TY - JOUR A1 - Vogel, Christian A1 - Hermann, P. A1 - Kästner, B. A1 - Adamczyk, Burkart A1 - Hoehl, A. A1 - Ulm, G. A1 - Adam, Christian T1 - Air and chlorine gas corrosion of different silicon carbides analyzed by nano-Fourier-transform infrared (nano-FTIR) spectroscopy N2 - The present study shows the potential of high-resolution imaging and nano-Fourier-transform infrared (nano-FTIR) spectroscopy for corrosion science. The protective oxidation layers of different chlorine-gas treated silicon carbides (SiCs) were characterized with these techniques. A nitrified SiC showed the highest resistant strength against chlorine corrosion at 1000 °C compared to the other SiCs. Nano-FTIR spectroscopy with a lateral resolution below 40 nm detected differences in the crystallinity of the bulk-SiC and in the transitional region to the protective layer. Furthermore, high-resolution imaging provides deep insight in the interfacial layer between bulk-SiC and the protective oxidation layer on sub-micrometer scale. KW - Nano-Fourier-transform infrared spectroscopy KW - Scattering-type scanning near-field optical microscopy (s-SNOM) KW - Synchrotron radiation KW - Corrosion KW - Silicon carbide KW - Chlorine PY - 2018 DO - https://doi.org/10.1016/j.corsci.2017.12.002 SN - 0010-938X VL - 131 SP - 324 EP - 329 PB - Elsevier AN - OPUS4-43648 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Huthwelker, T. A1 - Wittwer, Philipp A1 - Simon, Franz-Georg T1 - Investigation of per‑ and polyfluoroalkyl substances (PFAS) in soils and sewage sludges by fluorine K‑edge XANES spectroscopy and combustion ion chromatography N2 - For the first time, fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to detect per- and polyfluoroalkyl substances (PFAS) in various soil and sewage sludge samples. The method can be used to determine the speciation of inorganic and organic fluorides, without pre-treatment of solid samples. Therefore, XANES spectra of several inorganic fluorides as well as selected fluorinated organic compounds were recorded. While inorganic fluorides partially exhibit a variety of sharp spectral features in the XANES spectrum, almost all inspected organofluorine compounds show two distinct broad features at 688.5 and 692.0 eV. Moreover, the peak intensity ratio 688.5 eV/692.0 eV in the PFAS XANES spectrum can be inversely correlated to the chain length of the perfluoro sulfonic acid group. The detection of targeted PFAS by bulk-XANES spectroscopy in combination with linear combination fitting in soils and sewage sludges was not applicable due to the low organic fluorine to total fluorine ratio of the samples (0.01–1.84%). Nonetheless, direct analysis of pure PFAS revealed that analysis of organofluorine species might be achieved in higher concentrated samples. Furthermore, quantitative measurements by combustion ion chromatography (CIC) evaluated as sum parameters extractable organically bound fluorine (EOF) and total fluorine (TF) emphasize that besides soils, sewage sludges are a significant source of organic fluorine in agriculture (154–7209 μg/kg). KW - Sewage sludge KW - Combustion ion chromatography KW - Oil KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Per- and polyfluoroalkyl substances (PFAS) PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538953 DO - https://doi.org/10.1007/s11356-021-17838-z VL - 29 IS - 18 SP - 26889 EP - 26899 PB - Springer AN - OPUS4-53895 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Doolette, A. A1 - Huang, J. T1 - Combining diffusive gradients in thin-films (DGT) and 31P NMR spectroscopy to determine phosphorus species in soil N2 - The diffusive gradients in thin-films (DGT) technique shows in many publications a superior correlation to the amount of plant-available phosphorus (P) in soil. However, this technique cannot give information on the plant-available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time. KW - Phosphorus KW - Diffusive gradients in thin-films (DGT) KW - Passive sampling KW - fertilizer PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545759 DO - https://doi.org/10.1002/ael2.20068 VL - 7 IS - 1 SP - e20068 PB - Wiley online library AN - OPUS4-54575 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Roesch, Philipp T1 - Analytical Challenges for PFAS in Environmental Samples - Methods, Approaches and Applicability N2 - Per- and polyfluoroalkyl substances (PFAS) are anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include up to 1.7 M compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, because of the continuous contamination through PFAS containing commercial products, effluents and sewage sludge from WWTPs have been shown to be an important source of PFAS discharge into the aquatic environment. In the last few years, legacy PFAS (≥C4) have been found in various environments, including soil, water and wastewater, and their environmental pathways have been partly described. Several long-chain PFAS species, and their respective salts are considered as persistent organic pollutants by the United Nations Stockholm Convention. These pollutants have been linked to altered immune and thyroid function, liver disease, lipid and insulin dysregulation, kidney disease, adverse reproductive and developmental outcomes, and cancer. A significant shift in the chemical industry towards production of short (C4-C7) and ultrashort (C1-C3) alternatives was observed in response to recently intensified regulations and restrictions on the use of long-chain (≥C8) PFAS. PFAS analysis in environmental samples is currently mainly done by liquid chromatography tandem mass spectrometry (LC-MS/MS). This efficient method is conducted in a targeted fashion analyzing a small subset of PFAS. The US EPA method for analysis of PFAS using LC-MS/MS for example currently lists 40 PFAS (≥C4). However, to get a better overview of the amount of “total PFAS,” sum parameter methods like total oxidizable precursor (TOP) assay and methods based on combustion ion chromatography (CIC) are in development. CIC results in data regarding the sum of absorbable organic fluorine (AOF) or extractable organic fluorine (EOF), which can also quantify other organically bound fluorine compounds such as fluorinated pesticides and pharmaceutical. Moreover, non-target and suspect screening mass spectrometry can be used to identify novel emerging PFAS and partly unknown fluorinated compounds in environmental samples. Furthermore, to analyze ultrashort PFAS (C1-C3), supercritical fluid chromatography (SFC), hydrophilic interaction chromatography (HILIC) and gas chromatography-mass spectrometry (GC-MS) are available, but further research is needed to develop reliable and accurate methods to quantify several ultrashort PFAS in environmental samples. Additionally, for research purpose several spectroscopical methods like X-ray photoelectron spectroscopy (XPS), fluorine K-edge X-ray absorption near-edge structure (XANES)spectroscopy, particular induced gamma-ray emission (PIGE) spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy