%0 journal article %@ 2452-2236 %A Joerss, H., Menger, F. %D 2023 %J Current Opinion in Green and Sustainable Chemistry %P 100775 %R doi:10.1016/j.cogsc.2023.100775 %T The complex ‘PFAS world’ - how recent discoveries and novel screening tools reinforce existing concerns %U https://doi.org/10.1016/j.cogsc.2023.100775 %X In recent years, high-resolution mass spectrometry (HRMS)-based studies have highlighted an increasingly complex ‘PFAS world’ and thousands of per- and polyfluoroalkyl substances (PFAS) are known today. Major new discoveries were made when previously unexplored PFAS sources or transformation pathways were investigated and when HRMS was combined with other analytical methods. Advances in analysis and data treatment have pointed to blind spots, and extensive suspect screening lists and data evaluation approaches have become available. Research has a vital role in making HRMS fit for broad application and, considering ongoing discussions supporting a grouping of PFAS, transitioning society towards a fundamentally new way of regulating, monitoring and managing PFAS. %0 online contribution %@ %A Joerss, H., Lange, M., Takyar, H., Baldewein, L., Ebinghaus, R. %D 2022 %J Coastal Pollution Toolbox %T PFAS explorer %U %X The PFAS Explorer has been developed in the context and is part of the Coastal Pollution Toolbox (URL: https://www.coastalpollutiontoolbox.org), a knowledge hub, digital working environment and tool set to study contaminant, nutrient and carbon dynamics in temperate and polar coastal zones. %0 journal article %@ 0013-936X %A Garnett, J., Halsall, C., Winton, H., Joerss, H., Mulvaney, R., Ebinghaus, R., Frey, M., Jones, A., Lesson, A., Wynn, P. %D 2022 %J Environmental Science and Technology %N 16 %P 11246-11255 %R doi:10.1021/acs.est.2c02592 %T Increasing Accumulation of Perfluorocarboxylate Contaminants Revealed in an Antarctic Firn Core (1958–2017) %U https://doi.org/10.1021/acs.est.2c02592 16 %X Perfluoroalkyl acids (PFAAs) are synthetic chemicals with a variety of industrial and consumer applications that are now widely distributed in the global environment. Here, we report the measurement of six perfluorocarboxylates (PFCA, C4–C9) in a firn (granular compressed snow) core collected from a non-coastal, high-altitude site in Dronning Maud Land in Eastern Antarctica. Snow accumulation of the extracted core dated from 1958 to 2017, a period coinciding with the advent, use, and geographical shift in the global industrial production of poly/perfluoroalkylated substances, including PFAA. We observed increasing PFCA accumulation in snow over this time period, with chemical fluxes peaking in 2009–2013 for perfluorooctanoate (PFOA, C8) and nonanoate (PFNA, C9) with little evidence of a decline in these chemicals despite supposed recent global curtailments in their production. In contrast, the levels of perfluorobutanoate (PFBA, C4) increased markedly since 2000, with the highest fluxes in the uppermost snow layers. These findings are consistent with those previously made in the Arctic and can be attributed to chlorofluorocarbon replacements (e.g., hydrofluoroethers) as an inadvertent consequence of global regulation. %0 journal article %@ 0013-936X %A Joerss, H., Menger, F., Tang, J., Ebinghaus, R., Ahrens, L. %D 2022 %J Environmental Science and Technology %N 9 %P 5456-5465 %R doi:10.1021/acs.est.1c07987 %T Beyond the Tip of the Iceberg: Suspect Screening Reveals Point Source-Specific Patterns of Emerging and Novel Per- and Polyfluoroalkyl Substances in German and Chinese Rivers %U https://doi.org/10.1021/acs.est.1c07987 9 %X Only a few dozens of the several thousand existing per- and polyfluoroalkyl substances (PFAS) are monitored using conventional target analysis. This study employed suspect screening to examine patterns of emerging and novel PFAS in German and Chinese river water affected by industrial point sources. In total, 86 PFAS were (tentatively) identified and grouped into 18 structure categories. Homologue patterns revealed distinct differences between fluoropolymer production sites of the two countries. In the