V. Dulio, J. Koschorreck, B. van Bavel, P. van den Brink, J. Hollender, J. Munthe, M. Schlabach, R. Aalizadeh, M. Agerstrand, L. Ahrens, I. Allan, N. Alygizakis, D. Barcelo, P. Bohlin‑Nizzetto, S. Boutroup, W. Brack, A. Bressy, J. H. Christensen, L. Cirka, A. Covaci, A. Derksen, G. Deviller, M. M. L. Dingemans, M. Engwall, D. Fatta‑Kassinos, P. Gago‑Ferrero, F. Hernández, D. Herzke, K. Hilscherová, H. Hollert, M. Junghans, B. Kasprzyk‑Hordern, S. Keiter, S. A. E. Kools, A. Kruve, D. Lambropoulou, M. Lamoree, P. Leonards, B. Lopez, M. López de Alda, L. Lundy, J. Makovinská, I. Marigómez, J. W. Martin, B. McHugh, C. Miège, S. O’Toole, N. Perkola, S. Polesello, L. Posthuma, S. Rodriguez‑Mozaz, I. Roessink, P. Rostkowski, H. Ruedel, S. Samanipour, T. Schulze, E. L. Schymanski, M. Sengl, P. Tarábek, D. Ten Hulscher, N. Thomaidis, A. Togola, S. Valsecchi, S. van Leeuwen, P. von der Ohe, Katrin Vorkamp, B. Vrana, J. Slobodnik, The NORMAN Association and the European Partnership for Chemicals Risk Assessment (PARC): let’s cooperate!, Environmental Sciences Europe, Volume 32, (2020).
Abstract: The Partnership for Chemicals Risk Assessment (PARC) is currently under development as a joint research and innovation programme to strengthen the scientific basis for chemical risk assessment in the EU. The plan is to bring chemical risk assessors and managers together with scientists to accelerate method development and the production of necessary data and knowledge, and to facilitate the transition to next-generation evidence-based risk assessment, a non-toxic environment and the European Green Deal. The NORMAN Network is an independent, well-established and competent network of more than 80 organisations in the field of emerging substances and has enormous potential to contribute to the implementation of the PARC partnership. NORMAN stands ready to provide expert advice to PARC, drawing on its long experience in the development, harmonisation and testing of advanced tools in relation to chemicals of emerging concern and in support of a European Early Warning System to unravel the risks of contaminants of emerging concern (CECs) and close the gap between research and innovation and regulatory processes. In this commentary we highlight the tools developed by NORMAN that we consider most relevant to supporting the PARC initiative: (i) joint data space and cutting-edge research tools for risk assessment of contaminants of emerging concern; (ii) collaborative European framework to improve data quality and comparability; (iii) advanced data analysis tools for a European early warning system and (iv) support to national and European chemical risk assessment thanks to harnessing, combining and sharing evidence and expertise on CECs. By combining the extensive knowledge and experience of the NORMAN network with the financial and policy-related strengths of the PARC initiative, a large step towards the goal of a non-toxic environment can be taken.
Keywords: NORMAN network, Suspect screening, Non-target screening, Contaminants of emerging concern, Environmental monitoring, High-resolution mass spectrometry, Effect-based methods, Chemical risk assessment and prioritisation
K.S. Diamanti, N.A. Alygizakis, M.C. Nika, M. Oswaldova, P. Oswald, N.S. Thomaidis, J. Slobodnik, Assessment of the chemical pollution status of the Dniester River Basin by wide-scope target and suspect screening using mass spectrometric techniques, Analytical and Bioanalytical Chemistry, Volume 412 (20), (2020).
Abstract: The quality of the Dniester River Basin has been seriously impacted by the chemicals released by agriculture, industry, and wastewater discharges. To assess its current chemical pollution status, a transboundary monitoring campaign was conducted in May 2019. Thirteen surface water, 13 sediment, and three biota samples were collected and analyzed using generic sample preparation methods for the determination of organic substances by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and metals by inductively coupled plasma mass spectrometry (ICP-MS). Wide-scope target and suspect screening resulted in detection of Water Framework Directive (WFD) priority substances and emerging contaminants, whereas the raw data were stored in NORMAN Digital Sample Freezing Platform (DSFP) for future retrospective screening. Furthermore, risk assessment was performed to prioritize detected substances and propose a draft list of river basin–specific pollutants. All studied metals (As, Hg, Zn, Cu, Cr, Cd, Pb, Ni) were detected in the surface water and sediments. In total, 139 organic contaminants belonging to various chemical classes (pesticides, pharmaceuticals, drugs of abuse, stimulants, sweeteners, industrial chemicals, and their transformation products) were detected. The highest cumulative concentration of contaminants was observed in surface water from the Byk River, a tributary of the Dniester (Moldova). Concentrations of WFD priority substances diuron and mercury and EU Watch List neonicotinoid compounds imidacloprid and thiamethoxam exceeded their environmental quality standards (EQS), whereas concentrations of 23 emerging substances exceeded their predicted no-effect concentration (PNEC) at minimum one site. Emerging contaminants telmisartan, metolachlor, terbuthylazine, and 4-acetamidoantipyrine were prioritized as potential river basin–specific pollutants.
Keywords: Dniester River Basin, Transboundary monitoring, Metals, Contaminants of emerging concern, Risk assessment, River basin–specific pollutants, Transboundary monitoring
N.A. Alygizakis, J. Urík, V.G. Beretsou, I. Kampouris, A. Galani, M. Oswaldova, T. Berendonk, P. Oswald, N.S. Thomaidis, J. Slobodnik, B. Vrana, D. Fatta-Kassinos, Evaluation of chemical and biological contaminants of emerging concern in treated wastewater intended for agricultural reuse, Environment International, Volume 138, (2020).
Abstract: The occurrence of chemical and biological contaminants of emerging concern (CECs) was investigated in treated wastewater intended for reuse in agriculture. An agarose hydrogel diffusion-based passive sampler was exposed to the outlet of a wastewater treatment plant (WWTP) located in Cyprus, which is equipped with membrane bioreactor (MBR). Passive samplers in triplicate were exposed according to a time-series exposure plan with maximum exposure duration of 28 days. Composite flow-proportional wastewater samples were collected in parallel with the passive sampling exposure plan and were processed by solid phase extraction using HORIZON SPE-DEX 4790 and the same sorbent material (Oasis HLB) as in the passive sampler. The analysis of passive samplers and wastewater samples enabled (i) the field-scale calibration of the passive sampler prototype by the calculation of in situ sampling rates of target substances, and (ii) the investigation of in silico predicted transformation products of the four most ecotoxicologically hazardous antibiotics (azithromycin, clarithromycin, erythromycin, ofloxacin). Additionally, the wastewater samples were subjected to the analysis of seven preselected antibiotic resistant genes (ARGs) and one mobile resistant element (int1). All extracts were analyzed for chemicals in a single batch using a highly sensitive method for pharmaceuticals, antibiotics and illicit drugs by liquid chromatography tandem MS/MS (LC-QQQ) and for various other target compounds (2316 compounds in total) by liquid chromatography high-resolution mass spectrometry (LC-HRMS). 279 CECs and all investigated ARGs (except for blaCTX-M−32) were detected, highlighting potential chemical and biological hazards related to wastewater reuse practices. 16 CECs were prioritized following ecotoxicological risk assessment, whereas sul1 and the mobile resistant element (int1) showed the highest abundance. Comprehensive monitoring efforts using novel sampling methods such as passive sampling, wide-scope target screening and molecular analysis are required to assure safe application of wastewater reuse and avoid spread and crop uptake of potentially hazardous chemicals.
Keywords: Hydrogel-based passive sampler, Wastewater reuse, Contaminants of emerging concern, Transformation products, Antibiotics, Antibiotic resistance genes
J. van Gils, L. Posthuma, I. T. Cousins, W. Brack, R. Altenburger, H. Baveco, A. Focks, J. Greskowiak, R. Kühne, S. Kutsarova, C. Lindim, A. Markus, D. van de Meent, J. Munthe, R. Schueder, G. Schüürmann, J. Slobodnik, D. de Zwart, A. van Wezel, Computational material flow analysis for thousands of chemicals of emerging concern in European waters, Journal of Hazardous Materials, Volume 397, (2020).
Abstract: Knowledge of exposure to a wide range of chemicals, and the spatio-temporal variability thereof, is urgently needed in the context of protecting and restoring aquatic ecosystems. This paper discusses a computational material flow analysis to predict the occurrence of thousands of man-made organic chemicals on a European scale, based on a novel temporally and spatially resolved modelling framework. The goal was to increase understanding of pressures by emerging chemicals and to complement surface water monitoring data. The ambition was to provide a first step towards a “reallife” mixture exposure situation accounting for as many chemicals as possible. Comparison of simulated concentrations and chemical monitoring data for 226 substance/basin combinations showed that the simulated concentrations were accurate on average. For 65% and 90% of substance/basin combinations the error was within one and two orders of magnitude respectively. An analysis of the relative importance of uncertainties revealed that inaccuracies in use volume or use type information contributed most to the error for individual substances. To resolve this, we suggest better registration of use types of industrial chemicals, investigation of presence/absence of industrial chemicals in wastewater and runoff samples and more scientific information exchange.
Keywords: Water quality, Modelling, Emerging contaminants, Emissions, Fate and transport
P. C von der Ohe, F. Freeling, N. A Alygizakis, J. Slobodnik, P. Oswald, R. Aalizadeh, L. Cirka, N. S Thomaidis, M. Scheurer, Explaining the rationale behind the risk assessment of surfactants by Freeling et al. (2019), Science of the Total Environment, Volume 721, (2019).
Y. Zhang, M. Pavlovska, Elena Stoica, I. Prekrasna, J. Yang, J. Slobodnik, X. Zhang, E. Dykyi, Holistic pelagic biodiversity monitoring of the Black Sea via eDNA metabarcoding approach: From bacteria to marine mammals, Environment International, Volume 135, (2019).
Abstract: As the largest semi-closed marine ecosystem in the world, the Black Sea has been heavily affected by human activities for a long time. Describing the biodiversity of multi-trophic biota in pelagic zone of the Black Sea and identifying the dominant environmental factors are prerequisites for protecting the sustainability of ecosystems. However, up to now, the taxonomic and distributional information about the Black Sea biota is not clear. Here, we employed a Tree-of-Life metabarcoding to analyze the biodiversity of eight communities in the Black Sea, investigated their biogeographical distribution, and further analyzed the influence of biological and abiotic factors on biota on large scales. We found that, (1) Over 8900 OTUs were detected in the Black Sea, of which 630 species were identified, covering the holistic biota from single-celled (bacteria 5620 OTUs 141 species; algae 1096 OTUs 185 species; protozoa 546 OTUs 146 species) to multicellular organisms (invertebrate metazoans 150 OTUs 34 species; fishes 1369 OTUs 76 species; large marine mammals 39 OTUs 5 species). (2) Higher trophic organisms (fishes and large mammals) distributed more evenly in space than the lower (microorganisms, protozoa and invertebrates). For lower trophic organisms, the vertical stratification was more obvious than the horizontal stratification (vertical p < 0.02, horizontal p < 0.05). (3) The bottom trophic organisms (bacteria and algae) of the food web significantly affected the distribution and composition of the others through biological interactions (Mantel p < 0.05). (4) At the level of abiotic factors, the effect of local species sorting on the composition of communities was 15% higher than that of mass dispersal effect. For the first time, this study monitored and profiled the holistic biodiversity in the pelagic zone of the Black Sea, and provided technological advances and preliminary knowledge for the ongoing Black Sea ecosystem protection efforts.
