Development of a solubility parameter calculation-based method as a complementary tool to traditional techniques for indoor dust microplastic determination and risk assessment.

Herein, a method based on solubility parameter calculation was first used to analyze microplastics in indoor dust. The limit of quantification (LOQ) reached 0.2 mg/g, and the result of reference material SRM 2585 (n = 3) was 14.8 mg/g ± 1.8 %, suggesting satisfying sensitivity and precision. Recoveries of spiking experiments were > 80 % with no obvious matrix interferences observed, except ethylene propylene diene monomer (EPDM) MPs. Further, 69 indoor dust samples were analyzed to verify the method and to assess exposure scenarios for graduate students in Tianjin, China. EPDM was identified in an indoor environment for the first time as the second most widely detected type after PET in this work. The mass-based result is complementary to the outcomes from thermogravimetric analysis-gas chromatography-mass spectrometry and laser direct infrared imaging. Significant correlations were found between total organic carbon (TOC), microplastics, and BDE-209 concentrations, indicating microplastics important contaminant vectors in indoor dust. Dormitory stays and PET contributed the most to health risks among the three exposure scenarios and detected four polymers, respectively. This work provides an approach with the potential for the standardized determination of microplastics in complex environmental matrices and reveals exposure characteristics of indoor dust microplastics.

A novel approach for the assessment of invertebrate behavior and its use in behavioral ecotoxicology.

Sublethal effects are becoming more relevant in ecotoxicological test methods due to their higher sensitivity compared to lethal endpoints and their preventive nature. Such a promising sublethal endpoint is the movement behavior of invertebrates which is associated with the direct maintenance of various ecosystem processes, hence being of special interest for ecotoxicology. Disturbed movement behavior is often related to neurotoxicity and can affect drift, mate-finding, predator avoidance, and therefore population dynamics. We show the practical implementation of the ToxmateLab, a new device that allows monitoring the movement behavior of up to 48 organisms simultaneously, for behavioral ecotoxicology. We quantified behavioral reactions of Gammarus pulex (Amphipoda, Crustacea) after exposure to two pesticides (dichlorvos and methiocarb) and two pharmaceuticals (diazepam and ibuprofen) at sublethal, environmentally relevant concentrations. We simulated a short-term pulse contamination event that lasted 90 min. Within this short test period, we successfully identified behavioral patterns that were most pronounced upon exposure to the two pesticides: Methiocarb initially triggered hyperactivity, after which baseline behavior was restored. On the other hand, dichlorvos induced hypoactivity starting at a moderate concentration of 5 µg/L - a pattern we also found at the highest concentration of ibuprofen (10 µg/L). An additional acetylcholine esterase inhibition assay revealed no significant impact of the enzyme activity that would explain the altered movement behavior. This suggests that in environmentally realistic scenarios chemicals can induce stress - apart from mode-of-action - that affects non-target organisms' behavior. Overall, our study proves the practical applicability of empirical behavioral ecotoxicological approaches and thus represents a next step towards routine practical use.

Replacing animal-derived components in in vitro test guidelines OECD 455 and 487.

The evaluation of single substances or environmental samples for their genotoxic or estrogenic potential is highly relevant for human- and environment-related risk assessment. To examine the effects on a mechanism-specific level, standardized cell-based in vitro methods are widely applied. However, these methods include animal-derived components like fetal bovine serum (FBS) or rat-derived liver homogenate fractions (S9-mixes), which are a source of variability, reduced assay reproducibility and ethical concerns. In our study, we evaluated the adaptation of the cell-based in vitro OECD test guidelines TG 487 (assessment of genotoxicity) and TG 455 (detection of estrogenic activity) to an animal-component-free methodology. Firstly, the human cell lines A549 (for OECD TG 487), ERα-CALUX® and GeneBLAzer™ ERα-UAS-bla GripTite™ (for OECD TG 455) were investigated for growth in a chemically defined medium without the addition of FBS. Secondly, the biotechnological S9-mix ewoS9R was implemented in comparison to the induced rat liver S9 to simulate in vivo metabolism capacities in both OECD test guidelines. As a model compound, Benzo[a]pyrene was used due to its increased genotoxicity and endocrine activity after metabolization. The metabolization of Benzo[a]Pyrene by S9-mixes was examined via chemical analysis. All cell lines (A549, ERα-CALUX® and GeneBLAzer™ Erα-UAS-bla GripTite™) were successfully cultivated in chemically defined media without FBS. The micronucleus assay could not be conducted in chemically defined medium due to formation of cell clusters. The methods for endocrine activity assessment could be conducted in chemically defined media or reduced FBS content, but with decreased assay sensitivity. The biotechnological ewoS9R showed potential to replace rat liver S9 in the micronucleus in FBS-medium with A549 cells and in the ERα-CALUX® assay in FBS- and chemically defined medium. Our study showed promising steps towards an animal-component free toxicity testing. After further improvements, the new methodology could lead to more reproducible and reliable results for risk assessment.

