopted by all farmers (<61%), especially among farmers applying more hazardous pesticides. Conventional farmers from Costa Rica (14%) and Uganda (19%) reported disposing pesticide residuals into rivers. Using a logistic regression we found that organic farmers were more likely to having been trained on safe pesticide use practices. Using a robust regression, we observed that smallholder household income was primarily driven by education and not directly by the use of synthetic pesticides. Our results suggest that negative effects of pesticides can be managed over the whole life cycle, from purchase, via storage and application to residual and waste management by fostering professionalization of farmers. We advise future safe use and handling interventions to consider the pesticide use-related socioeconomic and demographic findings highlighted in this paper.

Konzentrationsspitzen von Pestiziden können von grosser biologischer und regulatorischer Bedeutung sein, werden aber selten und nur mit hohem Aufwand erfasst. Die neue MS²field-Plattform ist eine der ersten mobilen Messinfrastrukturen, die kontinuierliche und zeitlich hochaufgelöste Messungen von Mikroverunreinigungen in umweltrelevanten Konzentrationen im Feld erlaubt. Wie vielfältig Konzentrationsdynamiken von Pestiziden sein können und in welchem Ausmass Spitzenkonzentrationen mit konventionellen Probenahme- und Messtechniken bisher unterschätzt wurden, macht eine Messkampagne in einem landwirtschaftlich stark geprägten Bach sichtbar.

Gemäss Verfassungsauftrag ist die Schweizer Landwirtschaft stark multifunktional ausgerichtet. Diese Multifunktionalität kann Zielkonflikte auslösen zwischen der sicheren Versorgung der Bevölkerung, der Erhaltung der natürlichen Lebensgrundlagen, der Pflege der Kulturlandschaft und der dezentralen Besiedlung des Landes. Um derartige Zielkonflikte systematisch zu analysieren, künftige Forschungsvorhaben zu priorisieren und Massnahmen zur Ressourcenschonung zu formulieren, haben die Eawag, das Wasserforschungsinstitut des ETH-Bereichs, und das BLW unter Einbezug von Agroscope 2013 bis 2015 das Projekt Zukunftsfähige, gewässerschonende landwirtschaftliche Produktion in der Schweiz (AProWa) durchgeführt. Methodisch wurde die umfassende Auslegeordnung in eine multikriterielle Entscheidungsanalyse (MCDA) eingebettet. Folgende Resultate wurden durch das Projekt erarbeitet:
1. Eine systematische Aufstellung und Gliederung von Produktionszielen (z. B. hohe Ertragsmenge) und Erhaltungszielen (z. B. geringe Schadstoffkonzentrationen im Grundwasser) in Form einer Zielhierarchie.
2. Ein Vorschlag an messbaren Indikatoren («Attribute» genannt) zur Quantifizierung der Zielerreichung.
3. Eine Sammlung von relevanten Massnahmen im Bereich einer gewässerschonenden Landwirtschaft.
4. Testen des MCDA-Ansatzes zur quantitativen Bewertung verschiedener Handlungsoptionen hinsichtlich ihrer Wirkungen im Gesamtsystem.
5. Vorschläge für zukünftige Forschungsfragen basierend auf dem aufgezeigten Forschungsbedarf.
6. Vorschläge für den weiteren Einsatz der MCDA-Methode in der Praxis. [ ...]

Die schweizerische Agrarlandschaft weist ein dichtes Weg- und Strassennetz auf, dessen Entwässerung oft direkt in Oberflächengewässer führt. Es wirkt damit als hydraulischer Kurzschluss und als Transportpfad für Pflanzenschutzmittel (PSM). Felduntersuchungen und Modellrechnungen zeigen, dass gleich viel Ackerfläche über Kurzschlüsse mit einem Gewässer verbunden ist wie direkt angeschlossen ist. Zusätzlich wurden bedeutende PSM-Konzentrationen in Kurzschlüssen gemessen. Das weist darauf hin, dass Kurzschlüsse erheblich zur Belastung der Schweizer Gewässer mit PSM beitragen.

Exposure assessment of pesticides has substantially improved over time, with methods that now include a combination of advanced analytical techniques and fate/transport models to evaluate their spatiotemporal distribution. However, the current regulatory environmental risk assessment considers thresholds from laboratory studies completed under standardized conditions that do not reflect environmental dynamics. Using the General Unified Threshold model for Survival (GUTS) model framework, we predicted the impact of time-varying pesticide exposures on the survival of gammarids in a small agricultural stream. The LP₅₀ values were used as an additional metric for assessing risks (defined in GUTS as a multiplication factor applied to the concentration time series to induce 50% mortality by the end of exposure). Although real-case exposures to individual pesticides were predicted to produce little to no impact on survival, the LP₅₀ values indicate acute (LP₅₀ ≤ 100) and/or chronic (LP₅₀ ≤ 10) toxicities for azoxystrobin, chlorpyrifos, diazinon, and imidacloprid, while risk to propiconazole exposure was considered very low (LP₅₀ ≫ 100). Finally, the model was extended to reflect mixture toxicity via concentration addition. It predicted risks under acute and chronic exposures to organophosphates and neonicotinoids. Given that gammarids are simultaneously exposed to multiple chemicals and other stressors throughout their lifetime, a decline in survival probabilities due to chemical stress can likely influence their overall fitness. We recognize that some assumptions require validation, but our work included a level of realism that can assist risk managers when evaluating the cumulative consequences of chemical exposure.

Aquatic pesticide pollution from both agricultural and urban pest control is a concern in many parts of the world. Making an accurate assessment of pesticide exposure is the starting point to protecting aquatic ecosystems. This in turn requires the design of an effective monitoring program. Monitoring is also essential to evaluate the efficacy of mitigation measures aimed to curb pesticide pollution. However, empirical evidence for their efficacy can be confounded by additional influencing factors, most prominently variable weather conditions. This review summarizes the experiences gained from long-term (>5 years) pesticide monitoring studies for detecting trends and provides recommendations for their improvement. We reviewed articles published in the scientific literature, with a few complements from selected grey literature, for a total of 20 studies which fulfill our search criteria. Overall, temporal trends of pesticide use and hydrological conditions were the two most common factors influencing aquatic pesticide pollution. Eighteen studies demonstrated observable effects to surface water concentrations from changes in pesticide application rates (e.g., use restriction) and sixteen studies from interannual variability in hydrological conditions during the application period. Accounting for seasonal- and streamflow-related variability in trend analysis is important because the two factors can obscure trends caused by changes in pesticide use or management practices. Other mitigation measures (e.g., buffer strips) were only detectable in four studies where concentrations or loads were reduced by > 45%. Collecting additional agricultural (e.g., pesticide use, mitigation measures) and environmental (e.g., precipitation, stream flow) data, as well as establishing a baseline before the implementation of mitigation measures have been consistently reported as prerequisites to interpret water quality trends from long-term monitoring studies, but have rarely been implemented in the past.

Multiple anthropogenic drivers are changing ecosystems globally, with a disproportionate and intensifying impact on freshwater habitats. A major impact of urbanization are inputs from wastewater treatment plants (WWTPs). Initially designed to reduce eutrophication and improve water quality, WWTPs increasingly release a multitude of micropollutants (MPs; i.e., synthetic chemicals) and microbes (including antibiotic‐resistant bacteria) to receiving environments. This pollution may have pervasive impacts on biodiversity and ecosystem services. Viewed through multiple lenses of macroecological and ecotoxicological theory, we combined field, flume, and laboratory experiments to determine the effects of wastewater (WW) on microbial communities and organic‐matter processing using a standardized decomposition assay. First, we conducted a mensurative experiment sampling 60 locations above and below WWTP discharges in 20 Swiss streams. Microbial respiration and decomposition rates were positively influenced by WW inputs via warming and nutrient enrichment, but with a notable exception: WW decreased the activation energy of decomposition, indicating a "slowing" of this fundamental ecosystem process in response to temperature. Second, next‐generation sequencing indicated that microbial community structure below WWTPs was altered, with significant compositional turnover, reduced richness, and evidence of negative MP influences. Third, a series of flume experiments confirmed that although diluted WW generally has positive influences on microbial‐mediated processes, the negative effects of MPs are "masked" by nutrient enrichment. Finally, transplant experiments suggested that WW‐borne microbes enhance decomposition rates. Taken together, our results affirm the multiple stressor paradigm by showing that different aspects of WW (warming, nutrients, microbes, and MPs) jointly influence ecosystem functioning in complex ways. Increased respiration rates below WWTPs potentially generate ecosystem "disservices" via greater carbon evasion from streams and rivers. However, toxic MP effects may fundamentally alter ecological scaling relationships, indicating the need for a rapprochement between ecotoxicological and macroecological perspectives.

Drains can be installed to reduce saturated soil conditions and improve crop growth. This article evaluates the extent to which these systems may cause losses of plant protection products (PPP). To that end, we estimated the drained fraction of Swiss arable land using both existing drainage maps and machine learning. Our drainage map suggests that 25% of Swiss agricultural land has a moderate to high potential of being drained. We further evaluated the risk for PPP losses via drainage and the potential of selected mitigation measures based on a conceptual model summarising the relevant scientific literature. Although drainage losses are highly variable, they are strongly influenced by the extent of preferential flow (PF) in soils and are an important transport pathway to surface waters. Most agricultural soils in Switzerland are prone to PF, given their loamy texture, suggesting that PPP losses via tile drains are an important phenomenon in Switzerland's drained arable fields. The most common mitigation measures for drainage are those recommended for runoff, erosion and leaching. However, given the uncertainty of the local PPP losses and driving factors, no site- or PPP-specific measures can currently be proposed to reduce PPP drainage losses. This study also examines the effectiveness of the regulatory model EXPOSIT in predicting total PPP losses and peak concentrations in watercourses. When compared with experimental data from Agroscope at Zurich-Affoltern, our findings suggest that EXPOSIT does not yield the worst-case estimates for Swiss conditions.

Herbicide pollution in headwater streams due to agricultural practices is a major environmental concern and is characterized by episodic peak concentrations from fast transport paths. We rely on previous experimental studies in a small (1.2km²) agricultural catchment in the Swiss Plateau, to model dynamic diffuse herbicide pollution with emphasis on fast transport paths in a conceptual modelling framework at the catchment scale. We show how experimentalists’ understanding of the fate of herbicides (perceptual model) can be translated into conceptual models considering sorption, degradation, and fast transport of water and chemicals facilitated by impervious surfaces, tile drains and artificial shortcuts. Different types of experimental data (streamflow, high-frequency concentration measurements, and soil–water distribution coefficients) are used in a joint Bayesian inference of model parameters. We assess the ability of different spatial configurations of hydrological response units in explaining observed heterogeneity in transport behaviour of two corn herbicides. Thereby, we find that (1) relatively simple conceptual models can provide a realistic description of herbicide fate in small agricultural catchments, (2) accounting for spray drift onto hard surfaces is necessary to avoid a severe model bias during the first rainfall event after application, and (3) including catchment-specific experimentalist knowledge about important elements like artificial shortcuts and tile drains leads to a reduction in uncertainty of 30% compared to the more conventional conception of the proximity to the stream as the dominant risk factor.

Environmental risk assessment associated with aquatic and terrestrial contamination is mostly based on predicted or measured environmental concentrations of a limited list of chemicals in a restricted number of environmental compartments. High resolution mass spectrometry (HRMS) can provide a more comprehensive picture of exposure to harmful chemicals, particularly through the retrospective analysis of digitally stored HRMS data. Using this methodology, our study characterized the contamination of various environmental compartments including 154 surface water, 46 urban effluent, 67 sediment, 15 soil, 34 groundwater, 24 biofilm, 41 gammarid and 49 fish samples at 95 sites widely distributed over the Swiss Plateau. As a proof-of-concept, we focused our investigation on antifungal azoles, a class of chemicals of emerging concern due to their endocrine disrupting effects on aquatic organisms and humans. Our results demonstrated the occurrence of antifungal azoles and some of their (bio)transformation products in all the analyzed compartments (0.1-100 ng/L or ng/g d.w.). Comparison of actual and predicted concentrations showed the partial suitability of level 1 fugacity modelling in predicting the exposure to azoles. Risk quotient calculations additionally revealed risk of exposure especially if some of the investigated rivers and streams are used for drinking water production. The case study clearly shows that the retrospective analysis of HRMS/MS data can improve the current knowledge on exposure and the related risks to chemicals of emerging concern and can be effectively employed in the future for such purposes.