are available. T2 - CleanUp 2022 CY - Adelaide, Australia DA - 11.09.2022 KW - PFAS KW - Combustion ion chromatography KW - XANES spectroscopy PY - 2022 AN - OPUS4-55741 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp T1 - PFAS Sum Parameter and Structural Analysis N2 - Per- and polyfluoroalkyl substances (PFAS) are anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms (see Figure 1) and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, because of the continuous contamination through PFAS containing commercial products, effluents and sewage sludge from WWTPs have been shown to be an important source of PFAS discharge into the aquatic environment. In the last few years, legacy PFAS (≥C4) have been found in various environments, including soil, water and wastewater, and their environmental pathways have been partly described. To get a better overview of the amount of “total PFAS,” sum parameter methods like total oxidizable precursor (TOP) assay and methods based on combustion ion chromatography (CIC) are in development. CIC results in data regarding the sum of absorbable organic fluorine (AOF) or extractable organic fluorine (EOF), which can also quantify other organically bound fluorine compounds such as fluorinated pesticides and pharmaceutical. Additionally, for research purpose several spectroscopical methods like X-ray photoelectron spectroscopy (XPS), fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy, particular induced gamma-ray emission (PIGE) spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy are available. Therefore, an overview is given on various analytical techniques for PFAS in environmental samples and their application possibilities discussed for different kind of PFAS compounds T2 - CleanUp 2022 CY - Adelaide, Australia DA - 11.09.2022 KW - PFAS KW - Combustion ion chromatography KW - XANES spectroscopy KW - Soil PY - 2022 AN - OPUS4-55743 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Microspectroscopy reveals dust-derived apatite grains in highly-weathered soils from the Kohala climosequence on Hawaii N2 - Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to colocation with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition. T2 - BESSY Science Seminar CY - Online meeting DA - 01.04.2022 KW - Phosphorus KW - Soil KW - X-ray diffraction KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Fertilizer KW - Raman spectroscopy KW - infrared spectroscopy PY - 2022 AN - OPUS4-54584 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Diffusive Gradients in Thin-films (DGT) technique as screening tool for per- and polyfluoroalkyl substances (PFAS) contamination in wastewater-based fertilizers N2 - Per- and polyfluoroalkyl substances (PFAS) are a large group of organofluorine surfactants used in the formulations of thousands of consumer goods, including aqueous film-forming foams (AFFF) used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment, and plastic and leather products. As a result of the perpetual use of PFAS containing products, effluents and sewage sludge from wastewater treatment plants (WWTPs) have been observed to be an important pathway for PFAS into the environment. In Germany, phosphorus and other nutrients from sewage sludge and wastewater should be recycled in WWTPs of cities with a large population. However, it is not clear if PFAS contamination from wastewater and sewage sludge end up in novel wastewater-based fertilizers. Normally, PFAS are analyzed using PFAS protocols typically with time-consuming extraction steps and LC-MS-MS quantification. However, for screening of PFAS contaminations in sewage sludge or wastewater-based fertilizers also passive sampler based on the Diffusive Gradients in Thin-films (DGT) technique can be used for the PFAS extraction. Afterwards, combustion ion chromatography (CIC) can be applied to analyse the “total” amount of PFAS on the passive sampler. Here, we show results from the DGT method in comparison to those of the extractable organic fluorine (EOF) method for a variety of wastewater-based fertilizers. Additionally, we analysed the adsorption of PFAS on the weak anion exchanger (WAX) based DGT passive sampler binding layer by infrared and fluorine K-edge X-ray adsorption near-edge structure (XANES) spectroscopy. T2 - SETAC Europe 2022 CY - Copenhagen, Denmark DA - 15.05.2022 KW - Passive sampling KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Wastewater PY - 2022 AN - OPUS4-54883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Ludwig, S. A1 - Roesch, Philipp A1 - Vigelahn, L. A1 - Wittwer, Philipp A1 - Birke, V. A1 - Simon, Franz-Georg T1 - Mechanochemical Remediation of Per- and Polyfluoroalkyl Substanzes (PFAS) in Soils N2 - Per- and polyfluoroalkyl substances (PFAS) are a large group of anionic, cationic, or zwitterionic organofluorine surfactants used in the formulations of thousands of products and consumer goods, including aqueous film-forming foams (AFFF) used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment. Because PFAS have been extensively used in a variety of AFFF products they can be found in soils from industrial and military installations. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GCMS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy. T2 - CleanUp 2022 CY - Adelaide, Australia DA - 11.09.2022 KW - PFAS KW - Mechanochemical treatment KW - XANES spectroscopy PY - 2022 AN - OPUS4-55742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Piechotta, Christian A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Herzel, Hannes A1 - Huthwelker, T. A1 - Borca, C. A1 - Simon, Franz-Georg T1 - Levels of per- and polyfluoroalkyl substances (PFAS) in various wastewater-derived fertilizers - Analytical investigations from different perspectives N2 - Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. KW - Combustion ion chromatography KW - Per- and polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Fertilizer PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583429 DO - https://doi.org/10.1039/d3va00178d SN - 2754-7000 VL - 2 IS - 10 SP - 1436 EP - 1445 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-58342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind entscheidend für die Qualitätssicherung von Laboratorien. Diese nutzen Referenzmaterialien unter anderem zur Validierung von Messverfahren und zur Kalibrierung von Geräten. Dabei ist zu beachten, dass zertifizierte Merkmalswerte stets eine gewisse Unsicherheit aufweisen. