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REACH wirkt - Auf Anfrage Auskunftspflicht für über hundert Stoffe

Strengere Vorschriften auch für Umweltgifte in Outdoorkleidung Für eine Vielzahl an Chemikalien gelten von nun an schärfere Vorschriften. Dies sieht die europäische Chemikalienverordnung REACH vor. Davon betroffen sind unter anderem wasser- und fettabweisende Stoffe wie vier perfluorierte Carbonsäuren (PFC). Wegen ihrer schädlichen Wirkung auf die Umwelt werden sie zu besonders besorgniserregenden Stoffen. Eingesetzt werden PFC auch in Outdoorkleidung. Verbraucherinnen und Verbraucher haben nun das Recht beim Händler über diese Stoffe Auskunft zu erlangen. Das trifft auch auf 50 weitere Chemikalien zu. Das Umweltbundesamt (UBA) ist maßgeblich an der Identifizierung solcher Stoffe beteiligt. Jochen Flasbarth: „Wenn die REACH-Verordnung konsequent angewendet wird, ist sie ein wirksames Instrument für den Umwelt- und Verbraucherschutz. Durch die bessere Regulierung der Chemikalien sparen wir eine Menge an Gesundheits- und Umweltkosten.“ Schärfere Bestimmungen gibt es für vier perfluorierte Chemikalien, die wegen ihrer wasserabweisenden Eigenschaften unter anderem für Outdoorkleidung verwendet werden. Wegen ihrer wasser-, schmutz- und fettabweisenden Eigenschaften werden sie in einer Vielzahl von Verbraucherprodukten wie Textilien, Kochgeschirr oder Papier eingesetzt. ⁠ PFC ⁠ sind in der Umwelt sehr stabil, sodass sie weltweit in allen Umweltmedien gefunden werden, vor allem in Flüssen und Meeren. PFC können sich auch entlang der Nahrungskette anreichern und lassen sich in Blut und Muttermilch von Menschen und Tieren nachweisen. Daher wurden nun vier Vertreter als besonders besorgniserregende Stoffe eingestuft und als solche durch den Ausschuss der Mitgliedstaaten der Europäischen Chemikalienbehörde ECHA in die ⁠ REACH ⁠-Kandidatenliste aufgenommen. Aktuell hat der Ausschuss der Mitgliedstaaten der ECHA über sechs Dossiers des ⁠ UBA ⁠ beraten. Neben der Aufnahme der vier PFC wurden auch Nonylphenol und die Gruppe der Oktylphenolethoxylate auf die Kandidatenliste gesetzt. Nonylphenol ist ein hormonell wirksamer ⁠ Stoff ⁠, der u.a. als Hilfsmittel zum Herstellen von Textilien sowie in Harzen und Lacken eingesetzt wird. Oktylphenolethoxylate kommen in Farben, Lacken und Klebstoffen vor. Gelangen sie über das Abwasser in Kläranlagen und Gewässer, kann sich das hormonell wirksame Oktylphenol bilden. Insgesamt identifizierte der Ausschuss 54 weitere Stoffe als besonders besorgniserregend. Damit ist das von der EU Kommission gesetzte Ziel erreicht, bis Ende des Jahres 136 Stoffe auf der Liste zu haben. Auf die REACH-Kandidatenliste gehören Stoffe mit krebserregenden, erbgutverändernden oder fortpflanzungsgefährdenden Eigenschaften; Stoffe, die langlebig und giftig sind und sich in Organismen anreichern und - nach einer Einzelfallentscheidung - Stoffe, die auf das Hormonsystem wirken. Mit der Aufnahme in die Kandidatenliste erlangen Verbraucherinnen und Verbraucher ein Auskunftsrecht. Auf Nachfrage müssen Hersteller, Importeure oder der Handel darüber informieren, ob ein besonders besorgniserregender Stoff in einem Produkt enthalten ist.  Auf dieser Webseite lassen sich allein mit der Artikelnummer unter dem Strichcode des Produktes Anfragen an die Hersteller versenden. Weiterhin können gelistete Stoffe einer Zulassungspflicht unterworfen werden. Sie dürfen dann nur noch nach vorheriger behördlicher Genehmigung vermarktet und genutzt werden. Ziel der ⁠ REACH-Verordnung ⁠ ist es, dass diese Stoffe schrittweise durch geeignete Alternativstoffe oder -technologien ersetzt werden. Jochen Flasbarth: „Auch künftig bleibt viel zu tun beim Schutz der Umwelt und des Menschen vor schädlichen Auswirkungen von Chemikalien. Die Mitgliedstaaten, die EU-Kommission und die ECHA arbeiten weiter intensiv daran, die Kandidatenliste zu ergänzen. Die Europäische Kommission hat sich das Ziel gesetzt bis 2020 alle relevanten besonders besorgniserregenden Stoffe auf die Kandidatenliste zu bringen. Derzeit wird auf EU-Ebene diskutiert, auf welchem Weg dieses Ziel am besten erreicht werden kann.“ Das UBA hat intensiv an der Identifizierung von besonders besorgniserregenden Stoffen mitgearbeitet. Seit Inkrafttreten von REACH Mitte 2006 erstellte es Dossiers für 18 Stoffe. Davon gelangten 13 auf die Kandidatenliste. Jochen Flasbarth: „Das UBA hat bei REACH Pionierarbeit geleistet. Mit Oktyl- und Nonylphenol hat es die ersten Stoffe auf die Kandidatenliste gebracht, die alleine wegen ihrer hormonähnlichen Wirkungen als besonders besorgniserregend gelten.“ Oktylphenolethoxylate sind die erste Stoffgruppe, die ausschließlich aufgrund ihres umweltrelevanten Abbauproduktes (Oktylphenol) als besonders besorgniserregend gilt.

