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Veröffentlichung Spatial distribution and temporal trends of pharmaceuticals sorbed to suspended particulate matter of German rivers(2020) Boulard, Lise; Dierkes, Georg; Schlüsener, Michael P.; Koschorreck, JanAlthough several studies confirmed a wide distribution of pharmaceuticals in rivers and streams, a limited knowledge is available about the partitioning of pharmaceuticals between the water phase and suspended particulate matter (SPM). To close this gap of knowledge, we developed and validated a sensitive and high throughput analytical method for the analysis of 57 pharmaceuticals, 42 metabolites and transformation products (TP) as well as the artificial sweetener acesulfame sorbed to SPM. The method was based on pressurized liquid extraction (PLE) followed by a clean-up via solvent exchange and detection via direct injection-reversed phase LC-MS/MS and freeze-drying-HILIC-MS/MS. Freundlich isotherms were determined for 90 analytes. All showed a linear sorption behavior. Distribution coefficients (Kd) ranged from 0.64 L/kg to 9300 L/kg. For 18 pharmaceuticals, Kd values were found to be above 100 L/kg. SPM of annual composite samples were analyzed to determine the pharmaceutical concentrations between 2005 and 2015 at four sites of the river Rhine: Weil, Iffezheim, Koblenz and Bimmen as well as between 2006 and 2015 at one site of the river Saar, at Rehlingen. In these SPM samples, up to 61 of the 100 analytes were detected with concentrations up to 190 ng/g d.w. (dry weight) for guanylurea, a transformation product of the antidiabetic metformin. For most analytes, increasing concentrations were found along the length of the Rhine and higher concentrations were measured in Rehlingen/Saar. Normalization of the data with the antiepileptic drug carbamazepine as an intrinsic tracer for municipal wastewater indicated possible industrial discharges for four analytes. For most pharmaceuticals, the annual concentrations exhibited a good correlation with the consumption volumes in Germany. © 2019 Published by Elsevier Ltd.Veröffentlichung Retrospective analysis of cyclic volatile methylsiloxanes in archived German fish samples covering a period of two decades(2020) Radermacher, Georg; Böhnhardt, Anna; Rüdel, Heinz; Koschorreck, Jan; Wesch, CharlotteCyclic volatile methylsiloxanes (cVMS) are widely applied chemicals used as intermediates in the production of silicon polymers or as ingredients in personal care products. cVMS are under scrutiny due to their environmental properties and their potential for long-range atmospheric transport, persistence and food web magnification. In 2018, the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were identified as Substances of Very High Concern (SVHC) under the European REACH regulation. To obtain current data on the presence of cVMS in German waters, the spatial and temporal occurrence of D4, D5 and D6 in fillets of bream from major rivers archived in the German Environmental Specimen Bank (ESB) was analyzed with a GC-ICP-MS/MS coupling method. The spatial comparison of 17 sites for the year 2017 revealed that highest cVMS burdens occurred in samples from the Saar river (near to the French/German border). cVMS levels in fish from a lake in northern Germany did not exceed the limits of detection. For selected sites, time series covering the period from 1995 to 2017 were investigated. In most years D5 concentrations in fish were clearly higher than the observed D4 and D6 concentrations. Overall maximum D4 and D5 concentrations (about 320 and 7600 ng gâ Ì1 wet weight, respectively) were found at one Saar site in 2009. In three of five analyzed time series D5 concentrations peaked 2007â€Ì2011. In recent years, cVMS levels in fish decreased at almost all sites. To allow an assessment of the relevance of the detected cVMS fish concentrations these were compared to environmental quality standards (EQS) for D4 and D5 which were recently enacted in the context of the Swedish implementation of the European Water Framework Directive (WFD). The D5 EQS in fish was exceeded at four sites in several years in the investigated period and in the Saar even till 2017.Veröffentlichung Chemicals of emerging concern in marine specimens of the German Environmental Specimen Bank(2020) Fliedner, Annette; Rüdel, Heinz; Dreyer, Annekatrin; Koschorreck, JanBackground Descriptor 8 of the Marine Strategy Framework Directive (MSFD) (Directive 2008/56/EC) addresses the good environmental status with regard to pollution of marine waters by chemical contaminants. Commission decision (EU) 2017/848 lays down the criteria and methodological standards on good environmental status of marine waters. Member States, in regional or subregional cooperation, shall establish lists of relevant contaminants beside those already covered by the Water Framework Directive (WFD). To provide information on emerging contaminants in marine biota, the German