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Artikels. Des Weiteren wird ein Vorgehen beschrieben, wie die Unsicherheit von Messverfahren mit Hilfe eines Referenzmaterials bestimmt werden kann. KW - Referenzmaterial KW - Messunsicherheit KW - Qualitätskontrolle PY - 2024 DO - https://doi.org/10.1515/teme-2024-0025 SN - 0171-8096 SP - 1 EP - 7 PB - De Gruyter AN - OPUS4-60564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ronen, A. A1 - Vogel, Christian A1 - Leube, Peter A1 - Ben Efraim, R. A1 - Nir, O. A1 - Chaudhary, M. A1 - Futterlieb, M. A1 - Panglisch, S. T1 - DEFEAT-PFAS: Detection, Quantification, and Treatment of Per- and Polyfluoroalkyl Substances (PFAS) in Groundwater N2 - The research project focuses on tackling the detection, measurement, and elimination of per- and polyfluoroalkyl substances (PFAS) from polluted groundwater, with a particular emphasis on addressing short (C4-C7) and ultrashort (C1-C3) chain PFAS. Given the widespread use of PFAS in various products, they are commonly found in groundwater near industrial and military sites in Germany and Israel. Moreover, recent regulations limiting the use of long chain PFAS have led industries to shift towards shorter chain alternatives. Hence, our efforts are geared towards refining detection, quantification, and removal methods for short and ultrashort chain PFAS. In terms of detection, ww are developing passive sampling devices capable of collecting and tracking the temporal distribution of PFAS species in groundwater. This will enable us to analyze contaminations in German and Israeli groundwater using cutting-edge analytical techniques. Additionally, contaminated groundwater will undergo a two-stage treatment process aimed at concentrating the relatively low PFAS concentrations using innovative membrane technologies such as closed-circuit reverse osmosis and mixed matrix composite nanofiltration membrane adsorbers. Subsequently, the streams containing higher PFAS concentrations will be treated through coagulation, with the remaining PFAS being adsorbed onto carbonaceous nanomaterials. The outcome of this research will include the creation of advanced tools for detecting, measuring, and eliminating PFAS from polluted groundwater, while also enhancing our understanding of the scope of these contaminations. T2 - German Israeli Water Technology Status Seminar CY - Koblenz, Germany DA - 18.06.2024 KW - Ground water KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation PY - 2024 UR - https://indico.scc.kit.edu/event/4029/attachments/7552/12045/Proceedings_Ger-Isr-Coop_Status-Seminar-2024.pdf SP - 33 EP - 36 AN - OPUS4-60331 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ronen, A. A1 - Panglisch, S. A1 - Vogel, Christian A1 - Leube, Peter A1 - Ben Efrain, R. A1 - Nir, O. A1 - Chaudhary, M A1 - Futterlieb, M. T1 - Detection, Quantification and Treatment of Per and Polyfluoroalkyl substances (PFAS) in Groundwater N2 - The research project focuses on tackling the detection, measurement, and elimination of per- and polyfluoroalkyl substances (PFAS) from polluted groundwater, with a particular emphasis on addressing short (C4-C7) and ultrashort (C1-C3) chain PFAS. Given the widespread use of PFAS in various products, they are commonly found in groundwater near industrial and military sites in Germany and Israel. Moreover, recent regulations limiting the use of long chain PFAS have led industries to shift towards shorter chain alternatives. Hence, our efforts are geared towards refining detection, quantification, and removal methods for short and ultrashort chain PFAS. In terms of detection, ww are developing passive sampling devices capable of collecting and tracking the temporal distribution of PFAS species in groundwater. This will enable us to analyze contaminations in German and Israeli groundwater using cutting-edge analytical techniques. Additionally, contaminated groundwater will undergo a two-stage treatment process aimed at concentrating the relatively low PFAS concentrations using innovative membrane technologies such as closed-circuit reverse osmosis and mixed matrix composite nanofiltration membrane adsorbers. Subsequently, the streams containing higher PFAS concentrations will be treated through coagulation, with the remaining PFAS being adsorbed onto carbonaceous nanomaterials. The outcome of this research will include the creation of advanced tools for detecting, measuring, and eliminating PFAS from polluted groundwater, while also enhancing our understanding of the scope of these contaminations. T2 - German Israeli Water Technology Status Seminar CY - Koblenz, Germany DA - 18.06.2024 KW - Ground water KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation PY - 2024 AN - OPUS4-60328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Leube, Peter A1 - Vogel, Christian A1 - Simon, Franz-Georg T1 - Quantification of ultrashort per- and polyfluoroalkyl substances (PFAS) in water samples via headspace gas chromatographymass spectrometry (GC-MS) - a method development N2 - Ultrashort PFAS (≤ 3 carbon atoms) were overlooked for a long time in analytical monitoring. Beside through the use of these substances, they contribute to the PFAS background in the environment through (environmental/ bio-) degradation and incomplete destruction3 of PFAS with longer carbon chains or other fluorinated compounds. As part of the German-Israeli Cooperation in Water Technology Research project „Detection, quantification, and treatment of per- and polyfluoroalkyl substances in groundwater“ (DEFEAT-PFAS), we are developing an as simple as possible direct headspace (HS-)GC-MS method to detect trifluoroacetic acid (TFA) and perfluoropropanioc acid (PFPrA), as well as trifluoroethanol (TFEtOH), pentafluoropropanol(PFPrOH) and hexafluoroiospropanol (HFIP) in water samples. Here we present the results of the PFAS mentioned in spiked ultrapure water solutions. T2 - German Israeli Water Technology Status Seminar CY - Koblenz, Germany DA - 18.06.2024 KW - Ground water KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Gas chromatography - mass spectrometry (GC-MS) PY - 2024 AN - OPUS4-60330 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Pauw, Brian Richard A1 - Qu, Xintong A1 - Schönhals, Andreas T1 - Competition of nanoparticle-induced mobilization and immobilization effects on segmental dynamics of an epoxy-based nanocomposite N2 - The complex effects of nanoparticles on a thermosetting material based on an anhydride cured DGEBA/Boehmite nanocomposite with different particle concentrations is considered. A combination of X-ray scattering, calorimetry, including fast scanning calorimetry as well as temperature modulated calorimetry and dielectric spectroscopy, was employed to study the structure, the vitrification kinetics and the molecular dynamics of the nanocomposites. For the first time in the literature for an epoxy-based composite a detailed analysis of the X-ray data was carried out. Moreover, the unfilled polymer was found to be intrinsically heterogeneous, showing regions with different crosslinking density, indicated by two separate dynamic glass transitions. The glass transition temperature decreases with increasing nanoparticle concentration, resulting from a change in the crosslinking density. Moreover, on the one hand, for nanocomposites the incorporation of nanofiller increased the number of mobile segments for low nanoparticle concentrations, due to the altered crosslinking density. On the other hand, for higher loading degrees the number of mobile