Potential SVHC in environment and articles – information collection with the aim to prepare restriction proposals for PFAS

The report covers main findings of two information collection activities that have been performed with the aim to collect information about per- and polyfluoroalkyl substances (PFASs). The information collections (literature research, IT-based surveys and targeted interviews with stakeholders) were performed to support the preparation of ⁠ REACH ⁠ restriction dossiers of long-chain perfluoroalkyl carboxylic acids and short-chain PFASs. Also included were the salts of the two groups, precursor substances and substances that contain these substances as structural element. Furthermore, the report contains some general considerations on the use of IT–based surveys in the context of information collections in regulatory activities under REACH. Veröffentlicht in Texte | 144/2019.

Part I. A temporal study of PFCAs and its precursors in human plasma from two German cities 1982 - 2009

Yeung, Leo Wai-Yin; Robinson, Shona; Koschorreck, Jan; Mabury, Scott Andrew Environmental Science & Technology 47 (2013), 8, 3865-3874 A total of 420 human plasma samples from two cities (Halle and Münster, Germany), collected between 1982 and 2009, were analyzed for a suite of PFCAs (C6-C12) and selected PFCA precursors (4:2-, 4:2/6:2-, 6:2-, 6:2/8:2-, 8:2-, 8:2/10:2- and 10:2 diPAPs). PFCAs (C7 - C11, 13) were detected in over 80% of the samples (<0.005 - 39.4 ng/mL) while C12 PFCA was detected in fewer than 10% of the samples. In a range of 10-46% of the samples, 4:2-, 4:2/6:2-, 6:2, and 8:2- diPAPs were identified at concentrations of <0.0002 ng/mL to 0.687 ng/mL; fewer than 10% of the samples had detectable 10:2 diPAP. Temporal trends (2000-2009) showed increasing concentrations of PFNA, PFDA, and PFUnDA, whereas PFOA concentrations were decreasing. Calculated population halving time for PFOA varied between 8.2 - 14.5 years which contrasts to the generally accepted value of 3.8 years. This suggests an ongoing or additional exposure to PFOA or one of its precursor compounds. DiPAPs, known to metabolize rapidly to PFCAs, were detected in a significant number of samples and at concentrations that have not declined significantly over the past half-decade. The evidence suggests they have contributed to the continued presence of the longer chain PFCAs and perhaps contribute to the slow decline of PFOA. doi:10.1021/es303716k Zur Veröffentlichung Teil II: Part II. A temporal study of PFOS and its precursors in human plasma from two German cities 1982 - 2009

Part II. A temporal study of PFOS and its precursors in human plasma from two German cities 1982 - 2009

Yeung, Leo Wai-Yin; Robinson, Shona; Koschorreck, Jan; Mabury, Scott Andrew Environmental Science & Technology 47 (2013), 8, 3875–3882 A total of 420 human plasma from two cities (Halle and Münster, Germany) collected between 1982 and 2009, were analyzed for a suite of PFSAs (C4, C6, C8, C10) and selected PFOS precursors (MeFOSAA, EtFOSAA, FOSAA, di-SAmPAP). Among these target analytes, only di-SAmPAP was used in consumer products. PFSAs (C6 and C8), MeFOSAA, EtFOSAA, and FOSAA were detected in over 95% of the samples (<0.0011 - 116.0 ng/mL), PFDS was detected in approximately 40% of the samples (<0.005 - 0.0998 ng/mL), and SAmPAP was detected in 17% of the samples (<0.005 - 0.0137 ng/mL). Significant positive correlations were found between PFOS and PFHxS, MeFOSAA, EtFOSAA, and FOSAA. Temporal trends of decreasing concentration were identified for PFOS, MeFOSAA, EtFOSAA, and FOSAA, but not for PFHxS. Di-SAmPAP, a common food-contact paper surfactant and expected PFOS precursor, was detected infrequently (25% in samples prior to 2000) in samples before 2006. Population halving times of PFOS, MeFOSAA, EtFOSAA, and FOSAA were estimated. The observed reduction of these chemicals over time in human plasma is presumably related to the phase-out of POSF-based products beginning in 2000. The detection of di-SAmPAP in human sera is significant because this chemical is expected to be metabolized or degraded to PFOS in humans and the environment. Our detection of di-SAmPAP is the first confirmation of human exposure to this commercially available product which is a plausible source of PFOS in humans. doi:10.1021/es4004153 Zur Veröffentlichung Teil I: Part I. A temporal study of PFCAs and its precursors in human plasma from two German cities 1982 - 2009