What is the spatial-temporal behavior of a low, medium and high adsorptive compound in two contrasting natural sediments in OECD 218/219 test systems?

Artificial sediment used in studies according to OECD 218/219 (Sediment Water Chironomid Toxicity Test Using Spiked Sediment/Water) does not necessarily mirror the characteristics of natural sediments. To investigate the influence of sediment characteristics on the spatial-temporal behaviors of bixafen (KfOM = 2244 mL/g), fluopyram (KfOM = 162 mL/g) and N,N-dimethylsulfamide (KfOM ≈ 0 mL/g), experiments according to OECD 218/219 with two contrasting natural sediments were conducted. The silt loam sediment provided a high content of organic matter (OM) (13.1%), while the OM (0.45%) of the sandy sediment was low. Diffusion into (OECD 219) or out (OECD 218) of the sediment was dependent on the extent of adsorption, which is linked to the model compounds ́ adsorption affinities and the sediments ́ OM. Consequently, N,N-dimethylsulfamide showed unhindered mobility in each experimental set up, while the high adsorption affinities of fluopyram and bixafen limited the diffusion in the respective sediments. Therefore, in experiments with the silt loam sediment, both compounds revealed a limited mobility and either accumulated in the top 5 mm of the sediment (OECD 219) or remained homogenously distributed over the sediment depth (OECD 218). A greater mobility was observed within the sandy sediment.The influence of OM as found in a study using artificial sediment could be confirmed. Moreover, the applicability of a TOXSWA model was reassured to predict the measured concentrations at different sediment depths. TOXSWA is used in the regulatory exposure assessment to simulate the behavior of pesticides in surface waters. Calibration of three driving input parameters by inverse modelling (diffusion-, adsorption coefficient and OM) revealed no potential for improvement. The core sampling technique used and the model may contribute to a more realistic determination of concentration to which the Chironomid larvae are exposed to. This applies to water sediment test systems where the test organisms do not evenly inhabit the sediment.

A Novel Multispecies Toxicokinetic Modeling Approach in Support of Chemical Risk Assessment.

Standardized laboratory tests with a limited number of model species are a key component of chemical risk assessments. These surrogate species cannot represent the entire diversity of native species, but there are practical and ethical objections against testing chemicals in a large variety of species. In previous research, we have developed a multispecies toxicokinetic model to extrapolate chemical bioconcentration across species by combining single-species physiologically based toxicokinetic (PBTK) models. This "top-down" approach was limited, however, by the availability of fully parameterized single-species models. Here, we present a "bottom-up" multispecies PBTK model based on available data from 69 freshwater fishes found in Canada. Monte Carlo-like simulations were performed using statistical distributions of model parameters derived from these data to predict steady-state bioconcentration factors (BCFs) for a set of well-studied chemicals. The distributions of predicted BCFs for 1,4-dichlorobenzene and dichlorodiphenyltrichloroethane largely overlapped those of empirical data, although a tendency existed toward overestimation of measured values. When expressed as means, predicted BCFs for 26 of 34 chemicals (82%) deviated by less than 10-fold from measured data, indicating an accuracy similar to that of previously published single-species models. This new model potentially enables more environmentally relevant predictions of bioconcentration in support of chemical risk assessments.

Comparative toxicity assessment of in situ burn residues to initial and dispersed heavy fuel oil using zebrafish embryos as test organisms.