Chinese Xiaoqing River Basin, the C8 homologue was the most prevalent compound of the emerging series of chlorinated perfluoroalkyl carboxylic acids (Cl-PFCAs) and perfluoroalkylether carboxylic acids (PFECAs). In contrast, C6 and shorter homologues were dominant in the German Alz River. This indicates that the phaseout of long-chain compounds in Europe and their ongoing production in Asian countries also apply to unregulated emerging PFAS classes. Additional characteristics to differentiate the point sources were the peak area ratio of perfluorobutane sulfonic acid (PFBS) versus the emerging compound hydro-substituted PFBS (H-PFBS) as well as the occurrence of byproducts of the sulfonated tetrafluoroethylene-based polymer Nafion. The large number of identified unregulated PFAS underlines the importance of a grouping approach on a regulatory level, whereas the revealed contamination patterns can be used to estimate, prioritize, and minimize contributions of specific sources. %0 journal article %@ 0013-936X %A Garnett, J., Halsall, C., Vader, A., Joerss, H., Ebinghaus, R., Leeson, A., Wynn, P. %D 2021 %J Environmental Science and Technology %N 16 %P 11049-11059 %R doi:10.1021/acs.est.1c01676 %T High Concentrations of Perfluoroalkyl Acids in Arctic Seawater Driven by Early Thawing Sea Ice %U https://doi.org/10.1021/acs.est.1c01676 16 %X Poly- and perfluoroalkyl substances are synthetic chemicals that are widely present in the global environment including the Arctic. However, little is known about how these chemicals (particularly perfluoroalkyl acids, PFAA) enter the Arctic marine system and cycle between seawater and sea ice compartments. To evaluate this, we analyzed sea ice, snow, melt ponds, and near-surface seawater at two ice-covered stations located north of the Barents Sea (81 °N) with the aim of investigating PFAA dynamics in the late-season ice pack. Sea ice showed high concentrations of PFAA particularly at the surface with snow-ice (the uppermost sea ice layer strongly influenced by snow) comprising 26–62% of the total PFAA burden. Low salinities (<2.5 ppt) and low δ18OH20 values (<1‰ in snow and upper ice layers) in sea ice revealed the strong influence of meteoric water on sea ice, thus indicating a significant atmospheric source of PFAA with subsequent transfer down the sea ice column in meltwater. Importantly, the under-ice seawater (0.5 m depth) displayed some of the highest concentrations notably for the long-chain PFAA (e.g., PFOA 928 ± 617 pg L–1), which were ≈3-fold higher than those of deeper water (5 m depth) and ≈2-fold higher than those recently measured in surface waters of the North Sea infuenced by industrial inputs of PFAAs. The evidence provided here suggests that meltwater arising early in the melt season from snow and other surface ice floe components drives the higher PFAA concentrations observed in under-ice seawater, which could in turn influence the timing and extent of PFAA exposure for organisms at the base of the marine food web. %0 journal article %@ 2053-1400 %A Jin, T., Peydayesh, M., Joerss, H., Zhou, J., Bolisetty, S., Mezzenga, R. %D 2021 %J Environmental Science: Water Research & Technology %N 10 %P 1873-1884 %R doi:10.1039/D1EW00373A %T Amyloid fibril-based membranes for PFAS removal from water %U https://doi.org/10.1039/D1EW00373A 10 %X We introduce a green and efficient approach for removing per- and polyfluoroalkyl substances (PFASs) based on the β-lactoglobulin amyloid fibril membrane. The membrane exhibits superior adsorption capability for long-chain PFASs. At low pH, the membrane efficiency improved significantly due to enhanced electrostatic interactions between positively charged fibrils and negatively charged PFASs. Furthermore, intermolecular adhesion force measurements confirm the hydrophobic–hydrophobic interaction at the nanoscale with PFOS and PFOA representing perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs), respectively. For real PFAS-contaminated water from the Xiaoqing River basin and under single-step filtration mode, the membrane exhibits high efficiency for removing