Keywords: Black Sea, Multi-trophic biodiversity, eDNA metabarcoding, Interactome, Dispersal, Species sorting
N. Popović, M. Raković, J. Đuknić, B. Csányi, J. Szekeres, P. Borza, J. Slobodnik, I. Liška, D. Milošević, S. Kolarević, V. Simić, B. Tubić, M. Paunović, The relationship between river basin specific (RBS) pollutants and macroinvertebrate communities, Journal of limnology, Volume 79, (2019).
Abstract: This study was carried out to identify the relations between macroinvertebrate communities and river basin specific (RBS) pollutants in the Danube River. The investigation was performed at 68 sites along 2,500 km of the Danube. Forward selection (FS), canonical correspondence analyses (CCA), the Spearman correlation coefficient (SC) and BIO-ENV analysis (to detect synergistic effects) were used to identify the relations between the macroinvertebrate dataset and selected biological metrics with RBS pollutants. Of the 20 analysed pollutants (preselected based on NORMAN network methodology), seven (2,4-dinitrophenol, chloroxuron, bromacil, dimefuron, amoxicillin, bentazon and fluoranthene) were found to significantly correlate with macroinvertebrate communities. BIO-ENV analysis revealed 3 subsets of environmental variables that were in high correlation with the biota resemblance matrix, consisting mainly of a combination of the above-mentioned pollutants. Our results indicate that there are significant correlations between chemical determinants and aquatic biota. Moreover, this study contributes to the validation of the methodology used for prioritization of RBS pollutants proposed by the NORMAN network.
Keywords: Macroinvertebrate, Danube River, River basin-specific pollutants, Multiple stressors, Synergistic effects
W. Brack, S. Ait‑Aissa, R. Altenburger, I. Cousins, V. Dulio, B. Escher, A. Focks, A. Ginebreda, D. Hering, K. Hilscherova, J. Hollender, H. Hollert, A. Kortenkamp, M. López de Alda, L. Posthuma, E. Schymanski, H. Segner, J. Slobodnik, Let us empower the WFD to prevent risks of chemical pollution in European rivers and lakes, Environmental Sciences Europe, Volume 31, (2019).
L. Posthuma, J. Munthe, J. van Gils, R. Altenburger, C. Müller, J. Slobodnik, Werner Brack, A holistic approach is key to protect water quality and monitor, assess and manage chemical pollution of European surface waters, Environmental Sciences Europe, Volume 31 (67), (2019).
Abstract: Chemical pollution of surface waters is a societal concern around the globe. Key problems in current water quality protection, assessment and management are the narrow focus on a small fraction of the chemicals in commerce, concerns for increasingly diverse chemical emissions, and lack of effective diagnosis and management approaches. In reply, three key concepts to address these challenges were developed and tested. The approaches were developed in the context of the European Union Water Framework Directive, based on principles such as the DPSIR-causal framework (Drivers, Pressure, Status, Impact and Response) and the basic feature that water protection and management should be based on a water-system level approach. Collaborative actions of researchers and stakeholders resulted in: (1) an operationalization and implementation of the solution-focused risk assessment paradigm as proposed in 2009, to improve the utility of risk assessments, (2) the provision of a large set of tools and services to prevent, monitor, assess and manage complex mixture pollution problems, and (3) a strategy and a database on intervention options. These three elements were recognized as core elements to help protecting and improving water quality. Although the methods were developed in the context of water quality problems in Europe, the three elements can be applied globally in water quality protection and management.
J. Hollender, B. van Bavel, V. Dulio, E. Farmen, K. Furtmann, J. Koschorreck, U. Kunkel, M. Krauss, J. Munthe, M. Schlabach, J. Slobodnik, G. Stroomberg, T. Ternes, N. S. Thomaidis, A. Togola, V. Tornero, High resolution mass spectrometry-based non-target screening can support regulatory environmental monitoring and chemicals management, Environmental Sciences Europe, Volume 31, (2019).
Abstract: Non-target screening (NTS) including suspect screening with high resolution mass spectrometry has already shown its feasibility in detecting and identifying emerging contaminants, which subsequently triggered exposure mitigating measures. NTS has a large potential for tasks such as effective evaluation of regulations for safe marketing of substances and products, prioritization of substances for monitoring programmes and assessment of environmental quality. To achieve this, a further development of NTS methodology is required, including: (i) harmonized protocols and quality requirements, (ii) infrastructures for efficient data management, data evaluation and data sharing and (iii) sufficient resources and appropriately trained personnel in the research and regulatory communities in Europe. Recommendations for achieving these three requirements are outlined in the following discussion paper. In particular, in order to facilitate compound identification it is recommended that the relevant information for interpretation of mass spectra, as well as about the compounds usage and production tonnages, should be made accessible to the scientific community (via open-access databases). For many purposes, NTS should be implemented in combination with effect-based methods to focus on toxic chemicals.
Keywords: NORMAN network, Suspect screening, Non-target screening, Contaminants of emerging concern, Environmental monitoring, Chemical management, High resolution mass spectrometry, Data analysis
F. Freeling, N.A. Alygizakis, P.C. von der Ohe, J. Slobodnik, P. Oswald, R. Aalizadeh, L. Cirka, N.S. Thomaidis, M. Scheurer, Occurrence and potential environmental risk of surfactants and their transformation products discharged by wastewater treatment plants, The Science of The Total Environment, Volume 681, (2019).
Abstract: Seven-day composite effluent samples from a German monitoring campaign including 33 conventional wastewater treatment plants (WWTP) were analyzed for linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES) and were screened by wide-scope suspect screening for 1564 surfactants and their transformation products (TPs) by UHPLC-ESI-QTOF-MS. Corresponding seven-day composite influent samples of selected WWTPs showed high influent concentrations as well as very high removal rates for LAS and AES. However, average total LAS and AES effluent concentrations were still 14.4 μg/L and 0.57 μg/L, respectively. The LAS-byproducts di-alkyl tetralin sulfonates (DATSs), the TPs sulfophenyl alkyl carboxylic acids (SPACs) and sulfo-tetralin alkyl carboxylic acids (STACs) reached maximum effluent concentrations of 19 μg/L, 17 μg/L and 5.3 μg/L, respectively. In many cases the sum of the concentration of all LAS-related byproducts and TPs surpassed the concentration of the precursors. High concentrations of up to 7.4 μg/L were found for 41 polyethylenoglycol homologs. Quantified surfactants and their TPs and by-products together accounted for concentrations up to 82 μg/L in WWTP effluents. To determine the risk of individual surfactants and their mixtures, single homologs were grouped by a “weighted carbon number approach” to derive normalized Predicted No-Effect Concentrations (PNEC), based on experimental ecotoxicity data from existing risk assessments, complemented by suitable Quantitative Structure-Activity Relationships (QSAR) predictions. Predicted Environmental Concentrations (PEC) were derived by dividing effluent concentrations of surfactants by local dilution factors. Risks for all analyzed surfactants were below the commonly accepted PEC/PNEC ratio of 1 for single compounds, while contributions to mixture toxicity effects from background levels of LAS and DATS cannot be excluded. Maximum LAS concentrations exceeded half of its PNEC, which may trigger country-wide screening to investigate potential environmental risks.
Keywords: Surfactants, Linear alkylbenzene sulfonates, Alkyl ethoxysulfates, Wide-scope suspect screening, Effluent wastewater, Risk assessment
N.A. Alygizakis, H. Besselink, G.K. Paulus, P. Oswald, L.M. Hornstra, M. Oswaldova, G. Medema, N.S. Thomaidis, P.A. Behnisch, J. Slobodnik, Characterization of wastewater effluents in the Danube River Basin with chemical screening, in vitro bioassays and antibiotic resistant genes, Environment International, Volume 127, (2019).
Abstract: Averaged 7-day composite effluent wastewater samples from twelve wastewater treatment plants (WWTPs) in nine countries (Romania, Serbia, Hungary, Slovenia, Croatia, Slovakia, Czechia, Austria, Germany) in the Danube River Basin were collected. WWTPs' selection was based on countries' dominant technology and a number of served population with the aim to get a representative holistic view of the pollution status. Samples were analyzed for 2248 chemicals of emerging concern (CECs) by wide-scope target screening employing LC-ESI-QTOF-MS. 280 compounds were detected at least in one sample and quantified. Spatial differences in the concentrations and distribution of the compounds classes were discussed. Additionally, samples were analyzed for the possible agonistic/antagonistic potencies using a panel of in vitro transactivation reporter gene CALUX® bioassays including ERα (estrogenics), anti-AR (anti-androgens), GR (glucocorticoids), anti-PR (anti-progestins), PPARα and PPARγ (peroxisome proliferators) and PAH assays. The potency of the wastewater samples to cause oxidative stress and induce xenobiotic metabolism was determined using the Nrf2 and PXR CALUX® bioassays, respectively. The signals from each of the bioassays were compared with the recently developed effect-based trigger values (EBTs) and thus allowed for allocating the wastewater effluents into four categories based on their measured toxicity, proposing a putative action plan for wastewater operators. Moreover, samples were analyzed for antibiotics and 13 antibiotic-resistant genes (ARGs) and one mobile genetic element (intl1) with the aim to assess the potential for antibiotic resistance. All data collected from these various types of analysis were stored in an on-line database and can be viewed via interactive map at https://norman-data.eu/EWW_DANUBE.
Keywords: Emerging substances, Wide-scope target screening, Effluent wastewater, Bioassays, Antibiotic resistant genes, Danube River Basin
N.A. Alygizakis, P. Oswald, N.S. Thomaidis, E.L. Schymanski, R. Aalizadeh, T. Schulze, M. Oswaldova, J. Slobodnik, NORMAN digital sample freezing platform: A European virtual platform to exchange liquid chromatography high resolution-mass spectrometry data and screen suspects in “digitally frozen” environmental samples, TrAC Trends in Analytical Chemistry, Volume 115, (2019).
Abstract: A platform for archiving liquid chromatography high-resolution mass spectrometry (LC-HRMS) data was developed for the retrospective suspect screening of thousands of environmental pollutants with the ambition of becoming a European and possibly global standard. It was termed Digital Sample Freezing Platform (DSFP) and incorporates all the recent developments in the HRMS screening methods within the NORMAN Network. In the workflow, raw mass spectral data are converted into mzML, then mass spectral and chromatographic information on thousands of peaks of each sample is extracted into Data Collection Templates. The ‘digitally frozen’ samples can be retrospectively screened for the presence of virtually any compound amenable to LC–MS using a combination of information on its (i) exact mass, (ii) predicted retention time window in the chromatogram, (iii) isotopic fit and (iv) qualifier fragment ions. Its potential was demonstrated on monitoring of 670 antibiotics and 777 REACH chemicals from the Joint Black Sea Surveys (JBSS).
