Linking chemical surface water monitoring and pesticide regulation in selected European countries.

The progress in chemical analytics and understanding of pesticide dynamics in surface waters allows establishing robust data on compounds with frequent exceedances of quality standards. The current chemical, temporal, and spatial coverage of the pesticide monitoring campaigns differs strongly between European countries. A questionnaire revealed differences in monitoring strategies in seven selected European countries; Nordic countries prioritize temporal coverage, while others focus on spatial coverage. Chemical coverage has increased, especially for non-polar classes like synthetic pyrethroids. Sweden combines monitoring data with agricultural practices for derived quantities, while the Netherlands emphasizes spatial coverage to trace contamination sources. None of the EU member states currently has established a process for linking chemical surface water monitoring data with regulatory risk assessment, while Switzerland has recently established a legally defined feedback loop. Due to their design and objectives, most strategies do not capture concentration peaks, especially 2-week composite samples, but also grab samples. Nevertheless, for substances that appear problematic in many data sets, the need for action is evident even without harmonization of monitoring programs. Harmonization would be beneficial, however, for cross-national assessment including risk reduction measures.

Incorporation of sediment- and soil-specific aspects in the Criteria for Reporting and Evaluating Ecotoxicity Data (CRED).

In environmental risk assessment either for registration purposes or for retrospective assessments of monitoring data, the hazard assessment is predominantly based on effect data from ecotoxicity studies. Most regulatory frameworks require studies used for risk assessment to be evaluated for reliability and relevance. Historically, the Klimisch methodology was used in many regulatory procedures where reliability needed to be evaluated. More recently, the Criteria for Reporting and Evaluating Ecotoxicity Data (CRED) have been developed for aquatic ecotoxicity studies, providing more detailed guidance on the evaluation and reporting of not only the reliability but also the relevance of a scientific study. Here, we discuss the application of the CRED methodology for assessing sediment and soil ecotoxicity studies, addressing important sediment- and soil-specific criteria that should be included as part of the CRED evaluation system. We also provide detailed recommendations for the design and reporting of sediment and soil toxicity studies that can be used by scientists and researchers wishing to contribute ecotoxicological data for effect assessments carried out within regulatory frameworks. Integr Environ Assess Manag 2024;20:2162-2174. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Environmental Risk of Pesticides for Fish in Small- and Medium-Sized Streams of Switzerland.

This study assessed the acute and chronic risk of pesticides, singly and as mixtures, for fish using comprehensive chemical data of four monitoring studies conducted in small- and medium-sized streams of Switzerland between 2012 and 2018. Pesticides were ranked based on single substance risk quotients and relative contribution to mixture risk. Concentrations of the pyrethroid insecticides, λ-cyhalothrin, cypermethrin and deltamethrin, and the fungicides, carbendazim and fenpropimorph, posed acute or chronic single substance risks. Risk quotients of eighteen additional pesticides were equal or greater than 0.1, and thirteen of those contributed ≥30% to mixture risk. Relatively few substances dominated the mixture risk in most water samples, with chronic and acute maximum cumulative ratios never exceeding 5 and 7, respectively. A literature review of toxicity data showed that concentrations of several pesticides detected in Swiss streams were sufficient to cause direct sublethal effects on fish in laboratory studies. Based on the results of our study, we conclude that pesticides detected in Swiss streams, especially pyrethroid insecticides, fungicides and pesticide mixtures, pose a risk to fish health and can cause direct sublethal effects at environmental concentrations. Sensitive life stages of species with highly specialized life history traits may be particularly vulnerable; however, the lack of toxicity data for non-model species currently prevents a conclusive assessment across species.

Effect Modeling Quantifies the Difference Between the Toxicity of Average Pesticide Concentrations and Time-Variable Exposures from Water Quality Monitoring.