both high (>μg L−1) and trace (ng L−1) levels of the compounds. To demonstrate the scalability and generality, a commercial amyloid–carbon-based hybrid membrane is applied for removal of a range of long-chain and short-chain PFASs as well as their replacement compounds, offering complete removal of PFASs with ≥4 perfluorinated carbon atoms in the molecular structure and a removal efficiency of low molecular weight PFBA (3 perfluorinated carbon atoms) exceeding 96%. Analysis of the sustainability footprint reveals the superiority of the amyloid–carbon hybrid membrane for PFAS removal. Altogether, these results demonstrate a high potential of amyloid fibril membrane technology for the sustainable removal of PFASs from water. %0 journal article %@ 0013-936X %A Garnett, J., Halsall, C., Thomas, M., Crabeck, O., France, J., Joerss, H., Ebinghaus, R., Kaiser, J., Leeson, A., Wynn, P. %D 2021 %J Environmental Science and Technology %N 14 %P 9601-9608 %R doi:10.1021/acs.est.1c01645 %T Investigating the Uptake and Fate of Poly- and Perfluoroalkylated Substances (PFAS) in Sea Ice Using an Experimental Sea Ice Chamber %U https://doi.org/10.1021/acs.est.1c01645 14 %X Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern and are present in the marine environments of the polar regions. Their input to and fate within the marine cryosphere are poorly understood. We conducted a series of laboratory experiments to investigate the uptake, distribution, and release of 10 PFAS of varying carbon chain length (C4–C12) in young sea ice grown from artificial seawater (NaClsolution). We show that PFAS are incorporated into bulk sea ice during ice formation and regression analyses for individual PFAS concentrations in bulk sea ice were linearly related to salinity (r2 = 0.30 to 0.88, n = 18, p < 0.05). This shows that their distribution is strongly governed by the presence and dynamics of brine (high salinity water) within the sea ice. Furthermore, long-chain PFAS (C8–C12), were enriched in bulk ice up to 3-fold more than short-chain PFAS (C4–C7) and NaCl. This suggests that chemical partitioning of PFAS between the different phases of sea ice also plays a role in their uptake during its formation. During sea ice melt, initial meltwater fractions were highly saline and predominantly contained short-chain PFAS, whereas the later, fresher meltwater fractions predominantly contained long-chain PFAS. Our results demonstrate that in highly saline parts of sea ice (near the upper and lower interfaces and in brine channels) significant chemical enrichment (ε) of PFAS can occur with concentrations in brine channels greatly exceeding those in seawater from which it forms (e.g., for PFOA, εbrine = 10 ± 4). This observation has implications for biological exposure to PFAS present in brine channels, a common feature of first-year sea ice which is the dominant ice type in a warming Arctic. %0 journal article %@ 0043-1354 %A Tröger, R., Ren, H., Yin, D., Postigo, C., Nguyen, P., Baduel, C., Golovko, O., Been, F., Joerss, H., Boleda, M., Polesello, S., Roncoroni, M., Taniyasu, S., Menger, F., Ahrens, L., Lai, F., Wiberg, K. %D 2021 %J Water Research %P 117099 %R doi:10.1016/j.watres.2021.117099 %T What's in the water? – Target and suspect screening of contaminants of emerging concern in raw water and drinking water from Europe and Asia %U https://doi.org/10.1016/j.watres.2021.117099 %X There is growing worry that drinking water can be affected by contaminants of emerging concern (CECs), potentially threatening human health. In this study, a wide range of CECs (n = 177), including pharmaceuticals, pesticides, perfluoroalkyl substances (PFASs) and other compounds, were analysed in raw water and in drinking water collected from drinking water treatment plants (DWTPs) in Europe and Asia (n = 13). The impact of human activities was reflected in large numbers of compounds detected (n = 115) and high variation in concentrations in the raw water (range 15-7995 ng L−1 for ∑177CECs). The variation was less pronounced in drinking water, with total concentration ranging from 35 to 919 ng L−1. Treatment