Keywords: Digital sample freezing platform, High resolution mass spectrometry, Digital archiving, Suspect screening, Antibiotics, REACH, Black sea
W. Brack, J. Hollender, M. López de Alda, C. Müller, T. Schulze, E. Schymanski, J. Slobodnik, M. Krauss, High-resolution mass spectrometry to complement monitoring and track emerging chemicals and pollution trends in European water resources, Environmental Sciences Europe, Volume 31 (62), (2019).
Abstract: Currently, chemical monitoring based on priority substances fails to consider the majority of known environmental micropollutants not to mention the unexpected and unknown chemicals that may contribute to the toxic risk of complex mixtures present in the environment. Complementing component- and effect-based monitoring with wide-scope target, suspect, and non-target screening (NTS) based on high-resolution mass spectrometry (HRMS) data is recommended to support environmental impact and risk assessment. This will allow for detection of newly emerging compounds and transformation products, retrospective monitoring efforts, and the identification of possible drivers of toxicity by correlation with effects or modelling of expected effects for future and abatement scenarios. HRMS is becoming increasingly available in many laboratories. Thus, the time is right to establish and harmonize screening methods, train staff, and record HRMS data for samples from regular monitoring events and surveys. This will strongly enhance the value of chemical monitoring data for evaluating complex chemical pollution problems, at limited additional costs. Collaboration and data exchange on a European-to-global scale is essential to maximize the benefit of chemical screening. Freely accessible data platforms, inter-laboratory trials, and the involvement of international partners and networks are recommended.
W. Brack, S. Ait‑Aissa, T. Backhaus, S. Birk, D. Barceló, R. Burgess, I. Cousins, V. Dulio, B. I. Escher, A. Focks, J. van Gils, A. Ginebreda, D. Hering, L. Mark Hewitt, K. Hilscherová, J. Hollender, H. Hollert, M. Köck, A. Kortenkamp, M. López de Alda, C. Müller, L. Posthuma, G. Schüürmann, E. Schymanski, H. Segner, F. Sleeuwaert, J. Slobodnik, I. Teodorovic, G. Umbuzeiro, N. Voulvoulis, A. van Wezel, R. Altenburger, Strengthen the European collaborative environmental research to meet European policy goals for achieving a sustainable, non-toxic environment, Environmental Sciences Europe, Volume 31 (63), (2019).
Abstract: To meet the United Nations (UN) sustainable development goals and the European Union (EU) strategy for a nontoxic environment, water resources and ecosystems management require cost-efficient solutions for prevailing complex contamination and multiple stressor exposures. For the protection of water resources under global change conditions, specific research needs for prediction, monitoring, assessment and abatement of multiple stressors emerge with respect to maintaining human needs, biodiversity, and ecosystem services. Collaborative European research seems an ideal instrument to mobilize the required transdisciplinary scientific support and tackle the large scale dimension and develop options required for implementation of European policies. Calls for research on minimizing society’s chemical footprints in the water–food–energy–security nexus are required. European research should be complemented with targeted national scientific funding to address specific transformation pathways and support the evaluation, demonstration and implementation of novel approaches on regional scales. The foreseeable pressure developments due to demographic, economic and climate changes require solution-oriented thinking, focusing on the assessment of sustainable abatement options and transformation pathways rather than on status evaluation. Stakeholder involvement is a key success factor in collaborative projects as it allows capturing added value, to address other levels of complexity, and find smarter solutions by synthesizing scientific evidence, integrating governance issues, and addressing transition pathways. This increases the chances of closing the value chain by implementing novel solutions. For the water quality topic, the interacting European collaborative projects SOLUTIONS, MARS and GLOBAQUA and the NORMAN network provide best practice examples for successful applied collaborative research including multi-stakeholder involvement. They provided innovative conceptual, modelling and instrumental options for future monitoring and management of chemical mixtures and multiple stressors in European water resources. Advancement of EU water framework directive-related policies has therefore become an option.
J. Munthe, J. Lexén, T. Skårman, L. Posthuma, W. Brack, R. Altenburger, E. Brorström‑Lundén, D. Bunke, M. Faust, M. Rahmberg, F. Sleeuwaert, J. Slobodnik, J. van Gils, A. van Wezel, Increase coherence, cooperation and cross-compliance of regulations on chemicals and water quality, Environmental Sciences Europe, Volume 31 (64), (2019).
Abstract: An analysis of existing regulatory frameworks for chemicals reveals a fragmented situation with a number of regulatory frameworks designed for specific groups of chemicals; for protection of different end-points and covering different parts of the chemicals´ life cycle stages. Lack of- and fragmented information on chemicals (properties, use, emissions as well as fate, occurrence and effects in the environment) limit the ability for assessment and early action, and existing legislation would benefit from more transparency and openness of information and knowledge. To achieve harmonisation of existing legislation and an efficient control of chemical contamination of European waters, a solution-focused approach is proposed including increased ambitions (in monitoring, modelling, and risk assessment), cooperation and dialogue. More holistic and efficient development and implementation of existing legislation can be achieved by better cooperation, harmonisation and information exchange between different regulatory frameworks and by improved science–policy interactions. The introduction of an organisational structure and incentives for cooperation are proposed. Cooperation should focus on harmonisation of advanced monitoring activities, modelling, prioritisation, risk assessment and assessment of risk prevention (‘safe by design’) and minimisation options. A process for dialogue and information exchange between existing policy frameworks and with stakeholders (industry, NGO´s, etc.) should be included to identify feasible options for mitigation as well as regulatory gaps—on local and EU-scales. There is also a need to increase international cooperation and strengthen global agreements to cover the full life cycle of chemicals (produced and consumed globally) and for exchanging knowledge and experiences to allow early action. This recommended action would also provide knowledge and a framework for a shift towards a sustainable chemistry approach for chemical safety based on a “safe by design” concept.
W. Brack, S. Ait Aissa, T. Backhaus, V. Dulio, B. I. Escher, M. Faust, K. Hilscherova, J. Hollender, H. Hollert, C. Müller, J. Munthe, L. Posthuma, T.-B. Seiler, J. Slobodnik, I. Teodorovic, A. J. Tindall, G. de Aragão Umbuzeiro, X. Zhang and R. Altenburger, Effect-based methods are key. The European Collaborative Project SOLUTIONS recommends integrating effect-based methods for diagnosis and monitoring of water quality, Environmental Sciences Europe, Volume 31 (1), (2019).
Abstract: The present monitoring and assessment of the chemical status of water bodies fail to characterize the likelihood that complex mixtures of chemicals affect water quality. The European Collaborative Project SOLUTIONS suggests that this likelihood can be estimated with effect-based methods (EBMs) complemented by chemical screening and/or impact modelling. These methods should be used to identify the causes of impacted water quality and to develop programs of measures to improve water quality. Along this line of reasoning, effect-based methods are recommended for Water Framework Directive (WFD) monitoring to cover the major modes of action in the universe of environmentally relevant chemicals so as to evaluate improvements of water quality upon implementing the measures. To this end, a minimum battery of bioassays has been recommended including short-term toxicity to algae, Daphnia and fish embryos complemented with in vitro and short-term in vivo tests on mode-of-action specific effects as proxies for long-term toxicity. The likelihood of adverse impacts can be established with effect-based trigger values, which differentiate good from poor water quality in close alignment with Environmental Quality Standards for individual chemicals, while taking into account mixture toxicity. The use of EBMs is suggested in the WFD as one avenue to establish the likelihood of adverse effects due to chemical pollution in European water systems. The present paper has been written as one component of a series of policy briefs to support decisions on water quality monitoring and management under the WFD.
Keywords: Effect-based monitoring, Diagnosis, Complex mixtures of chemicals, Likelihood of impacts, Recommendations, Water Framework Directive
J. Slobodnik, J. Hollender, T. Schulze, E. L. Schymanski, W. Brack, Establish data infrastructure to compile and exchange environmental screening data on a European scale, Environmental Sciences Europe, Volume 31 (65), (2019).
Abstract: Robust techniques based on liquid (LC) and gas chromatography (GC) coupled with high-resolution mass spectrometry (HR-MS) enable sensitive screening, identification, and (semi)quantification of thousands of substances in a single sample. Recent progress in computational sciences has enabled archiving and processing of HR-MS ‘big data’ at the routine level. As a result, community-based databases containing thousands of environmental pollutants are rapidly growing and large databases of substances with unique identifiers allowing for inter-comparison at the global scale have become available. A data-archiving infrastructure is proposed, allowing for retrospective screening of HR-MS data, which will help define the ‘chemical universe’ of organic substances and enable prioritisation of toxicants causing adverse environmental effects at the local, river basin, and national and European scale in support of the European water and chemicals management policy.
M. Faust, T. Backhaus, R. Altenburger, V. Dulio, J. van Gils, A. Ginebreda, A. Kortenkamp, J. Munthe, L. Posthuma, J. Slobodnik, K. E. Tollefsen, A. van Wezel, W. Brack, Prioritisation of water pollutants: the EU Project SOLUTIONS proposes a methodological framework for the integration of mixture risk assessments into prioritisation procedures under the European Water Framework Directive, Environmental Sciences Europe, Volume 31 (66), (2019).
Abstract: Current prioritisation procedures under the EU Water Framework Directive (WFD) do not account for risks from chemical mixtures. SOLUTIONS proposes a multiple-lines-of-evidence approach to tackle the problem effectively. The approach merges all available evidence from co-exposure modelling, chemical monitoring, effect-based monitoring, and ecological monitoring. Full implementation of the proposed methodology requires changes in the legal text in adaptation to scientific progress.
Keywords: Water pollutants, Priority substances, Combined exposure, Mixture toxicity, Cumulative risks, European chemicals legislation, WFD revision
P. Movalli, G. Duke, G. Ramello, R. Dekker, A. Vrezec, R. F. Shore, A. García-Fernández, C. Wernham, O. Krone, N. Alygizakis, A. Badry, F. Barbagli, K. Biesmeijer, G. Boano, A. L. Bond, Y. Choresh, J. Bolding Christensen, A. Cincinelli, S. Danielsson, A. Dias, R. Dietz, M. Eens, S. Espín, I. Eulaers, S. Frahnert, T. I. Fuiz, G. Gkotsis, N. Glowacka, P. Gómez-Ramírez, M. Grotti, M. Guiraud, P. Hosner, U. Johansson, V. L. B. Jaspers, P. Kamminga, J. Koschorreck, B. Knopf, E. Kubin, S. LoBrutto, R. Lourenco, T. Martellini, E. Martínez-López, R. Mateo, M.-C. Nika, V. Nikolopoulou, D. Osborn, O. Pauwels, M. Pavia, M. Glória Pereira, H. Rüdel, P. Sanchez-Virosta, J. Slobodnik, C. Sonne, N. Thomaidis, T. Töpfer, G. Treu, R. Väinölä, J. Valkama, S. van der Mije, D. Vangeluwe, B. H. Warren, F. Woog, Progress on bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulation, Environmental Science and Pollution Research, Volume 26 (20), (2019).