Synthetic chemicals are frequently detected in water bodies, and their concentrations vary over time. Water monitoring programs typically employ either a sequence of grab samples or continuous sampling, followed by chemical analysis. Continuous time-proportional sampling yields the time-weighted average concentration, which is taken as proxy for the real, time-variable exposure. However, we do not know how much the toxicity of the average concentration differs from the toxicity of the corresponding fluctuating exposure profile. We used toxicokinetic-toxicodynamic models (invertebrates, fish) and population growth models (algae, duckweed) to calculate the margin of safety in moving time windows across measured aquatic concentration time series (7 pesticides) in 5 streams. A longer sampling period (14 d) for time-proportional sampling leads to more deviations from the real chemical stress than shorter sampling durations (3 d). The associated error is a factor of 4 or less in the margin of safety value toward underestimating and an error of factor 9 toward overestimating chemical stress in the most toxic time windows. Under- and overestimations occur with approximate equal frequency and are very small compared with the overall variation, which ranged from 0.027 to 2.4 × 1010 (margin of safety values). We conclude that continuous, time-proportional sampling for a period of 3 and 14 d for acute and chronic assessment, respectively, yields sufficiently accurate average concentrations to assess ecotoxicological effects. Environ Toxicol Chem 2020;39:2158-2168. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Temporal variation of pesticide mixtures in rivers of three agricultural watersheds during a major drought in the Western Cape, South Africa.

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.

Revising Environmental Quality Standards: Lessons Learned.

An environmental quality standard (EQS) is a threshold value applied in regulatory monitoring for retrospective environmental risk assessment. However, an EQS may vary with time and between countries with shared water bodies, challenging coherent risk management. This study aimed to analyze the underlying reasons for changes in EQS values following a revision of previously derived EQSs for 62 substances. Relevant data were retrieved from publicly accessible databases, available literature, registration dossiers, and, in some cases, provided by manufacturers. Ecotoxicological data were assessed regarding reliability and relevance. As in previous studies, EQS derivation followed the European Union guideline. Overall, 61 annual average EQSs (AA-EQS) and 58 maximum acceptable concentration EQSs (MAC-EQS) were derived. Size and completeness of data sets generally increased due to the revision. AA-EQSs increased in 13 cases and decreased in 21 cases. MAC-EQSs increased in 22 cases and decreased in 11 cases. Most EQSs were derived using the deterministic assessment factor (AF) method. The number of substances for which EQSs were derived probabilistically by reference to the species sensitivity distribution (SSD) method increased from 2 to 5 AA-EQSs and from 6 to 11 MAC-EQSs. For AA-EQS derivation, AFs were reduced in 14 cases and increased in 6 cases. For MAC-EQS derivation, AFs were reduced in 9 cases and increased in 2 cases. Results demonstrate that the revisions did not generally lead to either lower or higher EQSs. The majority of EQSs (>93%) changed less than 10-fold. Clearly, EQSs based on small or incomplete data sets with large AFs were more prone to considerable changes in their numeric values when revised than EQSs based on SSDs. Thus, revision can reduce uncertainty and increase robustness of an EQS. In this study, however, available data continued to be insufficient to construct SSDs for the majority of substances. This was mostly due to a lack of reliable data. Integr Environ Assess Manag 2019;00:1-13. © 2019 SETAC.

Pesticide Risks in Small Streams-How to Get as Close as Possible to the Stress Imposed on Aquatic Organisms.

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.

Aquatic exposures of chemical mixtures in urban environments: Approaches to impact assessment.

Urban regions of the world are expanding rapidly, placing additional stress on water resources. Urban water bodies serve many purposes, from washing and sources of drinking water to transport and conduits for storm drainage and effluent discharge. These water bodies receive chemical emissions arising from either single or multiple point sources, diffuse sources which can be continuous, intermittent, or seasonal. Thus, aquatic organisms in these water bodies are exposed to temporally and compositionally variable mixtures. We have delineated source-specific signatures of these mixtures for diffuse urban runoff and urban point source exposure scenarios to support risk assessment and management of these mixtures. The first step in a tiered approach to assessing chemical exposure has been developed based on the event mean concentration concept, with chemical concentrations in runoff defined by volumes of water leaving each surface and the chemical exposure mixture profiles for different urban scenarios. Although generalizations can be made about the chemical composition of urban sources and event mean exposure predictions for initial prioritization, such modeling needs to be complemented with biological monitoring data. It is highly unlikely that the current paradigm of routine regulatory chemical monitoring alone will provide a realistic appraisal of urban aquatic chemical mixture exposures. Future consideration is also needed of the role of nonchemical stressors in such highly modified urban water bodies. Environ Toxicol Chem 2018;37:703-714. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

The influence of particles on bioavailability and toxicity of pesticides in surface water.