efficiency was on average 65 ± 28%, with wide variation between different DWTPs. The DWTP with the highest ∑CEC concentrations in raw water had the most efficient treatment procedure (average treatment efficiency 89%), whereas the DWTP with the lowest ∑177CEC concentration in the raw water had the lowest average treatment efficiency (2.3%). Suspect screening was performed for 500 compounds ranked high as chemicals of concern for drinking water, using a prioritisation tool (SusTool). Overall, 208 features of interest were discovered and three were confirmed with reference standards. There was co-variation between removal efficiency in DWTPs for the target compounds and the suspected features detected using suspect screening, implying that removal of known contaminants can be used to predict overall removal of potential CECs for drinking water production. Our results can be of high value for DWTPs around the globe in their planning for future treatment strategies to meet the increasing concern about human exposure to unknown CECs present in their drinking water. %0 journal article %@ 1618-3258 %A Joerss, H., Ebinghaus, R. %D 2020 %J Mitteilungen der Fachgruppe Umweltchemie und Ökotoxikologie %N 3 %P 76-80 %T Per- und polyfluorierte Alkylsubstanzen im Rheinverlauf - Vorkommen und Verteilung in Wasser und Sedimenten %U 3 %X Zur Stoffgruppe der mehr als 4.700 per-und polyfluorierten Alkylsubstanzen (PFAS) gehören neben den gut untersuchten und bereits regulierten langkettigen PFAS auch Ersatzstoffe und weitere PFAS, die bislang nicht im Fokus standen. Um dieseSubstanzen im Rheinverlauf zu untersuchen, wurden 29 PFAS in Oberflächenwasser und Sedimenten analysiert. In 50% bzw. 42% der Wasserproben wurde der etherbasierte Er-satzstoff Hexafluorpropylenoxid-Dimersäure (HFPO-DA) und die cyclische Substanz Perfluor-4-ethylcyclohexansulfonsäure (PFECHS) nachgewiesen. Die Konzentration der bislang wenig untersuchten Perfluoralkylphosphinsäure 6:8 PFPiA in den Sedimentproben war vergleichbar mit den Konzentrationen langkettiger PFAS, die 78 ± 8 % der PFAS-Summe aus-machten. Das stellt die Rolle der Sedimente als Senke für langkettige PFAS heraus %0 journal article %@ 0269-7491 %A Joerss, H., Schramm, T., Sun, L., Guo, C., Tang, J., Ebinghaus, R. %D 2020 %J Environmental Pollution %P 115567 %R doi:10.1016/j.envpol.2020.115567 %T Per- and polyfluoroalkyl substances in Chinese and German river water – Point source- and country-specific fingerprints including unknown precursors %U https://doi.org/10.1016/j.envpol.2020.115567 %X This study aimed at comparing source-specific fingerprints of per- and polyfluoroalkyl substances (PFASs) in river water from China and Germany, selected as countries with different histories of PFAS production. Samples were collected from up- and downstream of seven suspected point sources in autumn 2018. Amongst the 29 analyzed legacy and emerging PFASs, 24 were detected, with a sum ranging from 2.7 ng/L (Alz River) to 420,000 ng/L (Xiaoqing River). While mass flow estimates for the Xiaoqing River and Yangtze River (mean: 20 and 43 t/y, respectively) indicated ongoing high emissions of the legacy compound PFOA in China, its ether-based replacements HFPO-DA and DONA showed the highest contribution downstream of a German fluoropolymer manufacturing site (50% and 40% of ΣPFASs measured, respectively). In river water impacted by manufacturing sites for pharmaceutical and pesticide intermediates, the short-chain compound PFBS was the most prevalent substance in both countries. The German Ruhr River, receiving discharges from the electroplating industry, was characterized by the PFOS replacement 6:2 FTSA. Isomer profiling revealed a higher proportion of branched isomers in the Chinese Xi River and Xiaoqing River than in other rivers. This points to different synthesis routes and underlines the importance of differentiating between linear and branched isomers in risks assessments. Upon oxidative conversion in the total oxidizable precursor (TOP) assay, the increase of the short-chain compound PFBA was higher in German samples than in