P. Rostkowski, P. Haglund, R. Aalizadeh, N. Alygizakis, N. Thomaidis, J. Beltran Arandes, P. Bohlin Nizzetto, P. Booij, H. Budzinski, P. Brunswick, A. Covaci, C. Gallampois, S. Grosse, R, Hindle, I. Ipolyi, K. Jobst, S. L. Kaserzon, P. Leonards, F. Lestremau, T. Letzel, J. Magnér, H. Matsukami, C. Moschet, P. Oswald, M. Plassmann, J. Slobodnik, C. Yang, The strength in numbers: comprehensive characterization of house dust using complementary mass spectrometric techniques, Analytical and Bioanalytical Chemistry, Volume 411 (10), (2019).
Abstract: Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography–mass spectrometry (LC-MS) and gas chromatography– mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.
Keywords: House dust, Suspect and nontarget analysis, Collaborative trial, Complementary analytical techniques, Mass spectrometry
G. K. Paulus, L. M. Hornstra, N. Alygizakis, J. Slobodnik, N. Thomaidis, G. Medema, The impact of on-site hospital wastewater treatment on the downstream communal wastewater system in terms of antibiotics and antibiotic resistance genes, International Journal of Hygiene and Environmental Health, Volume 222 (4), (2019).
Abstract: This study quantified antibiotic and antibiotic resistance gene (ARG) concentrations in hospital and communal wastewaters as well as the influents and effluents of the receiving urban wastewater treatment plants (UWWTP) in two Dutch cities. In only one city, hospital wastewater was treated on-site using advanced technologies, including membrane bioreactor treatment (MBR), ozonation, granulated activated carbon (GAC) and UV-treatment. On-site hospital wastewater (HWW) treatment reduced gene presence of hospital-related antibiotic resistance genes and antibiotic concentrations in the receiving urban wastewater treatment plant. These findings support the need for on-site treatment of high-risk point sources of antibiotic resistance genes. 13 antibiotic resistance genes, Integrase Class 1 and 16S rRNA concentrations were quantified using multiplex quantitative real-time PCR (qPCR) assays and the presence and/or concentration of 711 antibiotics were analyzed. Hospital wastewater contained approximately 25% more antibiotics and gene concentrations between 0.4 log to 1.8-fold higher than communal wastewater (CWW). blaKPC and vanA could be identified as hospital-related genes and were reduced to under the limit of detection (LOD) during on-site treatment. Advanced on-site treatment removed between 0.5 and 3.6-fold more genes than conventional biological urban wastewater treatment (activated sludge). Advanced on-site treatment was able to eliminate 12 out of 19 detected antibiotics, while urban waste water treatment eliminated up to 1 (out of 21 detected). Different advanced treatment technologies were able to target different pollutants to varying extents, making sequential alignment more effective. MBR treatment was most efficient in antibiotic resistance gene reduction and ozonation in antibiotic reduction. blaKPC could only be detected in the influent of the urban wastewater treatment plant receiving untreated hospital wastewater. Similarly, vanA was only consistently detected in this treatment plant. These results indicate a positive effect of on-site treatment of hospital wastewater on the communal sewage system.
Keywords: Advanced wastewater treatment, Antibiotic resistance, Contaminants of emerging concern, Pharmafilter
W. Brack, B. I. Escher, E. Müller, M. Schmitt-Jansen, T. Schulze, J. Slobodnik, H. Hollert, Towards a holistic and solution-oriented monitoring of chemical status of European water bodies: how to support the EU strategy for a non-toxic environment?, Environmental Sciences Europe, Volume 30 (33), (2018).
Abstract: The definition of priority substances (PS) according to the Water Framework Directive (WFD) helped to remove many of these chemicals from the market and to reduce their concentrations in the European water bodies. However, it could not prevent that many of these chemicals have been replaced by others with similar risks. Today, monitoring of the PS-based chemical status according to WFD covers only a tiny fraction of toxic risks, extensively ignores mixture effects and lacks incentives and guidance for abatement. Thus, we suggest complement this purely status-related approach with more holistic and solution-oriented monitoring, which at the same time helps to provide links to the ecological status. Major elements include (1) advanced chemical screening techniques supporting mixture risk assessment and unraveling of source-related patterns in complex mixtures, (2) effect-based monitoring for the detection of groups of chemicals with similar effects and the establishment of toxicity fingerprints, (3) effect-directed analysis of drivers of toxicity and (4) to translate chemical and toxicological fingerprints into chemical footprints for prioritization of management measures. The requirement of more holistic and solution-oriented monitoring of chemical contamination is supported by the significant advancement of appropriate monitoring tools within the last years. Non-target screening technology, effect-based monitoring and basic understanding of mixture assessment are available conceptually and in research but also increasingly find their way into practical monitoring. Substantial progress in the development, evaluation and demonstration of these tools, for example, in the SOLUTIONS project enhanced their acceptability. Further advancement, integration and demonstration, extensive data exchange and closure of remaining knowledge gaps are suggested as high priority research needs for the next future to bridge the gap between insufficient ecological status and cost-efficient abatement measures.
Keywords: Effect-based methods, Non target analysis, Water Framework Directive, Effect-directed analysis, Integrated assessment
Z. Toušová, B. Vrana, M. Smutná, J. Novák, V. Klučárová, R. Grabic, J. Slobodník, J. P. Giesy, K. Hilscherová, Analytical and bioanalytical assessments of organic micropollutants in the Bosna River using a combination of passive sampling, bioassays and multi-residue analysis, The Science of The Total Environment, Volume 650, (2018).
Abstract: Complex mixtures of contaminants from multiple sources, including agriculture, industry or wastewater enter aquatic environments and might pose hazards or risks to humans or wildlife. Targeted analyses of a few priority substances provide limited information about water quality. In this study, a combined chemical and effect screening of water quality in the River Bosna, in Bosnia and Herzegovina was carried out, with focus on occurrence and effects of contaminants of emerging concern. Chemicals in water were sampled at 10 sites along the Bosna River by use of passive sampling. The combination of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS) enabled sampling of a broad range of contaminants from hydrophobic (PAHs, PCBs, OCPs) to hydrophilic compounds (pesticides, pharmaceuticals and hormones), which were determined by use of GC–MS and LC-MS (MS). In vitro, cell-based bioassays were applied to assess (anti)androgenic, estrogenic and dioxin-like potencies of extracts of the samplers. Of a total of 168 targeted compounds, 107 were detected at least once. Cumulative pollutant concentrations decreased downstream from the city of Sarajevo, which was identified as the major source of organic pollutants in the area. Responses in all bioassays were observed for samples from all sites. In general, estrogenicity could be well explained by analysis of target estrogens, while the drivers of the other observed effects remained largely unknown. Profiling of hazard quotients identified two sites downstream of Sarajevo as hotspots of biological potency. Risk assessment of detected compounds revealed, that 7 compounds (diazinon, diclofenac, 17β-estradiol, estrone, benzo[k]fluoranthene, fluoranthene and benzo[k]fluoranthene) might pose risks to aquatic biota in the Bosna River. The study brings unique results of a complex water quality assessment in a region with an insufficient water treatment infrastructure.
Keywords: Contaminants of emerging concern - passive sampling, In vitro bioassay - endocrine disruption, Hazard profiling - water quality monitoring
N. Alygizakis, S. Samanipour, J. Hollender, M. Ibáñez, S. Kaserzon, V. Kokkali, J. van Leerdam, J. Mueller, M. Pijnappels, M. Reid, E. Schymanski, J. Slobodnik, N. Thomaidis, K. Thomas, Exploring the Potential of a Global Emerging Contaminant Early Warning Network through the use of Retrospective Suspect Screening with High-Resolution Mass Spectrometry, Environmental Science & Technology, Volume 52 (9), (2018).
Abstract: A key challenge in the environmental and exposure sciences is to establish experimental evidence of the role of chemical exposure in human and environmental systems. High resolution and accurate tandem mass spectrometry (HRMS) is increasingly being used for the analysis of environmental samples. One lauded benefit of HRMS is the possibility to retrospectively process data for (previously omitted) compounds that has led to the archiving of HRMS data. Archived HRMS data affords the possibility of exploiting historical data to rapidly and effectively establish the temporal and spatial occurrence of newly identified contaminants through retrospective suspect screening. We propose to establish a global emerging contaminant early warning network to rapidly assess the spatial and temporal distribution of contaminants of emerging concern in environmental samples through performing retrospective analysis on HRMS data. The effectiveness of such a network is demonstrated through a pilot study, where eight reference laboratories with available archived HRMS data retrospectively screened data acquired from aqueous environmental samples collected in 14 countries on 3 different continents. The widespread spatial occurrence of several surfactants (e.g., polyethylene glycols ( PEGs ) and C12AEO-PEGs ), transformation products of selected drugs (e.g., gabapentin-lactam, metoprolol-acid, carbamazepine-10-hydroxy, omeprazole-4-hydroxy-sulfide, and 2-benzothiazole-sulfonic-acid), and industrial chemicals (3-nitrobenzenesulfonate and bisphenol-S) was revealed. Obtaining identifications of increased reliability through retrospective suspect screening is challenging, and recommendations for dealing with issues such as broad chromatographic peaks, data acquisition, and sensitivity are provided.
B. Vrana, F. Smedes, I. Allan, T. Rusina, K. Okonski, K. Hilscherová, J. Novák, P. Tarábek, J. Slobodník, Mobile dynamic passive sampling of trace organic compounds: Evaluation of sampler performance in the Danube River, Science of the Total Environment, Volume 636, (2018).
Abstract: A “dynamic” passive sampling (DPS) device, consisting of an electrically driven large volume water pumping device coupled to a passive sampler exposure cell, was designed to enhance the sampling rate of trace organic compounds. The purpose of enhancing the sampling rate was to achieve sufficient method sensitivity, when the period available for sampling is limited to a few days. Because the uptake principle in the DPS remains the same as for conventionally-deployed passive samplers, free dissolved concentrations can be derived from the compound uptake using available passive sampler calibration parameters. This was confirmed by good agreement between aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) derived from DPS and conventional caged passive sampler. The DPS device enhanced sampling rates of compounds that are accumulated in samplers under water boundary layer control (WBL) more than five times compared with the conventionally deployed samplers. The DPS device was deployed from a ship cruising downstream the Danube River to provide temporally and spatially integrated concentrations. A DPS-deployed sampler with surface area of 400 cm2 can reach sampling rates up to 83 L d−1. The comparison of three passive samplers made of different sorbents and co-deployed in the DPS device, namely silicone rubber (SR), low density polyethylene (LDPE) and SDB-RPS Empore™ disks showed a good correlation of surface specific uptake for compounds that were sampled integratively during the entire exposure period. This provided a good basis for a cross-calibration between the samplers. The good correlation of free dissolved PAHs, PCBs and HCB concentration estimates obtained using SR and LDPE confirmed that both samplers are suitable for the identification of concentration gradients and trends in the water column. We showed that the differences in calculated aqueous concentrations between sampler types are mainly associated with different applied uptake models.