Environmental risk assessment is an essential part of the approval process for pesticides. Exposure concentrations are compared with ecotoxicological data obtained from standardized laboratory studies and, if available, from field studies to determine the risk of a substance or formulation for aquatic communities. Predicted concentrations in surface waters are derived using, for example, the European FOrum for the Co-ordination of pesticide fate models and their USe (FOCUS) or the German Exposit models, which distinguish between exposure to dissolved and particle-associated pesticide concentrations, because the dissolved concentration is thought to be the best predictor of bioavailability and toxicity. Water and particle-associated concentrations are estimated based on the organic carbon-water partitioning coefficient (KOC ). This review summarizes published information on the influence of natural suspended solids on bioavailability and toxicity of pesticides to aquatic organisms (algae, invertebrates and fish), and the value of log KOC and log KOW (octanol-water coefficient) as sole predictors of the bioavailable fraction is discussed. The information showed that: 1) the quality and origin of suspended solids played an important role in influencing pesticide bioavailability and toxicity; 2) a decrease in toxicity due to the presence of suspended solids was shown only for pyrethroid insecticides with log KOW greater than 5, but the extent of this reduction depended on particle concentration and size, and potentially also on the ecotoxicological endpoint; 3) for pesticides with a log KOW less than 3 (e.g., triazines, carbamates, and organophosphates), the impact of particles on bioavailability and toxicity is small and species dependent; and 4) pesticide bioavailability is greatly influenced by the test species and their physiology (e.g., feeding behavior or digestion). We conclude that exposure of aquatic organisms to pesticides and environmental risk of many pesticides might be underestimated in prospective risk assessment, when predicted environmental concentration is estimated based on the KOC of a compound. Integr Environ Assess Manag 2017;13:585-600. © 2016 SETAC.

Assessing the reliability of ecotoxicological studies: An overview of current needs and approaches.

In general, reliable studies are well designed and well performed, and enough details on study design and performance are reported to assess the study. For hazard and risk assessment in various legal frameworks, many different types of ecotoxicity studies need to be evaluated for reliability. These studies vary in study design, methodology, quality, and level of detail reported (e.g., reviews, peer-reviewed research papers, or industry-sponsored studies documented under Good Laboratory Practice [GLP] guidelines). Regulators have the responsibility to make sound and verifiable decisions and should evaluate each study for reliability in accordance with scientific principles regardless of whether they were conducted in accordance with GLP and/or standardized methods. Thus, a systematic and transparent approach is needed to evaluate studies for reliability. In this paper, 8 different methods for reliability assessment were compared using a number of attributes: categorical versus numerical scoring methods, use of exclusion and critical criteria, weighting of criteria, whether methods are tested with case studies, domain of applicability, bias toward GLP studies, incorporation of standard guidelines in the evaluation method, number of criteria used, type of criteria considered, and availability of guidance material. Finally, some considerations are given on how to choose a suitable method for assessing reliability of ecotoxicity studies. Integr Environ Assess Manag 2017;13:640-651. © 2016 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Pesticides drive risk of micropollutants in wastewater-impacted streams during low flow conditions.

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.

Amphibians and plant-protection products: what research and action is needed?

BACKGROUND: The majority of Swiss amphibians are threatened. There is a range of factors which have been discussed as possible causes for their decline, including plant protection products (PPPs). RESULTS: The influence of PPPs on amphibian populations has not yet been studied to any great extent, neither for active ingredients nor for the wetting agents, breakdown products or tank mixtures. A further topic of discussion was how to better protect amphibians by reducing their exposure to PPPs in agricultural fields. CONCLUSION: Experts at a workshop concluded that further research is needed.