Environmental Specimen Bank (ESB) has compiled data of blue mussels and eelpouts from coastal sites in the North and Baltic Seas. Substances identified by the International Council for the Exploration of the Sea (ICES) as of emerging concern for the marine environment have been used as a starting point. Results and conclusions The study presents data of 19 emerging flame retardants and degradation products, 40 per- and polyfluoroalkyl substances (PFAS) and three cyclic volatile methylsiloxanes (cVMS). Among the emerging flame retardants, only Dec 602 was detected in all samples of 2015. Dec 604, Cl10-antiDP, 1,5-DPMA, EH-TBB, PBEB, TBP-AE, BATE, BTBPE and HBBz were constantly <†limit of quantification (LOQ). Time trends were barely detected. Legacy PBDE still dominates in most samples. PFAS concentrations were usually higher in samples from the North Sea sites compared to samples from the Baltic Sea. PFOS dominated in most samples. Increasing trends over time were detected for PFNA, PFDA and PFDoDA at the Baltic Sea site and for PFDA at one North Sea site. Concentrations of the cVMS D4, D5 and D6 were below the detection limit at the ESB sampling sites. Based on the results, it should be considered to include the emerging flame retardants DP and Dec 602 and the long-chain perfluoroalkyl substances PFNA, PFDA, PFUnDA and PFDoDA in a regular monitoring in the North and Baltic Seas. © The Author(s) 2020Veröffentlichung Seasonal variability in metal and metalloid burdens of mussels: using data from the German Environmental Specimen Bank to evaluate implications for long-term mussel monitoring programs(2020) Knopf, Burkhard; Fliedner, Annette; Radermacher, Georg; Koschorreck, JanBackground Metal and metalloid concentrations in mussels can vary between seasons. In biota monitoring, the sampling time is therefore an important issue. Within the German Environmental Specimen Bank (ESB) program blue mussels (Mytilus edulis Complex) are sampled regularly since the 1980s. The samples are collected in two-monthly intervals at two North Sea sites and in 6-month intervals at one Baltic Sea site. All samples from one site and year are combined to annual composite samples and archived as sub-samples under cryogenic conditions. In order to investigate a possible reduction of the number of annual sampling intervals while maintaining comparability with the long-term composite sample data, the seasonal variability of metals/metalloids was analyzed based on the half-yearly and bimonthly samples of 2013, 2015 and 2017. Results In mussels from the North Sea site Eckwarderhoerne seasonality of metals/metalloids was comparable in all 3 years (arsenic being the only exception). At the North Sea site Koenigshafen seasonality of cobalt, nickel, cadmium, copper, lead, and arsenic was comparable in 2013 and 2015 but not in 2017, while selenium showed the same seasonality in all 3 years. Within 1 year, concentrations of metals and metalloids can vary by the same order of magnitude as observed between annual composite samples of different years making it impossible to select just one representative sampling time point per year that would provide the same information as the respective annual composite sample. Conclusions The findings highlight the importance of carefully selecting the sampling time point when using mussels in biota monitoring. For the German ESB program it is recommended to continue with the current sampling strategy and analyze annual composite samples in order to maintain comparability with the long-term data series, which are a special feature of the ESB. © The Author(s) 2020Veröffentlichung The NORMAN Association and the European Partnership for Chemicals Risk Assessment (PARC): let's cooperate!(2020) Dulio, Valeria; Bavel, Bert van; Koschorreck, Jan; von der Ohe, Peter C.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. © The Author(s) 2020Veröffentlichung Aquatic suspended particulate matter as source of eDNA for fish metabarcoding(2020) Díaz, Cecilia; Wege, Franziska-Frederike; Koschorreck, Jan; Tang, Cuong Q.The use of environmental DNA (eDNA) for monitoring aquatic macrofauna allows the non-invasive species determination and measurement of their DNA abundance and typically involves the analysis of eDNA captured from water samples. In this proof-of-concept study, we focused on the novel use of eDNA extracted from archived suspended particulate matter (SPM) for identifying fish species using metabarcoding, which benefits from the prospect of retrospective monitoring and also analysis of fish communities through time. We used archived SPM samples of the German Environmental Specimen Bank (ESB), which were collected using sedimentation traps from different riverine points in Germany. Environmental DNA was extracted from nine SPM samples differing in location, organic content, and porosity (among other factors) using four different methods for the isolation of high-quality DNA. Application of the PowerSoil DNA Isolation