Occurrence and risk assessment of an azo dye - The case of Disperse Red 1.

Water quality criteria to protect aquatic life are not available for most disperse dyes which are often used as commercial mixtures in textile coloration. In this study, the acute and chronic toxicity of the commercial dye Disperse Red 1 (DR1) to eight aquatic organisms from four trophic levels was evaluated. A safety threshold, i.e. Predicted No-Effect Concentration (PNEC), was derived based on the toxicity information of the commercial product and the purified dye. This approach was possible because the toxicity of DR1 was accounting for most of the toxicity of the commercial mixture. A long-term PNEC of 60 ng L(-1) was proposed, based on the most sensitive chronic endpoint for Daphnia similis. A short-term PNEC of 1800 ng L(-1) was proposed based on the most sensitive acute endpoint also for Daphnia similis. Both key studies have been evaluated with the new "Criteria for Reporting and Evaluating ecotoxicity Data" (CRED) methodology, applying more objective criteria to assess the quality of toxicity tests, resulting in two reliable and relevant endpoints with only minor restrictions. HPLC-MS/MS was used to quantify the occurrence of DR1 in river waters of three sites, influenced by textile industry discharges, resulting in a concentration range of 50-500 ng L(-1). The risk quotients for DR1 obtained in this work suggest that this dye can pose a potential risk to freshwater biota. To reduce uncertainty of the derived PNEC, a fish partial or full lifecycle study should be performed.

Distinguishing the effects of habitat degradation and pesticide stress on benthic invertebrates using stressor-specific metrics.

Hydromorphological degradation is a well known stressor for running waters, while the effects of elevated levels of pesticides are widely ignored. Hence, distinguishing between the effects of these two stressors is an urgent task for water managers that aim at appropriate remediation measures. We used a large monitoring data set on benthic invertebrates, habitat descriptors, and physico-chemical variables to develop the SPEAR[%](habitat) metric that indicates the effects of in-stream habitat degradation. SPEAR[%](habitat) correlated significantly with the habitat degradation score (HDS; based on substratum and vegetation coverage), while it did not respond to any physico-chemical variables (r(2)=0.20). This relationship improved for streams with low modeled pesticide inputs (r(2)=0.33), and improved even further for a subset of streams dominated by soft-bottom substrata, i.e. for similar stream-types (r(2)=0.65). These relationships were confirmed for an independent dataset that was not used in the derivation of the HDS (r(2)=0.57 and r(2)=0.65, respectively). These findings show that the SPEAR[%](habitat) had a high degree of specificity for the effects of habitat degradation. Conversely, neither the commonly used EPT and ASPT metrics, nor the German Fauna Index or SPEAR[%](pesticides) showed significant relationships with HDS. These metrics instead correlated significantly with the run-off potential (RP), a proxy of pesticide contamination of streams. Similarly, RP was also the most important explanatory variable for SPEAR[%](pesticides), followed by alkalinity and the number of forested upstream stretches (r(2)=0.61). The latter are expected to alleviate pesticide effects, as indicated by higher SPEAR[%](pesticides) values. These findings show that an integrated analysis of the two stressor-specific SPEAR-metrics in combination with the metrics of general ecological degradation can help water managers to distinguish between the effects of habitat degradation and pesticide stress, two co-occurring stressors in agricultural landscapes.

Occurrences and potential risks of 16 fragrances in five German sewage treatment plants and their receiving waters.

Fragrances are used in a wide array of everyday products and enter the aquatic environment via wastewater. While several musk compounds have been studied in detail, little is known about the occurrence and fate of other fragrances. We selected 16 fragrance compounds and scrutinized their presence in Bavarian sewage treatment plants (STP) influents and effluents and discussed their ecological risks for the receiving surface waters. Moreover, we followed their concentrations along the path in one STP by corresponding time-related water sampling and derived the respective elimination rates in the purification process. Six fragrance substances (OTNE, HHCB, lilial, acetyl cedrene, menthol, and, in some grab samples, also methyl-dihydrojasmonate) could be detected in the effluents of the investigated sewage treatment plants. The other fragrances under scrutiny were only found in the inflow and were eliminated in the purification process. Only OTNE and HHCB were found in the receiving surface waters of the STP in congruent concentrations, which exceeded the preliminary derived environmental thresholds by a factor of 1.15 and 1.12, respectively, indicating potential risks. OTNE was also detected in similar concentration ranges as HHCB in muscles and livers of fish from surface waters and from ponds that are supplied with purified wastewater. The findings show that some fragrance compounds undergo high elimination rates, whereas others-not only musks-are present in receiving surface water and biota and may present a risk to local aquatic biota. Hence, our results suggest that the fate and potential effects of fragrance compounds in the aquatic environment deserve more attention.