Keywords: Passive sampling, Mass transfer, Trace organic compounds, Joint Danube survey, Water quality
V. Dulio, B. van Bavel, E. Brorström-Lundén, J. Harmsen, J. Hollender, M. Schlabach, J. Slobodnik, K. Thomas, J. Koschorreck, Emerging pollutants in the EU: 10 years of NORMAN in support of environmental policies and regulations, Environmental Sciences Europe, Volume 30 (5), (2018).
Abstract: In 2005, the European Commission funded the NORMAN project to promote a permanent network of reference laboratories and research centers, including academia, industry, standardization bodies, and NGOs. Since then, NORMAN has (i) facilitated a more rapid and wide-scope exchange of data on the occurrence and effects of contaminants of emerging concern (CECs), (ii) improved data quality and comparability via validation and harmonization of common sampling and measurement methods (chemical and biological), (iii) provided more transparent information and monitoring data on CECs, and (iv) established an independent and competent forum for the technical/scientific debate on issues related to emerging substances. NORMAN plays a significant role as an independent organization at the interface between science and policy, with the advantage of speaking to the European Commission and other public institutions with the “bigger voice” of more than 70 members from 20 countries. This article provides a summary of the first 10 years of the NORMAN network. It takes stock of the work done so far and outlines NORMAN’s vision for a Europe-wide collaboration on CECs and sustainable links from research to policy-making. It contains an overview of the state of play in prioritizing and monitoring emerging substances with reference to several innovative technologies and monitoring approaches. It provides the point of view of the NORMAN network on a burning issue—the regulation of CECs—and presents the positions of various stakeholders in the field (DG ENV, EEA, ECHA, and national agencies) who participated in the NORMAN workshop in October 2016. The main messages and conclusions from the round table discussions are briefly presented.
Keywords: NORMAN network, Emerging substances, Contaminants of emerging concern, Science-to-policy, Environmental monitoring
Z. Tousova, P. Oswald, J. Slobodnik, L. Blaha, M. Muz, M. Hu, W. Brack, M. Krauss, C. Di Paolo, Z. Tarcai, T.-B. Seiler, H. Hollert, S. Koprivica, M. Ahel, J. E Schollée, J. Hollender, M. J-F Suter, A. O Hidasi, K. Schirmer, M.Sonavane, S. Ait-Aissa, N. Creusot, F. Brion, J. Froment, A. C. Almeida, K. Thomas, K. E. Tollefsen, S. Tufi, X. Ouyang, P. Leonards, M. Lamoree, V. Osorio Torrens, A. Kolkman, M. Schriks, P. Spirhanzlova, A. Tindall, T. Schulze, European demonstration program on the effect-based and chemical identification and monitoring of organic pollutants in European surface waters, Science of the Total Environment, Volume 601-602, (2017).
Abstract: Growing concern about the adverse environmental and human health effects of a wide range of micropollutants requires the development of novel tools and approaches to enable holistic monitoring of their occurrence, fate and effects in the aquatic environment. A European-wide demonstration program (EDP) for effect-based monitoring of micropollutants in surface waters was carried out within the Marie Curie Initial Training Network EDA-EMERGE. The main objectives of the EDP were to apply a simplified protocol for effect-directed analysis, to link biological effects to target compounds and to estimate their risk to aquatic biota. Onsite large volume solid phase extraction of 50 L of surface water was performed at 18 sampling sites in four European river basins. Extracts were subjected to effect-based analysis (toxicity to algae, fish embryo toxicity, neurotoxicity, (anti-)estrogenicity, (anti-)androgenicity, glucocorticoid activity and thyroid activity), to target analysis (151 organic micropollutants) and to nontarget screening. The most pronounced effects were estrogenicity, toxicity to algae and fish embryo toxicity. In most bioassays, major portions of the observed effects could not be explained by target compounds, especially in case of androgenicity, glucocorticoid activity and fish embryo toxicity. Estrone and nonylphenoxyacetic acid were identified as the strongest contributors to estrogenicity, while herbicides, with a minor contribution from other micropollutants, were linked to the observed toxicity to algae. Fipronil and nonylphenol were partially responsible for the fish embryo toxicity. Within the EDP, 21 target compounds were prioritized on the basis of their frequency and extent of exceedance of predicted no effect concentrations. The EDP priority list included 6 compounds, which are already addressed by European legislation, and 15 micropollutants that may be important for future monitoring of surface waters. The study presents a novel simplified protocol for effect-based monitoring and draws a comprehensive picture of the surface water status across Europe.
Keywords: Adverse effects, EDA-EMERGE, Environmental health, Human health, Large volume solid phase extraction, Simplified effect-directed analysis protocol
J. Munthe, E. Brorström‑Lundén, M. Rahmberg, L. Posthuma, R. Altenburger, W. Brack, D. Bunke, G. Engelen, B. M. Gawlik, J. van Gils, D. López Herráez, T. Rydberg, J. Slobodnik, A. van Wezel, An expanded conceptual framework for solution-focused management of chemical pollution in European waters, Environmental Sciences Europe, Volume 29 (13), (2017).
Abstract: Background: This paper describes a conceptual framework for solutions-focused management of chemical contaminants built on novel and systematic approaches for identifying, quantifying and reducing risks of these substances. Methods: The conceptual framework was developed in interaction with stakeholders representing relevant authorities and organisations responsible for managing environmental quality of water bodies. Stakeholder needs were compiled via a survey and dialogue. The content of the conceptual framework was thereafter developed with inputs from relevant scientific disciplines. Results: The conceptual framework consists of four access points: Chemicals, Environment, Abatement and Society, representing different aspects and approaches to engaging in the issue of chemical contamination of surface waters. It widens the scope for assessment and management of chemicals in comparison to a traditional (mostly) perchemical risk assessment approaches by including abatement- and societal approaches as optional solutions. The solution-focused approach implies an identification of abatement- and policy options upfront in the risk assessment process. The conceptual framework was designed for use in current and future chemical pollution assessments for the aquatic environment, including the specific challenges encountered in prioritising individual chemicals and mixtures, and is applicable for the development of approaches for safe chemical management in a broader sense. The four access points of the conceptual framework are interlinked by four key topics representing the main scientific challenges that need to be addressed, i.e.: identifying and prioritising hazardous chemicals at different scales; selecting relevant and efficient abatement options; providing regulatory support for chemicals management; predicting and prioritizing future chemical risks. The conceptual framework aligns current challenges in the safe production and use of chemicals. The current state of knowledge and implementation of these challenges is described. Conclusions: The use of the conceptual framework, and addressing the challenges, is intended to support: (1) forwarding sustainable use of chemicals, (2) identification of pollutants of priority concern for cost-effective management, (3) the selection of optimal abatement options and (4) the development and use of optimised legal and policy instruments.
Keywords: Conceptual framework, Emerging pollutants, Solutions-focused, Prioritisation, Detection, Effects, Abatement, Mixtures
J. Fick, T. Brodin, M. Heynen, J. Klaminder, M. Jonsson, K. Grabicova, T. Randak, R. Grabic, V. Kodes, J. Slobodnik, A. Sweetman, M. Earnshaw, A. Barra Caracciolo, T. Lettieri, R. Loosh, Screening of benzodiazepines in thirty European rivers, Chemosphere, Volume 176, (2017).
Abstract: Pharmaceuticals as environmental contaminants have received a lot of interest over the past decade but, for several pharmaceuticals, relatively little is known about their occurrence in European surface waters. Benzodiazepines, a class of pharmaceuticals with anxiolytic properties, have received interest due to their behavioral modifying effect on exposed biota. In this study, our results show the presence of one or more benzodiazepine(s) in 86% of the analyzed surface water samples (n = 138) from 30 rivers, representing seven larger European catchments. Of the 13 benzodiazepines included in the study, we detected 9, which together showed median and mean concentrations (of the results above limit of quantification) of 5.4 and 9.6 ng L−1, respectively. Four benzodiazepines (oxazepam, temazepam, clobazam, and bromazepam) were the most commonly detected. In particular, oxazepam had the highest frequency of detection (85%) and a maximum concentration of 61 ng L−1. Temazepam and clobazam were found in 26% (maximum concentration of 39 ng L−1) and 14% (maximum concentration of 11 ng L−1) of the samples analyzed, respectively. Finally, bromazepam was found only in Germany and in 16 out of total 138 samples (12%), with a maximum concentration of 320 ng L−1. This study clearly shows that benzodiazepines are common micro-contaminants of the largest European river systems at ng L−1 levels. Although these concentrations are more than a magnitude lower than those reported to have effective effects on exposed biota, environmental effects cannot be excluded considering the possibility of additive and sub-lethal effects.
Keywords: Anxiolytics, Oxazepam, Temazepam, Clobazam, Bromazepam
T. Schulze, M. Ahel, J. Ahlheim, S. Aït-Aïssa, F. Brion, C. Di Paolo, J. Froment, A. O. Hidasi, J. Hollender, H. Hollert, M. Hu, A. Kloß, S. Koprivica, M. Krauss, M. Muz, P. Oswald, M. Petre, J. E. Schollée, T.-B. Seiler, Y. Shao, J. Slobodnik, M. Sonavane, M. J.-F. Suter, K. E. Tollefsen, Z. Tousova, K.-H. Walz, W. Brack, 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, Science of the Total Environment, Volume 581-582, (2017).
Abstract: 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 pH 7.0) 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 (1 ng L−1 to 2400 ng L−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.
Keywords: Automated water sampler, Chemical analysis, Bioassay analysis, Effect-based analysis, Applicability domain, Large-volume solid phase extraction, LVSPE
B. Deutschmann, S. Kolarevic, W. Brack, S. Kaisarevic, J. Kostic, M. Kracun-Kolarevic, I. Liska, M. Paunovic, T.-B. Seiler, Y. Shao, S. Sipos, J. Slobodnik, I. Teodorovic, B. Vukovic-Gacic, H. Hollert, Longitudinal profile of the genotoxic potential of the River Danube on erythrocytes of wild common bleak (Alburnus alburnus) assessed using the comet and micronucleus assay, Science of The Total Environment (2016).
Abstract: The Joint Danube Survey 3 (JDS3; the biggest river expedition in 2013) had offered the unique opportunity for a large-scale monitoring approach for biomarker response in feral fish collected along a Danube stretch from Kehlheim (DE) to Sulina (RO). The advantage of genotoxicity as a marker for pollution exposure in fish is the early detection of possible long-term effects such as cancer. Therefore, genotoxicity was in the focus of the biomarker investigations in fish during the expedition. Blood samples of common bleak (Alburnus alburnus) for the investigation of the micronucleus frequency and comet tail intensity of fragmented DNA material in erythrocytes were collected at 18 and 12 sampling sites, respectively. For 9 sampling sites same samples were used to compare the in-situ data for the comparable genotoxic endpoint in the micronucleus (MN) and comet assay (CM). The data of both in-situ assays showed a significant correlation, indicating the strength and comparability of the data sets. Significant variation in DNA damage in fish along the longitudinal profile of the Danube was demonstrated for both assays compared to reference sites. The results suggest that DNA damage in erythrocytes of fish was mainly affected by wastewater of highly populated regions. No linkage between the results and the general health/dietary status of the fish were revealed, whereas correlation with some genotoxicity drivers in the water phase, suspended particulate matter and sediments could be demonstrated.