Although the exposure assessment of wastewater-derived micropollutants via chemical, bioanalytical, and modeling methods in environmental compartments is becoming more frequent, the whole-body burden (i.e., internal concentrations) in nontarget organisms is rarely assessed. An understanding of the internal concentration fluctuation is especially important when exploring the mechanistic linkage between exposure and effects. In this study, we coupled a simple river model with a first-order toxicokinetic (TK) model to predict the concentrations of wastewater-derived micropollutants in freshwater invertebrates (Gammarus spp.). We applied Monte Carlo simulations and conducted laboratory experiments to account for the uncertain input data and the lack of uptake/depuration rate constants required for the TK model. The internal concentrations in field gammarids were predicted well, and the estimates varied only by a factor of 0.1-1.9. Fast equilibrium may also be assumed such that bioconcentration factors (BCFs) are used together with the daily river dilution patterns to predict internal concentrations. While this assumption is suitable for compounds observed in our experiment to reach the steady state within 48 h in gammarids, the model overpredicted the concentrations of substances that reach this condition after longer periods. Nevertheless, this approach provides conservative estimates and simplifies the coupling of models as BCFs are slightly more accessible than the rate constants. However, if one is interested in a more detailed exposure information (e.g., peak concentration and the whole-body burden recovery after a spill), then the nonsteady-state formulation should be employed.

Wastewater treatment plant effluents are important point sources of micropollutants. To assess how the discharge of treated wastewater affects the ecotoxicity of small to medium-sized streams we collected water samples up- and downstream of 24 wastewater treatment plants across the Swiss Plateau and the Jura regions of Switzerland. We investigated estrogenicity, inhibition of algal photosynthetic activity (photosystem II, PSII) and growth, and acetylcholinesterase (AChE) inhibition. At four sites, we measured feeding activity of amphipods (Gammarus fossarum) in situ as well as water flea (Ceriodaphnia dubia) reproduction in water samples. Ecotoxicological endpoints were compared with results from analyses of general water quality parameters as well as a target screening of a wide range of organic micropollutants with a focus on pesticides and pharmaceuticals using liquid chromatography high-resolution tandem mass spectrometry. Measured ecotoxicological effects in stream water varied substantially among sites: 17β-estradiol equivalent concentrations (EEQ_bio, indicating the degree of estrogenicity) were relatively low and ranged from 0.04 to 0.85 ng/L, never exceeding a proposed effect-based trigger (EBT) value of 0.88 ng/L. Diuron equivalent (DEQ_bio) concentrations (indicating the degree of photosystem II inhibition in algae) ranged from 2.4 to 1576 ng/L and exceeded the EBT value (70 ng/L) in one third of the rivers studied, sometimes even upstream of the WWTP. Parathion equivalent (PtEQ_bio) concentrations (indicating the degree of AChE inhibition) reached relatively high values (37 to 1278 ng/L) mostly exceeding the corresponding EBT (196 ng/L PtEQ_bio). Decreased feeding activity by amphipods or decreased water flea reproduction downstream compared to the upstream site was observed at one of four investigated sites only. Results of the combined algae assay (PSII inhibition) correlated best with results of chemical analysis for PSII inhibiting herbicides. Estrogenicity was partly and AChE inhibition strongly underestimated based on measured steroidal estrogens respectively organophosphate and carbamate insecticides. An impact of dissolved organic carbon on results of the AChE inhibition assay was obvious. For this assay more work is required to further explore the missing correlation of bioassay data with chemical analytical data. Overall, the discharge of WWTP effluent led to increased estrogenicity, PSII and AChE inhibition downstream, irrespective of upstream land use.

Wastewater treatment plant (WWTP) effluents release not only chemical constituents in watersheds, but also contain microorganisms. Thus, an understanding of what microorganisms are released and how they change microbial communities within natural streams is needed. To characterize the community shifts in streams receiving WWTP effluent, we sampled water-column microorganisms from upstream, downstream, and the effluent of WWTPs located on 23 headwater streams in which no other effluent was released upstream. We characterized the bacterial community by sequencing the V3-V4 region of the 16S rRNA gene. We hypothesized that the downstream community profile would be a hydraulic mixture between the two sources (i.e., upstream and effluent). In ordination analyses, the downstream bacterial community profile was a mixture between the upstream and effluent. For 14 of the sites, the main contribution (>50%) to the downstream community originated from bacteria in the WWTP effluent and significant shifts in relative abundance of specific sequence variants were detected. These shifts in sequence variants may serve as general bioindicators of wastewater-effluent influenced streams, with a human-gut related Ruminococcus genus displaying the highest shift (30-fold higher abundances downstream). However, not all taxa composition changes were predicted based on hydraulic mixing alone. Specifically, the decrease of Cyanobacteria/Chloroplast reads was not adequately described by hydraulic mixing. The potential alteration of stream microbial communities via a high inflow of human-gut related bacteria and a decrease in autotrophic functional groups resulting from WWTP effluent creates the potential for general shifts in stream ecosystem function.

South Africa is the leading pesticide user in Sub-Saharan Africa. However, little is known about the occurrence of pesticide mixtures in surface water and potential environmental risks in Africa.
This study investigated the occurrence of pesticides mixtures in three watersheds during a drought year in South Africa. The study was conducted in the Krom River, Berg River and Hex River watersheds within larger agriculture systems in the Western Cape. Pesticide spray records were collected from 38 farms. A total of 21 passive water samplers (styrenedivinylbenzene disks (SDB)) were deployed, each for two weeks per month, over seven sampling rounds during the main pesticide application period between July 2017 and January 2018. Samples were analyzed for 248 pesticide compounds using LC-HR-MS/MS. Pesticide occurrence was analyzed for temporal agreement with pesticide spraying events (Cohen’s κ) and correlation with rainfall patterns and river discharge (Pearson correlation (r_p)). Pesticide time-weighted average concentrations were estimated and compared to environmental quality standards (EQS). According to the farm spray records, 96 different pesticides were sprayed during the sampling period and differed considerably between the three study areas, seasons and crops grown. In total, 53 compounds were detected in river water. We detected 39% of compounds from the spraying records and demonstrated close temporal correlations of seasonal patterns for 11 pesticide compounds between reported on spraying records and observations in the streams (κ = 0.90). However, 23 detected pesticides were not found on spray records, many of them being herbicides. Most of the estimated two-week average pesticide concentrations were below 40 ng/L. The insecticides imidacloprid, thiacloprid, chlorpyrifos and acetamiprid and the herbicide terbuthylazine exceeded at least once their EQS 58-fold (EQS 13 ng/L), 12-fold (EQS 10 ng/L), 9-fold (EQS 0.46 ng/L), 5-fold (EQS 24 ng/L) and 3-fold (EQS 220 ng/L), respectively. Our study substantially widens the view on pesticide pollution in surface water compared to previous studies in Sub-Saharan Africa by targeting more than 200 pesticides using passive sampling systems. This broad assessment revealed the presence of 53 compounds, some of them in high concentrations, indicating possible adverse effects on biota and the quality of the ecosystem. Whether the observed concentration levels in the year 2017 were exceptional due to the lowest ever recorded rainfall and river discharge needs to be tested with additional data to better understand how pesticide pollution levels manifest under average rainfall and river discharge conditions.

In sechs kleinen bis mittelgrossen Fliessgewässern wurden die für aquatische Organismen extrem toxischen Pyrethroid- und Organophosphatinsektizide mittels einer Spezialanalytik bis in den Picogramm-pro-Liter-Bereich quantifiziert. An fünf der sechs untersuchten Standorte überschritten die gemessenen Insektizidkonzentrationen regelmässig chronische und zum Teil akute Qualitätskriterien. Die chronische Mischungsrisikobewertung zeigte während 43 bis 100% des Untersuchungszeitraums Risiken für die Invertebratengemeinschaft an.

Soil erosion and associated sediment transfer are among the major causes of aquatic ecosystem and surface water quality impairment. Through land use and agricultural practices, human activities modify the soil erosive risk and the catchment connectivity, becoming a key factor of sediment dynamics. Hence, restoration and management plans of water bodies can only be efficient if the sediment sources and the proportion attributable to different land uses are identified. According to this aim, we applied two approaches, namely compound-specific isotope analysis (CSIA) of long-chain fatty acids (FAs) and triterpenoid biomarker analysis, to a eutrophic lake, Lake Baldegg, and its agriculturally used catchment (Switzerland). Soils reflecting the five main land uses of the catchment (arable lands, temporary and permanent grasslands, mixed forests, orchards) were subjected to CSIA. The compound-specific stable isotope δ¹³C signatures clearly discriminate between potential grasslands (permanent and temporary) and forest sources. Signatures of agricultural land and orchards fall in between. The soil signal was compared to the isotopic signature of a lake sediment sequence covering ca. 130 years (before 1885 to 2009). The recent lake samples (1940 to 2009, with the exception of 1964 to 1972) fall into the soil isotopic signature polygon and indicate an important contribution of the forests, which might be explained by (1) the location of the forests on steep slopes, resulting in a higher connectivity of the forests to the lake, and/or (2) potential direct inputs of trees and shrubs growing along the rivers feeding the lake and around the lake. However, the lake sediment samples older than 1940 lie outside the source soils' polygon, as a result of FA contribution from a not yet identified source, most likely produced by an in situ aquatic source, either algae, bacteria or other microorganisms or an ex-site historic source from wetland soils and plants (e.g. Sphagnum species). Despite the overprint of the yet unknown source on the historic isotopic signal of the lake sediments, land use and catchment history are clearly reflected in the CSIA results, with isotopic shifts being synchronous with changes in the catchment, land use and eutrophication history. The investigated highly specific biomarkers were not detected in the lake sediment, even though they were present in the soils. However, two trimethyltetrahydrochrysenes (TTHCs), natural diagenetic products of pentacyclic triterpenoids, were found in the lake sediments. Their origin is attributed to the in situ microbial degradation of some of the triterpenoids. While the need to apportion sediment sources is especially crucial in eutrophic systems, our study stresses the importance of exercising caution with CSIA and triterpenoid biomarkers in such environments, where the active metabolism of bacteria might mask the original terrestrial isotopic signals.

Climate change is one of the largest and possibly most impactful ongoing but also future environmental drivers. Understanding effects of climate change on aquatic ecosystems and their function is thus of high importance. Within the framework of the Hydro-CH2018 project, the Swiss Federal Office for the Environment (FOEN) initiated a synthesis of climate change effects on water quality and the ecological status of freshwater ecosystems. The present report is the result of these synthesis efforts.

Our goal was to summarize available knowledge on how climatic change affects freshwater ecosystems in Switzerland. The work was performed between fall 2017 and fall 2018. We aimed to provide a synthesis of existing knowledge that is as consistent and complete as possible, but also to identify possible knowledge gaps. The work is based on extensive literature surveys and expert interviews. Whenever possible, we included quantitative conclusions. At the same time, we also wanted to be specific and relevant for natural Swiss water systems, so we also included qualitative effects and case studies. While many of the major ongoing and expected effects of climate change on aquatic systems are already well known, we also faced several challenges. For example: (i) some effects of climate change are still only partly understood, (ii) many of the focal endpoints, both with respect to water quality and ecological status, are not only affected by climate change, but also by other anthropogenic drivers, and disentangling these drivers is challenging if not infeasible, (iii) specific effects can be dependent on specific local factors, and (iv) the research field is so vast that the available resources for this one-year synthesis did not allow us to go into as much detail and data analysis as the topic would deserve. As a result, our report is a snapshot of scientific knowledge, at the period of realization, of the effects of climate change on aquatic ecosystems in Switzerland, set into the context of other environmental drivers.

While we see that climate change will have major effects on Swiss water systems, we also identify possible ways of mitigating these effects. We thereby hope that our synthesis is not only an overview of current and future changes, but will also help in policy- and decisionmaking about how to best deal with these changes and challenges.