The 2015 Annual Meeting of SETAC German Language Branch in Zurich (7-10 September, 2015): Ecotoxicology and environmental chemistry-from research to application.

This report provides a brief review of the 20th annual meeting of the German Language Branch of the Society of Environmental Toxicology and Chemistry (SETAC GLB) held from September 7th to 10th 2015 at ETH (Swiss Technical University) in Zurich, Switzerland. The event was chaired by Inge Werner, Director of the Swiss Centre for Applied Ecotoxicology (Ecotox Centre) Eawag-EPFL, and organized by a team from Ecotox Centre, Eawag, Federal Office of the Environment, Federal Office of Agriculture, and Mesocosm GmbH (Germany). Over 200 delegates from academia, public agencies and private industry of Germany, Switzerland and Austria attended and discussed the current state of science and its application presented in 75 talks and 83 posters. In addition, three invited keynote speakers provided new insights into scientific knowledge 'brokering', and-as it was the International Year of Soil-the important role of healthy soil ecosystems. Awards were presented to young scientists for best oral and poster presentations, and for best 2014 master and doctoral theses. Program and abstracts of the meeting (mostly in German) are provided as Additional file 1.

Multiple stressor effects in Chlamydomonas reinhardtii--toward understanding mechanisms of interaction between effects of ultraviolet radiation and chemical pollutants.

The effects of chemical pollutants and environmental stressors, such as ultraviolet radiation (UVR), can interact when organisms are simultaneously exposed, resulting in higher (synergistic) or lower (antagonistic) multiple stressor effects than expected based on the effects of single stressors. Current understanding of interactive effects is limited due to a lack of mechanism-based multiple stressor studies. It has been hypothesized that effect interactions may generally occur if chemical and non-chemical stressors cause similar physiological effects in the organism. To test this hypothesis, we exposed the model green alga Chlamydomonas reinhardtii to combinations of UVR and single chemicals displaying modes of action (MOA) similar or dissimilar to the impact of UVR on photosynthesis. Stressor interactions were analyzed based on the independent action model. Effect interactions were found to depend on the MOA of the chemicals, and also on their concentrations, the exposure time and the measured endpoint. Indeed, only chemicals assumed to cause effects on photosynthesis similar to UVR showed interactions with UVR on photosynthetic yield: synergistic in case of Cd(II) and paraquat and antagonistic in case of diuron. No interaction on photosynthesis was observed for S-metolachlor, which acts dissimilarly to UVR. However, combined effects of S-metolachlor and UVR on algal reproduction were synergistic, highlighting the importance of considering additional MOA of UVR. Possible mechanisms of stressor effect interactions are discussed.

How a complete pesticide screening changes the assessment of surface water quality.

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.

Critical issues in using the common mixture toxicity models concentration addition or response addition on species sensitivity distributions: a theoretical approach.

The risk of chemical mixtures to ecosystems is often assessed by applying the model of concentration addition or response addition combined with species sensitivity distribution (SSD) curves. Mixture effect predictions have been shown to be consistent only when these models are applied for a single species, however, and not with several species simultaneously aggregated to SSDs. The more stringent procedure for mixture risk assessment would hence be to apply first the concentration addition or response addition models to each species separately and, in a second step, to combine the results to construct an SSD for a mixture. Unfortunately, this methodology is not applicable in most cases because the large data sets it requires are usually unavailable. Based on theoretical data sets generated, the authors aimed to characterize the difference that can exist between these 2 methodologies. Results show that the use of concentration addition on SSD directly may lead to underestimations of the mixture concentration affecting 5% or 50% of species, especially when substances present a large standard deviation in ecotoxicity data constructing their SSD. The application of response addition can lead to over- or underestimations, depending mainly on the slope of the dose­response curves of the individual species. When assessing the risk of mixtures, one must therefore keep in mind this source of error when applying concentration addition or response addition to SSDs directly.