Physiological sensitivity of freshwater macroinvertebrates to heavy metals.

Macroinvertebrate species traits, such as physiological sensitivity, have successfully been introduced in trait-based bioassessment approaches and are important predictors of species sensitivity in the field. The authors ranked macroinvertebrate species according to their physiological sensitivity to heavy metals using toxicity data from acute laboratory assays. Rankings for each of the heavy metals, Cd, Cu, Cr, Ni, Pb, Zn, and Hg, were standardized based on all available species data. Rankings for different heavy metals on the species level showed no significant difference between compounds and were reasonably well correlated pairwise (0.50

Thresholds for the effects of pesticides on invertebrate communities and leaf breakdown in stream ecosystems.

We compiled data from eight field studies conducted between 1998 and 2010 in Europe, Siberia, and Australia to derive thresholds for the effects of pesticides on macroinvertebrate communities and the ecosystem function leaf breakdown. Dose-response models for the relationship of pesticide toxicity with the abundance of sensitive macroinvertebrate taxa showed significant differences to reference sites at 1/1000 to 1/10,000 of the median acute effect concentration (EC50) for Daphnia magna, depending on the model specification and whether forested upstream sections were present. Hence, the analysis revealed effects well below the threshold of 1/100 of the EC50 for D. magna incorporated in the European Union Uniform Principles (UP) for registration of single pesticides. Moreover, the abundances of sensitive macroinvertebrates in the communities were reduced by 27% to 61% at concentrations related to 1/100 of the EC50 for D. magna. The invertebrate leaf breakdown rate was positively linearly related to the abundance of pesticide-sensitive macroinvertebrate species in the communities, though only for two of the three countries examined. We argue that the low effect thresholds observed were not mainly because of an underestimation of field exposure or confounding factors. From the results gathered we derive that the UP threshold for single pesticides based on D. magna is not protective for field communities subject to multiple stressors, pesticide mixtures, and repeated exposures and that risk mitigation measures, such as forested landscape patches, can alleviate effects of pesticides.

Triclosan--the forgotten priority substance?

INTRODUCTION: Triclosan (TCS) is a multi-purpose biocide. Its wide use in personal care products (PCPs) fosters its dispersal in the aquatic environment. Despite enhanced awareness of both scientists and the public in the last decade with regard to fate and effects, TCS received little attention regarding its prioritisation as a candidate river basin-specific pollutant or even priority substance, due to scarce monitoring data. METHODS: Applying a new prioritisation methodology, the potential risk of TCS was assessed based on a refined hazard assessment and occurrences at 802 monitoring sites in the Elbe River basin. RESULTS: The suggested acute-based predicted no-effect concentration (PNEC) of 4.7 ng/l for the standard test species Selenastrum capricornutum was in good agreement with effect concentrations in algal communities and was exceeded in the Elbe River basin at 75% of the sites (limit of quantification of 5 ng/l). The 95th percentile of the maximum environmental concentrations at each site exceeded the PNEC by a factor of 12, indicating potential hazards for algal communities. Among 500 potential river basin-specific pollutants which were recently prioritised, triclosan ranks on position 6 of the most problematic substances, based on the Elbe River data alone. CONCLUSION: Considering the worldwide application of PCPs containing triclosan, we expect that the TCS problem is not restricted to the Elbe River basin, even if monitoring data from other river basins are scarce. Thus, we suggest to include TCS into routine monitoring programmes and to consider it as an important candidate for prioritisation at the European scale.

Water toxicity assessment and spatial pollution patterns identification in a Mediterranean River Basin District. Tools for water management and risk analysis.

In compliance with the requirements of the EU Water Framework Directive, monitoring of the ecological and chemical status of Catalan river basins (NE Spain) is carried out by the Catalan Water Agency. The large amount of data collected and the complex relationships among the environmental variables monitored often mislead data interpretation in terms of toxic impact, especially considering that even pollutants at very low concentrations might contribute to the total toxicity. The total dataset of chemical monitoring carried out between 2007 and 2008 (232 sampling stations and 60 pollutants) has been analyzed using sequential advanced modeling techniques. Data on concentrations of contaminants in water were pre-treated in order to calculate the bioavailable fraction, depending on substance properties and local environmental conditions. The resulting values were used to predict the potential impact of toxic substances in complex mixtures on aquatic biota and to identify hot spots. Exposure assessment with Species Sensitivity Distribution (SSD) and mixture toxicity rules were used to compute the multi-substances Potentially Affected Fraction (msPAF). The combined toxicity of the pollutants analyzed in the Catalan surface waters might potentially impact more than 50% of the species in 10% of the sites. In order to understand and visualize the spatial distribution of the toxic risk, Self Organising Map (SOM), based on the Kohonen's Artificial Neural Network (ANN) algorithm, was applied on the output data of these models. Principal Component Analysis (PCA) was performed on top of Neural Network results in order to identify main influential variables which account for the pollution trends. Finally, predicted toxic impacts on biota have been linked and correlated to field data on biological quality indexes using macroinvertebrate and diatom communities (IBMWP and IPS). The methodology presented could represent a suitable tool for water managers in environmental risk assessment and management.