Background: Pesticide use is increasing in low- and middle-income countries (LMICs) including Costa Rica. This increase poses health risks to farm owners, farm workers, and communities living near agricultural farms.

Objective: We aimed to examine the health effects associated with occupational pesticide exposure in farm owners and workers from conventional and organic smallholder farms in Costa Rica.

Methods: We conducted a cross-sectional study involving 300 owners and workers from organic and conventional horticultural smallholder farms in Zarcero County, Costa Rica. During the baseline study visit, we administered a structured, tablet-based questionnaire to collect data on sociodemographic characteristics, pesticide exposure, and health conditions (eg, respiratory and allergic outcomes and acute pesticide intoxication symptoms) and administered a neurobehavioral test battery (eg, Finger Tapping Test and Purdue Pegboard); we measured blood pressure, anthropometry (height, weight, and waist circumference), and erythrocytic acetylcholinesterase activity and also collected urine samples. In addition, a functional neuroimaging assessment using near-infrared spectroscopy was conducted with a subset of 50 study participants. During the follow-up study visit (~2-4 weeks after the baseline), we administered participants a short questionnaire on recent pesticide exposure and farming practices and collected hair, toenail, and urine samples. Urine samples will be analyzed for various pesticide metabolites, whereas toenails and hair will be analyzed for manganese (Mn), a biomarker of exposure to Mn-containing fungicides. Self-reported pesticide exposure data will be used to develop exposure intensity scores using an exposure algorithm. Furthermore, exposure-outcome associations will be examined using linear and logistic mixed-effects regression models.

Results: Fieldwork for our study was conducted between May 2016 and August 2016. In total, 113 farm owners and 187 workers from 9 organic and 83 conventional horticultural smallholder farms were enrolled. Data analyses are ongoing and expected to be published between 2019 and 2020.

Conclusions: This study is one of the first to examine differences in health effects due to pesticide exposure between farm owners and workers from organic and conventional smallholder farms in an LMIC. We expect that this study will provide critical data on farming practices, exposure pathways, and how occupational exposure to pesticides may affect farm owners and workers’ health. Finally, we hope that this study will allow us to identify strategies to reduce pesticide exposure in farm owners and workers and will potentially lay the groundwork for a future longitudinal study of health outcomes in farm owners and workers exposed to pesticides.

Cette synthèse de deux projets 62a illustre à l’aide d’exemples les effets des mesures de réduction des risques liés aux produits phytosanitaires (PPh) sur les données du monitoring. Au vu des multiples facteurs d’influence externes aux projets, ce lien entre les mesures prises par les agriculteurs et les données chimiques, biologiques et écotoxicologiques est parfois difficile à caractériser. Néanmoins, l’analyse des données de ces deux projets pilotes en Suisse permet de tirer de nombreuses leçons pour les projets en cours ou futurs, ainsi que pour le plan d’action PPh.

Water pollution is ubiquitous globally, yet how the effects of pollutants propagate through natural ecosystems remains poorly understood. This is because the interactive effects of multiple stressors are generally hard to predict. Agriculture and municipal wastewater treatment plants (WWTPs) are often major sources of contaminants for streams, but their relative importance and the role of different pollutants (e.g. nutrients or pesticides) are largely unknown. Using a 'real world experiment' with sampling locations up- and downstream of WWTPs, we studied how effluent discharges affected water quality and macroinvertebrate communities in 23 Swiss streams across a broad land-use gradient.
Variation partitioning of community composition revealed that overall water quality explained approximately 30% of community variability, whereby nutrients and pesticides each independently explained 10% and 2%, respectively. Excluding oligochaetes (which were highly abundant downstream of the WWTPs) from the analyses, resulted in a relatively stronger influence (3%) of pesticides on the macroinvertebrate community composition, whereas nutrients had no influence. Generally, the macroinvertebrate community composition downstream of the WWTPs strongly reflected the upstream conditions, likely due to a combination of efficient treatment processes, environmental filtering and organismal dispersal. Wastewater impacts were most prominently by the Saprobic index, whereas the SPEAR index (a trait-based macroinvertebrate metrics reflecting sensitivity to pesticides) revealed a strong impact of arable cropping but only a weak impact of wastewater.
Overall, our results indicate that agriculture can have a stronger impact on headwater stream macroinvertebrate communities than discharges from WWTP. Yet, effects of wastewater-born micropollutants were clearly quantifiable among all other influence factors. Improving our ability to further quantify the impacts of micropollutants requires highly-resolved water quality and taxonomic data with adequate spatial and temporal sampling. These improvements would help to better account for the underlying causal pathways that drive observed biological responses, such as episodic contaminant peaks and dispersal-related processes.

In densely populated areas, surface waters are affected by many sources of pollution. Besides classical pollutants like nutrients and organic matter that lead to eutrophication, micropollutants from various point- and non-point sources are getting more attention by water quality managers. For cost-effective management an integrated assessment is needed that takes into account all relevant pollutants and all sources of pollution within a catchment. Due to the difficulty of identifying and quantifying sources of pollution and the need for considering long-term changes in boundary conditions, typically substantial uncertainty exists about the consequences of potential management alternatives to improve surface water quality. We therefore need integrated assessment methods that are able to deal with multiple objectives and account for various sources of uncertainty.
This paper aims to contribute to integrated, prospective water management by combining a) multi-criteria decision support methods to structure the decision process and quantify preferences, b) integrated water quality modelling to predict consequences of management alternatives accounting for uncertainty, and c) scenario planning to consider uncertainty from potential future climate and socio-economic developments, to evaluate the future cost-effectiveness of water quality management alternatives at the catchment scale. It aims to demonstrate the usefulness of multi-attribute value functions for water quality assessment to i) propagate uncertainties throughout the entire assessment procedure, ii) facilitate the aggregation of multiple objectives while avoiding discretization errors when using categories for sub-objectives, iii) transparently communicate the results. We show how to use such multi-attribute value functions for model-based decision support in water quality management.
We showcase the procedure for the Mönchaltorfer Aa catchment on the Swiss Plateau. We evaluate ten different water quality management alternatives, including current practice, that tackle macro- and micropollutants from a wide spectrum of agricultural and urban sources. We evaluate costs and water quality effects of the alternatives under four different socio-economic scenarios for the horizon 2050 under present and future climate projections and visualize their uncertainty. While the performance of alternatives is catchment specific, the methods can be transferred to other places and other management situations. Results confirm the need for cross-sectoral coordination of different management actions and interdisciplinary collaboration to support the development of prospective strategies to improve water quality.

Internal concentrations link external exposure to the potential effect, as they reflect what the organisms actually take up and experience physiologically. In this study, we investigated whether frequently detected risk-driving substances in water were found in the exposed organisms and if they are classified the same based on the whole body internal concentrations. Field gammarids were collected upstream and downstream of ten wastewater treatment plants in mixed land use catchments. The sampling was conducted in autumn and winter, during low flow conditions when diffuse agricultural input was reduced. The field study was complemented with laboratory and flume experiments to determine the bioaccumulation potentials of selected substances. For 32 substances, apparent bioaccumulation factors in gammarids were determined for the first time. With a sensitive multiresidue method based on online-solid phase extraction followed by liquid chromatography coupled to high resolution mass spectrometry, we detected 63 (semi-) polar organic substances in the field gammarids, showing higher concentrations downstream than upstream. Interestingly, neonicotinoids, which are particularly toxic toward invertebrates, were frequently detected and were further determined as major contributors to the toxic pressure based on the toxic unit approach integrating internal concentration and toxic potency. The total toxic pressure based on internal concentrations was substantially higher compared to when external concentrations were used. Thus, internal concentrations may add more value to the current environmental risk assessment that is typically based solely on external exposure.

Impairment of water quality by organic micropollutants such as pesticides, pharmaceuticals or household chemicals is a problem in many catchments worldwide. These chemicals originate from different urban and agricultural usages and are transferred to surface waters from point or diffuse sources by a number of transport pathways. The quantification of this form of pollution in streams is challenging and especially demanding for diffuse pollution due to the high spatio-temporal concentration dynamics, which require large sampling and analytical efforts to obtain representative data on the actual water quality.
Models can also be used to predict to what degree streams are affected by these pollutants. However, spatially distributed modelling of water quality is challenging for a number of reasons. Key issues are the lack of such models that incorporate both urban and agricultural sources of organic micropollutants, the large number of parameters to be estimated for many available water quality models, and the difficulty to transfer parameter estimates from calibration sites to areas where predictions are needed.
To overcome these difficulties, we used the parsimonious iWaQa model that simulates herbicide transport from agricultural fields and diffuse biocide losses from urban areas (mainly façades and roof materials) and tested its predictive capabilities in the Rhine River basin. The model only requires between one and eight global model parameters per compound that need to be calibrated. Most of the data requirements relate to spatially distributed land use and comprehensive time series of precipitation, air temperature and spatial data on discharge. For larger catchments, routing was explicitly considered by coupling the iWaQa to the AQUASIM model.
The model was calibrated with datasets from three different small catchments (0.5–24.6km²) for three agricultural herbicides (isoproturon, S-metolachlor, terbuthylazine) and two urban biocides (carbendazim, diuron). Subsequently, it was validated for herbicides and biocides in Switzerland for different years on 12 catchments of much larger size (31–35899km²) and for herbicides for the entire Rhine basin upstream of the Dutch–German border (160000km2) without any modification. For most compound–catchment combinations, the model predictions revealed a satisfactory correlation (median r²: 0.5) with the observations. The peak concentrations were mostly predicted within a factor of 2 to 4 (median: 2.1 fold difference for herbicides and 3.2 for biocides respectively). The seasonality of the peak concentration was also well simulated; the predictions of the actual timing of peak concentrations, however, was generally poor.
Limited spatio-temporal data, first on the use of the selected pesticides and second on their concentrations in the river network, restrict the possibilities to scrutinize model performance. Nevertheless, the results strongly suggest that input data and model structure are major sources of predictive uncertainty. The latter is for example seen in background concentrations that are systematically overestimated in certain regions, which is most probably linked to the modelled coupling of background concentrations to land use intensity.
Despite these limitations the findings indicate that key drivers and processes are reasonably well approximated by the model and that such a simple model that includes land use as a proxy for compound use, weather data for the timing of herbicide applications and discharge or precipitation as drivers for transport is sufficient to predict the timing and level of peak concentrations within a factor of 2 to 3 in a spatially distributed manner at the scale of large river basins.

Agricultural intensification has led to a large increase in drained arable land and pastures worldwide over the last two centuries. The installation of land drains not only affects the water balance of a landscape, but also influences the susceptibility to erosion, nutrient cycling, transport of plant protection products (PPPs) and greenhouse gas emissions. Due to the complex nature of environmental systems, the direction in which the substance flows are affected remains unclear, as does the strength of the effects. In this literature review, the focus is on the most relevant site-specific factors that affect the soil moisture regime, erosion, nitrogen (N) and phosphorus (P) fluxes, and PPP fluxes under undrained and drained conditions. The considered factors are the topography, soil characteristics, drainage types, rainfall characteristics and land management. Case studies from temperate climate zones represent the basis of the discussion, with a focus on continental Europe and the USA.
In most cases, drainage enhances the total annual water flows from arable fields, while the effects on peak flows were variable, with the local topography playing a crucial role. There exists a certain level of consensus in the literature that subsurface drainage methods reduce the risk of erosion, while surface drainage may increase erosion at the edge of drainage channels. Nitrogen fluxes are generally enhanced following drainage. This is especially true for organic soils with large stores of organically bound N and, therefore, a high loss potential. For P losses, the trend goes in the opposite direction, with generally reduced losses seen following drainage installation. Similar findings are expected in relation to PPP losses. However, these trends may reverse on flat terrain, where subsurface drainage may reduce the on-site retention of these compounds. Overall, the literature reveals the patterns by which drainage affects hydrology, nutrient and PPP fluxes, although it is also evident that the combination of site-specific factors is influential. This hence needs to be considered as part of any risk assessment or management decisions.