In situ burning (ISB) is discussed to be one of the most suitable response strategies to combat oil spills in extreme conditions. After burning, a highly viscous and sticky residue is left and may over time pose a risk of exposing aquatic biota to toxic oil compounds. Scientific information about the impact of burn residues on the environment is scarce. In this context, a comprehensive ISB field experiment with approx. 1000L IFO 180 was conducted in a fjord in Greenland. The present study investigated the toxicity of collected ISB residues to early life stages of zebrafish (Danio rerio) as a model for potentially exposed pelagic organisms. The toxicity of ISB residues on zebrafish embryos was compared with the toxicity of the initial (unweathered) IFO 180 and chemically dispersed IFO 180. Morphological malformations, hatching success, swimming behavior, and biomarkers for exposure (CYP1A activity, AChE inhibition) were evaluated in order to cover the toxic response on different biological organization levels. Across all endpoints, ISB residues did not induce greater toxicity in zebrafish embryos compared with the initial oil. The application of a chemical dispersant increased the acute toxicity most likely due to a higher bioavailability of dissolved and particulate oil components. The results provide insight into the adverse effects of ISB residues on sensitive life stages of fish in comparison with chemical dispersant application.

Ecological risk assessment of fifty pharmaceuticals and personal care products (PPCPs) in Chinese surface waters: A proposed multiple-level system.

Interest in the risks posed by trace concentrations of pharmaceuticals and personal care products (PPCPs) in surface waters is increasing, particularly with regard to potential effects of long-term, low-dose exposures of aquatic organisms. In most cases, the actual studies on PPCPs were risk assessments at screening-level, and accurate estimates were scarce. In this study, exposure and ecotoxicity data of 50 PPCPs were collected based on our previous studies, and a multiple-level environmental risk assessment was performed. The 50 selected PPCPs are likely to be frequently detected in surface waters of China, with concentrations ranging from the ng L-1 to the low-g L-1, and the risk quotients based on median concentrations ranged from 2046 for nonylphenol to 0 for phantolide. A semi-probabilistic approach screened 33 PPCPs that posed potential risks to aquatic organisms, among which 15 chemicals (nonylphenol, sulfamethoxazole, di (2-ethylhexyl) phthalate, 17ß-ethynyl estradiol, caffeine, tetracycline, 17ß-estradiol, estrone, dibutyl phthalate, ibuprofen, carbamazepine, tonalide, galaxolide, triclosan, and bisphenol A) were categorized as priority compounds according to an optimized risk assessment, and then the refined probabilistic risk assessment indicated 12 of them posed low to high risk to aquatic ecosystem, with the maximum risk products ranged from 1.54% to 17.38%. Based on these results, we propose that the optimized risk assessment was appropriate for screening priority contaminants at national scale, and when a more accurate estimation is required, the refined probability risk assessment is useful. The methodology and process might provide reference for other research of chemical evaluation and management for rivers, lakes, and sea waters.

Toxicity of 10 organic micropollutants and their mixture: Implications for aquatic risk assessment.

Micropollutants, as a serious water pollution issue, raise considerable toxicological concerns, particularly when present as components of complex mixtures. Due to the interactions of environmental pollution components (contaminant), the micropollutant problem is increasingly complex, thus, water quality of organic chemical contamination assessed substance-by-substance might lead to underestimation in aquatic environmental risk assessment. To assess the aquatic environmental risk of micropollutants mixture, a total of 10 organic micropollutants were selected and analysed by an approach of integration of literature data, laboratory experiments and prediction techniques. The experiment results showed that all 10 micropollutants were capable of causing toxicity in zebrafish embryos, aquatic invertebrates and algae with the LC50 (50% lethal concentration) values from 1.14 mg/L to 14.37 mg/L. Triclosan, carbamazepine, diazinon and diuron were the most hazardous compounds in the Danube River and the Rhine River. The artificial mixture presented a strong antagonistic relationship, which demonstrated an independent action (IA) model of the mixture. Based on the observed toxicity data, the risk quotients (RQs) of environmental mixtures of the Danube River and the Rhine River were extrapolated. It can be concluded that the micropollutant mixture may pose a potential risk for aquatic ecosystems with the present environmentally measured concentrations in the Danube River and Rhine River. Mixture risk assessment results suggested that the toxicity of studied chemicals might be induced by dissimilar actions, which is in agreement with the mixture toxicity prediction of the IA model. The observed findings could be useful to establish an overview of the pressures, vision, measures and expectations for hazardous substances pollution, which can help in making to informed decisions to reduce the concentration and bioactive fraction of pollutants.

Optimization of screening-level risk assessment and priority selection of emerging pollutants - The case of pharmaceuticals in European surface waters.