Levels and trends of industrial chemicals (PCBs, PFCs, PBDEs) in archived herring gull eggs from German coastal regions

Fliedner, Annette; Rüdel, Heinz; Jürling, Heinrich; Müller, Josef; Neugebauer, Frank; Schröter-Kermani, Christa Environmental Sciences Europe 2012, 24:7 Polychlorinated biphenyls [PCBs], perfluorinated compounds, and polybrominated diphenyl ethers [PBDEs] were retrospectively analyzed in archived herring gull (Larus argentatus) eggs from the North and the Baltic Sea over the last 20 years. The aim was to assess temporal trends and effects of regulatory measures. PCBs (sum of 7 congeners) were highest in eggs from the North Sea island Trischen, i.e., 3,710 to 20,760 ng/g lipid weight [lw] compared to 2,530 to 11,650 ng/g lw on the North Sea island Mellum and 4,840 to 9,190 ng/g lw on the Baltic Sea island Heuwiese. During the study period, PCBs decreased significantly. Concentrations of PFOS ranged between 46 and 170 ng/g wet weight [ww] at Trischen, 39 to 99 ng/g ww at Mellum, and 20 to 159 ng/g ww at Heuwiese. Since 2000 and 2003, concentration levels decreased in eggs from Mellum and Heuwiese, respectively. Perfluorooctanoic acid was the dominant perfluorinated carboxylic acid in the North Sea eggs (Trischen 2.0 to 74 ng/g ww; Mellum 2.6 to 118 ng/g ww), whereas perfluoroundecanoate [PFUnA] and perfluorodecanoate [PFDA] (means 3.9 +/- 3.6 ng/g and 2.9 +/- 2.3 ng/g ww, respectively) dominated in the Baltic Sea eggs. At all three locations, longer-chained perfluorinated carboxylic acids (perfluorononanoate, PFDA, PFUnA, perfluorododecanoate) increased during the monitoring period. PBDE concentrations (sum of 35 congeners) in eggs were in the ranges of 282 to 2,059 ng/g lw (Mellum), 116 to 1,722 ng/g (Trischen), and 232 to 2,021 ng/g lw (Heuwiese). Congeners associated with commercial Penta- and Octa-BDE formulations decreased during the study period. No decrease was observed for technical Deca-BDE. Effects of regulatory measures were apparent for PCBs and Penta- and Octa-BDE, while no consistent trend is noticeable for PFOS. doi:10.1186/2190-4715-24-7 (open access)

Human biomonitoring of per- and polyfluoroalkyl substances in German blood plasma samples from 1982 to 2019

Göckener, Bernd; Weber, Till; Rüdel, Heinz; Bücking, Mark; Kolossa-Gehring, Marike Environment International 145 (2020), Dezember 2020, 106123; online 17. September 2020 The findings of per- and polyfluoroalkyl substances (PFAS) in humans and the environment all over the world have raised concerns and public awareness for this group of man-made chemicals. In the last three decades, this led to different regulatory restrictions for specific PFAS as well as shifts in the production and usage of these substances. In this study, we analyzed the PFAS levels of 100 human blood plasma samples collected from 2009 to 2019 for the German Environmental Specimen Bank (ESB) to further elucidate the time course of exposure towards this substance group as shown by Schröter-Kermani et al., (2013) with samples from 1982 to 2010. A spectrum of 37 PFAS, including perfluorocarboxylic (PFCA) and –sulfonic acids (PFSA) as well as potential precursors and substitutes like ADONA, GenX or F-53B was analyzed by UHPLC coupled with high-resolution mass spectrometry. Validation was successful for 33 of the substances. The two legacy substances perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in every sample of the 2009–2019 dataset and showed the highest concentrations with ranges of 0.27–14.0 ng/mL and 1.21–14.1 ng/mL, respectively. A significant portion of total PFOS analytes was present as branched isomers (mean: 34 ± 7%). High detection frequencies of 95% and 82% were also found for perfluorohexane sulfonic acid (PFHxS) and perfluorononanoic acid (PFNA), respectively, but in lower concentrations (PFHxS: <LOQ – 4.62 ng/mL; PFNA: <LOQ – 3.66 ng/mL) than PFOA and PFOS. Besides other PFCA and PFSA only 8:2 fluorotelomer sulfonic acid (8:2 FtS) and N-methyl perfluorooctane sulfonamidoacetic acid were detected in very few samples. In combination with the previous results from 1982 to 2010, declining temporal trends were observed for all PFAS (PFOA, PFNA, PFHxS, and PFOS) frequently detected in the ESB samples. The results of this study indicate a decrease in human exposure to known PFAS in Germany over the last three decades and emphasize the importance of long-term human biomonitoring studies for investigating the effects of chemical regulation. doi: 10.1016/j.envint.2020.106123

