Person: Koschorreck, Jan
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Veröffentlichung Nutzung der Erfahrungen und Ergebnisse des Biotamonitorings der Umweltprobenbank für die Umsetzung des WRRL-Fischmonitorings(2019) Fliedner, Annette; Rüdel, Heinz; Koschorreck, JanDie Umweltprobenbank des Bundes (UPB) ist ein wichtiger Grundpfeiler der Umweltbeobachtung in Deutschland und ist bestrebt, die Länderbehörden bei neuen Anforderungen an das Umweltmonitoring zu unterstützen. So wurde eine Reihe von Studien durchgeführt, die für die Umsetzung des Wasserrahmenrichtlinien-Fischmonitorings von Interesse sind. Zum einen wurde die Wirksamkeit einer Datennormalisierung auf 26 % Trockenmasse (TM) oder 5 % Fettgehalt und Trophiestufe 4 (TS 4) erprobt, die im EU WRRL-Leitfaden Nr. 32 vorgeschlagen wird und dazu dienen soll, die Vergleichbarkeit heterogener Monitoringdaten zu erhöhen. Zum anderen wurde die Umrechnung von Schadstoffkonzentrationen im Filet auf Ganzfischkonzentrationen geprüft, um angepasste Risikobewertungen für Wildtiere und die menschliche Gesundheit zu ermöglichen. Darüber hinaus wurden die Einhaltung der Umweltqualitätsnormen (UQN) und die zeitlichen Verläufe der im Rahmen des WRRLFischmonitorings zu erfassenden organischen Stoffe an den 17 UPB-Messstellen (MS) in deutschen Flüssen und Seen untersucht. Die Ergebnisse zeigen, dass die Normalisierung von Quecksilber- und PFOS-Daten auf 26 % TM die Vergleichbarkeit unterschiedlicher Datensätze nicht erhöht. Eine Normalisierung auf 5 % Fett bei lipophilen Stoffen hatte dagegen deutliche Effekte. Eine Standardisierung auf TS 4, die sich auf Standardwerte für die Trophiestufen der Fische stützt und nicht auf tatsächlich gemessenen TS- Werte, führte nicht zu einer erhöhten Vergleichbarkeit zwischen verschiedenen Fischarten. Die UQN von Dicofol, HBCDD und HCB wurden von Brassen aller MS eingehalten, während flächendeckende Überschreitungen für PBDE beobachtet wurden. Die UQN-Einhaltung der übrigen Stoffe war abhängig vom Standort. An den meisten MS hat die Belastung der Fische seit Anfang der 2000er Jahre abgenommen. In: Korrespondenz Wasserwirtschaft : KW ; Organ der DWA ; Wasser, Boden, Natur - 12 (2019), Heft 6, Seite 336Veröffentlichung Exploring unknown per- and polyfluoroalkyl substances in the German environment - The total oxidizable precursor assay as helpful tool in research and regulation(2021) Göckener, Bernd; Fettig, Ina; Fliedner, Annette; Rüdel, Heinz; Koschorreck, JanLimnetic, marine and soil samples of the German environmental specimen bank (ESB) were analyzed for per- and polyfluoroalkyl substances (PFAS) using target analysis and a modified total oxidizable precursor (TOP) assay (direct TOP assay (dTOP)) that works without prior extraction. Target analysis determined (Sigma)PFAS concentrations in bream livers of 8.7-282 (my)g kg-1 wet weight (ww) in 2019, with highest contaminations in the Rhine and lower Elbe. In bream fillet, concentrations were lower (<0.5-10.6 (my)g kg-1 (Sigma)PFAS). Contamination of suspended particulate matter (SPM) was highest in the upper Elbe downstream the Czech border (5.5 (my)g kg-1 dry weight (dw) in 2018). Herring gull eggs from the North and Baltic Seas showed (Sigma)PFAS levels around 53.0-69.6 (my)g kg-1 ww in 2019. In soil, concentrations ranged between <0.5 and 4.6 (my)g kg-1 dw with highest levels in the Dueben Heath near Leipzig and the low mountain range Solling. PFOS dominated in most samples. Of the targeted precursors, only FOSA, EtFOSAA, MeFOSAA, 6:2-FtS and 6:2 diPAP were found. Replacement chemicals (ADONA, HFPO-DA, F-53B) were not detected. The dTOP assay revealed that considerable amounts of precursors were present at most riverine sampling sites. Particularly high precursor concentrations were observed in samples from the Upper Elbe at the Czech border and the Upper and Middle Rhine. In herring gull eggs and most soil samples, though, concentrations of precursors were low. Time trend analysis showed decreasing trends for most detected PFAS since 2005. In SPM, however, C4-C6 perfluoroalkyl carboxylic acids seem to increase indicating growing use of precursors based on shorter fluorinated chains. The results demonstrate that target analysis detects only a minor fraction of the PFAS burdens in environmental samples. The dTOP assay can support risk assessment and chemical monitoring with more comprehensive exposure data of the actual contamination. © 2021 The Author(s).Veröffentlichung Current levels and trends of selected EU Water Framework Directive priority substances in freshwater fish from the German environmental specimen bank(2016) Fliedner, Annette; Lohmann, Nina; Koschorreck, Jan; Rüdel, Heinz; Teubner, Diana; Wellmitz, JörgUnder