segments decreased, resulting from the formation of an immobilized interphase (RAF). The simultaneous mobilization and immobilization of the segmental dynamics cannot be separated unambiguously. Taking the sample with highest number of mobile segments as reference state it was possible to estimate the amount of RAF. KW - Nanocomposite PY - 2020 DO - https://doi.org/10.1039/d0sm00744g SN - 1744-683X VL - 16 IS - 23 SP - 5406 EP - 5421 PB - Royal Chemical Society AN - OPUS4-50883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zorn, R. A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Malpass-Evans, R. A1 - McKeown, N. A1 - Tyagi, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Low frequency vibrations and diffusion in disordered polymers bearing an intrinsic microporosity as revealed by neutron scattering N2 - The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules. KW - Polymer of intrisic microporosity KW - Neutron scattering KW - Boson peak KW - Methyl group rotation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538490 DO - https://doi.org/10.3390/cryst11121482 VL - 11 IS - 12 SP - 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-53849 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Böhning, Martin A1 - Zamponi, M. A1 - Frick, B. A1 - Appel, M. A1 - Günther, G. A1 - Russina, M. A1 - Alentiev, D. A1 - Bermeshev, M. A1 - Zorn, R. T1 - Microscopic dynamics of highly permeable super glassy polynorbornenes revealed by quasielastic neutron scattering N2 - The molecular dynamics of addition-type poly(tricyclononenes) with Si-substituted bulky side groups has been investigated by a combination of neutron time-of-flight and neutron backscattering spectroscopy methods on a time scale from 0.1 ps to ca. 3 ns. The investigated poly(tricyclononenes) PTCNSi1 and PTCNSi2g both bear a high microporosity which makes them promising candidates for active separation layers for gas separation membranes. At least for larger gas molecules it is assumed that the pathways for diffusion require an enlargement of pre-existing micropores in terms of an activated zone. A low temperature relaxation process was found for both polymers by the performed neutron scattering experiments. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized. For PTCNSi1 (3 methyl groups in the monomeric unit) it was found that all methyl groups take part in the methyl group rotation whereas for PTCNSi2g (6 methyl groups in monomeric unit) a considerable number of methyl groups are blocked in their rotation. This immobilization of methyl groups is due to the sterically demanding arrangement of the methyl groups in PTCNSi2g. This conclusion is further supported by the result that the activation energy for the methyl group rotation is three times higher for PTCNSi2g than that of PTCNSi1. KW - Highly permeably polynorbornenes KW - Polymers of intrinsic microporosity KW - Gas separation membranes KW - Quasielastic neutron scattering PY - 2021 DO - https://doi.org/10.1016/j.memsci.2021.119972 SN - 0376-7388 VL - 642 PB - Elesevier B.V. AN - OPUS4-53508 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cano Murillo, Natalia A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Sturm, Heinz A1 - Schönhals, Andreas T1 - Electrospun nanocomposites fibers of polycarbonate and taurine modified boehmite nanoparticles - What can be learned from structural and thermal investigations N2 - Though the reinforcing properties of inorganic particles in thermosetting nanocomposites, has been exploited, the integration of nanoparticles continues to be challenging in terms of their homogeneous distribution and their manipulation which can contribute to occupational hazards. Due to a second encapsulations of nanoparticles, electrospun nanocomposite fibers containing nanoparticles might be an alternative for overcoming these issues, as the fiber nonwovens contains the nanoparticles allowing for safer manipulation. Here, the morphology, and the thermal properties of electrospun polycarbonate fibers containing taurine modified boehmite nanoparticles (BNP) are investigated by means of small and wide-angle X-ray scattering as well as fast scanning and temperature modulated fast scanning calorimetry for the first time. The latter techniques allow the investigation of the thermal properties of single fibers at heating rates up to 10^4 K s^-1 keeping its structure intact. A quantitative analysis of the scattering data reveals a porous structure of the fibers. The porous structure is quantified regarding the pore volume and the pore size. A constant amount of aggregation is found even for the highly BNP loaded fibers. Thermal analysis on the fibers reveals a rigid amorphous fraction (RAF) where it is known that RAF determinates the properties of a nanocomposite to a large extent. For the fibers RAF amounts up to 40 wt%, which is essential higher compared to equally formulated PC/BNP composite cast films. The RAF in the case of the fibers, is not only due to the presence of particles in the polymer but also due to orientation effects induced by the electrospinning process. KW - Nanocomposite fibers KW - Electrospinning KW - X-ray scattering KW - Fast scanning calorimetry KW - Rigid amorphous fraction PY - 2021 DO - https://doi.org/10.1021/acsapm.1c01265 VL - 3 IS - 12 SP - 6572 EP - 6585 PB - ACS AN - OPUS4-53871 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Qu, Xintong A1 - Abbasi, M. A1 - Pauw, Brian Richard A1 - Henning, S. A1 - Li, Z. A1 - Wang, D.-Y. A1 - Schick, C. A1 - Saalwächter, K. A1 - Schönhals, Andreas T1 - Spatial inhomogeneity, Interfaces and Complex Vitrification Kinetics in a Network Forming Nanocomposite N2 - A detailed calorimetric study on an epoxy-based nanocomposite system was performed employing bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) as the polymer matrix and taurine-modified MgAL layered double hydroxide (T-LDH) as nanofiller. The -NH2 group of taurine can react with DGEBA improving the interaction of the polymer with the filler. The combined X-ray scattering, and electron microscopy data showed that the nanocomposite has a partially exfoliated morphology. Calorimetric studies were performed with conventional DSC, temperature modulated DSC (TMDSC) and fast scanning calorimetry (FSC) in the temperature modulated approach (TMFSC) to investigate the vitrification and molecular mobility in dependence of the filler concentration. First, TMDSC and NMR were used to estimate the amount of the rigid amorphous fraction which consists of immobilized polymer segments at the nanoparticle surface. It was found to be 40 wt% for the highest filler concentration, indicating that the interface dominates the overall macroscopic properties and behavior of the material to a great extent. Second, the relaxation rates of the α-relaxation obtained by TMDSC and TMFSC were compared with the thermal and dielectric relaxation rates measured by static FSC. The investigation revealed that the system shows two distinct α-relaxation processes. Furthermore, also