Occurrence and toxicity of 331 organic pollutants in large rivers of north Germany over a decade (1994 to 2004).

We analyzed the detection frequencies and concentrations for 331 organic compounds measured between 1994 and 2004 in the four largest rivers of north Germany, the Elbe, Weser, Aller, and Ems Rivers, and we assessed the potential risk for aquatic fauna using experimental and predicted acute toxicity data for the green alga Pseudokirchneriella subcapitata, the crustacean Daphnia magna, and the fish Pimephales promelas. The detection frequency for most compounds decreased significantly from 1994 to 2004. Polycyclic aromatic hydrocarbons (PAHs) were most frequently detected, while pesticides were the most important chemical group concerning toxicity for the standard test organisms. The predicted toxicity for D. magna was significantly higher than for the other organisms and reached levels envisaging acute toxic effects on the invertebrate fauna, still in 2004. Most of the compounds responsible for potential acute effects on aquatic organisms are currently not considered as priority substances in the European Union, while only 2 of 25 priority substances that have been measured occurred at levels that may be relevant in terms of toxicity for the selected test organisms. We conclude that attenuation of pesticides and other organic toxicants should play an increased role in river basin management.

A new risk assessment approach for the prioritization of 500 classical and emerging organic microcontaminants as potential river basin specific pollutants under the European Water Framework Directive.

Given the huge number of chemicals released into the environment and existing time and budget constraints, there is a need to prioritize chemicals for risk assessment and monitoring in the context of the European Union Water Framework Directive (EU WFD). This study is the first to assess the risk of 500 organic substances based on observations in the four European river basins of the Elbe, Scheldt, Danube and Llobregat. A decision tree is introduced that first classifies chemicals into six categories depending on the information available, which allows water managers to focus on the next steps (e.g. derivation of Environmental Quality Standards (EQS), improvement of analytical methods, etc.). The priority within each category is then evaluated based on two indicators, the Frequency of Exceedance and the Extent of Exceedance of Predicted No-Effect Concentrations (PNECs). These two indictors are based on maximum environmental concentrations (MEC), rather than the commonly used statistically based averages (Predicted Effect Concentration, PEC), and compared to the lowest acute-based (PNEC(acute)) or chronic-based thresholds (PNEC(chronic)). For 56% of the compounds, PNECs were available from existing risk assessments, and the majority of these PNECs were derived from chronic toxicity data or simulated ecosystem studies (mesocosm) with rather low assessment factors. The limitations of this concept for risk assessment purposes are discussed. For the remainder, provisional PNECs (P-PNECs) were established from read-across models for acute toxicity to the standard test organisms Daphnia magna, Pimephales promelas and Selenastrum capricornutum. On the one hand, the prioritization revealed that about three-quarter of the 44 substances with MEC/PNEC ratios above ten were pesticides. On the other hand, based on the monitoring data used in this study, no risk with regard to the water phase could be found for eight of the 41 priority substances, indicating a first success of the implementation of the WFD in the investigated river basins.

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis.

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC(50) of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K(ow) = 3.62) compared with DCF (log D(ow) = 2.04) at pH 7.0.

Water quality indices across Europe--a comparison of the good ecological status of five river basins.

The European Water Framework Directive (WFD) requires the definition of near-natural reference conditions to determine the extent of water bodies' deviation from "good ecological status" caused by stress gradients. However, the classification of ecological quality depends on the assessment method applied and the stressor concerned. While assessment methods that are generally applicable would be favourable, many European countries employ the locally developed water quality metrics that assess the impact of organic pollution (including eutrophication) and the associated decrease in dissolved oxygen. These indices do not specifically address stress from organic toxicants, such as pesticides. The aim of this study was to examine the performance of presently used assessment methods to identify reference conditions of non-contaminated streams in five selected European river basins, covering the geographical region from Spain to Finland, as a crucial prerequisite to indicate toxic gradients. The analysis comprised the Belgium biotic index (BBI), the biological monitoring working party (BMWP) scoring system and the revised German saprobic index. For comparison, we included an adaptation of the recently developed SPEAR index. In two previous field studies, this metric highly correlated with measured pesticide gradients. In this study, SPEAR was the only indicator that was generally applicable to all monitoring data and capable of determining "high ecological status" of reference conditions in all basins. Thus, based upon previous and own results, the authors suggest the species at risk (SPEAR) index to be potentially useful as a European-wide index to address deviations from "good ecological status" due to organic toxicants and recommend it for consideration in integrated water-resource evaluations under the WFD.