the German environmental specimen bank programme bream (Abramis brama) were sampled in six German rivers and analysed for the priority hazardous substances dicofol, hexabromocyclododecane (HBCDD), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD), heptachlor þ heptachlor epoxide (HC þ HCE), polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins and -furans and dioxin-like polychlorinated biphenyls (PCDD/Fs þ dl-PCBs), and perfluorooctane sulfonic acid (PFOS). The aim was to assess compliance with the EU Water Framework Directive environmental quality standards for biota (EQSBiota) for the year 2013, and to analyse temporal trends for those substances that are of special concern. General compliance was observed for dicofol, HBCDD and HCBD whereas PBDEs exceeded the EQSBiota at all sites. For all other substances compliance in 2013 varied between locations. No assessment was possible for HC þ HCE at some sites where the analytical sensitivity was not sufficient to cover the EQSBiota. Trend analysis showed decreasing linear trends for HCB and PFOS at most sampling sites between 1995 and 2014 indicating that the emission reduction measures are effective. Mostly decreasing trends or constant levels were also observed for PCDD/Fs and dl-PCBs. In contrast, increasing trends were detected for PBDEs and HBCDD which were especially pronounced at one Saar site located downstream of the industries and conurbation of Saarbrücken and V€olklingen. This finding points to new sources of emissions which should be followed in the coming years. Quelle: www.sciencedirect.comVeröffentlichung 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) 2020Veröffentlichung Tissue concentrations of per- and polyfluoroalkyl substances (PFAS) in German freshwater fish: derivation of fillet-to-whole fish conversion factors and assessment of potential risks(2022) Rüdel, Heinz; Duffek, Anja; Radermacher, Georg; Fliedner, Annette; Koschorreck, JanThe European Water Framework Directive requires monitoring of bioaccumulative contaminants in fish to assess risks to human health by fish consumption and wildlife by secondary poisoning of predators. The list of priority substances for which environmental quality standards (EQSs) have been derived covers also perfluorooctane sulfonic acid (PFOS). No EQSs have yet been set for other per- and polyfluoroalkyl substances (PFAS) that are frequently detected in fish and of which some have a non-negligible risk potential compared to PFOS. As a case study, burdens for a set of PFAS were investigated for different fish species from five German freshwater sites and a Baltic Sea lagoon. PFAS concentrations were determined for composite samples of both, fillet and whole fish. On average, sum concentrations of C9-C14 perfluoroalkyl carboxylic acids, which will be banned in the European Union in 2023, reached 87% and 82% of the PFOS burdens in fillet and whole fish, respectively. The potential risk of several PFAS other than PFOS was assessed using a previously suggested relative potency factor approach, which is also applied for a proposed EQS revision. Only five of 36 fillet samples (mostly perch) exceeded the current EQS for PFOS alone. By contrast, all fillet samples exceeded the newly proposed draft EQS, which considers potential effects of further PFAS but also a lower tolerable intake value. Additionally, the dataset was used to derive fillet-to-whole fish conversion factors, which can be applied to assess human health risks by consumption of fillet if only whole fish concentrations are available. © 2021 The AuthorsVeröffentlichung Assessment of seafood contamination under the marine strategy framework directive: contributions of the German environmental specimen bank(2018) Fliedner, Annette; Rüdel, Heinz; Knopf, Burkhard; Koschorreck, JanDescriptor 9 (D9) of the European Union Marine Strategy Framework Directive refers to the compliance of contaminant levels in fish and other seafood of a defined marine region or subregion with human health threshold values. This requires georeferenced samples that are often difficult to obtain when relying on commercial fisheries or programs designed for monitoring human exposure. The present study examines whether georeferenced samples of blue mussel (Mytilus edulis) and eelpout (Zoarces viviparus) fillet of the German environmental specimen bank (ESB) can be used in this context. The suitability of the ESB samples, procedures, and analytical methods is evaluated with respect to D9 requirements. Based on ESB data for the D9 relevant contaminants Pb, Cd, Hg, â Ì4 PAHs, PCDD/Fs, dioxin-like (dl)-PCBs, and indicator non-dl-PCBs and the