Fertilization, crop uptake followed by plant harvest, runoff and erosion, and transformations of phosphorus (P) in soil are the major factors influencing the P balance of croplands. It is important to integrate plant-soil-management interactions into consistent modeling systems to determine the effect of P fertilization conditions on yields and to quantify P losses. Previous assessment of P losses on large scales did not consider the interactions among these factors. Here we applied a grid-based crop model to estimate global P losses from three most produced crops: maize, rice, and wheat. The model was forced by detailed P input data sets over the period 1998–2002. According to our simulations, global P losses from the three crops reached 1.2 Tg P/year, and about 44% of it was due to soil erosion. The global total P losses were dominated by contributions from a few hot spot regions. Reducing P fertilizer in regions experiencing excessive P uses and hence losses, especially in China and India, could achieve the same yields as today and save about two thirds of global total P inputs, with the cobenefits of declining global total P losses by 41% and downstream water quality improvement. Reducing soil erosion and retaining more crop residues on croplands could further save P inputs and alleviate P losses. This study is of significance to determine the major factors influencing P balance across regions of the world and help policy makers to propose efficient strategies for tackling P-driven environmental problems.

Ecosystems face multiple anthropogenic threats globally, and the effects of these environmental stressors range from individual‐level organismal responses to altered system functioning. Understanding the combined effects of stressors on process rates mediated by individuals in ecosystems would greatly improve our ability to predict organismal multifunctionality (e.g. multiple consumer‐mediated functions). We conducted a laboratory experiment to test direct and indirect, as well as immediate and delayed effects of a heat wave (pulsed stress) and micropollutants (MPs) (prolonged stress) on individual consumers (the great pond snail Lymnaea stagnalis) and their multifunctionality (i.e. consumption of basal resources, growth, reproduction, nutrient excretion and organic‐matter cycling). We found that stressful conditions increased the process rates of multiple functions mediated by individual consumers. Specifically, the artificial heat wave increased process rates in the majority of the quantified functions (either directly or indirectly), whereas exposure to MPs increased consumption of basal resources which led to increases in the release of nutrients and fine particulate organic matter. Moreover, snails exposed to a heat wave showed decreased reproduction and nutrient excretion after the heat‐wave, indicating the potential for ecologically relevant delayed effects. Our study indicates that the immediate and delayed effects of stressors on individual organisms may directly and indirectly impact multiple ecosystem functions. In particular, delayed effects of environmental stress on individual consumers may cumulatively impede recovery due to decreased functioning following a perturbation. Reconciling these results with studies incorporating responses at higher levels of biological complexity will enhance our ability to forecast how individual responses upscale to ecosystem multifunctionality.

Many pharmaceuticals inevitably end up in surface waters, exerting unwanted biological activity in non‐target organisms. This effect is confined by the compound's environmental persistence. Regulatory laboratory simulation tests are used in persistence assessment and exposure modelling. While doubt has been expressed about the usefulness of laboratory‐derived persistence indicators under field conditions, these remain the only inputs for chemical fate models due to difficulties of measuring persistence in situ, especially at large scales. To improve understanding about relationships between laboratory experiments and the environmental fate in streams, we developed a mathematical model of biodegradation in stream networks and combined it with in‐stream monitoring data to (i) test if persistence could be evaluated from field data, (ii) check if persistence extracted from laboratory tests applied in the field, and (iii) locate hot‐spots of biodegradation in a large river basin. The model describes partitioning, and particle settling and resuspension, and is structurally compatible with those applied for evaluating laboratory simulation tests. Application to the Rhine river basin suggests that biotransformation rate constants extracted from laboratory tests underestimate those in the field, yet the percentage of biotransformation in the Rhine basin is less than in the laboratory tests due effective biotransformation being limited to small and medium‐sized streams. In conclusion, our data show that biotransformation rates can accurately predicted if (i) monitoring is performed across a wide range in stream order, and (ii) precise estimates for consumption and removal rates at wastewater treatment plants are known.

The risks associated with pesticides in small streams remain poorly characterized. The challenges reside in understanding the complexities of (1) the highly dynamic concentration profiles of (2) several hundred active substances with (3) differing seasonality. The present study addressed these three challenges simultaneously. Five small streams in catchments under intensive agricultural land use were sampled using half-day composite samples from March to August 2015. Of 213 active substances quantified using liquid chromatography–high resolution mass spectrometry, a total of 128 was detected at least at one of the sites. Ecotoxicological acute and/or chronic quality criteria were exceeded for a total of 32 different active substances. The evaluation of risks over time revealed the necessity to evaluate the sequences of different active substances that are imposed on aquatic organisms. In contrast, a substance-specific perspective provides only a very limited assessment. Scenarios for reduction of either temporal resolution, number of substances or seasonal coverage were defined. It could be shown that risks can be underestimated by more than a factor of 10 in vulnerable catchments and that an increased temporal resolution is essential to cover acute risks but that a focused selection of substances is a possibility to reduce expenditures.

One open question in environmental sciences is whether effective management of natural resources depends on the fit between the bio-physical and the governance system. To address this question, we investigate water quality in transboundary rivers and ask to what extent a fit between the area covered by the physical extent of pollution and the area in which this pollution is addressed through management and policy regulation can be observed. We adopt a spatial approach and argue that the visualization of social-ecological overlap and misfit supports science and practice when taking decisions about how best to explain or address ineffectiveness and cause-effect mismatches in transboundary river management.
We focus on drinking water supply in the international river basin of the Rhine focusing on micropollutants. These persistent trace compounds have potential toxic effects on humans and ecosystems, which makes them a relevant type of pollution that needs to be taken into consideration. Based on a combination of mass flow and social network analysis, we can conclude that the Rhine River is characterized by large social-ecological overlap, but that some parts of the catchment area still lack integration.

1. Multiple anthropogenic changes, such as climate change and chemical pollution, threaten the persistence of natural populations. Yet, their potential additive and interactive effects on organismal performance and fitness are poorly understood, thus limiting our ability to predict the effects of the global change.
2. We conducted a laboratory experiment to study the singular and combined effects of experimental heat waves and micropollutants (i.e. low-concentration toxicants; henceforth micropollutants [MPs]) on the freshwater snail, Lymnaea stagnalis. To comprehensively understand physiological and ecological consequences of stress, we studied a broad range of traits from respiration rate to feeding performance and growth. We also determined traits contributing to fitness and immune responses, as these are key traits in determining both organismal fitness and interspecific (e.g. host–parasite) interactions. We tested whether a constant exposure to MPs affects the ability of snails to tolerate heat waves (8 days of 23.5°C), and subsequently to recover from them, and whether the effects are immediate or delayed.
3. We found strong immediate additive effects of both stressors on reproduction, while they synergistically increased respiration and antagonistically decreased food consumption. Moreover, these effects were transient. Although the heat wave increased metabolic rates, individuals did not increase their resource uptake. This caused an apparent imbalance in resource levels—a probable cause for the observed trade-off between immune function and reproductive traits (i.e. phenoloxidase-like activity decreased, while reproductive output increased). In addition, exposure to MPs led to a temporarily reduced reproductive output.
4. Our results indicate that even short-term heat waves and low concentrations of chemical pollution can have large, mainly additive impacts on organismal fitness (e.g. altering susceptibility to infections and reproductive output). This suggests that long-term effects of existing stressors and heat waves need to be considered when assessing the resilience of natural populations.

To properly estimate and manage pesticide occurrence in urban rivers, it is essential, but often highly challenging, to identify the key pesticide transport pathways in association to the main sources. This study examined the concentration-discharge hysteresis behaviour (hysteresis analysis) for three pesticides and the parent-metabolite concentration dynamics for two metabolites at sites with different levels of urban influence in a mixed land use catchment (25 km²) within the Swiss Greifensee area, aiming to identify the dominant pesticide transport pathways. Combining an adapted hysteresis classification framework with prior knowledge of the field conditions and pesticide usage, we demonstrated the possibility of using hysteresis analysis to qualitatively infer the dominant pesticide transport pathway in mixed land-use catchments. The analysis showed that hysteresis types, and therefore the dominant transport pathway, vary among pesticides, sites and rainfall events. Hysteresis loops mostly correspond to dominant transport by flow components with intermediate response time, although pesticide sources indicate that fast transport pathways are responsible in most cases (e.g. urban runoff and combined sewer overflows). The discrepancy suggests the fast transport pathways can be slowed down due to catchment storages, such as topographic depressions in agricultural areas, a wastewater treatment plant (WWTP) and other artificial storage units (e.g. retention basins) in urban areas. Moreover, the WWTP was identified as an important factor modifying the parent-metabolite concentration dynamics during rainfall events. To properly predict and manage pesticide occurrence in catchments of mixed land uses, the hydrological delaying effect and chemical processes within the artificial structures need to be accounted for, in addition to the catchment hydrology and the diversity of pesticide sources. This study demonstrates that in catchments with diverse pesticide sources and complex transport mechanisms, the adapted hysteresis analysis can help to improve our understanding on pesticide transport behaviours and provide a basis for effective management strategies.

The design and evaluation of solutions for integrated surface water quality management requires an integrated modelling approach. Integrated models have to be comprehensive enough to cover the aspects relevant for management decisions, allowing for mapping of larger-scale processes such as climate change to the regional and local contexts. Besides this, models have to be sufficiently simple and fast to apply proper methods of uncertainty analysis, covering model structure deficits and error propagation through the chain of sub-models. Here, we present a new integrated catchment model satisfying both conditions. The conceptual "iWaQa" model was developed to support the integrated management of small streams. It can be used to predict traditional water quality parameters, such as nutrients and a wide set of organic micropollutants (plant and material protection products), by considering all major pollutant pathways in urban and agricultural environments. Due to its simplicity, the model allows for a full, propagative analysis of predictive uncertainty, including certain structural and input errors. The usefulness of the model is demonstrated by predicting future surface water quality in a small catchment with mixed land use in the Swiss Plateau. We consider climate change, population growth or decline, socio-economic development, and the implementation of management strategies to tackle urban and agricultural point and non-point sources of pollution. Our results indicate that input and model structure uncertainties are the most influential factors for certain water quality parameters. In these cases model uncertainty is already high for present conditions. Nevertheless, accounting for today's uncertainty makes management fairly robust to the foreseen range of potential changes in the next decades. The assessment of total predictive uncertainty allows for selecting management strategies that show small sensitivity to poorly known boundary conditions. The identification of important sources of uncertainty helps to guide future monitoring efforts and pinpoints key indicators, whose evolution should be closely followed to adapt management. The possible impact of climate change is clearly demonstrated by water quality substantially changing depending on single climate model chains. However, when all climate trajectories are combined, the human land use and management decisions have a larger influence on water quality against a time horizon of 2050 in the study.

This study was conducted to determine physicochemical and microbiological characteristics of well water for agricultural and domestic uses in Korhogo’s department. The physicochemical and microbiological parameters were analyzed following techniques described by AFNOR. 18 wells were sampled during the rainy and dry seasons. Physicochemical results indicated that the water is slightly acidic and weakly mineralized with conductivity values between 59.5 μS/cm and 225 μS/cm. Dissolved oxygen concentrations are between 0.78 mg/l and 4.93 mg/l. Furthermore, the levels of nitrate and ammonium in this water show that they are not affected by nitrogen pollution. Pesticides such as chlorpyrifos-ethyl, ethyl parathion, thiamethoxam, spirodiclofen, deltamethrin, carbaryl and zoxamide were discovered in 16 wells. The concentration of individual pesticides reached 3.61 μg/l in some wells. The total pesticide concentration detected in the wells ranged from 0.01 μg/l and 6.36 μg/l. Microbiological analysis showed the presence of total coliforms at high levels (2,3.10³ CFU/ml). Consumption of this water can cause a real health risks for the population.