MODELKEY. Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity.

BACKGROUND: Triggered by the requirement of Water Framework Directive for a good ecological status for European river systems till 2015 and by still existing lacks in tools for cause identification of insufficient ecological status MODELKEY (http:// www.modelkey.org), an Integrated Project with 26 partners from 14 European countries, was started in 2005. MODELKEY is the acronym for 'Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity'. The project is funded by the European Commission within the Sixth Framework Programme. OBJECTIVES: MODELKEY comprises a multidisciplinary approach aiming at developing interlinked tools for an enhanced understanding of cause-effect-relationships between insufficient ecological status and environmental pollution as causative factor and for the assessment and forecasting of the risks of key pollutants on fresh water and marine ecosystems at a river basin and adjacent marine environment scale. New modelling tools for risk assessment including generic exposure assessment models, mechanistic models of toxic effects in simplified food chains, integrated diagnostic effect models based on community patterns, predictive component effect models applying artificial neural networks and GIS-based analysis of integrated risk indexes will be developed and linked to a user-friendly decision support system for the prioritisation of risks, contamination sources and contaminated sites. APPROACH: Modelling will be closely interlinked with extensive laboratory and field investigations. Early warning strategies on the basis of sub-lethal effects in vitro and in vivo are provided and combined with fractionation and analytical tools for effect-directed analysis of key toxicants. Integrated assessment of exposure and effects on biofilms, invertebrate and fish communities linking chemical analysis in water, sediment and biota with in vitro, in vivo and community level effect analysis is designed to provide data and conceptual understanding for risk arising from key toxicants in aquatic ecosystems and will be used for verification of various modelling approaches. CONCLUSION AND PERSPECTIVE: The developed tools will be verified in case studies representing European key areas including Mediterranean, Western and Central European river basins. An end-user-directed decision support system will be provided for cost-effective tool selection and appropriate risk and site prioritisation.

Analyzing effects of pesticides on invertebrate communities in streams.

The aim of this investigation was to find patterns in aquatic invertebrate community composition that are related to the effects of pesticides. Investigations were carried out in 20 central European streams. To reduce the site-specific variation of community descriptors due to environmental factors other than pesticides, species were classified and grouped according to their vulnerability to pesticides. They were classified as species at risk (SPEAR) and species not at risk (SPEnotAR). Ecological traits used to define these groups were sensitivity to toxicants, generation time, migration ability, and presence of aquatic stages during time of maximum pesticide application. Results showed that measured pesticide concentrations of 1:10 of the acute 48-h median lethal concentration (LC50) of Daphnia magna led to a short- and long-term reduction of abundance and number of SPEAR and a corresponding increase in SPEnotAR. Concentrations of 1:100 of the acute 48-h LC50 of D. magna correlated with a long-term change of community composition. However, number and abundance of SPEAR in disturbed stream sections are increased greatly when undisturbed stream sections are present in upstream reaches. This positive influence compensated for the negative effect of high concentrations of pesticides through recolonization. The results emphasize the importance of considering ecological traits and recolonization processes on the landscape level for ecotoxicological risk assessment.

Relative sensitivity distribution of aquatic invertebrates to organic and metal compounds.

In the field, a multitude of species can be exposed to numerous toxicants; thus, the sensitivity of individual species to particular toxicants must be known to predict effects and to analyze changes in species composition. For most species, no information about their toxicant sensitivity is available. To address this limitation, we have grouped the available information to assign sensitivities to aquatic invertebrate taxa relative to Daphnia magna. With respect to organic compounds, most taxa of the orders Anisoptera, Basommatophora, Coleoptera, Decapoda, Diptera, Ephemeroptera, Eulamellibranchiata, Heteroptera, Hirudinea, Isopoda, Oligochaeta, Prosobranchia, Trichoptera, Tricladida, and Zygoptera are less sensitive than D. magna. Some taxa of the Amphipoda, Plecoptera, and Cladocera (other than D. magna) are significantly more sensitive. For organic compounds, approximately 22% of the investigated taxa were more sensitive than D. magna. Most taxa of the orders Amphipoda, Basommatophora, Diptera, Ephemeroptera, Eulamellibranchiata, Heteroptera, Isopoda, Oligochaeta, and Tricladida are significantly less sensitive than D. magna to metal compounds. The taxa belonging to the Crustacea, with the exception of the order Isopoda, are much more sensitive. For metal compounds, approximately 30% of the investigated taxa were more sensitive than D. magna. Hence, D. magna is among the most sensitive taxa regarding both groups of toxicants. The sensitivities for several taxa are listed, and use of the relative sensitivity distribution to link toxicant effects in mesocosm studies and field investigations is discussed.