Kit with an overnight incubation in lysis buffer, resulted in DNA extraction with the highest purity and eDNA metabarcoding of these eDNA fragments was used to detect a total of 29 fish taxa among the analyzed samples. Here we demonstrated for the first time that SPM is a promising source of eDNA for metabarcoding analysis, which could provide valuable retrospective information (when using archived SPM) for fish monitoring, complementing the currently used approaches. © 2020 Springer Nature LimitedVeröffentlichung Organohalogen compounds of emerging concern in Baltic Sea biota: Levels, biomagnification potential and comparisons with legacy contaminants(2020) De Wit, Cynthia A.; Bossi, Rossana; Dietz, Rune; Koschorreck, Jan; Treu, GabrieleWhile new chemicals have replaced major toxic legacy contaminants such as polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT), knowledge of their current levels and biomagnification potential in Baltic Sea biota is lacking. Therefore, a suite of chemicals of emerging concern, including organophosphate esters (OPEs), short-chain, medium-chain and long-chain chlorinated paraffins (SCCPs, MCCPs, LCCPs), halogenated flame retardants (HFRs), and per- and polyfluoroalkyl substances (PFAS), were analysed in blue mussel (Mytilus edulis), viviparous eelpout (Zoarces viviparus), Atlantic herring (Clupea harengus), grey seal (Halichoerus grypus), harbor seal (Phoca vitulina), harbor porpoise (Phocoena phocoena), common eider (Somateria mollissima), common guillemot (Uria aalge) and white-tailed eagle (Haliaeetus albicilla) from the Baltic Proper, sampled between 2006 and 2016. Results were benchmarked with existing data for legacy contaminants. The mean concentrations for (Sigma)OPEs ranged from 57 to 550 ng g-1 lipid weight (lw), for (Sigma)CPs from 110 to 640 ng g-1 lw for (Sigma)HFRs from 0.42 to 80 ng g-1 lw, and for (Sigma)PFAS from 1.1 to 450 ng g-1 wet weight. Perfluoro-4-ethylcyclohexanesulfonate (PFECHS) was detected in most species. Levels of OPEs, CPs and HFRs were generally similar or higher than those of polybrominated diphenyl ethers (PBDEs) and/or hexabromocyclododecane (HBCDD). OPE, CP and HFR concentrations were also similar to PCBs and DDTs in blue mussel, viviparous eelpout and Atlantic herring. In marine mammals and birds, PCB and DDT concentrations remained orders of magnitude higher than those of OPEs, CPs, HFRs and PFAS. Predator-prey ratios for individual OPEs (0.28-3.9) and CPs (0.40-5.0) were similar or somewhat lower than those seen for BDE-47 (5.0-29) and HBCDD (2.4-13). Ratios for individual HFRs (0.010-37) and PFAS (0.15-47) were, however, of the same order of magnitude as seen for p,p'2-DDE (4.7-66) and CB-153 (31-190), indicating biomagnification potential for many of the emerging contaminants. Lack of toxicity data, including for complex mixtures, makes it difficult to assess the risks emerging contaminants pose. Their occurence and biomagnification potential should trigger risk management measures, particularly for MCCPs, HFRs and PFAS. © 2020 The Author(s)Veröffentlichung Per- and polyfluoroalkyl substances in the German environment - Levels and patterns in different matrices(2020) Kotthoff, Matthias; Biegel-Engler, Annegret; Fliedner, Annette; Rüdel, Heinz; Koschorreck, JanPer- and polyfluoroalkyl substances (PFAS) in the environment mostly originate from emissions of previously unregulated PFAS. However, there are also many documented incidents of accidental releases. To track such releases, it is essential to distinguish between typical background contamination and legally relevant incidents. This requires a comprehensive overview of all PFAS present in the environment, which is currently only possible to a limited extent due to the large variety of individual compounds. In the present study, a multimethod for capturing 41 PFAS including perfluoroalkyl acid (PFAA) precursors is introduced. The applicability of the method was tested on terrestrial, freshwater and marine samples from the German Environmental Specimen Bank (ESB), thereby providing a rough overview of PFAS contamination in German environment. Special focus was put on soil samples from ESB sites across Germany in comparison to soil samples from a polluted site in south-west Germany. The method was successfully applied to environmental samples. In total, 31 PFAS were detected, among them PFAA precursors and fluorinated ethers. Substance patterns differed between sites and matrices. In ESB soil samples from 2014 (n = 11), the sum of all captured PFAS ranged between 0.75 and 19.5 (my)g kg-1 dry weight (dw), while concentrations between 416 (my)g kg-1 and 3530 (my)g kg-1 were detected in samples from the incident site (n = 10). In other matrices, total PFAS concentrations were magnitudes lower. Highest concentrations were observed for PFOS in bream livers from the Saale (226 (my)g kg-1). Given the heterogeneous patterns, it will require further broadly-based monitoring data