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.