Chinese samples (88 ± 30% versus 12 ± 14%), suggesting the presence of a higher proportion of unknown precursors to PFBA in the German environment. Amongst the ether-based replacements, DONA and 6:2 Cl-PFESA were fully or partially degraded to non-targeted oxidation products, whereas HFPO-DA showed no degradation. This indicates that the inclusion of ether-based PFASs and their oxidation products in the TOP assay can help in capturing a larger amount of the unknown PFAS fraction. %0 journal article %@ 0013-936X %A Joerss, H., Xie, Z., Wagner, C., von Appen, W., Sunderland, E., Ebinghaus, R. %D 2020 %J Environmental Science and Technology %N 16 %P 9958-9967 %R doi:10.1021/acs.est.0c00228 %T Transport of Legacy Perfluoroalkyl Substances and the Replacement Compound HFPO-DA through the Atlantic Gateway to the Arctic Ocean—Is the Arctic a Sink or a Source? %U https://doi.org/10.1021/acs.est.0c00228 16 %X The spatial distribution of 29 per- and polyfluoroalkyl substances (PFASs) in seawater was investigated along a sampling transect from Europe to the Arctic and two transects within Fram Strait, located between Greenland and Svalbard, in the summer of 2018. Hexafluoropropylene oxide-dimer acid (HFPO-DA), a replacement compound for perfluorooctanoic acid (PFOA), was detected in Arctic seawater for the first time. This provides evidence for its long-range transport to remote areas. The total PFAS concentration was significantly enriched in the cold, low-salinity surface water exiting the Arctic compared to warmer, higher-salinity water from the North Atlantic entering the Arctic (260 ± 20 pg/L versus 190 ± 10 pg/L). The higher ratio of perfluoroheptanoic acid (PFHpA) to perfluorononanoic acid (PFNA) in outflowing water from the Arctic suggests a higher contribution of atmospheric sources compared to ocean circulation. An east–west cross section of the Fram Strait, which included seven depth profiles, revealed higher PFAS concentrations in the surface water layer than in intermediate waters and a negligible intrusion into deep waters (>1000 m). Mass transport estimates indicated a net inflow of PFASs with ≥8 perfluorinated carbons via the boundary currents and a net outflow of shorter-chain homologues. We hypothesize that this reflects higher contributions from atmospheric sources to the Arctic outflow and a higher retention of the long-chain compounds in melting snow and ice. %0 journal article %@ 0048-9697 %A Wang, P., Mi, W., Xie, Z., Tang, J., Apel, C., Joerss, H., Ebinghaus, R., Zhang, Q. %D 2020 %J Science of the Total Environment %P 139535 %R doi:10.1016/j.scitotenv.2020.139535 %T Overall comparison and source identification of PAHs in the sediments of European Baltic and North Seas, Chinese Bohai and Yellow Seas %U https://doi.org/10.1016/j.scitotenv.2020.139535 %X An international sampling campaign was carried out to comprehensively investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs) in the marine sediments from the European Baltic and North Seas, Chinese Bohai and Yellow Seas. The concentrations of ∑18PAHs in the samples from these four seas were in the range of 0.91–5361 ng/g dry weight (dw), 0.46–227 ng/g dw, 25.0–308 ng/g dw and 4.3–659 ng/g dw, respectively. 4-rings PAHs, e.g., fluoranthene, pyrene and benzo(b)fluoranthene, were commonly the dominant compounds in all the samples. The PAH sources were identified via composition patterns, diagnostic ratios, principal component analysis (PCA) and positive matrix factorization (PMF). Coal combustion, vehicular emission, coke plant and petroleum residue were apportioned as the main sources in these marine sediments. However, through PMF modeling, different contributions of these sources were quantified to the deposited PAHs in the seas, suggesting distinct anthropogenic impacts on the adjacent marine system. It is note-worthy that biomass combustion may not be the main source of PAHs in the majority of sediments from these seas. This was evidenced by the ratios of naphthalene against its methylated derivatives (i.e. 1-,2-methylnaphthalenes) other than the composition pattern in the