Micropollutants enter surface waters through various pathways, of which wastewater treatment plants (WWTPs) are a major source. The large diversity of micropollutants and their many modes of toxic action pose a challenge for assessing environmental risks. In this study, we investigated the potential impact of WWTPs on receiving ecosystems by describing concentration patterns of micropollutants, predicting acute risks for aquatic organisms and validating these results with macroinvertebrate biomonitoring data. Grab samples were taken upstream, downstream and at the effluent of 24 Swiss WWTPs during low flow conditions across independent catchments with different land uses. Using liquid chromatography high resolution tandem mass spectrometry, a comprehensive target screening of almost 400 organic substances, focusing mainly on pesticides and pharmaceuticals, was conducted at two time points, and complemented with the analysis of a priority mixture of 57 substances over eight time points. Acute toxic pressure was predicted using the risk assessment approach of the multi-substance potentially affected fraction, first applying concentration addition for substances with the same toxic mode of action and subsequently response addition for the calculation of the risk of the total mixture. This toxic pressure was compared to macroinvertebrate sensitivity to pesticides (SPEAR index) upstream and downstream of the WWTPs. The concentrations were, as expected, especially for pharmaceuticals and other household chemicals higher downstream than upstream, with the detection frequency of plant protection products upstream correlating with the fraction of arable land in the catchments. While the concentration sums downstream were clearly dominated by pharmaceuticals or other household chemicals, the acute toxic pressure was mainly driven by pesticides, often caused by the episodic occurrence of these compounds even during low flow conditions. In general, five single substances explained much of the total risk, with diclofenac, diazinon and clothianidin as the main drivers. Despite the low predicted acute risk of 0%–2.1% for affected species, a significant positive correlation with macroinvertebrate sensitivity to pesticides was observed. However, more effect data for pharmaceuticals and a better quantification of episodic pesticide pollution events are needed for a more comprehensive risk assessment.

Surface waters can contain a range of micropollutants from point sources, such as wastewater effluent, and diffuse sources, such as agriculture. Characterizing the source of micropollutants is important for reducing their burden and thus mitigating adverse effects on aquatic ecosystems. In this study, chemical analysis and bioanalysis were applied to assess the micropollutant burden during low flow conditions upstream and downstream of three wastewater treatment plants (WWTPs) discharging into small streams in the Swiss Plateau. The upstream sites had no input of wastewater effluent, allowing a direct comparison of the observed effects with and without the contribution of wastewater. Four hundred and five chemicals were analyzed, while the applied bioassays included activation of the aryl hydrocarbon receptor, activation of the androgen receptor, activation of the estrogen receptor, photosystem II inhibition, acetylcholinesterase inhibition and adaptive stress responses for oxidative stress, genotoxicity and inflammation, as well as assays indicative of estrogenic activity and developmental toxicity in zebrafish embryos. Chemical analysis and bioanalysis showed higher chemical concentrations and effects for the effluent samples, with the lowest chemical concentrations and effects in most assays for the upstream sites. Mixture toxicity modeling was applied to assess the contribution of detected chemicals to the observed effect. For most bioassays, very little of the observed effects could be explained by the detected chemicals, with the exception of photosystem II inhibition, where herbicides explained the majority of the effect. This emphasizes the importance of combining bioanalysis with chemical analysis to provide a more complete picture of the micropollutant burden. While the wastewater effluents had a significant contribution to micropollutant burden downstream, both chemical analysis and bioanalysis showed a relevant contribution of diffuse sources from upstream during low flow conditions, suggesting that upgrading WWTPs will not completely reduce the micropollutant burden, but further source control measures will be required.

Human land uses and population growth represent major global threats to biodiversity and ecosystem services. Understanding how biological communities respond to multiple drivers of human-induced environmental change is fundamental for conserving ecosystems and remediating degraded habitats. Here, we used a replicated ‘real-world experiment’ to study the responses of invertebrate communities to wastewater perturbations across a land-use intensity gradient in 12 Swiss streams. We used different taxonomy and trait-based community descriptors to establish the most sensitive indicators detecting impacts and to help elucidate potential causal mechanisms of change. First, we predicted that streams in catchments adversely impacted by human land-uses would be less impaired by wastewater inputs because their invertebrate communities should be dominated by pollution-tolerant taxa (‘environmental context’). Second, we predicted that the negative effects of wastewater on stream invertebrate communities should be larger in streams that receive proportionally more wastewater (‘magnitude of disturbance’). In support of the ‘environmental context’ hypothesis, we found that change in the Saprobic Index (a trait-based indicator of tolerance to organic pollution) was associated with upstream community composition; communities in catchments with intensive agricultural land uses (e.g., arable cropping and pasture) were generally more resistant to eutrophication associated with wastewater inputs. We also found support for the ‘magnitude of disturbance’ hypothesis. The SPEAR Index (a trait-based indicator of sensitivity to pesticides) was more sensitive to the relative input of effluent, suggesting that toxic influences of wastewater scale with dilution. Whilst freshwater pollution continues to be a major environmental problem, our findings highlight that the same anthropogenic pressure (i.e., inputs of wastewater) may induce different ecological responses depending on the environmental context and community metrics used. Thus, remediation strategies aiming to improve stream ecological status (e.g., rehabilitating degraded reaches) need to consider upstream anthropogenic influences and the most appropriate indicators of restoration success.

Human-induced environmental changes are causing major shifts in ecosystems around the globe. To support environmental management, scientific research has to infer both general trends and context dependency in these shifts at global and local scales. Combining replicated real-world experiments, which take advantage of implemented mitigation measures or other forms of human impact, with research-led experimental manipulations can provide powerful scientific tools for inferring causal drivers of ecological change and the generality of their effects. Additionally, combining these two approaches can facilitate communication with stakeholders involved in implementing management strategies. We demonstrate such an integrative approach using the case study EcoImpact, which aims at empirically unravelling the impacts of wastewater-born micropollutants on aquatic ecosystems.

During rain events, biocides and plant protection products are transported from agricultural fields but also from urban sources to surface waters. Originally designed to be biologically active, these compounds may harm organisms in aquatic ecosystems. Although several models allow either urban or agricultural storm events to be predicted, only few combine these two sources, and none of them include biocide losses from building envelopes. This study therefore aims to develop a model designed to predict water and substance flows from urban and agricultural sources to surface waters. We developed a model based on physical principles for water percolation and substance flow including micro- (also called matrix-) and macropore-flows for the agricultural areas together with a model representing sources, sewer systems and a wastewater treatment plant for urban areas. In a second step, the combined model was applied to a catchment where an extensive field study had been conducted. The modelled and measured discharge and compound results corresponded reasonably well in terms of quantity and dynamics. The total cumulative discharge was only slightly lower than the total measured discharge (factor 0.94). The total modelled losses of the agriculturally used herbicide atrazine were slightly lower (∼25%) than the measured losses when the soil pore water distribution coefficient (describing the partition between soil particles and pore water) (K_d) was kept constant and slightly higher if it was increased with time. The modelled urban losses of diuron from facades were within a factor of three with respect to the measured values. The results highlighted the change in importance of the flow components during a rain event from urban sources during the most intensive rain period towards agricultural ones over a prolonged time period. Applications to two other catchments, one neighbouring and one on another continent showed that the model can be applied using site specific data for land use, pesticide application, weather and literature data for soil related parameters such as saturated water content, hydraulic conductivity or lateral distances of the drainage pipes without any further calibration of parameters. This is a promising basis for using the model in a wide range of catchments.

Diffuse entry of pesticide residues from agriculture into rivers is spatially unevenly distributed. Therefore, the identification of critical source areas (CSAs) may support water quality management in agricultural catchments. In contrast to former studies, we followed the hypothesis that not only hydrological and topographical characteristics but also physico-chemical properties of pesticide residues have a major influence on their loss to rivers and on corresponding formation of CSAs. We designed a virtual experiment, i.e. a numerical experiment as close as possible to environmental conditions, in a headwater catchment where pronounced spatial differences in hydrological transport processes were identified in the past. 144 scenarios with different combinations of adsorption coefficients (K_OC = 10–1000 ml/g) and transformation half-lives (DT50 = 3–60 days) for pesticide parent compounds (PCs) and their transformation products (TPs) were simulated using the catchment-scale spatially distributed reactive transport model ZIN-AgriTra.
Export fractions of substances in the virtual experiment ranged from 0.001–15% for pesticides and 0.001–1.8% for TPs. The results of the scenario investigations suggest that more of the calculated export mass variability could be attributed to K_OC than to DT50 for both PCs and TPs. CSAs for TPs were spatially more equally distributed in the catchment than for PC export which was likely an effect of changing physico-chemical properties during transformation. The ranking of highest export fields was different between PCs and TPs for most of the investigated scenarios but six fields appeared among the top ten export fields in 95% of the scenarios, which shows the influence of site characteristics such as tile drains or soil properties in the catchment. Thus, the highest export fields were determined by a combination of site characteristics and substance characteristics. Therefore, despite the challenge of widely differing physico-chemical characteristics of pesticides on the market, these characteristics are an important consideration when delineating pesticide residue CSAs.

The series of papers in this issue of AMBIO represent technical presentations made at the 7th International Phosphorus Workshop (IPW7), held in September, 2013 in Uppsala, Sweden. At that meeting, the 150 delegates were involved in round table discussions on major, predetermined themes facing the management of agricultural phosphorus (P) for optimum production goals with minimal water quality impairment. The six themes were (1) P management in a changing world; (2) transport pathways of P from soil to water; (3) monitoring, modeling, and communication; (4) importance of manure and agricultural production systems for P management; (5) identification of appropriate mitigation measures for reduction of P loss; and (6) implementation of mitigation strategies to reduce P loss. This paper details the major challenges and research needs that were identified for each theme and identifies a future roadmap for catchment management that cost-effectively minimizes P loss from agricultural activities.

Using macroinvertebrates as ecological indicators for different stressors has a long tradition. However, when applied to field data, one often observes correlations between different macroinvertebrate indices that can be attributed to both correlations of stressors and inherent correlations due to the sensitivity of taxa to different stressors. Ignoring the source of any given correlation leads to ambiguous conclusions about the impact of different stressors.
Here, we demonstrate how to distinguish the causes of correlation by means of Monte Carlo simulations. We assessed to which degree trait-based indices are stressor-specific and whether this depends on the pool of taxa and its taxonomic resolution. Therefore, we (1) analysed the frequencies of "sensitive" and "insensitive" taxa for pairwise combinations of different indices, (2) analysed the inherent correlation of indices with random samples from different taxon pools derived from field samples and from a complete species list of a whole ecoregion, and (3) compared this inherent correlation with the actual correlation of the field samples. We exemplified this approach by analysing two existing indices (SPEAR_pesticides, Saprobic Index) and new indices for temperature, flow and pH stress. We used these new indices to illustrate our approach while in-depth testing of their applicability was not the focus of our study. < BR/> We found strong correlations between several indices in our study area at the Swiss Plateau. The probability that this correlation is only due to inherent correlation in the taxa sensitivities was low (maximum of 0.34). The problem of inherent correlation between indices is more severe for the smaller taxon pool with lower taxonomic resolution.
Correlation in the sensitivity of different taxa to different stressors leads to an inherent correlation in trait-based indices, which weakens their explanatory power. Our results highlight the importance of correlation analyses when using trait-based indices to guide ecosystem-management, especially in regions with reduced biodiversity.

Micropollutants (MPs) as individual compounds or in complex mixtures are relevant for water quality and may trigger unwanted ecological effects. MPs originate from different point and diffuse sources and enter water bodies via different flow paths. Effluents from conventional wastewater treatment plants (WWTPs), in which various MPs are not or not completely removed, is one major source. To improve the water quality and avoid potential negative ecological effects by micropollutants, various measures to reduce the discharge should be taken. In this feature we discuss one of these measures; the benefits of upgrading WWTPs toward reduced MP loads and toxicities from wastewater effluents, using the recently decided Swiss strategy as an example. Based on (i) full-scale case studies using ozonation or powder activated carbon treatment, showing substantial reduction of MP discharges and concomitant reduced toxicities, (ii) social and political acceptance, (iii) technical feasibility and sufficient cost-effectiveness, the Swiss authorities recently decided to implement additional wastewater treatment steps as mitigation strategy to improve water quality. Since MPs are of growing global concern, the concepts and considerations behind the Swiss strategy are explained in this feature, which could be of use for other countries as well. It should be realized that upgrading WWTPs is not the only solution to reduce the discharge of MPs entering the environment, but is part of a broader, multipronged mitigation strategy.