two separate vitrification mechanisms were found for a bulk network-former without geometrical confinement as also confirmed by NMR. This was discussed in terms of the intrinsic spatial heterogeneity on a molecular scale, which becomes more pronounced with increasing nanofiller content. KW - Polymer based Nanocomposites PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523199 DO - https://doi.org/10.1039/d0sm01992e SN - 1744-6848 VL - 17 IS - 10 SP - 2775 EP - 2790 PB - Royal Society of Chemistry AN - OPUS4-52319 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gawek, Marcel A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Radnik, Jörg A1 - Schönhals, Andreas T1 - Energy Dependent XPS Measurements on Thin Films of a Poly(vinyl methyl ether)/Polystyrene Blend in Dependence on Film Thickness – Concentration Profile on a Nanometer Resolution to Understand the Behavior of Nanofilms N2 - The composition of the surface layer in dependence from the distance of the polymer/air interface in thin films with thicknesses below 100 nm of miscible polymer blends in a spatial region of a few nanometers is not investigated completely. Here, thin films of the blend poly vinyl methyl ether) (PVME)/polystyrene (PS) with a composition of 25/75 wt% are investigated by Energy Resolved X-ray Photoelectron Spectroscopy (ER-XPS) at a synchrotron storage ring using excitation energies lower than 1 keV. By changing the energy of the photons the information depth is varied in the range from ca. 1 nm to 10 nm. Therefore, the PVME concentration could be estimated in dependence from the distance of the polymer/air interface for film thicknesses below 100 nm. Firstly, as expected for increasing information depth the PVME concentration decreases. Secondly, it was found that the PVME concentration at the surface has a complicated dependence on the film thickness. It increases with decreasing film thickness until 30 nm where a maximum is reached. For smaller film thicknesses the PVME concentration decreases. A simplified layer model is used to calculate the effective PVME concentration in the different spatial regions of the surface layer. KW - Energy dependent XPS KW - Soft X-ray KW - Thin films PY - 2021 DO - https://doi.org/10.1039/d1sm00656h VL - 17 IS - 29 SP - 6985 EP - 6994 PB - The Royal Chemical Society AN - OPUS4-53039 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bäßler, Ralph A1 - Aristia, Gabriela A1 - Nofz, Marianne A1 - Sojref, Regine A1 - Le, Quynh Hoa T1 - Preliminary Study on Al2O3 Sol-Gel Coating for Corrosion Protection of Martensitic Stainless Steel in Artificial Geothermal Water N2 - Al2O3 coatings are often used as protective layers on steels against electrochemical and high-temperature corrosion because they are chemically inert and stable at elevated temperatures. This study presents preliminary work on the possibilities of using Al2O3 sol-gel coatings for corrosion protection of martensitic stainless steels in geothermal environments. Al2O3 sol-gel coatings were applied on UNS S42000, which is known to be susceptible to uniform and localized corrosion. The coated steel specimens were then tested in two types of artificial geothermal water, which simulate the geothermal fluids found in Sibayak (SBY), Indonesia, and North German Basin (NGB), Germany, respectively. SBY has pH 4 and 1.5 g/L of chloride ions, whereas NGB has a pH of 6 and 166 g/L of chloride ions. All experiments were carried out in autoclaves at 150 °C and 1 MPa under the deaerated condition. Evaluations were performed by investigating the surface profiles of both uncoated and coated steels before and after the corrosion test using a Laser Scanning Microscope (LSM) and Scanning Electron Microscope (SEM). Finally, Electrochemical Impedance Spectroscopy (EIS) was performed to compare the corrosion resistance of Al2O3 coated steels in SBY and NGB solutions. It was observed from the corrosion test that Al2O3 coatings are more suitable for use in the geothermal water with a higher pH. T2 - AMPP Annual International Corrosion Conference 2021 CY - Online Meeting DA - 19.04.2021 KW - Protective coating KW - Sol-gel coating KW - Geothermal KW - Martensitic steel KW - Corrosion PY - 2021 AN - OPUS4-52500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Beck, Joana T1 - Review: Fitz's Atlas™of coating surveys N2 - Fitz's Atlas of coating surveys is designed as loose‐leave binder with a resistant cover that not only provides the possibility of updating the Atlas easily but also makes it practicable for on‐site use. This binder is well structured by sheet dividers with tabs for each of the 16 chapters. All in all, this atlas supports the surveyor by giving practicable hints and advice, lists and pictures to prepare and conduct investigations and write surveys. KW - Coating KW - Survey KW - Protection PY - 2019 DO - https://doi.org/10.1002/maco.201970084 SN - 1521-4176 SN - 0947-5117 VL - 70 IS - 8 SP - 1508 PB - Wiley VCH-Verlag CY - Weinheim AN - OPUS4-48720 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Sekine, R. A1 - Steckenmesser, D. A1 - Steffens, D. A1 - Huthwelker, T. A1 - Borca, C. A1 - Adam, Christian T1 - Effect of Nitrification Inhibitor on Nitrogen Forms in Soil analyzed by Nitrogen K edge micro XANES Spectroscopy N2 - Specific co-fertilization of nutrients can enhance their plant-availability and thus the yield of plants. To investigate this effect, we performed a pot experiment with three different P-fertilizers and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of nitrogen (N) in the soil via novel X-ray spectroscopic method. The application of NI with the N fertilizer led to a higher dry matter yield of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand. T2 - Workshop for X-ray and neutron imaging applications in soil sciences CY - Lund, Sweden DA - 17.06.2019 KW - Nitrogen KW - Phosphorus recycling KW - Fertilizer KW - XANES spectroscopy KW - Pot experiment PY - 2019 AN - OPUS4-48237 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Application of Diffusive Gradients in Thin-films (DGT) and spectroscopic techniques to analyze phosphorus in soils N2 - A wide range of analytical methods are used to estimate the plant-availability of soil phosphorus (P). Previous investigations showed that analytical methods based on the Diffusive Gradients in Thin films (DGT) technique provide a very good correlations to the amount of bioavailable nutrients and pollutants in environmental samples (Davison 2016, Vogel et al. 2017). However, the DGT results do not identify which P compound of the soil has the high bioavailability. But there are various spectroscopic techniques (infrared, Raman, P K-edge and L-edge XANES and P NMR spectroscopy) available to characterize P species in soils. Therefore, spectroscopic investigation of DGT binding layers after deployment allow us to determine the specific compounds. Nutrients such as phosphorus and nitrogen are often, together with other elements, present as molecules in the environment. These ions are