Person: Duffek, Anja
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Veröffentlichung Under the influence of regulations: spatio-temporal trends of the UV filter 2-Ethylhexyl-4-methoxycinnamate (EHMC) in German rivers(2021) Duffek, Anja; Nagorka, RegineBackground Globally, 2-Ethylhexyl-4-methoxycinnamate (EHMC) is one of the most commonly used UV filters in sunscreen and personal care products. Due to its widespread usage, the occurrence of EHMC in the aquatic environment has frequently been documented. In the EU, EHMC is listed under the European Community Rolling Action Plan (CoRAP) as suspected to be persistent, bioaccumulative, and toxic (PBT) and as a potential endocrine disruptor. It was included in the first watch list under the Water Framework Directive (WFD) referring to a sediment PNEC of 200 (my)g/kg dry weight (dw). In the light of the ongoing substance evaluation to refine the environmental risk assessment, the objective of this study was to obtain spatio-temporal trends for EHMC in freshwater. We analyzed samples of suspended particulate matter (SPM) retrieved from the German environmental specimen bank (ESB). The samples covered 13 sampling sites from major German rivers, including Rhine, Elbe, and Danube, and have been collected since mid-2000s. Results Our results show decreasing concentrations of EHMC in annual SPM samples during the studied period. In the mid-2000s, the levels for EHMC ranged between 3.3 and 72 ng/g dw. The highest burden could be found in the Rhine tributary Saar. In 2017, we observed a maximum concentration ten times lower (7.9 ng/g dw in samples from the Saar). In 62% of all samples taken in 2017, concentrations were even below the limit of quantification (LOQ) of 2.7 ng/g dw. Conclusions The results indicate a general declining discharge of EHMC into German rivers within the last 15 years and correspond to the market data. Although the measured levels are below the predicted no-effect level (PNEC) in sediment, further research should identify local and seasonal level of exposure, e.g., at highly frequented bathing waters especially in lakes. In addition, possible substitutes as well as their potentially synergistic effects together with other UV filters should be investigated. © The Author(s) 2021Veröffentlichung Identification of contamination hotspots along a river by silicone-based passive sampling(2016) Becker, Benjamin; Duffek, Anja; Lepom, Peter; Möhlenkamp, Christel; Claus, Evelyn; Schäfer, SabineVeröffentlichung 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 Per- and polyfluoroalkyl substances in blood plasma - Results of the German Environmental Survey for children and adolescents 2014-2017 (GerES V)(2020) Conrad, André; Duffek, Anja; Kolossa-Gehring, Marike; Lange, Rosa; Rucic, Enrico; Schulte, Christoph; Wellmitz, JörgThe 5th cycle of the German Environmental Survey (GerES V) investigated the internal human exposure of children and adolescents aged 3-17 years in Germany to per- and polyfluoroalkyl substances (PFAS). The fieldwork of the population-representative GerES V was performed from 2014 to 2017. In total, 1109 blood plasma samples were analysed for 12 PFAS including perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS). PFOS was quantified in all and PFOA in almost all samples, demonstrating ubiquitous exposure. The highest geometric mean concentrations measured were 2.49 ng/mL for PFOS, followed by PFOA (1.12 ng/mL) and PFHxS (0.36 ng/mL), while concentrations of other PFAS were found in much lower concentrations. The 95th percentile levels of PFOS and PFOA were 6.00 and 3.24 ng/mL, respectively. The results document a still considerable exposure of the young generation to the phased out chemicals PFOS and PFOA. The observed exposure levels vary substantially between individuals and might be due to different multiple sources. The relative contribution of various exposure parameters such as diet or the specific use of consumer products need to be further explored. Although additional investigations on the time trend of human exposure are warranted, GerES V underlines the need for an effective and sustainable regulation of PFAS as a whole. Source: © 2020 Elsevier GmbHVeröffentlichung Biological effect and chemical monitoring of Watch List substances in European surface waters: steroidal estrogens and diclofenac - effect-based methods for monitoring frameworks(2022) Simon, Eszter; Duffek, Anja; Stahl, CordulaThree steroidal estrogens, 17(alpha)-ethinylestradiol (EE2), 17(beta)-estradiol (E2), estrone (E1), and the non-steroidal anti-inflammatory drug (NSAID), diclofenac have been included in the first Watch List of the Water Framework Directive (WFD, EU Directive 2000/60/EC, EU Implementing Decision 2015/495). This triggered the need for more EU-wide surface water monitoring data on these micropollutants, before they can be considered for inclusion in the list of priority substances regularly monitored in aquatic ecosystems. The revision of the priority substance list of the WFD offers the