Climate change impact assessments have become more and more popular in hydrology since the middle 1980s with a recent boost after the publication of the IPCC AR4 report. From hundreds of impact studies a quasi-standard methodology has emerged, to a large extent shaped by the growing public demand for predicting how water resources management or flood protection should change in the coming decades. The "standard" workflow relies on a model cascade from global circulation model (GCM) predictions for selected IPCC scenarios to future catchment hydrology. Uncertainty is present at each level and propagates through the model cascade. There is an emerging consensus between many studies on the relative importance of the different uncertainty sources. The prevailing perception is that GCM uncertainty dominates hydrological impact studies. Our hypothesis was that the relative importance of climatic and hydrologic uncertainty is (among other factors) heavily influenced by the uncertainty assessment method. To test this we carried out a climate change impact assessment and estimated the relative importance of the uncertainty sources. The study was performed on two small catchments in the Swiss Plateau with a lumped conceptual rainfall runoff model. In the climatic part we applied the standard ensemble approach to quantify uncertainty but in hydrology we used formal Bayesian uncertainty assessment with two different likelihood functions. One was a time series error model that was able to deal with the complicated statistical properties of hydrological model residuals. The second was an approximate likelihood function for the flow quantiles. The results showed that the expected climatic impact on flow quantiles was small compared to prediction uncertainty. The choice of uncertainty assessment method actually determined what sources of uncertainty could be identified at all. This demonstrated that one could arrive at rather different conclusions about the causes behind predictive uncertainty for the same hydrological model and calibration data when considering different objective functions for calibration.

Dieser im Rahmen des NFP 61 entstandene Bericht beschreibt die Bewirtschaftung der Wasserressourcen in der Schweiz und die daraus resultierenden Nutzungskonflikte und Synergiepotenziale heute und - so weit absehbar - in der Zukunft. Wo immer möglich, stützt er sich auf Erkenntnisse aus den NFP 61-Forschungsprojekten, bezieht darüber hinaus aber auch Ergebnisse anderer Forschungsprojekte, behördliche Fachberichte und sonstige Publikationen ein. Der Bericht fasst damit den Stand des Wissens zum Thema Wasserbewirtschaftung in der Schweiz zusammen. [...]

This report describes how water and aquatic ecosystems in Switzerland are presently being utilised. It also documents present and – as far as foreseeable – future conflicts and potential synergies resulting from the different uses. The analysis is based wherever possible on knowledge gained by NRP 61 research projects, yet also draws on insights of other research projects, official reports and publications. The report hence lays out the current state of knowledge on water utilisation in Switzerland. To identify the relevant synergies and conflicts, all important demands on water and aquatic ecosystems have been examined. This includes activities that do not originally intend to make use of water or water bodies, but do have an impact on their condition and hence on other water users. [...]

A comprehensive assessment of pesticides in surface waters is challenging due to the large number of potential contaminants. Most scientific studies and routine monitoring programs include only 15–40 pesticides, which leads to error-prone interpretations. In the present study, an extensive analytical screening was carried out using liquid chromatography–high-resolution mass spectrometry, covering 86% of all polar organic pesticides sold in Switzerland and applied to agricultural or urban land (in total 249 compounds), plus 134 transformation products; each of which could be quantified in the low ng/L range. Five medium-sized rivers, containing large areas of diverse crops and urban settlements within the respective catchments, were sampled between March and July 2012. More than 100 parent compounds and 40 transformation products were detected in total, between 30 and 50 parent compounds in each two-week composite sample in concentrations up to 1500 ng/L. The sum of pesticide concentrations was above 1000 ng/L in 78% of samples. The chronic environmental quality standard was exceeded for 19 single substances; using a mixture toxicity approach, exceedances occurred over the whole measurement period in all rivers. With scenario calculations including only 30–40 frequently measured pesticides, the number of detected substances and the mixture toxicity would be underestimated on average by a factor of 2. Thus, selecting a subset of substances to assess the surface water quality may be sufficient, but a comprehensive screening yields substantially more confidence.

Pesticides applied onto agricultural fields are frequently found in adjacent rivers. To what extent and along which pathways they are transported is influenced by intrinsic pesticide properties such as sorption and degradation. In the environment, incomplete degradation of pesticides leads to the formation of transformation products (TPs), which may differ from the parent compounds regarding their intrinsic fate characteristics. Thus, the export processes of TPs in catchments and streams may also be different. In order to test this hypothesis, we extended a distributed hydrological model by the fate and behaviour of pesticides and transformation products and applied it to a small, well-monitored headwater catchment in Switzerland. The successful model evaluation of three pesticides and their TPs at three sampling locations in the catchment enabled us to estimate the quantity of contributing processes for pollutant export. Since all TPs were more mobile than their parent compounds (PCs), they exhibited larger fractions of export via subsurface pathways. However, besides freshly applied pesticides, subsurface export was found to be influenced by residues of former applications. Export along preferential flow pathways was less dependent on substance fate characteristics than soil matrix export, but total soil water flow to tile drains increased more due to preferential flow for stronger sorbing substances. Our results indicate that runoff generation by matrix flow to tile drains gained importance towards the end of the modelling period whereas the contributions from fast surface runoff and preferential flow decreased. Accordingly, TPs were to a large extent exported under different hydrological conditions than their PCs, due to their delayed formation and longer half-lives. Thus, not only their different intrinsic characteristics but also their delayed formation could be responsible for the fact that TPs generally took different pathways than their PCs. We suggest that these results should be considered in risk assessment for the export of agricultural chemicals to adjacent rivers and that models should be extended to include both PCs and TPs.

Eutrophication of surface waters due to diffuse phosphorus (P) losses continues to be a severe water quality problem worldwide, causing the loss of ecosystem functions of the respective water bodies. Phosphorus in runoff often originates from a small fraction of a catchment only. Targeting mitigation measures to these critical source areas (CSAs) is expected to be most efficient and cost-effective, but requires suitable tools.
Here we investigated the capability of the parsimonious Rainfall-Runoff-Phosphorus (RRP) model to identify CSAs in grassland-dominated catchments based on readily available soil and topographic data. After simultaneous calibration on runoff data from four small hilly catchments on the Swiss Plateau, the model was validated on a different catchment in the same region without further calibration. The RRP model adequately simulated the discharge and dissolved reactive P (DRP) export from the validation catchment. Sensitivity analysis showed that the model predictions were robust with respect to the classification of soils into "poorly drained" and "well drained", based on the available soil map. Comparing spatial hydrological model predictions with field data from the validation catchment provided further evidence that the assumptions underlying the model are valid and that the model adequately accounts for the dominant P export processes in the target region. Thus, the parsimonious RRP model is a valuable tool that can be used to determine CSAs. Despite the considerable predictive uncertainty regarding the spatial extent of CSAs, the RRP can provide guidance for the implementation of mitigation measures. The model helps to identify those parts of a catchment where high DRP losses are expected or can be excluded with high confidence. Legacy P was predicted to be the dominant source for DRP losses and thus, in combination with hydrologic active areas, a high risk for water quality.

A proper uncertainty assessment of rainfall-runoff predictions has always been an important objective for modelers. Several sources of uncertainty have been identified, but their representation was limited to complicated mechanistic error propagation frameworks only. The typical statistical error models used in the modeling practice still build on outdated and invalidated assumptions like the independence and homoscedasticity of model residuals and thus result in wrong uncertainty estimates. The primary reason for the popularity of the traditional faulty methods is the enormous computational requirement of full Bayesian error propagation frameworks. We introduce a statistical error model that can account for the effect of various uncertainty sources present in conceptual rainfall-runoff modeling studies and at the same time has limited computational demand. We split the model residuals into three different components: a random noise term and two bias processes with different response characteristics. The effects of the input uncertainty are simulated with a stochastic linearized rainfall-runoff model. While the description of model bias with Bayesian statistics cannot directly help to improve on the model's deficiencies, it is still beneficial to get realistic estimates on the overall predictive uncertainty and to rank the importance of different uncertainty sources. This feature is particularly important if the error sources cannot be addressed individually, but it is also relevant for the description of remaining bias when input and structural errors are considered explicitly.

During rain events, herbicides can be transported from their point of application to surface waters, where they may harm aquatic organisms. Since the spatial pattern of mobilisation and transport is heterogeneous, the contributions of different fields to the herbicide load in the stream may vary considerably within one catchment. Therefore, the prediction of contributing areas could help to target mitigation measures efficiently to those locations where they reduce herbicide pollution the most.
Such spatial predictions require sufficient insight into the underlying transport processes. To improve the understanding of the process chain of herbicide mobilisation on the field and the subsequent transport through the catchment to the stream, we performed a controlled herbicide application on corn fields in a small agricultural catchment (ca. 1 km²) with intensive crop production in the Swiss Plateau. Water samples were collected at different locations in the catchment (overland flow, tile drains and open channel) for two months after application in 2009, with a high temporal resolution during rain events. We also analysed soil samples from the experimental fields and measured discharge, groundwater level, soil moisture and the occurrence of overland flow at several locations. Several rain events with varying intensities and magnitudes occurred during the study period. Overland flow and erosion were frequently observed in the entire catchment. Infiltration excess and saturation excess overland flow were both observed. However, the main herbicide loss event was dominated by infiltration excess.
Despite the frequent and wide-spread occurrence of overland flow, most of this water did not reach the channel directly, but was retained in small depressions in the catchment. From there, it reached the stream via macropores and tile drains. Manholes of the drainage system and storm drains for road and farmyard runoff acted as additional shortcuts to the stream.
Although fast flow processes such as overland and macropore flow reduce the influence of the herbicide's chemical properties on transport due to short travel times, sorption properties influenced the herbicide transfer from ponding overland flow to tile drains (macropore flow). However, no influence of sorption was observed during the mobilisation of the herbicides from soil to overland flow. These observations on the role of herbicide properties contradict previous findings to some degree. Furthermore, they demonstrate that valuable insight can be gained by making spatially detailed observations along the flow paths.

Temporally resolved environmental risk assessment of fluctuating concentrations of micropollutants is presented. We separated the prediction of toxicity over time from the extrapolation from one to many species and from acute to sublethal effects. A toxicokinetic–toxicodynamic (TKTD) model predicted toxicity caused by fluctuating concentrations of diazinon, measured by time-resolved sampling over 108 days from three locations in a stream network, representing urban, agricultural and mixed land use. We calculated extrapolation factors to quantify variation in toxicity among species and effect types based on available toxicity data, while correcting for different test durations with the TKTD model. Sampling from the distribution of extrapolation factors and prediction of time-resolved toxicity with the TKTD model facilitated subsequent calculation of the risk of undesired toxic events. Approximately one-fifth of aquatic organisms were at risk and fluctuating concentrations were more toxic than their averages. Contribution of urban and agricultural sources of diazinon to the overall risk varied. Thus using fixed concentrations as water quality criteria appears overly simplistic because it ignores the temporal dimension of toxicity. However, the improved prediction of toxicity for fluctuating concentrations may be small compared to uncertainty due to limited diversity of toxicity data to base the extrapolation factors on.

A distributed hydrological model was used to simulate the distribution of fast runoff formation as a proxy for critical source areas for herbicide pollution in a small agricultural catchment in Switzerland. We tested to what degree predictions based on prior knowledge without local measurements could be improved upon relying on observed discharge. This learning process consisted of five steps: For the prior prediction (step 1), knowledge of the model parameters was coarse and predictions were fairly uncertain. In the second step, discharge data were used to update the prior parameter distribution. Effects of uncertainty in input data and model structure were accounted for by an autoregressive error model. This step decreased the width of the marginal distributions of parameters describing the lower boundary (percolation rates) but hardly affected soil hydraulic parameters. Residual analysis (step 3) revealed model structure deficits. We modified the model, and in the subsequent Bayesian updating (step 4) the widths of the posterior marginal distributions were reduced for most parameters compared to those of the prior. This incremental procedure led to a strong reduction in the uncertainty of the spatial prediction. Thus, despite only using spatially integrated data (discharge), the spatially distributed effect of the improved model structure can be expected to improve the spatially distributed predictions also. The fifth step consisted of a test with independent spatial data on herbicide losses and revealed ambiguous results. The comparison depended critically on the ratio of event to preevent water that was discharged. This ratio cannot be estimated from hydrological data only. The results demonstrate that the value of local data is strongly dependent on a correct model structure. An iterative procedure of Bayesian updating, model testing, and model modification is suggested.