detectable and distinguishable by infrared, P K- and L-edge X-ray absorption near-edge structure (XANES) and NMR spectroscopy, respectively. Additionally, microspectroscopic techniques make it also possible to analyze P compounds on the DGT binding layer with a lateral resolution down to 1 μm2. Therefore, species of elements and compounds of e.g. a spatial soil segment (e.g. rhizosphere) can be mapped and analyzed, providing valuable insight to understand the dynamics of nutrients in the environment. T2 - SPP1685 Closing Conference: New Approaches to Ecosystem Nutrition - Phosphorus and Beyond CY - Freiburg, Germany DA - 25.10.2021 KW - Phosphorus KW - Diffusive gradients in thin-films (DGT) KW - Passive sampling PY - 2021 AN - OPUS4-53641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gehrenkemper, Lennart A1 - Simon, Fabian A1 - Roesch, Philipp A1 - Fischer, Emily A1 - von der Au, Marcus A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Wittwer, Philipp A1 - Vogel, Christian A1 - Simon, Franz-Georg A1 - Meermann, Björn T1 - Organically bound fluorine in river water - A methode comparison of CIC and HR-CS-GFMAS N2 - Abstract: Since it is unknown for many applications, which PFASs are used and how they enter the environment, target analysis-based methods reach their limits. The two most frequently used sum parameters are the adsorbable organically bound fluorine (AOF) and the extractable organically bound fluorine (EOF). Both can be quantified using either combustion ion chromatography (CIC) or high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Here we provide an insight on the advantageous and disadvantageous of both sum parameters and both detection methods. Our study is based on the analysis of surface water samples. Next to total fluorine (TF) analysis, AOF and EOF were determined as well as CIC and HR-CS-GFMAS are compared and results are comparatively discussed. Fluorine mass balancing revealed that, the AOF/TF proportion was higher than the EOF/TF proportion. The AOF made up 0.14–0.81% of TF and the EOF 0.04–0.28% of TF. Although, organically bound fluorine represents only a small portion of TF, PFASs are of worldwide concern, because of their extreme persistence and their bioaccumulation potential. The EOF-HR-CS-GFMAS method turned out to be more precise and sensitive than the AOF-CIC method and is a promising tool for future monitoring studies/routine analysis of PFASs in the environment. T2 - SALSA Make and Measure 2020: Advanced Characterization of Materials CY - Online meeting DA - 15.10.2020 KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Combustion ion chromatography (CIC) KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Adsorbable organically bound fluorine (AOF) KW - Extractable organically bound fluorine (EOF) KW - Surfacewaters PY - 2020 AN - OPUS4-52451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ruyle, B. A1 - Pickard, H. A1 - Schultes, L. A1 - Fredriksson, F. A1 - Heffernan, A. A1 - Knappe, D. A1 - Lord, H. A1 - Meng, P. A1 - Mills, M. A1 - Ndungu, K. A1 - Roesch, Philipp A1 - Rundberget, J.T. A1 - Tettenhorst, D. A1 - Van Buren, J. A1 - Vogel, Christian A1 - Westerman, D. A1 - Yeung, L. A1 - Sunderland, E. T1 - Interlaboratory Comparison of Extractable Organofluorine Measurements in Groundwater and Eel (Anguilla rostrata): Recommendations for Methods Standardization N2 - Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds. KW - Extractable organic fluorine KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Combustion ion chromatography (CIC) PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587726 DO - https://doi.org/10.1021/acs.est.3c04560 SN - 0013-936X VL - 57 IS - 48 SP - 20159 EP - 20168 PB - American Chemical Society (ACS) AN - OPUS4-58772 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - PFAS analytics and their relation to PFAS remediation N2 - Per- and polyfluoroalkyl substances (PFAS) are a large group of more than 10,000 anionic, cationic, zwitterionic or neutral organofluorine surfactants. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. While liquid chromatography tandem mass spectrometry (LC-MS/MS) is commonly used technique to characterize targeted PFAS in environmental samples, there are more than 10,000 different PFAS known, which have various headgroups and properties. Therefore, several analytical techniques are available to analyse various groups or pools of PFAS or “all” PFAS as a sum parameter. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy. T2 - International workshop of CAR-PFAS (Consortium for analysis and remediation of per- and polyfluoroalkyl substances) Japan CY - Tokyo, Japan DA - 17.10.2023 KW - Mechanochemical treatment KW - Per- and Polyfluoroalkyl substances (PFAS) KW - XANES spectroscopy KW - Soil PY - 2023 AN - OPUS4-58609 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Ronen, A. A1 - Leube, Peter A1 - Ben Efrain, R. A1 - Nir, O. A1 - Chaudhary, M. A1 - Futterlieb, M. A1 - Panglisch, S. T1 - Detection, quantification, and treatment of per- and polyfluoroalkyl substances (PFAS) in groundwater (DFEAT-PFAS) N2 - Over the past century, a range of synthetic compounds have been produced to improve humanity’s quality of life. These include pharmaceuticals, plastics, and other chemical compounds that possess properties making them potentially harmful when released to the environment (e.g., ecological and health impacts to humans and animals). Per- and polyfluoroalkyl substances (PFAS) are a large group of chemicals used in the formulations of thousands of consumer goods, including aqueous film-forming foams used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment, and plastic and leather products. Because of the recent regulations and restrictions on the use of long chain (≥C8) PFAS a significant shift in the industry towards short (C4-C7) and ultrashort (C1-C3) chain alternatives has been recognized the last years. Due to the high polarity and water solubility of ultrashort PFAS, the potential for bioaccumulation is low. However, the high persistence of ultrashort-chain PFAS will result in environmental accumulation, especially in aquatic environments, leading to potential risks for aquatic organisms and increased human external exposure through drinking water. Ultrashort PFAS like trifluoroacetic acid (TFA) are low to moderately toxic to a range of organisms. In addition, ultrashort PFAS can penetrate natural and anthropogenic barriers and eventually reach drinking water sources. Because common drinking water treatment techniques do not sufficiently remove them, they may reach human consumption. In the project we are focusing on detecting and removing PFAS, especially ultrashort-chain PFAS from contaminated groundwater. We are designing passive sampling devices, which can collect and monitor the temporal profile of PFAS species in groundwater. This will allow us to analyze PFAS contaminations in German and Israeli groundwater using state-of-the-art and novel analytical techniques and understand the extent