opportunity to incorporate more holistic bioanalytical approaches, such as effect-based monitoring, alongside single substance chemical monitoring. Effect-based methods (EBMs) are able to measure total biological activities (e.g., estrogenic activity or cyxlooxygenase [COX]-inhibition) of specific group of substances (such as estrogens and NSAIDs) in the aquatic environment at low concentrations (pg/L). This makes them potential tools for a cost-effective and ecotoxicologically comprehensive water quality assessment. In parallel, the use of such methods could build a bridge from chemical status assessments towards ecological status assessments by adressing mixture effects for relevant modes of action. Our study aimed to assess the suitability of implementing EBMs in the WFD, by conducting a large-scale sampling and analysis campaign of more than 70 surface waters across Europe. This resulted in the generation of high-quality chemical and effect-based monitoring data for the selected Watch List substances. Overall, water samples contained low estrogenicity (0.01-1.3 ng E2-Equivalent/L) and a range of COX-inhibition activity similar to previously reported levels (12-1600 ng Diclofenac-Equivalent/L). Comparison between effect-based and conventional analytical chemical methods showed that the chemical analytical approach for steroidal estrogens resulted in more (76%) non-quantifiable data, i.e., concentrations were below detection limits, compared to the EBMs (28%). These results demonstrate the excellent and sensitive screening capability of EBMs. © 2021 The AuthorsVeröffentlichung Technical guidance on monitoring for the Marine Strategy Framework Directive(Amt für Amtliche Veröff. der Europ. Gemeinschaften, 2014) Zampoukas, N.; Duffek, Anja; Palialexis, A.; Weiß, Andrea; Europäische Union. Amt für VeröffentlichungenVeröffentlichung Assessing the toxic potential of river water by combining passive sampling with bioassays(2016) Becker, B.; Duffek, Anja; Lepom, Peter; Claus, E.; Schäfer, S.Veröffentlichung Waters in Germany(2017) Arle, Jens; Blondzik, Katrin; Claussen, Ulrich; Duffek, Anja; Grimm, Sabine; Hilliges, Falk; Kirschbaum, Bernd; Kirst, Ingo; Koch, Dietmar; Koschorreck, Jan; Lepom, Peter; Leujak, Wera; Mohaupt, Volker; Naumann, Stephan; Rechenberg, Jörg; Schilling, Petra; Ullrich, Antje; Wellmitz, Jörg; Werner, Stefanie; Wolter, Rüdiger; Deutschland. UmweltbundesamtVeröffentlichung A field study in support of the monitoring of priority substances in German freshwater fish: derivation of fillet-to-whole fish conversion factors(2020) Rüdel, Heinz; Duffek, Anja; Radermacher, Georg; Fliedner, AnnetteBackground
Bioaccumulating contaminants in surface waters are preferably monitored in fish for assessing the related risks to and via the aquatic environment. Consequently, the European Water Framework Directive (WFD) requires a monitoring of certain priority substances such as mercury, polybrominated diphenyl ethers (PBDE), perfluorooctane sulfonic acid and its derivatives (PFOS), hexachlorobenzene (HCB), hexabromocyclododecanes (HBCDD) and polychlorinated dioxins/dioxin-like compounds (dioxins) in freshwater and coastal fish. Tissue levels have to comply with biota environmental quality standards (EQSs) given in Directive 2013/39/EU. EQSs are justified either by risks for human health (assessed on the basis of fillet) or secondary poisoning of wildlife (based on whole fish). To support the practical implementation of the WFD biota monitoring in Germany, comparative investigations of target fish species caught at six sites were performed.Results
At each site, at least three fish species listed in a national guidance document were sampled (e.g., chub, roach, bream, perch). Beside biometric data, concentrations of seven priority substances were determined in pooled fillet and carcass samples and whole fish data were calculated. The EQSs for PBDE and mercury were exceeded in nearly all fillet and whole fish samples. PFOS was above the EQS at several sites especially in perch, while HCB exceeded the EQS only at one site (Elbe River). All fillet and whole fish samples complied with the EQSs for dioxins and HBCDD. Based on wet weight concentrations of a homogeneous set of 20 composite sample pairs of 3â€Ì5 year-old fish, the following fillet-to-whole fish conversion factors were derived: mercury 0.81, PBDE 5.4, HCB 3.6, PFOS 2.7, dioxins 5.3, and HBCDD 1.8.Conclusions
Recommendations on selection of target fish species, age or tissue given by EU and national guidance documents are practical and feasible. However, further adjustments of the samplings such as the determination of site-specific length-age relationships are required from both ecological and risk assessment perspectives. The derived conversion factors allow the translation of fillet-to-whole fish concentrations (and vice versa), and thus the EQS compliance assessment for the appropriate tissue (fillet for human health, whole fish for wildlife risks) if only one tissue is investigated. Quelle: https://link.springer.com