Relative contributions of agricultural and urban uses to the glyphosate contamination of surface waters were studied in a small catchment (25 km²) in Switzerland. Monitoring in four sub-catchments with differing land use allowed comparing load and input dynamics from different sources. Agricultural as well as urban use was surveyed in all sub-catchments allowing for a detailed interpretation of the monitoring results. Water samples from the river system and from the urban drainage system (combined sewer overflow, storm sewer and outflow of wastewater treatment plant) were investigated. The concentrations at peak discharge during storm events were elevated throughout the year with maximum concentrations of 4.15 μg L⁻¹. Glyphosate concentrations mostly exceeded those of other commonly used herbicides such as atrazine or mecoprop. Fast runoff from hard surfaces led to a fast increase of the glyphosate concentration shortly after the beginning of rainfall not coinciding with the concentration peak normally observed from agricultural fields. The comparison of the agricultural application and the seasonal concentration and load pattern in the main creek from March to November revealed that the occurrence of glyphosate cannot be explained by agricultural use only. Extrapolations from agricultural loss rates and from concentrations found in the urban drainage system showed that more than half of the load during selected rain events originates from urban areas. The inputs from the effluent of the wastewater treatment plant, the overflow of the combined sewer system and of the separate sewer system summed up to 60% of the total load.

The prediction of diffuse herbicide losses to surface waters using process-based models is data and time demanding. There is a need for simpler and more efficient catchment screening tools. We developed and tested a new proxy for screening catchments for their vulnerability to diffuse herbicide losses relying on widely available river flow data only. The proxy combines the fast flow index (FFI) (i.e., the long-term average proportion of fast flow to total discharge) and the fast flow volume (FFVs) (i.e., the stormflow component of the hydrograph during the spring flush period). We tested the proxy and the underlying hypotheses by regression analyses of existing high-frequency, multiannual monitoring datasets of atrazine, metolachlor, alachlor, and acetochlor concentrations from six US and European catchments. The percentages of applied amounts of three of the four herbicides lost to surface water were positively correlated with the FFV, and the slope of the correlation was positively correlated with the FFI. Based on the empirical data, we derived quantitative proxies to estimate atrazine and metolachlor losses based on the measured FFI and FFV values. The application to 65 European catchments revealed that many of them had a lower vulnerability than the six test catchments. The observed FFI dependency of the slope seems reasonable because with increasing FFI less rain is needed to trigger fast flow and more herbicide is available in the topsoil. The proposed FFI-FFVs proxy can guide researchers and authorities in selecting monitoring areas, setting monitoring results into context, and prioritizing mitigation strategies according to catchment vulnerability.

Biocides and pesticides are designed to control the occurrence of unwanted organisms. From their point of application, these substances can be mobilized and transported to surface waters posing a threat to the aquatic environment. Historically, agricultural pesticides have received substantially more attention than biocidal compounds from urban use, despite being used in similar quantities.
This study aims at improving our understanding of the influence of mixed urban and agricultural land use on the overall concentration dynamics of biocides and pesticides during rain events throughout the year. A comprehensive field study was conducted in a catchment within the Swiss plateau (25 km²). Four surface water sampling sites represented varying combinations of urban and agricultural sources. Additionally, the urban drainage system was studied by sampling the only wastewater treatment plant (WWTP) in the catchment, a combined sewer overflow (CSO), and a storm sewer (SS). High temporal resolution sampling was carried out during rain events from March to November 2007.
The results, based on more than 600 samples analyzed for 23 substances, revealed distinct and complex concentration patterns for different compounds and sources. Five types of concentration patterns can be distinguished: a) compounds that showed elevated background concentrations throughout the year (e.g. diazinon >50 ng L⁻¹), indicating a constant household source; b) compounds that showed elevated concentrations driven by rain events throughout the year (e.g. diuron 100–300 ng L⁻¹), indicating a constant urban outdoor source such as facades; c) compounds with seasonal peak concentrations driven by rain events from urban and agricultural areas (e.g. mecoprop 1600 ng L⁻¹ and atrazine 2500 ng L⁻¹ respectively); d) compounds that showed unpredictably sharp peaks (e.g. atrazine 10,000 ng L⁻¹, diazinon 2500 ng L⁻¹), which were most probably due to improper handling or even disposal of products; and finally, e) compounds that were used in high amounts but were not detected in surface waters (e.g. isothiazolinones).
It can be safely concluded that in catchments of mixed land use, the contributions of biocide and pesticide inputs into surface waters from urban areas are at least as important as those from agricultural areas.

Ten conceptually different models in predicting discharge from the artificial Chicken Creek catchment in North-East Germany were used for this study. Soil texture and topography data were given to the modellers, but discharge data was withheld. We compare the predictions with the measurements from the 6 ha catchment and discuss the conceptualization and parameterization of the models. The predictions vary in a wide range, e.g. with the predicted actual evapotranspiration ranging from 88 to 579 mm/y and the discharge from 19 to 346 mm/y. The predicted components of the hydrological cycle deviated systematically from the observations, which were not known to the modellers. Discharge was mainly predicted as subsurface discharge with little direct runoff. In reality, surface runoff was a major flow component despite the fairly coarse soil texture. The actual evapotranspiration (AET) and the ratio between actual and potential ET was systematically overestimated by nine of the ten models. None of the model simulations came even close to the observed water balance for the entire 3-year study period. The comparison indicates that the personal judgement of the modellers was a major source of the differences between the model results. The most important parameters to be presumed were the soil parameters and the initial soil-water content while plant parameterization had, in this particular case of sparse vegetation, only a minor influence on the results.

Reducing herbicide applications on hydrologically contributing areas has been suggested as an effective approach to mitigate diffuse herbicide pollution. We report on controlled herbicide applications in two small neighboring catchments in the Swiss Plateau investigating the persistence of contributing areas in time and the influence of herbicide properties on the spatial loss patterns and on the extent of herbicides loads. A mixture of atrazine, dimethenamide, metolachlor, and sulcotrione was applied to four corn fields on the same day. Simazine was used as an additional tracer to the wettest part of one field. Irrespective of rainfall timing and for all compounds, spatial differences in the herbicide losses relative to the amounts applied were large (factors 15-18). The water table fluctuations in the fields suggest that soil hydrology differentiated between "high" and "low loss" fields. The spatial patterns were consistent with results obtained under very different weather conditions in an earlier study indicating that contributing areas prevail in time. Simazine losses from a wet hot spot were exceptionally large exceeding 24% of the applied mass. Avoiding atrazine applications on this small area corresponding to 1% of the field size would have resulted in a 30% decrease of the overall losses. Hence, land use strategies should not only account for soil (hydrological) differences between fields but should pay sufficient attention to small-scale heterogeneity within fields.

In recent years, human and veterinary pharmaceuticals have received much attention as pollutants of water bodies or drinking water resources due to possible negative effects on humans or the ecosystem even at very low concentrations. Over the last 10 years, considerable progress has been made regarding the knowledge of the exposure of water bodies to those drugs. This review summarizes the present understanding in this broad and interdisciplinary field incorporating contributions ranging from trace analytics to spatially distributed modelling of point-source and diffuse pollution. It discusses the main factors and processes controlling the environmental fate of pharmaceuticals from their usage to their spatial and temporal occurrence in water bodies. The current research is still rather phenomenological and further advancement of the field requires more integrated, quantitative mass flux analyses. Such analyses should also consider the explicit incorporation of uncertainties that appropriately reflect the current limited understanding and data availability.

Sulfonamides (SA), ionizable, polar antimicrobial compounds, may reach the environment in substantial amounts by the spreading of manure. The environmental behavior of SA is still difficult to predict. We investigated the influence of the main factors supposed to control SA sorption to organic materials: composition of sorbent, solute chemistry, and contact time. For that purpose, sulfathiazole (STA) sorption to compost, manure, and humic acid after 1 and 14 d was studied under sterile conditions. The experiments demonstrated that sorption was most strongly affected by contact time and pH. Irrespective of sorbent and pH, sorption continued substantially after the fast initial sorption within 1 d. For all sorbents and both contact times, STA sorption exhibited a pronounced pH dependence. Species-specific K_oc values decreased in the order K_oc^cation > <i<K</I>_oc^neutral > K_oc^anion. Differences in sorbent composition influenced STA sorption weaker. For the neutral STA species, NMR chemical shift regions assignable to ketonic, carboxylic, and phenolic C as well as aromatic C-H and methoxyl/N-alkyl C seemed to control sorption. For the cations, sorption followed the cation exchange capacities of the sorbents. STA sorption to manure and humic acid increased with higher ionic strength (0.31 M compared to 0.06 M) at pH 7.5.

Phosphorus (P) losses from many agricultural soils are driven by fast transport processes, such as surface runoff, shallow interflow and macropore flow. Close interaction of rain with topsoil layers (0-5 cm), rich in available P, results in high P concentrations in these rapid runoff pathways. This is particularly pronounced in permanent grassland soils typically characterized by a P enrichment of the topsoil. One option to mitigate P losses from grassland is therefore to reduce soil P content, particularly available P, in this critical surface layer. Omitting application of P fertilizer will reduce soil P in the long term but more drastic methods may be necessary to achieve P loss reductions in shorter timescales. In this study, three management options to reduce P in runoff from grassland soils were evaluated in a field experiment lasting 2 years on two grassland sites: (i) no P inputs, (ii) no P inputs plus soil tillage and (iii) no P inputs plus tillage combined with application of a P sorbing soil amendment (iron oxide). Withholding P inputs did not decrease either the available P in the soil or the P concentrations in runoff from sprinkler experiments over a 2-year period. Both the treatments which included tillage caused immediate reductions in both soil available P and runoff P, with Fe/OH amendment being more effective. However, in the second year the effects of both tillage treatments were less apparent and only the Fe/OH treatment significantly decreased runoff P. The results indicate that the long-term enrichment of soils due to P application in excess of plant needs is unlikely to be remedied by short-term treatments. However, further work is required to assess the applicability of our conclusion to other sites.

Predicting discharge in ungauged catchments or contaminant movement through soil requires knowledge of the distribution and spatial heterogeneity of hydrological soil properties.
Because hydrological soil information is not available at a European scale, we reclassified the Soil Geographical Database of Europe (SGDBE) at 1:1 million in a hydrological manner by adopting the Hydrology Of Soil Types (HOST) system developed in the UK. The HOST classification describes dominant pathways of water movement through soil and was related to the base flow index (BFI) of a catchment (the long-term proportion of base flow on total stream flow). In the original UK study, a linear regression of the coverage of HOST classes in a catchment explained 79% of BFI variability.
We found that a hydrological soil classification can be built based on the information present in the SGDBE. The reclassified SGDBE and the regression coefficients from the original UK study were used to predict BFIs for 103 catchments spread throughout Europe. The predicted BFI explained around 65% of the variability in measured BFI in catchments in Northern Europe, but the explained variance decreased from North to South. We therefore estimated new regression coefficients from the European discharge data and found that these were qualitatively similar to the original estimates from the UK. This suggests little variation across Europe in the hydrological effect of particular HOST classes, but decreasing influence of soil on BFI towards Southern Europe.
Our preliminary study showed that pedological information is useful for characterising soil hydrology within Europe and the long-term discharge regime of catchments in Northern Europe. Based on these results, we draft a roadmap for a refined hydrological classification of European soils.