to allow for a solid estimation of relevant background levels. The data provided here may support the differentiation between background levels and hotspot contaminations. ©2020 The AuthorsVeröffentlichung Trends for plasticizers in German freshwater environments - Evidence for the substitution of DEHP with emerging phthalate and non-phthalate alternatives(2020) Koschorreck, Jan; Nagorka, ReginePlasticizers are marketed in high volumes and Di(2-ethylhexyl) phthalate (DEHP) is frequently detected in the environment and human populations. Industry had largely relied on DEHP until regulation started to restrict its marketing in 1999 due to environmental and human health concerns. The aim of this study was to obtain spatial-temporal trends for DEHP and its substitutes in German rivers. We have investigated suspended particulate matter (SPM) samples from the German Environmental Specimen Bank (ESB) for the presence of 23 plasticizers, i.e. 17 phthalates and 6 non-phthalates. The samples were collected in the last 10 years at 13 sites in large river basins in Germany such as the Rhine, Elbe and Danube. A decrease in DEHP concentrations was observed at all sampling sites between the mid-2000s and 2017. The maximum concentration for DEHP was determined in 2006 in samples from Rehlingen/Saar (6720 ng/g dry weight (dw)). By 2017, the DEHP concentration in Rehlingen had dropped to 2080 ng/g dw. Currently, Diisononyl phthalate (DINP) is the plasticizer with the highest levels in the SPM samples (maximum value 4150 ng/g dw in Rehlingen/Saar). Our results show that novel plasticizers such as Diisononylcyclohexane-1,2-dicarboxylate (DINCH) spread rapidly in surface waters after their market introduction. We have found several plasticizers of emerging concern in the environmental samples, the further use of which is currently under review under the EU chemicals regulation (REACH, registration, evaluation, authorisation and restriction of chemicals). In particular for Di(2-propylheptyl) phthalate (DPHP) a significant increase in concentration was observed at almost all sites between the mid-2000s and 2017, for example in Prossen/Elbe from 24 ng/g dw (2005) to 1380 ng/g dw (2017). © 2020 The Authors.Veröffentlichung Selection and application of trophic magnification factors for priority substances to normalize freshwater fish monitoring data under the European Water Framework Directive: a case study(2020) Rüdel, Heinz; Duffek, Anja; Kosfeld, Verena; Fliedner, Annette; Koschorreck, Jan; Rauert, CarenBackground The European Water Framework Directive (WFD) requires the monitoring of biota-preferably fish - to check the compliance of tissue concentrations of priority substances (PS) against substance-specific environmental quality standards (EQSs). In monitoring programs, different fish species are covered, which often are secondary consumers with a trophic level (TL) of about 3. For harmonization, a normalization of monitoring data to a common trophic level is proposed, i.e., TL 4 (predatory fish) in freshwaters, so that data would be sufficiently protective. For normalization, the biomagnification properties of the chemicals can be considered by applying substance-specific trophic magnification factors (TMFs). Alternatively, TL-corrected biomagnification factors (BMFTLs) may be applied. Since it is impractical to derive site-specific TMFs or BMFTLs, often data from literature will be used for normalization. However, available literature values for TMFs and BMFTLs are quite varying. In the present study, the use of literature-derived TMFs and BMFTLs in data normalization is studied more closely. Results An extensive literature evaluation was conducted to identify appropriate TMFs for the WFD PS polybrominated diphenyl ethers (PBDE), hexachlorobenzene, perfluorooctane sulfonate (PFOS), dioxins and dioxin-like compounds (PCDD/F+dl-PCB), hexabromocyclododecane, and mercury. The TMFs eventually derived were applied to PS monitoring data sets of fish from different trophic levels (chub, bream, roach, and perch) from two German rivers. For comparison, PFOS and PBDE data were also normalized using literature-retrieved BMFTLs. Conclusions The evaluation illustrates that published TMFs and BMFTLs for WFD PS are quite variable and the selection of appropriate values for TL 4 normalization can be challenging. The normalized concentrations partly included large uncertainties when considering the range of selected TMFs, but indicated whether an EQS exceedance at TL 4 can be expected. Normalization of the fish monitoring data revealed that levels of substances accumulating in the food web (TMF or BMF>1) can be underestimated when relying on fish with TL<4 for EQS compliance assessment. The evaluation also revealed that TMF specifically derived for freshwater ecosystems in Europe would be advantageous. Field-derived BMFTLs seemed to be no appropriate alternative to TMFs, because they can vary even stronger than TMFs. © The Author(s) 2020