Keywords: Genotoxicity; Comet assay; Micronucleus assay; In-situ; Fish; Danube; Joint Danube Survey 3
X. Ouyang, P. E. G. Leonards, Z. Tousova, J. Slobodnik, J. de Boer, M. H. Lamoree, Rapid Screening of Acetylcholinesterase Inhibitors by Effect-Directed Analysis Using LC × LC Fractionation, a High Throughput in Vitro Assay, and Parallel Identification by Time of Flight Mass Spectrometry, Analytical Chemistry 88(4), (2016).
Abstract: Effect-directed analysis (EDA) is a useful tool to identify bioactive compounds in complex samples. However, identification in EDA is usually challenging, mainly due to limited separation power of the liquid chromatography based fractionation. In this study, comprehensive two-dimensional liquid chromatography (LC × LC) based microfractionation combined with parallel high resolution Time of Flight (HR-ToF) mass spectrometric detection and a high throughput acetylcholinesterase (AChE) assay was developed. The LC × LC fractionation method was validated using analytical standards and a C18 and pentafluorophenyl (PFP) stationary phase combination was selected for the two dimensional separation and fractionation in four 96 well plates. The method was successfully applied to identify AChE inhibitors in a wastewater treatment plant (WWTP) effluent. Good orthogonality (>0.9) separation was achieved and three AChE inhibitors (tiapride, amisulpride, lamotrigine), used as antipsychotic medicines, were identified and confirmed by two dimensional retention alignment as well as their AChE inhibition activity.
V. Dulio, J. Slobodnik, In Response: The NORMAN perspectives on prioritization of emerging pollutants, Environmental Toxicology and Chemistry 34(10):2183-2185 (2015).
P. Pavlović, M. Mitrović, D. Đorđević, S. Sakan, J. Slobodnik, I. Liška, B. Csanyi, S. Jarić, O. Kostić, D. Pavlović, N. Marinković, B. Tubić, M. Paunović, Assessment of the contamination of riparian soil and vegetation by trace metals - A Danube River case study, Science of The Total Environment (2015).
Abstract: The aim of this study was to assess the spatial distribution of arsenic and heavy metals (Cd, Cr, Cu Hg, Ni, Pb and Zn) in a riparian area influenced by periodical flooding along a considerable stretch of the Danube River. This screening was undertaken on soil and plant samples collected from 43 sites along 2386km of the river, collected during the international Joint Danube Survey 3 expedition (ICPDR, 2015). In addition, data on the concentration of these elements in river sediment was used in order to describe the relationship between sediment, riparian soil and riparian plants. A significant positive correlation (Spearman r, for p<0.05) was found for trace metal concentrations in river sediment and soil (r=0.817). A significant correlation between soil and plants (r=0.438) and sediment and plants (r=0.412) was also found for trace metal concentrations. Elevated levels of Cd, Cr, Cu, and Ni were found at certain sites along the Serbian stretch, while elevated concentrations of Hg were also detected in Hungary, of Pb along the Romanian stretch and of As along the Bulgarian stretch (the Lower Danube). These results point to the presence of naturally-occurring metals derived from ore deposits in the Danube River Basin and anthropogenic metals, released by mining and processing of metal ores and other industrial facilities, which are responsible for the entry of metals such as Cu, Ni and Zn. Our results also indicated toxic Cd and Zn levels in plant samples, measured at the Hercegsznato site (Middle Danube, Hungary), which highlighted these elements as a potential limiting factor for riparian vegetation in that area. The distribution of the analysed elements in plant material also indicates the species-specific accumulation of trace metals. Based on our results, the Lower and Middle Danube were found to be more polluted in terms of the analysed elements.
Keywords: Danube River; Riparian soil; Riparian vegetation; Trace metal pollution
S. Kolarević, M. Kračun-Kolarević, J. Kostić, J. Slobodnik, I. Liška, Z. Gačić, M. Paunović, J. Knežević-Vukčević, B. Vuković-Gačić, Assessment of the genotoxic potential along the Danube River by application of the comet assay on haemocytes of freshwater mussels: The Joint Danube Survey 3, Science of The Total Environment 540 (2015).
Abstract: In this study we assessed the level of genotoxic pollution along the Danube River by measuring the level of DNA damage in the haemocytes of freshwater mussels of Unio sp. (Unio pictorum/Unio tumidus) and Sinanodonta woodiana. The comet assay was used for the assessment of DNA damage. The research was performed on 34 out of 68 sites analysed within the Joint Danube Survey 3 - the world's biggest river research expedition of its kind in 2013. During research, 2285 river kilometres were covered with an average distance of 68km between the sites. The complex data set on concentrations of various substances present in water, suspended particulate matter and sediment on investigated sites gave the opportunity to identify the groups of xenobiotics which mostly affect the studied biomarker - DNA damage. The highest levels of DNA damage were recorded in the section VI (Panonnian Plain), which is under the impact of untreated wastewater discharges. Both positive and negative influences of the large tributaries on the level of genotoxicity in the Danube River were evident. Significant correlation in response was detected between the studied species of freshwater mussels. The level of DNA damage in mussels correlated with concentrations of compounds from the group of hazardous priority substances (polycyclic aromatic hydrocarbons), persistent organic pollutants (dioxins) and emerging pollutants (Oxazepam, Chloridazon-desphenyl).
Keywords: The Danube River; Genotoxicity; Comet assay; Unio pictorum
E. L. Schymanski, H. P. Singer, J. Slobodnik, I. M. Ipolyi, P. Oswald, M. Krauss, T. Schulze, P. Haglund, T. Letzel, S. Grosse, N. S. Thomaidis, A. Bletsou, C. Zwiener, M. Ibáñez, T. Portolés, R. de Boer, M. J. Reid, M. Onghena, U. Kunkel, W. Schulz, A. Guillon, N. Noyon, G. Leroy, P. Bados, S. Bogialli, D. Stipaničev, P. Rostkowski, J. Hollender, Non-target screening with high-resolution mass spectrometry: Critical review using a collaborative trial on water analysis, Analytical and Bioanalytical Chemistry 407(21), (2015).
B. Vrana, F. Smedes, T. Rusina, K. Okonski, I. Allan, M. Grung, K. Hilscherova, J. Novák, P. Tarábek, J. Slobodník, Passive sampling: chemical analysis and toxicological profiling, in Joint Danube Survey 3, I. Liška, F. Wagner, M. Sengl, K. Deutsch, and J. Slobodník, Eds. Vienna: ICPDR – International Commission for the Protection of the Danube River, 304–315 (2015).
Abstract: Organic pollutants are often present in the water column at trace concentrations that are difficult to detect when conventional low volume spot sampling of water is applied. The scope of the sampling campaign performed using passive samplers was the screening of trace organic pollutants and their toxic potentials in the water column of the Danube, as well as the assessment of their spatial distribution along the river. Freely dissolved concentrations of priority substances in the water phase (cfree) can be derived from the uptake of these substances by passive samplers, and because accumulated contaminants represent a large water volume, low limits of quantification can be obtained. Cfree is a more stable parameter than a concentration measured in whole water as the level is not influenced by variable amounts of the substance bound to dissolved and suspended particulate organic matter. Thus, it is very suitable for assessment of trends. Cfree is further considered to play a key role in chemical uptake by aquatic organisms. It is proportional to the chemical activity (Mayer et al., 2003) and if in equilibrium with surrounding environmental compartments it also represents chemical activity of those environmental compartments, including the biota at the base of the food chain (Reichenberg and Mayer, 2006). We used an “active” passive sampling system (APS) for temporally and spatially integrative sampling of trace organic pollutants. APS is used in a concept similar to that of a Ferry-Box (“Website of the European Ferrybox Community,” 2014) to obtain a representative picture of pollution situation along defined stretches or transects of large water bodies including rivers, lakes or seas. The uptake principle in the APS remains the same as in classical static passive sampling and the monitoring results can be evaluated using usual passive sampler calibration parameters. The APS enhances the uptake rate of contaminants into passive samplers, thereby allowing to drastically reduce the exposure time needed for accumulation of sufficient chemicals for analysis. The application of temporal- and spatial- integrative passive sampling approach resulted in samples that provide a representative picture of pollution situation in eight defined stretches of the Danube River.
R. Altenburger, S. Ait-Aissa, P. Antczak, T. Backhaus, D. Barceló, T.-B. Seiler, F. Brion, W. Busch, K. Chipman, M. López de Alda, G. de Aragão Umbuzeiro, B. I. Escher, F. Falciani, M. Faust, A. Focks, K. Hilscherova, J. Hollender, H. Hollert, F. Jäger, A. Jahnke, A. Kortenkamp, M. Krauss, G. F. Lemkine, J. Munthe, S. Neumann, E. L. Schymanski, M. Scrimshaw, H. Segner, J. Slobodnik, F. Smedes, S. Kughathas, I. Teodorovic, A. J. Tindall, K. Erik Tollefsen, K.-H. Walz, T. D. Williams, P. J. Van den Brink, J. van Gils, B. Vrana, X. Zhang, W. Brack, Future water quality monitoring - Adapting tools to deal with mixtures of pollutants in water resource management, Science of The Total Environment 512-513C:540-551 (2015).
Abstract: Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.
J. Slobodnik, P. Carsten von der Ohe, Identification of the Danube River Basin Specific Pollutants and Their Retrospective Risk Assessment (2015).
Abstract: Following the requirements of the European Water Framework Directive (WFD), a process of selecting pollutants relevant at the river basin scale started in 2001. In the Danube river basin, the process was aided by two Joint Danube Surveys (JDS1 and JDS2) organised by the International Commission for the Protection of the Danube River (ICPDR) in 2001 and 2007, respectively. This study was retrospectively analysing all data on organic substances identified in the water samples collected within the two surveys and comparing them to the latest Environmental Quality Standards (EQSs) as well as ecotoxicological threshold values (Predicted No Effect Concentrations; PNECs) that were not available at the time of writing the JDS1/2 Final Scientific Reports. The results showed that 26 out of 89 substances detected in the samples exceeded the EQS/PNEC values in at least one sampling site and 53 substances were found above their limit of quantification (LOQ) at more than five sampling sites within the basin. The above-mentioned 26 substances deserve closer attention as candidates for the list of Danube River Basin Specific Pollutants (DRBSPs). A novel approach of ranking gas chromatography–mass spectrometry (GC–MS) nontarget screening data, based on the assessment of (1) available literature PNEC values (19 substances), (2) derived provisional PNEC (P-PNEC) values (160 substances) and (3) estimated concentrations of tentatively identified substances, has been applied too. Sixty-five out of a total of 179 compounds identified in the JDS samples exceeded the ecotoxicological threshold value in at least one sampling site, which makes them potential candidates for inclusion into future investigative monitoring schemes.