Long-Term Trends of Per- and Polyfluoroalkyl Substances (PFAS) in Suspended Particular Matter from German Rivers Using the Direct Total Oxidizable Precursor (dTOP) Assay

Göckener, Bernd; Fliedner, Annette; Rüdel, Heinz; Badry, Alexander; Koschorreck, Jan Environmental Science & Technology 56 (2022), 1, 208-217; online 15. Dezember 2021 Suspended particulate matter (SPM) from 13 riverine sampling sites of the German Environmental Specimen Bank collected between 2005 and 2019 was retrospectively investigated for per- and polyfluoroalkyl substances (PFAS). The samples were analyzed both by target analysis for 41 PFAS and by a modified total oxidizable precursor (dTOP) assay to capture also unknown precursors. Temporal trends and spatial differences were investigated by generalized linear modeling (GLM). Time trend analysis across all rivers showed decreasing trends for ∑PFCA and ∑PFSA concentrations in SPM. Trends based on target analysis (∑PFCA target : −10.0%, ∑PFSA target : −8.2%) were more pronounced than in the dTOP analysis (∑PFCA dTOP : −4.2%; ∑PFSA dTOP : −5.3%), suggesting that conventional target analysis overestimated actual decreases as precursors are not considered. ∑PFAS concentrations determined by dTOP assay were 1.3–145 times higher as compared to target analysis, indicating substantial amounts of unknown precursors in the samples. The ∑PFAS dTOP /∑PFAS target ratio increased at all sites between 2005 and 2019. Contamination was highest in SPM from the Elbe tributary Mulde downstream of a large industrial park. The results underscore the need to go beyond conventional target analysis and include precursors when assessing PFAS contamination in the environment. The dTOP assay is a suitable tool for this purpose. doi: 10.1021/acs.est.1c04165

Exploring unknown per- and polyfluoroalkyl substances in the German environment – The total oxidizable precursor assay as helpful tool in research and regulation

Göckener, Bernd; Fliedner, Annette; Rüdel, Heinz; Fettig, Ina; Koschorreck, Jan Science of The Total Environment 782 (2021), 146825; online 29. März 2021 Limnetic, 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 ∑PFAS concentrations in bream livers of 8.7–282 μg 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 μg kg−1 ∑PFAS). Contamination of suspended particulate matter (SPM) was highest in the upper Elbe downstream the Czech border (5.5 μg kg−1 dry weight (dw) in 2018). Herring gull eggs from the North and Baltic Seas showed ∑PFAS levels around 53.0–69.6 μg kg−1 ww in 2019. In soil, concentrations ranged between <0.5 and 4.6 μg 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. doi: 10.1016/j.scitotenv.2021.146825

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

Rüdel, Heinz; Radermacher, Georg; Fliedner, Annette; Lohmann, Nina; Koschorreck, Jan; Duffek, Anja Chemosphere , 292 (2022), 133483; online 31. Dezember 2021 The 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. doi: 10.1016/j.chemosphere.2021.133483 Rüdel, Heinz; Radermacher, Georg; Fliedner, Annette; Lohmann, Nina; Koschorreck, Jan; Duffek, Anja Chemosphere 292 (2022), 133483, online 31.Dezem The 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. doi: 10.1016/j.chemosphere.2021.133483

138 besonders besorgniserregende Stoffe auf der Kandidatenliste

Für eine Vielzahl an Chemikalien gelten seit Dezember 2012 strengere Vorschriften. Dies sieht die europäische Chemikalienverordnung REACH vor. Davon betroffen sind unter anderem wasser- und fettabweisende Stoffe wie vier perfluorierte Carbonsäuren (PFC). Wegen ihrer schädlichen Wirkung auf die Umwelt werden sie zu besonders besorgniserregenden Stoffen. Damit stehen am 19. Dezember 2012, 138 besonders besorgniserregenden Stoffe auf der Kanidatenliste.

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