potentially relevant substances TBT, PFOS, PBDE, and HBCDD, the Good Environmental Status for D9 is assessed at the ESB sites in the North and Baltic Seas. The overall evaluation indicates that ESB samples are suitable for D9 assessment with the limitation that only coastal areas of the North and Baltic Seas are covered. Over a period of up to 30 years, concentrations of the D9 relevant contaminants were well below the maximum levels allowed for human consumption. © The Author(s) 2018Veröffentlichung 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 Environmental specimen banks and the European Green Deal(2022) Fliedner, Annette; Rüdel, Heinz; Göckener, Bernd; Koschorreck, JanThe study highlights the potential of Environmental Specimen Banks (ESBs) for implementing the Zero Pollution Ambition and the Biodiversity Strategy of the European Green Deal. By drawing on recent monitoring studies of European ESBs, we illustrate the role ESBs already play in assessing the state of ecosystems in Europe and how they help to make developments over time visible. The studies reveal the ubiquitous presence of per- and polyfluoroalkyl substances, halogenated flame retardants, chlorinated paraffins, plasticizers, cyclic volatile methyl siloxanes, UV-filters, pharmaceuticals, and microplastics in the European environment. Temporal trends demonstrate the effectiveness of European regulations on perfluorooctane sulfonic acid, pentabrominated diphenylethers and diethylhexyl phthalate, but also point to the rise of substitutes such as non-phthalate plasticizers and short-chain perfluoroalkyl substances. Other studies are wake-up calls indicating the emergence of currently unregulated compounds such as long-chain chlorinated paraffins. Ecological studies show temporal trends in biometric parameters and stable isotope signatures that suggest long-term changes in environmental conditions. Studies on biodiversity of ecosystems using environmental DNA are still in their beginnings, but here too there is evidence of shifts in community composition that can be linked to changing environmental conditions. This review demonstrates the value of ESBs (a) for describing the status of the environment, (b) for monitoring temporal changes in environmental pollution and the ecologic condition of ecosystems and thereby (c) for supporting regulators in prioritizing their actions towards the objectives of the Green Deal. © 2022 ElsevierVeröffentlichung 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 Levels, accumulation patterns and retrospective trends of perfluoroalkyl acids (PFAAs) in terrestrial ecosystems over the last three decades(2019) Falk, Sandy; Stahl, Thorsten; Fliedner, Annette; Koschorreck, JanAs a result of their ubiquitous presence in the environment perfluoroalkyl acids (PFAAs) have been demonstrated in numerous organisms worldwide, in particular in those of higher trophic levels. The fact that PFAAs have been detected in various human matrices, together with the resultant potential human health risks, knowledge of possible paths of entry and distribution in various ecosystems, is of great importance. In this context pooled samples of terrestrial ecosystems - roe deer liver (n=141), earthworms (n=44) as well as leaves from beech and poplar trees (n=70) - from the year 1989-2015 were obtained from the German Environmental Specimen Bank and examined for the presence of 11 PFAAs for the first time. In addition to determining individual and total PFAA concentrations, temporal trends have been deduced in order to determine the effectiveness of regulatory measures. The highest total mean concentration of PFAAs (sum of the concentrations of the 11 analytes) were 9.9 (Mü)g/kg in the roe deer liver samples, followed by earthworm samples with a mean PFAA concentration of 3.5 (Mü)g/kg and leaves with a mean total concentration of 2.5 (Mü)g/kg. In regard to temporal trends there was a significant reduction of concentrations for perfluorooctane sulfonate, perfluorooctanoic acid, perfluorononanoic acid and perfluorodecanoic acid in roe deer liver from 2003 to 2015, an indication of the effectiveness of regulatory measures. The same is true for the perfluorooctane sulfonate concentrations in earthworms and for perfluorooctanoic acid concentrations in the leaves. In contrast, an increase in perfluorobutanoic acid concentrations was observed from 2003 to 2015 in all three matrices. In summary it must be noted that in spite of the discernible effectiveness of minimization strategies, PFAAs are still detectable in terrestrial matrices and concentrations of other PFAAs as perfluorobutanoic acid appear to be increasing. Quelle: http://www.sciencedirect.com