Pharmaceuticals in surface waters have raised significant concern in recent years for their potential environmental effects. This study identified that at present a total of 477 substances (including 66 metabolites and transformation products) have been analyzed in European surface waters. Around 60% (284) of these compounds belonging to 16 different therapeutic groups were positively detected in one or more of 33 European countries. To conveniently and effectively prioritize potential high-risk compounds, an optimized method that considers the frequency of concentrations above predicted no effects levels was developed on the basis of the traditional method, and it was then used to identify and screen candidate priority pollutants in European surface waters. The results proved the feasibility and advantages of the optimized method. Pharmaceuticals detected in European surface waters were classified into 5 categories (high, moderate, endurable, negligible and safe) depending on their potential environmental effects and the distribution of pharmaceuticals. Circa 9% (45 out of 477) analyzed compounds showed a potential environmental risk to aquatic ecosystems. Among these 45 compounds, 12 compounds were indicated to have high environmental risk in aquatic environments, while 17 and 7 compounds showed moderate and small-scale environmental risks, respectively.

Approach for analytical characterization and toxicological assessment of ozonation products in drinking water on the example of acesulfame.

The monitoring and control of drinking water quality is generally important as it significantly contributes to the health of the population. In this context, particular attention has to be paid to the use of treatment techniques during drinking water treatment. It is known that the formation of reaction products (transformation products) has to be taken into account when oxidizing agents such as ozone are used. Different transformation products are classified as critical to health and require analytical examination. The risk assessment for previously unknown transformation products can be difficult as far as not all transformation products are present as single substances or the individual substances are not present in a sufficient high concentration or cannot be isolated from the original solution. The aim of this work is to show exemplarily the identification and quantification of ozonation products (OPs) after ozonation and their toxicological characterization, using the artificial sweetener acesulfame. It was shown that OPs can be fully characterized using ion chromatography in combination with different detection systems. A major OP could be recovered as a pure substance by crystallization and direct genotoxicological testing was possible without previous enrichment processes. Acesulfame samples of different concentrations in ultrapure and in drinking water after ozonation were tested in several genotoxicity tests. These tests revealed genotoxic effects of acesulfame after ozonation in ultrapure water in several genotoxicological test systems (micronucleus test, umu test, Ames-fluctuation-test and comet assay). In contrast, the crystallized ozonation product OP168 did not show any positive effects. Therefore, it seems likely that the observed effect was caused by the second major product OP170. However, a sufficiently large amount of analytically pure substance OP170 could not be obtained. It was also shown that the rate of the OP170 formation in drinking water is significantly lower than in ultrapure water and that ozonation in drinking water did not induce genotoxic effects.

Marine microplastics bound dioxin-like chemicals: Model explanation and risk assessment.

Microplastics have become one of the most pervasive emerging pollutants in the marine environment because of their wide occurrence and high sorption ability for hydrophobic organic contaminants (HOCs). Among the associated HOCs, dioxin-like chemicals (DLCs) can pose severe health risks; however, information on effects of microplastics bound DLCs is lacking. To fill this knowledge gap, this study integrated chemical analysis and in vitro bioassays to elucidate the potential dioxin-like effects of microplastics bound DLCs. Chemical analysis results demonstrated that styrofoams possessed significantly greater DLCs than other coastal or open ocean plastic particles. This was probably due to the presence of additives and greater sorption ability of expanded polystyrene. However, styrofoams did not show as strong dioxin-like effects as predicted by the bioanalysis equivalent model in bioassays. This could be attributed to the decreased DLC bioavailability and increased competition with the presence of styrene oligomers. Besides, bioassay results also demonstrated that aging increased the associated DLC concentrations, since extra sorption from surrounding environment occurred during prolonged retention periods. Finally, it was estimated that the leaching of DLCs could induce dioxin-like effects in marine organisms under 100% (11/11) and 18% (2/11) scenarios for aged pellets and styrofoams through aqueous or dietary exposures.

Integrated zebrafish-based tests as an investigation strategy for water quality assessment.