of contamination. In addition to quantification, PFAS contaminated groundwater will be treated via a two-stage process to produce PFAS-free drinking water. As ultrashort-chain PFAS are difficult to analyze with the current target (LC-MS/MS) and sum parameter (AOF, EOF) analysis methods, we additionally using gas chromatography – mass spectrometry (GC-MS). Therefore, an analytical method based on GC-MS is in development to analyze the volatile ultrashort-chain PFAS (TFA, PFPrA, TFMS, PFEtS, PFPrS, trifluoroethanol, pentafluoropropanol and hexafluoro isopropanol) directly in contaminated groundwater samples with the headspace technique and in eluates of organic solvents from the developed passive sampler after direct injection. Moreover, a two-stages process is designed to increase the low concentrations found in groundwater using novel membranes processes such as closed-circuit reverse osmosis (CCRO) and mixed matrix composite nanofiltration membranes (MMCM). Next, the rejected streams containing higher concentrations of PFAS will be treated by coagulation, and the remaining PFAS adsorbed onto carbonaceous nanomaterials (CNMs). The DEFEAT-PFAS project will result in the development of novel tools to detect, quantify, and remove PFAS, especially ultrashort-chain PFAS from contaminated groundwater, and will acquire a new understanding of the extent of these contaminations. T2 - Dioxin Konferenz CY - Maastricht, Netherlands DA - 10.09.2023 KW - Ground water KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation PY - 2023 AN - OPUS4-58346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Lisec, Jan A1 - Borca, C. A1 - Huthwelker, T. A1 - Simon, Franz-Georg T1 - Combining DGT and combustion ion chromatography (CIC) as screening tool for per- and polyfluoroalkyl substances (PFAS) contamination in wastewater-based fertilizers N2 - Per- and polyfluoroalkyl substances (PFAS) are a large group of organofluorine surfactants used in the formulations of thousands of consumer goods. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system have been resulted in contaminated effluents and sewage sludge from wastewater treatment plants (WWTPs) which became an important pathway for PFAS into the environment. Because sewage sludge is often used as fertilizer its application on agricultural soils has been observed as significant input path for PFAS into our food chain. To produce high-quality phosphorus fertilizers for a circular economy from sewage sludge, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Normally, PFAS are analyzed using PFAS protocols typically with time-consuming extraction steps and LC-MS/MS target quantification. However, for screening of PFAS contaminations in wastewater-based fertilizers also the DGT technique can be used for the PFAS extraction. Afterwards, combustion ion chromatography (CIC) can be applied to analyze the “total” amount of PFAS on the DGT binding layer. The DGT method was less sensitive and only comparable to the extractable organic fluorine (EOF) method values of the fertilizers in samples with >150 µg/kg, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. However, the DGT approach has the advantage that almost no sample preparation is necessary. Moreover, the PFAS adsorption on the DGT binding layer was investigated via surface sensitive spectroscopical methods, such as Fourier-transform infrared (FT-IR) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy. T2 - DGT Konferenz CY - Paris, France DA - 11.10.2023 KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Sewage sludge PY - 2023 AN - OPUS4-58575 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Mechanochemical remediation of PFAS in soils – Does it work? N2 - Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. These approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well as the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy. T2 - Baltic Sea PFAS Network Coffee Session CY - Online meeting DA - 25.08.2023 KW - Mechanochemical treatment KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation KW - X-ray absorption near-edge structure (XANES) spectroscopy PY - 2023 AN - OPUS4-58114 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Doolette, A. A1 - Huang, J. T1 - Combining DGT and 31P NMR spectroscopy to determine phosphorus species in soil N2 - The amount of plant-available phosphorus (P) in soil strongly influences the yield of plants in agriculture. Therefore, various simple chemical extraction methods have been developed to estimate the plant-available P pools in soil. More recently, several experiments with the DGT technique have shown that it has a much better correlation to plant-available P in soils than standard chemical extraction methods (e.g. calcium-acetate-lactate (CAL), Colwell, Olsen, water) when soils with different characteristics are considered. However, the DGT technique cannot give information on the plant-available P species in the soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time. T2 - DGT Konferenz CY - Paris, France DA - 11.10.2023 KW - Soil KW - Phosphorus KW - Plant-availability PY - 2023 AN - OPUS4-58574 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind unter anderem ein wichtiges Werkzeug zur Qualitätskontrolle von Messungen bestimmter Merkmalswerte. Dabei ist zu berücksichtigen, dass zertifizierte Merkmalswerte immer eine gewisse Unsicherheit haben. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Vortrags. Referenzmaterialien sind gleichzeitig ein wertvolles Werkzeug zur Ermittlung der Unsicherheit von Messverfahren und -Analysen unbekannter Proben. Die Vorgehensweise bei der Ermittlung der Messunsicherheit mit Hilfe eines Referenzmaterials wird beschrieben. T2 - Jahrestagung des GDMB-Chemiker-Ausschusses CY - Kassel, Germany DA - 07.11.2023 KW - Referenzmaterial KW - Messunsicherheit KW - ISO Guide 35 PY - 2023 AN - OPUS4-58929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Leube, Peter A1 - Vogel, Christian A1 - Simon, Franz-Georg T1 - Quantification of ultrashort per- and polyfluoroalkyl substances (PFAS) in water samples via headspace gas chromatography-mass spectrometry (GC-MS) - a method development N2 - Per- and polyfluoroalkyl substances (PFAS) were classified as a group of highly concerning chemicals over the last decades. Because of the high persistence of PFAS, their previous use led to contamination of the environment and human population. Due to ongoing use and incomplete remediation or destruction methods, the PFAS background in the environment is growing continuously. The presence of ultrashort PFAS (with ≤3 carbon atoms) in the environment is often overlooked despite their contributions to PFAS levels. These compounds may directly contaminate the environment and arise from degradation of polyfluorinated compounds as well as incomplete PFAS destruction in certain industrial processes. Nonetheless, few approaches for targeted analysis of ultrashort PFASs have been developed, except for trifluoroacetic acid (TFA). Beside liquid (LC-MS/MS), supercritical