samples, of which the approach is in prospect of developing in future studies. %0 journal article %@ 0048-9697 %A Joerss, H., Apel, C., Ebinghaus, R. %D 2019 %J Science of the Total Environment %P 360-369 %R doi:10.1016/j.scitotenv.2019.05.363 %T Emerging per- and polyfluoroalkyl substances (PFASs) in surface water and sediment of the North and Baltic Seas %U https://doi.org/10.1016/j.scitotenv.2019.05.363 %X Along with the phase-out of legacy long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their precursors, attention has been drawn to emerging per- and polyfluoroalkyl substances (PFASs). This study is aimed at investigating the importance of selected emerging PFASs as pollutants in European coastal environments and a possible transition from legacy long-chain PFCAs and PFSAs to replacement compounds. Therefore, the spatial distribution of 29 PFASs was analysed in surface water and sediment of the North and Baltic Seas sampled in 2017. Levels of the replacement compound HFPO-DA were approximately three times higher than those of its predecessor PFOA in surface water from the North Sea, which is characterised by the influence of point sources and constant exchange with open water. Reanalysis of sample extracts from the last decade showed that HFPO-DA had already been present in 2011, when it had not yet been in focus. In the Baltic Sea with a limited water exchange and dominance of diffuse sources, the proportion of HFPO-DA was negligible, whereas long-chain PFCAs and PFSAs still contributed to ∑PFASs with about 30%. The emerging cyclic compound perfluoro-4-ethylcyclohexanesulfonate (PFECHS), which has not yet been reported in European coastal environments, was detected in 86% of the Baltic Sea samples. Influenced by sediment characteristics in addition to source-specific contributions, the spatial distribution of PFASs in surface sediments was more variable than for water samples. The linear isomer of the long-chain legacy substance PFOS was the predominant compound found over the entire study area. Of the emerging PFASs, 6:6 and 6:8 perfluoroalkyl phosphinic acids (PFPiAs) were identified close to potential industrial inputs and in sedimentation areas. The results show that particular emerging PFASs play a relevant role in the investigated coastal environments and that a shift to replacements is dependent on sources and geographical conditions. %0 journal article %@ 0045-6535 %A Apel, C., Joerss, H., Ebinghaus, R. %D 2018 %J Chemosphere %P 254-261 %R doi:10.1016/j.chemosphere.2018.08.105 %T Environmental occurrence and hazard of organic UV stabilizers and UV filters in the sediment of European North and Baltic Seas %U https://doi.org/10.1016/j.chemosphere.2018.08.105 %X UV absorbing compounds are of emerging concern due to their large production volumes, their persistence or pseudo-persistence, and their potential adverse effects. This is the first study investigating the environmental occurrence and potential hazard of organic UV stabilizers and UV filters in the North and Baltic Sea surface sediments, including the connecting Skagerrak and Kattegat straits. In total, nineteen substances were identified over the entire study area, including the rarely studied compounds ethylhexyl triazone (EHT) and bisoctrizole (UV-360). Octocrylene (OC) was the predominant compound in this study with regard to detection frequency (79%) and concentrations (up to 9.7 ng/g dw). OC accounted for more than 65% of UV stabilizer contamination in the German Bight. The triazine derivative EHT was quantified in the Rhine-Meuse-Delta and the German Bight in concentrations up to 2.0 ng/g dw. In the Baltic Sea, benzotriazole UV stabilizers accounted for 60% of the contamination, with UV-360 as the main substance. The estimated environmental hazard quotients indicated a negligible impact on benthic and sediment-dwelling organisms in the North and Baltic Seas. Region-specific contamination pattern and riverine influences were revealed. The results suggest that both direct and indirect sources contribute to the UV stabilizer and UV filter contamination in the study ar