Water pollution risks to human health and the environment are emerging as serious concerns in the European Union and worldwide. With the aim to achieve good ecological and chemical status of all European water bodies, the "European Water Framework Directive" (WFD) was enacted. With the framework, bioanalytical techniques have been recognized as an important aspect. However, there are limitations to the application of bioassays directly for water quality assessment. Such approaches often fail to identify pollutants of concern, since the defined priority and monitored pollutants often fail to explain the observed toxicity. In this study, we integrated an effect-based risk assessment with a zebrafish-based investigation strategy to evaluate water sample extracts and fractions collected from the Danube. Four tiered bioassays were implemented, namely RNA-level gene expression assay, protein-level ethoxyresorufin-O-deethylase (EROD) assay, cell-level micronucleus assay and organism-level fish embryo test (FET). The results show that teratogenicity and lethality during embryonic development might be induced by molecular or cellular damages mediated by the aryl hydrocarbon receptor (AhR) -mediated activity, estrogenic activity and genotoxic activity. With the combination of high-throughput fractionation, this effect-based strategy elucidated the major responsible mixtures of each specific toxic response. In particularly, the most toxic mixture in faction F4, covering a log Kow range from 2.83 to 3.42, was composed by 12 chemicals, which were then evaluated as a designed mixture. Our study applied tiered bioassays with zebrafish to avoid interspecies differences and highlights effect-based approaches to address toxic mixtures in water samples. This strategy can be applied for large throughput screenings to support the main toxic compounds identification in water quality assessment.

Simulation-based assessment of the impact of fertiliser and herbicide application on freshwater ecosystems at the Three Gorges Reservoir in China.

Dams have profound impacts on river ecosystems, amongst them inundation of land, altered dynamics of the water body or uprising reservoir backwaters influencing tributary or upstream river sections. Along the outstandingly ecologically important Yangtze River in China, the Three Gorges Reservoir (TGR) is the largest project, covering an area of 1080 km2. From the beginning, the dam-project came in for criticism on increasing environmental risks due to sub-merging former industrial and urban areas. We simulated dynamics of biotic and abiotic components of the TGR ecosystem (trophic guilds of aquatic organisms, hydrodynamics, nutrients), as well as the behaviour of the herbicidal substance propanil and its metabolites 3,4-Dichloroaniline (DCA) and 3,3',4,4'-tetrachloroazoxybenzene (TCAB). A modelling environment, provided by the AQUATOX software, was adapted to the specific situation at a tributary reach to the Yangtze river 'Daning River'. As the simulated food web contained several interconnected trophic levels, a significant biomagnification of metabolites was demonstrated by our simulation studies. In particular, newly emerging stagnant downstream sections of tributaries exhibited high probabilities due to accumulating pesticides from upstream sources. The common problem of algal blooms in the TGR-region was addressed by dose-response simulation experiments with essential nutrients. Impacts on structure and abundance of populations of aquatic organisms were shown. However, even high nutrient loads resulted in only slight changes of densities of organisms of all trophic levels. Nevertheless, the probabilities for large-scale algal blooms affecting drinking water quality were considered low because of high flow velocities and discharge rates towards the Yangtze River. We see high potential of simulation-based assessments that provide information for risk managers dealing with whole catchment areas. They are put in the position to differentiate the magnitude of impacts of various factors and decide about the most effective remediation measures.

Comparison of in vitro test systems using bacterial and mammalian cells for genotoxicity assessment within the "health-related indication value (HRIV) concept.

In numerous cases, the German health-related indication value (HRIV) concept has proved its practicability for the assessment of drinking water relevant trace substances (Umweltbundesamt 2003). The HRIV is based on the toxicological profile of a substance. An open point of the HRIV concept has been the assignment of standardized test procedures to be used for the assessment. The level of the HRIV is at its lowest as soon as the genotoxicity of the substance is detected. As a single test on its own, it is not sufficient enough to assess the human toxicological relevance of a genotoxic effect or exclude it in the case of a negative result; a reasonable test battery was required, technically oriented towards the already harmonized international, hierarchical evaluation for toxicological assessment of chemicals. Therefore, an important aim of this project was to define a strategy for the genotoxicological assessment of anthropogenic trace substances. The basic test battery for genotoxicity of micropollutants in drinking water needs to fulfill several requirements. Although quick test results are needed for the determination of HRIV, a high degree of transferability to human genotoxicity should be ensured. Therefore, an in vitro genotoxicity test battery consisting of the Ames fluctuation test with two tester strains (ISO 11350), the umu test and the micronucleus test, or from the Ames test with five tester strains (OECD 471) and the micronucleus test is proposed. On the basis of selected test substances, it could be shown that the test battery leads to positive, indifferent, and negative results. Given indifferent results, the health authority and the water supplier must assume that it is a genotoxic substance. Genetically modified tester strains are being sensitive to different chemical classes by expression of selected mammalian key enzymes for example nitroreductase, acetyltransferase, and glutathione-S-transferase. These strains may provide valuable additional information and may give a first indication of the mechanism of action. To check this hypothesis, various additional strains expressing specific human-relevant enzymes were investigated. It could be shown that the additional use of genetically modified tester strains can enhance the detectable substance spectrum with the bacterial genotoxicological standard procedures or increase the sensitivity. The additional use provides orienting information at this level as a lot of data can be obtained quite quickly and with little effort. These indications of the mechanism of action should be however verified with a test system that uses mammalian cells, better human cells, to check their actual relevance. The selection of appropriate additional tester strains has to be defined from case to case depending on the molecular structure and also still requires some major expertise.