Monitoring programs throughout America and Europe have demonstrated the common occurrence of herbicides in surface water. Nevertheless, mixtures are rarely taken into account in water quality regulation. Taking mixtures into account is only feasible if the water quality criteria (WQC) of the single compounds are derived by a common and consistent methodology, which overcomes differences in data quality without settling on the lowest common denominator but making best use of all available data. In this paper, we present a method of defining a risk quotient for mixtures of herbicides with a similar mode of action (RQ_m). Consistent and comparable WQC are defined for single herbicides as a basis for the calculation of the RQ_m. Derived from the concentration addition model, the RQ_m can be expressed as the sum of the ratios of the measured environmental concentration and the WQC for each herbicide. The RQ_m should be less than one to ensure an acceptable risk to aquatic life. This approach has the advantage of being easy to calculate and communicate, and is proposed as a replacement for the current limit of 0.1 μg/L for herbicides in Switzerland. We illustrate the proposed approach on the example of five commonly applied herbicides (atrazine, simazine, terbuthylazine, isoproturon, and diuron). Their risk profile, i.e., the RQ_m as a function of time for one exemplary river, clearly shows that the single compounds rarely exceeded their individual WQC. However, the contribution of peaks of different seasonally applied herbicides, whose application periods partially overlap, together with the continuously emitted herbicides from nonagricultural use, results in the exceedance of the RQ_m threshold value of one upon several occasions.

A pressurized liquid extraction (PLE) method was developed for the quantification of five sulfonamide antibiotics (sulfadiazine, sulfadimethoxine, sulfamethazine, sulfamethoxazole, and sulfathiazole) in aged soil samples. To account for sequestration effects the extraction was optimized using a composite grassland soil sample collected 11 days after the application of manure containing these substances. The optimized method uses a mixture of buffered water (pH 8.8) and acetonitrile (85:15) as solvent for the extraction at 200 degrees C and 100 bar during five min. The most important parameter for the extraction efficiency was temperature whereas the pH of the extraction solvent did hardly influence extraction efficiency between pH 4.1 and 8.8. A temperature increase from 100 to 200 degrees C improved the extraction efficiency up to a factor of six for aged residues in soils. In contrast, no temperature dependence was observed during short-term spike experiment. After 90 min exposure in these spike experiments we recovered 62-93% of the sulfonamides, except for sulfamethoxazole with only 41%. These percentages decreased substantially after a contact time of 6 and 17 days. The reasons for this decline remained unknown. Inter-day precision of the method was very satisfactory: relative standard deviations from the average were below 10%. Limits of detection for the extraction procedure were lower than 15 mu g/kg. The performance of the developed extraction method was demonstrated by measuring the decrease of sulfonamide concentration in a top soil after manure application. Within 3 months the concentration of sulfadiazine dropped from 450 to 150 mu g/kg.

Despite their common use in animal production the environmental fate of the veterinary sulfonamide antibiotics after excretion is only poorly understood. We performed irrigation experiments to investigate the transport of these substances with surface runoff on grassland. Liquid manure from pigs treated with sulfadimidine was spiked with sulfadiazine, sulfathiazole, the herbicide atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), and the conservative tracer bromide and spread onto eight plots. Four plots received the same amounts of the spiked substances in aqueous solution (controls). Apart from the application matrix we varied the time between application and irrigation. Manure increased the runoff volume up to six times compared with the controls. It seemed that manure enhanced the runoff by sealing the soil surface. On manured plots the relative antibiotic concentrations in runoff were higher than on the controls, reaching an average of 0.3% (sulfadiazine), 0.8% (sulfathiazole), and 1.4% (sulfadimidine) of the input concentrations after a 1-d contact time. The corresponding values on the controls were 0.16% for sulfadiazine and 0.08% for sulfathiazole. After 3 d, the maximum values on the manured plots were even higher, whereas they had fallen below the limit of quantification on the controls. As a consequence, the sulfonamide losses were 10 to 40 times larger on the manured plots. The relative mobility of the sulfonamides on the control plots followed the trend expected from their chromatographic separation but the opposite was found on the manured plots. Hence it is important to consider explicitly the physical and chemical effects of manure when assessing the environmental fate of sulfonamides.

Phosphorus (P) export from agricultural catchments is often event-driven and variable in time. Accordingly, a proper monitoring requires high-temporal resolution sampling during flow events. We report on a comparative study on the P export dynamics from two grassland catchments in Switzerland, where concentrations of dissolved reactive Phosphorus (DRP) have been monitored at a high temporal resolution for periods of 1.2 and 5 y, respectively. The data set is complemented by measurements on total P (TP), total dissolved P (TDP) and particulate P (PP) obtained from routine sampling ongoing since 1984 in both catchments. In one area, the high-temporal resolution monitoring revealed a pattern of the P export dynamic as expected from other studies. During flow events DRP concentrations usually increased significantly exceeding 1000 mg DRP m^-3 during peak flow, while the values remained low between 20 and 100 mg DRP m^-3 at base flow. This pattern was partially confirmed in the second catchment. The expected pattern was observed in 1998 and 1999 but was partially replaced by a new one for the following years. In the growing season, DRP only weakly increased with flow rate or remained almost constant. During flow events values larger than 300-400 mg DRP m^-3 were rare. In contrast to these relatively low peak flow concentrations, high values (200-300 mg m^-3) were recorded at base flow during the years 2000-2002. During the same period, DRP concentrations exhibited strong daily oscillations. Independent sampling and analytical control measurements verify the findings. Point sources like leaks from manure tanks could be ruled out based on the ammonia measurements. We suggest that biogeochemical processes within the brook are responsible for this change in the P export dynamics. Despite these changes in the pattern of the P export dynamic and ecological measures implemented on the farms no significant effect on the annual P loads could be observed during the last 10 years.

Many remote sensing applications, including those of future space missions, require accurate knowledge of the influence of topsoil structure on the water content as measured using L-band radiometry. We report on field-measured L-band (1.4 GHz) microwave emission from a bare soil. Of special interest in this work is the procedure used to transform remotely sensed data to soil water content and its comparability with time domain reflectometer (TDR) in situ measurements. Surface roughness of the soil was characterized on a millimeter scale using an optical measurement technique. Different models for interpreting the microwave signals in terms of the water content were investigated. The agreement between in situ water contents and surface water contents estimated with radiometry data using the Fresnel equation was found to be poor. A coherent layer model, with and without considering roughness effects, was tested to compare radiometrically measured and modeled soil reflectivities. The correspondence remained unsatisfactory, even when we considered a dielectric gradient fitted to the TDR profiles and surface roughness represented by a scattering model. We developed a new air-to-soil transition model, which includes dielectric mixing effects due to small-scale surface structures. This model considerably improved agreement between measured and modeled results. We conclude that small-scale structures of the topsoil cannot be neglected in interpreting L-band measurements.

Diffuse losses from agricultural fields are a major input source for herbicides in surface waters. In this and in a companion paper,we present the results of a comprehensive field study aimed at assessing the overall loss dynamics of three model herbicides (i.e., atrazine, dimethenamid, and metolachlor) from a small agricultural catchment (2.1 km²) and evaluating the relative contributions of various fields having different soil and topographical characteristics. An identical mixture of the three model herbicides as well as an additional pesticide for identification of a given field were applied within 12 h on 13 cornfields (total area ~12 ha), thus ensuring that the herbicides were exposed to identical meteorological conditions. After the simultaneous application, the concentrations of the compounds were monitored in the soils and at the outlets of three subcatchments containing between 4 and 5 cornfields each. Particular emphasis was placed on the two rain events that led to the major losses of the herbicides. The rank orders of herbicide dissipation in the soils and of the compound-specific mobilization into runoff were the same in all three subcatchments and were independent of the field characteristics. In Contrast, the field properties caused the relative losses from two subcatchments to differ by up to a factor of 56 during the most important event, whereas compound-specific differences of the three neutral herbicides caused the losses to vary only by a factor of 2 during the same event. The enormous spatial variability was mainly caused by factors influencing the fraction of rain that was lost to surface water by fast transport mechanisms. Thus, the key factors determining the spatially variable herbicide losses were the permeability of the soils, the topography, and the location of subsurface drainage systems. These results illustrate the large potential to reduce herbicide losses by avoiding application on risk areas.

Dye tracer experiments have often been used to study the prevailing flow regime, such as in investigating the role and extent of preferential flow of water. Flow patterns in two-dimensional profiles provide qualitative information on the infiltration regime but are difficult to analyze and compare quantitatively. The scope of this study was to develop a quantitative method to analyze the spatial distribution of the stained areas in vertical profiles, to identify differing transport mechanisms on the basis of the pattern information, and to analyze how the discriminated patterns correspond with soil properties and structure. Dye tracer infiltration experiments were performed on 25 plots at eight sites. The spatial distribution of the stained areas in vertical profiles was analyzed and compared using digital image processing. We first split the flow patterns into similarly stained horizontal layers based on the width distribution of stained areas. All of these layers identified in the flow patterns of all 25 plots were then partitioned into groups of layers with similar patterns by hierarchical clustering. The sequence of layers found in the pattern was finally interpreted with respect to transport mechanisms and qualitatively compared with the sequence of morphological layers observed in the soil profiles. The obtained classification reliably distinguished between zones of homogeneous infiltration and zones of preferential flow, but also between zones of narrow stained structures and zones of lateral spreading (e.g., sand or gravel lenses). Dye coverage and mean width of stained structures were the most indicative factors for the different clusters. We often found an agreement between the sequences of layers found in the flow patterns and the soil horizons. However, in all profiles we observed layers in the flow patterns that did not correspond to textural and structural layers observed in the filed. It seems that knowing the pedological horizons is important but not sufficient to understand the observed flow patterns. Since the flow pattern in a given layer always depends on the overlying soil layers, similarly textured soil layers do not necessarily exhibit equal patterns. However, soil layers with a given textural sequence (e.g., fine-course-fine) are reflected by typical flow patterns.

Fresh applications of phosphorus (P) may cause 'incidental' losses of dissolved and particulate P forms in land runoff when rainfall interacts directly with fertilizers and manures which are spread, or excreted, onto the soil surface. Research indicates that when incidental P losses (IPL) occur, they often make the dominant (50-98%) contribution to measured P loads in surface and sub-surface runoff from field plots, with increased risk of eutrophication where P-enriched runoff is routed directly to the watercourse. Rates of P loss are temporally and spatially very variable (<1 to 25% of total P applied) depending on the amount of P applied; the P release properties of the materials applied (% P extractable in water), the timing of storm events after application and the amounts of runoff generated. Large P applications left on the surface of wet, frozen, compacted, and intensively underdrained soils in high rainfall areas are particularly vulnerable to IPL. Concentrations of P in runoff are often greatest during the first storm event following P application, but can remain high for several weeks, or even months after application. Catchment scale impacts are more difficult to quantify due to the effects of dilution with runoff from fields without IPL, and the contributions of P from other sources. Approaches to predicting IPL are discussed and need to be improved in order to assess the contribution of IPL to catchment P loads in river basin management planning. Strategies to control IPL should focus on adoption of more sensitive management practices in fields with a high risk of rapid runoff or preferential flow, and are likely to very effective.

Phosphorus is the limiting factor for primary production in most freshwater ecosystems. In many areas, diffuse P losses from intensively cultivated land cause severe eutrophication of surface waters. We investigated the P export from two drainage systems under intensively used grassland in a catchment of the Swiss Plateau. Flow rate and nutrient concentrations were measured with a high temporal resolution during discharge events. During most flow peaks, P concentrations strongly increased with increasing flow rates. Concentrations of soluble-reactive P (SRP) reached up to 155 µmol L⁻¹. Phosphorus was mainly transported as soluble-reactive and particulate P. Organic P compounds, as well as P associated with colloids between 0.05 and 0.45 µm in effective diameter, were of minor importance. Estimated P loads from the drainage systems were 227 g SRP ha⁻¹ within a period of 2.5 mo at site I and 1290 g ha⁻¹ during 6 mo at site II. Estimation uncertainty was large (±21 and ±36% for the two sites, respectively) due to the weak correlation between discharge and concentration for all data from a given site. Water-extractable P in the soil was concentrated in the uppermost layer of the profiles or, for short periods after spreading of manure, deposited on the vegetation. The discharge-concentration relationship indicated that P was transported through preferential flow paths extending from close to the surface to the drains. Sprinkling experiments with a blue dye confirmed this conclusion. At one site, we observed preferential flow in a downhill direction within the saturated zone.