T. Schulze, M. Krauss, J. Novak, K. Hilscherova, S. Ait-Aissa, N. Creusot, M. Macova, P. Neale, B. I. Escher, T. Gomes, K. Erik Tollefsen, Z. Tarcai, Y. Shao, B. Deutschmann, T.-B. Seiler, H. Hollert, P. Tarabek, Z. Tusova, J. Slobodnik, K.-H. Walz, W. Brack, Large volume sampling and effect-based screening, in Joint Danube Survey 3, I. Liška, F. Wagner, M. Sengl, K. Deutsch, and J. Slobodník, Eds. Vienna: ICPDR – International Commission for the Protection of the Danube River, 304–315 (2015).
C. Ort, A. L. N. van Nuijs, J.-D. Berset, L. Bijlsma, S. Castiglioni, A. Covaci, P. de Voogt, E. Emke, D. Fatta-Kassinos, P. Griffiths, F. Hernández, I. González-Mariño, R. Grabic, B. Kasprzyk-Hordern, N. Mastroianni, A. Meierjohann, T. Nefau, M. Östman, Y. Pico, I. Racamonde, M. Reid, J. Slobodnik, S. Terzic, N. Thomaidis, K. V. Thomas, Spatial differences and temporal changes in illicit drug use in Europe quantified by wastewater analysis, Addiction (2014).
Abstract: AimsTo perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population.DesignAnalyses of raw wastewater over a 1-week period in 2012 and 2013.Setting and ParticipantsCatchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million).MeasurementsExcretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrometry.FindingsSpatial differences were assessed and confirmed to vary greatly across European metropolitan areas. In general, results were in agreement with traditional surveillance data, where available. While temporal changes were substantial in individual cities and years (P ranging from insignificant to <10−3), overall means were relatively stable. The overall mean of methamphetamine was an exception (apparent decline in 2012), as it was influenced mainly by four cities.Conclusions Wastewater analysis performed across Europe provides complementary evidence on illicit drug consumption and generally concurs with traditional surveillance data. Wastewater analysis can measure total illicit drug use more quickly and regularly than is the current norm for national surveys, and creates estimates where such data does not exist.
Keywords: Amphetamine; cannabis; cocaine; drugs of abuse; ecstasy; methamphetamine; sewage
W. Brack, R. Altenburger, G. Schüürmann, M. Krauss, D. López Herráez, J. van Gils, J. Slobodnik, J. Munthe, B. Manfred Gawlik, A. van Wezel, M. Schriks, J. Hollender, K. Erik Tollefsen, O. Mekenyan, S. Dimitrov, D. Bunke, I. Cousins, L. Posthuma, P. J. van den Brink, M. López de Alda, D. Barceló, M. Faust, A. Kortenkamp, M. Scrimshaw, S. Ignatova, G. Engelen, G. Massmann, G. Lemkine, I. Teodorovic, K.-H. Walz, V. Dulio, M. T.O. Jonker, F. Jäger, K. Chipman, F. Falciani, I. Liska, D. Rooke, X. Zhang, H. Hollert, B. Vrana, K. Hilscherova, K. Kramer, S. Neumann, R. Hammerbacher, T. Backhaus, J. Mack, H. Segner, B. Escher, G. de Aragão Umbuzeiro, The SOLUTIONS project: Challenges and responses for present and future emerging pollutants in land and water resources management, Science of The Total Environment (2014).
Abstract: SOLUTIONS (2013 to 2018) is a European Union Seventh Framework Programme Project (EU-FP7). The project aims to deliver a conceptual framework to support the evidence-based development of environmental policies with regard to water quality. SOLUTIONS will develop the tools for the identification, prioritisation and assessment of those water contaminants that may pose a risk to ecosystems and human health. To this end, a new generation of chemical and effect-based monitoring tools is developed and integrated with a full set of exposure, effect and risk assessment models. SOLUTIONS attempts to address legacy, present and future contamination by integrating monitoring and modelling based approaches with scenarios on future developments in society, economy and technology and thus in contamination. The project follows a solutions-oriented approach by addressing major problems of water and chemicals management and by assessing abatement options. SOLUTIONS takes advantage of the access to the infrastructure necessary to investigate the large basins of the Danube and Rhine as well as relevant Mediterranean basins as case studies, and puts major efforts on stakeholder dialogue and support. Particularly, the EU Water Framework Directive (WFD) Common Implementation Strategy (CIS) working groups, International River Commissions, and water works associations are directly supported with consistent guidance for the early detection, identification, prioritisation, and abatement of chemicals in the water cycle. SOLUTIONS will give a specific emphasis on concepts and tools for the impact and risk assessment of complex mixtures of emerging pollutants, their metabolites and transformation products. Analytical and effect-based screening tools will be applied together with ecological assessment tools for the identification of toxicants and their impacts. The SOLUTIONS approach is expected to provide transparent and evidence-based candidates or River Basin Specific Pollutants in the case study basins and to assist future review of priority pollutants under the WFD as well as potential abatement options.
Jaroslav Slobodnik and Valeria Dulio, NORMAN Association: A Network Approach to Scientific Collaboration on Emerging Contaminants and their Transformation Products in Europe (2014) 915-928
W. Brack, V. Dulio and J. Slobodnik, The NORMAN Network and its activities on emerging environmental substances with a focus on effect-directed analysis of complex environmental contamination, Environmental Sciences Europe (2012) 24:29.
Abstract: The need to look beyond the conventional target pollutants when assessing the hazards of chemicals to human health and to ecosystems is now generally recognised as a priority issue in all environmental policy areas at both the European level and national level in the various countries. It has also become clear that it is not possible for individual countries alone to develop the knowledge and methodologies needed for measuring and evaluating the effects and associated risks of a vast number of emerging pollutants. Further to these priority needs, the NORMAN project (www.norman-network.net) was funded in 2005 by the European Commission in order to promote the creation of a permanent network among reference laboratories and research centres, in collaboration with the parties involved (industry, standardisation bodies, NGOs, etc.), to ensure (i) a more rapid and wide-scope exchange of data and information on the occurrence and effects of emerging substances, (ii) better data quality and comparability via validation and harmonisation of common measurement methods (chemical and biological) and monitoring tools, (iii) more transparent information (need for information, not just data) and (iv) the establishment of an independent and competent forum for the technical/scientific debate on issues related to emerging substances. NORMAN plays a significant role as an interface organisation between science and policy, with the advantage of speaking with a “bigger voice” to the European Commission and other public institutions. The activities of the network range from a scientific watch and the feeding of data on emerging substances into NORMAN databases (information gateway on emerging pollutants) to the organisation of working groups and workshops (producing position papers on research priorities), the setting-up of interlaboratory studies and the organisation of measurement campaigns. This article presents the objectives and scope of the activities of the NORMAN network, together with a summary of its concrete achievements after six years of existence. Moreover, the article gives a special insight in the work done by the NORMAN Working Group on effect-directed analysis for the identification of hazardous pollutants.
Keywords: Emerging substances, Effect-directed analysis, Monitoring
J. Slobodnik, L. Mrafkova, M. Carere, F. Ferrara, B. Pennelli, G. Schuurmann, P. C. von der Ohe, Identification of river basin specific pollutants and derivation of environmental quality standards: A case study in the Slovak Republic, Trends in Analytical Chemistry, Vol. 41 (2012) 133 - 145.
Abstract: Following the requirements of the European Water Framework Directive (WFD), a process of selecting relevant dangerous substances and developing related Pollution Reduction Programme (PRP) has started in the Slovak Republic in 2001. Based on the results of a three years investigative screening campaign, 59 chemical substances were identified as relevant dangerous substances in 2004 and included in the national PRP. This study describes two independent prioritization approaches that have been applied to revise the list of relevant dangerous substances in 2010. The first approach was using a classification system based on the occurrence monitoring data of these substances combined with self-monitoring data by industries on their emissions into wastewaters and data on production/usage of chemicals and agricultural pesticides. As an outcome, 41 of the 59 relevant substances were proposed to be retained in the updated PRP. The second approach was based on the evaluation of the Frequency of exceedance and the Extent of exceedance of environmental thresholds, referred to as predicted no effect concentrations (PNEC), for all organic compounds monitored in the river systems of the Slovak Republic from 2001 to 2010, with exclusion of WFD priority substances (PS). The results showed that 18 of 87 monitored compounds deserve closer attention in future revisions of the list, out of which 11 pollutants were new candidates to expand the list of relevant substances. The two approaches were found complementary. The methodology included a“safety net” to capture new pollutants not previously listed among the above target substances. A novel approach of prioritizing gas chromatography - mass spectrometry (GC-MS) non-target screening data, based on the assessment of (i) derived provisional PNEC (P-PNEC) values and (ii) estimated concentrations of tentatively identified substances, has been applied for the first time. P-PNEC values were derived for 242 substances and the prioritization effort resulted in a list of 60 new substances that might be potential candidates for inclusion into investigative monitoring schemes and, if their relevance confirmed, into the updated PRP.
Keywords: Dangerous substance; Emission; Environmental quality standard (EQS); Environmental threshold; Monitoring; Pesticide; Pollution Reduction Programme (PRP); River basin specific pollutant; Slovak Republic; Wastewater
P.C. von der Ohe, M. Schmitt-Jansen, J. Slobodnik, W. Brack, Triclosan - the forgotten priority substance, Environ. Sci. Pollut. Res. (2011).
Abstract: 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.
Keywords: Triclosan, Prioritisation, Priority substance, River basin-specific pollutant, Biocide.
P. C. von der Ohe, V. Dulio, J. Slobodnik, E. De Deckere, R. Kühne, R-U Ebert, A. Ginebreda, W. De Cooman, G. Schüürmann, W. Brack, 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, Science of the Total Env., 409 (2011) 2064-2077.
Abstract: 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 (PNECacute) or chronic-based thresholds (PNECchronic). 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.
Keywords: PNECacute; PNECchronic; P-PNEC; River Basin specific pollutants; Prioritization; River basin specific pollutants; Pesticides
D. Schwesig, U. Borchers, L. Chancerelle, V. Dulio, U. Eriksson, M. Farré, A. Goksoyr , M. Lamoree, P. Leonards, P. Lepom, D. Leverett, A. O’Neill, R. Robinson, K. Silharova, J. Slobodnik, P. Tolgyessy, R. Tutundjian, J-W. Wegener, D. Westwood, A Harmonised European Framework for Method Validation to Support Research on Emerging Pollutants, Trends in Analytical Chemistry, Vol. 30, No. 8 (2011) 1233 - 1242.