Life cycle assessment and sustainable engineering in the context of near net shape grown components: striving towards a sustainable way of future production.

Technical product harvesting (TEPHA) is a newly developing interdisciplinary approach in which bio-based production is investigated from a technical and ecological perspective. Society's demand for ecologically produced and sustainably operable goods is a key driver for the substitution of conventional materials like metals or plastics through bio-based alternatives. Technical product harvesting of near net shape grown components describes the use of suitable biomass for the production of technical products through influencing the natural shape of plants during their growth period. The use of natural materials may show positive effects on the amount of non-renewable resource consumption. This also increases the product recyclability at the end of its life cycle. Furthermore, through the near net shape growth of biomass, production steps can be reduced. As a consequence such approaches may save energy and the needed resources like crude oil, coal or gas. The derived near net shape grown components are not only considered beneficial from an environmental point of view. They can also have mechanical advantages through an intrinsic topology optimization in contrast to common natural materials, which are influenced in their shape after harvesting. In order to prove these benefits a comprehensive, interdisciplinary scientific strategy is needed. Here, both mechanical investigations and life cycle assessment as a method of environmental evaluation are used.

A versatile and low-cost open source pipetting robot for automation of toxicological and ecotoxicological bioassays.

In the past decades, bioassays and whole-organism bioassay have become important tools not only in compliance testing of industrial chemicals and plant protection products, but also in the monitoring of environmental quality. With few exceptions, such test systems are discontinuous. They require exposure of the biological test material in small units, such as multiwell plates, during prolonged incubation periods, and do not allow online read-outs. It is mostly due to these shortcomings that applications in continuous monitoring of, e.g., drinking or surface water quality are largely missing. We propose the use of pipetting robots that can be used to automatically exchange samples in multiwell plates with fresh samples in a semi-static manner, as a potential solution to overcome these limitations. In this study, we developed a simple and low-cost, versatile pipetting robot constructed partly using open-source hardware that has a small footprint and can be used for online monitoring of water quality by means of an automated whole-organism bioassay. We tested its precision in automated 2-fold dilution series and used it for exposure of zebrafish embryos (Danio rerio)-a common model species in ecotoxicology-to cadmium chloride and permethrin. We found that, compared to conventional static or semi-static exposure scenarios, effects of the two chemicals in zebrafish embryos generally occurred at lower concentrations, and analytically verified that the increased frequency of media exchange resulted in a greater availability of the chemical. In combination with advanced detection systems this custom-made pipetting robot has the potential to become a valuable tool in future monitoring strategies for drinking and surface water.

Assessment of a novel device for onsite integrative large-volume solid phase extraction of water samples to enable a comprehensive chemical and effect-based analysis.

The implementation of targeted and nontargeted chemical screening analysis in combination with in vitro and organism-level bioassays is a prerequisite for a more holistic monitoring of water quality in the future. For chemical analysis, little or no sample enrichment is often sufficient, while bioanalysis often requires larger sample volumes at a certain enrichment factor for conducting comprehensive bioassays on different endpoints or further effect-directed analysis (EDA). To avoid logistic and technical issues related to the storage and transport of large volumes of water, sampling would benefit greatly from onsite extraction. This study presents a novel onsite large volume solid phase extraction (LVSPE) device tailored to fulfill the requirements for the successful effect-based and chemical screening of water resources and complies with available international standards for automated sampling devices. Laboratory recovery experiments using 251 organic compounds in the log D range from -3.6 to 9.4 (at pH7.0) spiked into pristine water resulted in acceptable recoveries and from 60 to 123% for 159 out of 251 substances. Within a European-wide demonstration program, the LVSPE was able to enrich compounds in concentration ranges over three orders of magnitude (1ngL-1 to 2400ngL-1). It was possible to discriminate responsive samples from samples with no or only low effects in a set of six different bioassays (i.e. acetylcholinesterase and algal growth inhibition, androgenicity, estrogenicity, fish embryo toxicity, glucocorticoid activity). The LVSPE thus proved applicable for onsite extraction of sufficient amounts of water to investigate water quality thoroughly by means of chemical analysis and effect-based tools without the common limitations due to small sample volumes.

Towards the review of the European Union Water Framework Directive: Recommendations for more efficient assessment and management of chemical contamination in European surface water resources.

Water is a vital resource for natural ecosystems and human life, and assuring a high quality of water and protecting it from chemical contamination is a major societal goal in the European Union. The Water Framework Directive (WFD) and its daughter directives are the major body of legislation for the protection and sustainable use of European freshwater resources. The practical implementation of the WFD with regard to chemical pollution has faced some challenges. In support of the upcoming WFD review in 2019 the research project SOLUTIONS and the European monitoring network NORMAN has analyzed these challenges, evaluated the state-of-the-art of the science and suggested possible solutions. We give 10 recommendations to improve monitoring and to strengthen comprehensive prioritization, to foster consistent assessment and to support solution-oriented management of surface waters. The integration of effect-based tools, the application of passive sampling for bioaccumulative chemicals and an integrated strategy for prioritization of contaminants, accounting for knowledge gaps, are seen as important approaches to advance monitoring. Including all relevant chemical contaminants in more holistic "chemical status" assessment, using effect-based trigger values to address priority mixtures of chemicals, to better consider historical burdens accumulated in sediments and to use models to fill data gaps are recommended for a consistent assessment of contamination. Solution-oriented management should apply a tiered approach in investigative monitoring to identify toxicity drivers, strengthen consistent legislative frameworks and apply solutions-oriented approaches that explore risk reduction scenarios before and along with risk assessment.

Bioassay battery interlaboratory investigation of emerging contaminants in spiked water extracts - Towards the implementation of bioanalytical monitoring tools in water quality assessment and monitoring.

Bioassays are particularly useful tools to link the chemical and ecological assessments in water quality monitoring. Different methods cover a broad range of toxicity mechanisms in diverse organisms, and account for risks posed by non-target compounds and mixtures. Many tests are already applied in chemical and waste assessments, and stakeholders from the science-police interface have recommended their integration in regulatory water quality monitoring. Still, there is a need to address bioassay suitability to evaluate water samples containing emerging pollutants, which are a current priority in water quality monitoring. The presented interlaboratory study (ILS) verified whether a battery of miniaturized bioassays, conducted in 11 different laboratories following their own protocols, would produce comparable results when applied to evaluate blinded samples consisting of a pristine water extract spiked with four emerging pollutants as single chemicals or mixtures, i.e. triclosan, acridine, 17α-ethinylestradiol (EE2) and 3-nitrobenzanthrone (3-NBA). Assays evaluated effects on aquatic organisms from three different trophic levels (algae, daphnids, zebrafish embryos) and mechanism-specific effects using in vitro estrogenicity (ER-Luc, YES) and mutagenicity (Ames fluctuation) assays. The test battery presented complementary sensitivity and specificity to evaluate the different blinded water extract spikes. Aquatic organisms differed in terms of sensitivity to triclosan (algae > daphnids > fish) and acridine (fish > daphnids > algae) spikes, confirming the complementary role of the three taxa for water quality assessment. Estrogenicity and mutagenicity assays identified with high precision the respective mechanism-specific effects of spikes even when non-specific toxicity occurred in mixture. For estrogenicity, although differences were observed between assays and models, EE2 spike relative induction EC50 values were comparable to the literature, and E2/EE2 equivalency factors reliably reflected the sample content. In the Ames, strong revertant induction occurred following 3-NBA spike incubation with the TA98 strain, which was of lower magnitude after metabolic transformation and when compared to TA100. Differences in experimental protocols, model organisms, and data analysis can be sources of variation, indicating that respective harmonized standard procedures should be followed when implementing bioassays in water monitoring. Together with other ongoing activities for the validation of a basic bioassay battery, the present study is an important step towards the implementation of bioanalytical monitoring tools in water quality assessment and monitoring.