Abstract: Any investigation of environmental processes related to chemical substances or their effects depends on reliable, comparable analytical data. This also holds true for the impact of climate change on occurrence, distribution and effects of emerging pollutants, with respect to which there is particular concern regarding the reliability of analytical data, due to lack of harmonization in method validation and requirements for quality assurance and quality control (QA/QC). We present a recent European approach to developing a harmonized framework for method validation, QA/QC and provision of environmental data on emerging pollutants. The validation approach has been tested and improved by three case studies. We outline the main concept of the validation approach as well as the results of the case studies. This European validation framework turned out to be a feasible tool to check the fitness for purpose of analytical methods and to improve the reliability of environmental analytical data, particularly for emerging pollutants. Keywords: Analytical data; Climate change; Emerging pollutant; European validation framework; Environmental data; Fitness for purpose; Harmonization; Method validation; Quality assurance; Quality control
J. Tschmelak, G. Proll, J. Riedt, J. Kaiser, P. Kraemmer, L. Barzaga. J. S. Wilkinson, P. Hua, J. P. Hole, R. Nudd, M. Jackson, R. Abuknesha, D. Barcelo, S. Rodriguez-Mozaz, M. J. Lopez de Alda, F. Sacher, J. Stien, J. Slobodnik, P. Oswald, H. Kozmenko, E. Korenkova, L. Tothova, Z. Krascsenits, G. Gauglitz, Automated water analyser computer supported system (AWACSS)–part I: project objectives, basic technology, immunoassay development, software design and networking, Biosensors and Bioelectronics 20 (2005) 1499–1508.
Abstract: A novel analytical system AWACSS (automated water analyser computer-supported system) based on immunochemical technology has been developed that can measure several organic pollutants at low nanogram per litre level in a single few-minutes analysis without any prior sample pre-concentration nor pre-treatment steps. Having in mind actual needs of water-sector managers related to the implementation of the Drinking Water Directive (DWD) (98/83/EC, 1998) and Water Framework Directive WFD (2000/60/EC, 2000), drinking, ground, surface, and waste waters were major media used for the evaluation of the system performance. The instrument was equipped with remote control and surveillance facilities. The system's software allows for the internet-based networking between the measurement and control stations, global management, trend analysis, and early-warning applications. The experience of water laboratories has been utilised at the design of the instrument's hardware and software in order to make the system rugged and user-friendly. Several market surveys were conducted during the project to assess the applicability of the final system. A web-based AWACSS database was created for automated evaluation and storage of the obtained data in a format compatible with major databases of environmental organic pollutants in Europe. This first part article gives the reader an overview of the aims and scope of the AWACSS project as well as details about basic technology, immunoassays, software, and networking developed and utilised within the research project. The second part article reports on the system performance, first real sample measurements, and an international collaborative trial (inter-laboratory tests) to compare the biosensor with conventional anayltical methods.
J. Tschmelak, G. Proll, J. Riedt, J. Kaiser, P. Kraemmer, L. Barzaga. J. S. Wilkinson, P. Hua, J. P. Hole, R. Nudd, M. Jackson, R. Abuknesha, D. Barcelo, S. Rodriguez-Mozaz, M. J. Lopez de Alda, F. Sacher, J. Stien, J. Slobodnik, P. Oswald, H. Kozmenko, E. Korenkova, L. Tothova, Z. Krascsenits, G. Gauglitz, Automated Water Analyser Computer Supported System (AWACSS) Part II. Intelligent, remote-controlled, cost-effective, on-line, water-monitoring measurement system, Biosensors and Bioelectronics 20 (2005) 1509–1519.
Abstract: A novel analytical system AWACSS (Automated Water Analyser Computer Supported System) based on immunochemical technology has been evaluated that can measure several organic pollutants at low nanogram per litre level in a single few-minutes analysis without any prior sample pre-concentration or pre-treatment steps. Having in mind actual needs of water-sector managers related to the implementation of the Drinking Water Directive (DWD) [98/83/EC, 1998. Council Directive (98/83/EC) of 3 November 1998 relating to the quality of water intended for human consumption. Off. J. Eur. Commun. L330, 32-54] and Water Framework Directive (WFD) [2000/60/EC, 2000. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Off. J. Eur. Commun. L327, 1-72], drinking, ground, surface, and waste waters were major media used for the evaluation of the system performance. The first part article gave the reader an overview of the aims and scope of the AWACSS project as well as details about basic technology, immunoassays, software, and networking developed and utilised within the research project. The second part reports on the system performance, first real sample measurements, and an international collaborative trial (inter-laboratory tests) to compare the biosensor with conventional anayltical methods. The systems' capability for analysing a wide range of environmental organic micro-pollutants, such as modern pesticides, endocrine disrupting compounds and pharmaceuticals in surface, ground, drinking and waste water is shown. In addition, a protocol using reconstitution of extracts of solid samples, developed and applied for analysis of river sediments and food samples, is presented. Finally, the overall performance of the AWACSS system in comparison to the conventional analytical techniques, which included liquid and gas chromatographic systems with diode-array UV and mass spectrometric detectors, was successfully tested in an inter-laboratory collaborative trial among six project partners.
J. Tschmelak, G. Proll, J. Riedt, J. Kaiser, P. Kraemmer, L. Barzaga. J. S. Wilkinson, P. Hua, J. P. Hole, R. Nudd, M. Jackson, R. Abuknesha, D. Barcelo, S. Rodriguez-Mozaz, M. J. Lopez de Alda, F. Sacher, J. Stien, J. Slobodnik, P. Oswald, H. Kozmenko, E. Korenkova, L. Tothova, Z. Krascsenits, G. Gauglitz, Biosensors for unattended, cost-effective and continuous monitoring of environmental pollution: Automated Water Analyser Computer Supported System (AWACSS) and River Analyser (RIANA), Intern. J. Environ. Anal. Chem., 85, No. 12–13, (2005) 837–852.
Abstract: This work describes our recent progress and achievements in the field of fully automated biosensors (Automated Water Analyser Computer Supported System (AWACSS) and River Analyser (RIANA)) for unattended, cost-effective and continuous monitoring of environmental pollution. We report on ultra-sensitive immunoassays for the hormones progesterone, testosterone and estrone and the pesticides propanil and isoproturon as examples of the outstanding progress made on biosensors in the field of environmental monitoring and water analysis. Most of the bio-active organic pollutants (estrone, progesterone, propanil and isoproturon) were detected at levels as low as 1.0 pg/mL or even below. In fact, the reported limits of detection (LOD) were between 0.2 and 6.0 pg/mL. For the first time, commercially available derivatives and antibodies were incorporated into immunoassays (progesterone and testosterone) for fully automated biosensors. To verify the assay performance for quantifying testosterone, progesterone, and isoproturon in real-world samples using our immunosensors, we spiked river and drinking water at six different levels from 0.9 pg/mL to 90 ng/mL. Nearly all recovery rates could be obtained between 70 and 120% as the AOAC International recommends it chiefly for water analysis.
E. Korenková, E. Matisová, J. Slobodník, Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash, Waste Management 02/2006; 26(9):1005-16.
Abstract: Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.
E. Korenková, E. Matisová, J. Slobodník, Optimization of conditions for PTV large-volume injection combined with fast GC-MS, J. Chromatogr. Sci. 42 (10) (2004) 531.
Abstract: Large-volume injection utilizing programmable temperature vaporizer in solvent vent mode is combined with fast capillary gas chromatography and mass spectrometric detection. Optimized injection and chromatographic conditions made possible manual injection of a 20-microL ethyl acetate extract containing 15 organochlorine pesticides and their separation on a short, 0.1-mm-i.d. column in less than 8 min.
E. Korenková, E. Matisová, J. Slobodník, Study on the feasibility of coupling large-volume injection to fast gas chromatography with mass spectrometric detection for analysis of organochlorine pesticides, J. Sep. Sci., 26 (2003) 1193 - 1197.
Abstract: A combined use of programmable temperature vaporisation injector, fast oven temperature ramp, 0.1 mm ID analytical column and hydrogen carrier gas enabled injection of up to 20 μL of extract containing 15 organochlorine pesticides and separation of all analytes in less than 8 minutes.
F.Ariese, K. Swart, R. Morabito, C.Brunori, S. Balzamo, J.Slobodník, E. Korenková, P. Janoš, M. Wildnerova, J. Hlavay, K. Polyák, P. Fodor and H. Muntau, Leaching studies of inorganic and organic compounds from fly ash, Intern. J. Environ. Anal. Chem., 82, 11 – 12 (2003) 751.
E. Korenková, E. Matisová, J. Slobodník, Dávkovanie veľkých objemov v kapilárnej plynovej chromatografii s injektorom s programovateľnou teplotou odparovania, Chemické Listy 96 (2002) 82.
J. Slobodník – co-author, Joint Danube Survey, Technical Report of the International Commission for the Protection of the Danube River, Sept. 2002.
J. Slobodník, I. Liska, Basin-wide crusade against pollution of the Danube, International Commission for the Protection of the Danube River, Danube Watch 1 (2001) 6.
E. Korenková, E. Matisová, J. Slobodník, Large volume injection in capillary gas chromatography, Chem. Letters 95 (2001) 528-539.
Abstract: The review deals with large-volume injection techniques in capillary GC. Basic principles, advantages and limitations of cool on-column injection in standard setup and with the use of solvent vapour exit, as well as of loop-type injection are described. An overview of applications is summarized.
E. Korenková, E. Matisová, J. Slobodník, Dávkovanie veľkých objemov v kapilárnej plynovej chromatografii, Chemické Listy 95 (2001) 528.
J. Krupčík, P. Oswald, E. Benická, D. Oktavec, I. Skačáni, P. Daučík, P. Sandra, Determination of high boiling petroleum hydrocarbons in environmental samples, J. High Resolut. Chrom. 23, (2000) 286.
J. Slobodník and U.A.Th Brinkman, LC/MS interfacing systems: applications to polar pesticides, in D. Barcelo (ed.) Environmental Analysis, Sample Handling and Trace Analysis of Pollutants, Elsevier, 2000.
J. Slobodník, S. Ramalho, B.L.M. van Baar, A.J.H. Louter and U.A.Th. Brinkman, Determination of microcontaminants in sediments by on-line solid-phase extraction-gas chromatography-mass spectrometry, Chemosphere, 41 (2000) 1469.
Abstract: Two simple and straightforward analytical procedures for the screening of sediment samples are reported. They involve extraction with ethyl acetate or methanol and subsequent analysis by means of gas chromatography-mass spectrometry (GC-MS) using large-volume injection (LVI) or solid-phase extraction (SPE). The latter, which was originally developed for the analysis of aqueous samples, can be used without any modification. In general, 10 ml of organic solvent were added to 2 g of sediment, and the mixture was shaken and allowed to stand overnight. The methanolic extracts were then diluted in water and subjected to preconcentration and analysis using on-line SPE-GCMS. The ethyl acetate extracts were injected directly into the GC using LVI. Both methods were used for the detection and identification of microcontaminants during a monitoring study of the river Nitra (Slovak Republic). They included polyaromatic hydrocarbons (PAHs), chlorofluorohydrocarbons, alkoxylated and alkylated phenols and benzothiazole derivatives. Semi-quantitative profiles of the contaminants were constructed and provisionally interpreted. The results indicate that SPE-GC-MS, and also LVI-GC-MS, have good potential for a rapid screening of sediment samples and the identification of microcontaminants. The analytical procedures pose no problems, and the on-line set-up is user-friendly. (C) 2000 Elsevier Science Ltd. All rights reserved.