fluid (SFC-MS/MS), and ion chromatography (IC-MS)-based systems, gas chromatography coupled with mass spectrometry (GC-MS) is a promising method for detection and quantification of ultrashort PFAS. The goal of this study was to develop a simple headspace GC-MS method for the quantification of ultrashort perfluorocarboxylic acids (PFCAs) and polyfluorinated alcohols (PFOHs) in water samples. In contrast to PFOHs, functionalization of PFCAs was required for quantification. This was done by esterification with methanol at 80 °C, which can be carried out directly in the headspace GC-MS system. Moreover, several parameters were optimized to achieve a low limit of quantification (LOQ) for the analytes used: i) The ratio of the aqueous solution, methanol, and available gas phase within the analysis vessel, ii) the concentration of additional acid in esterification mixtures of PFCAs, iii) shaking frequency and iv) shaking time before analysis. After optimizing the procedure, we were able to quantify ultrashort PFCAs and PFOHs. Thus, our developed headspace GC-MS method has the potential to be used as an alternative target analysis for ultrashort-chain PFCAs and PFOHs in various water samples (groundwater, wastewater). T2 - SETAC Europe 34th Annual Meeting CY - Seville, Spain DA - 05.05.2024 KW - Ultrashort PFAS KW - Headspace GC-MS KW - Perfluorocarboxylic acid (PFCA) KW - Polyfluorinated alcohol (PFOH) PY - 2024 AN - OPUS4-60042 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Hoffmann, Marie A1 - Taube, Mareike A1 - Krüger, O. A1 - Baran, R. A1 - Adam, Christian T1 - Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers N2 - Phosphorus (P) is an essential element for all forms of life and is thus often applied as phosphate rock-based P-fertilizers in agriculture to enable continuous farming. However, these P-fertilizers contain also hazardous uranium (U) and thorium (Th), up to 660 and 220 mg/kg, respectively. On the contrary, novel P-fertilizers made from sewage sludge (ash) contain only low mass fractions of U and Th. In addition to the total amount of U and Th in P-fertilizers, their mobility and bioavailability is important, which depends to a large extent on their chemical state, especially oxidation state and chemical bonding. Thus, we analyzed their chemical state in various P-fertilizers by U and Th L3-edge HERFD-XANES spectroscopy. Phosphate rocks and sewage sludge-based P-fertilizers contain mainly U(IV) compounds which have only a low bioavailability. In contrast, acidic treatment of phosphate rock to produce super phosphates lead to an oxidation to U(VI) compounds (including formation of uranium phosphates) with a strongly increased bioavailability. On the contrary, all analyzed P-fertilizers contain Th in form of strongly insoluble phosphates and oxides with a low bioavailability. Additionally performed water extractions and Diffusive Gradients in Thin-films (DGT) experiments support these findings. KW - Phosphorus fertilizer KW - Sewage sludge KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Diffusive Gradients in Thin-films (DGT) KW - Extraction PY - 2020 DO - https://doi.org/10.1016/j.jhazmat.2019.121100 SN - 0304-3894 VL - 382 SP - 121100, 1 EP - 6 AN - OPUS4-48872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Sekine, R. A1 - Huang, J. A1 - Steckenmesser, D. A1 - Steffens, D. A1 - Huthwelker, T. A1 - Borca, C. A1 - Pradas del Real, A. A1 - Castillo-Michel, H. A1 - Adam, Christian T1 - Effect of Nitrification Inhibitor on Nitrogen Forms in Soil and Phosphorus Uptake of Plants N2 - Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P-fertilizers from recycled materials which often have a lower plant-availability compared to commercial P-fertilizers but are expected to play an increasingly important role into the future (Kratz et al. 2019). One promising way to increase the plant-availability of the fertilizer P is a co-fertilization with specific nitrogen (N) forms which can enhance the P uptake and make P-fertilizers from recycled material more competitive to commercial phosphate rock-based P-fertilizers (Rahmatullah et al. 2006; Vogel et al. 2018). To investigate this effect, we performed a pot experiment with three different P-fertilizers (sewage sludge-based, phosphate rock and triple superphosphate) and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of N and P in soil via a suite of chemical and novel X-ray spectroscopic methods. The application of NI with the P and N fertilizers led to a higher dry matter yield and a higher P uptake of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield and nutrient uptake. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand. T2 - Annual Meeting of the German Society of Plant Nutrition (DGP) CY - Berlin, Germany DA - 25.09.2019 KW - Fertilzer KW - X-ray adsorption near-edge structure (XANES) spectroscopy KW - Nitrification inhibitor KW - Agronomic performance PY - 2019 AN - OPUS4-49144 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Krüger, O. A1 - Hoffmann, Marie A1 - Adam, Christian T1 - Determination of chromium(VI) in phosphorus fertilizers made from recycled materials by DGT N2 - Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizer can also contain toxic pollutants e.g. chromium (Cr) in the hexavalent state (Cr(VI)), which is regulated with low limit values in agricultural products (German fertilizer ordinance limit: 2 mg/kg Cr(VI)). The determination of Cr(VI) in these novel fertilizer matrices can be hampered by redox processes that lead to false results with the standard wet chemical extraction method (German norm DIN EN 15192). Therefore, we analyzed Cr(VI) in various P-fertilizers with the DGT technique. DGT devices equipped with a APA (polyacrylamide) diffusion layer and Cr(VI) selective N-methyl-D-glucamine (NMDG) binding layer were used for the study. After a 24 h conditioning period of the fertilizer at 60% of the water holding capacity (WHC), the fertilizers were brought to 100% WHC, transferred onto the DGT devices and deployed for 24 h at 25°C. The extraction of Cr from the DGT binding layer was carried out with 1 M HNO3 for 24 h. The Cr-concentrations of the extract were determined by means of ICP-MS. We found a good correlation between the standard wet chemical extraction and the DGT method for the whole range of P-fertilizers. However, partly soluble Cr(VI) compounds cannot be detected in full extent by the DGT method that is best suited for mobile Cr(VI). Furthermore, Cr K-edge XANES spectroscopy showed that the Cr(VI)-selective DGT binding layer also adsorbs mobile Cr(III) compounds from acid treatment of phosphates which can therefore cause an overestimation of Cr(VI). The DGT method was very sensitive and in most cases selective for the analysis of Cr(VI) in P-fertilizers made from recycled materials. However, the results of certain types of P-fertilizers containing mobile Cr(III) or partly immobile Cr(VI) show that still some optimization of the method is required to avoid over- or underestimation of Cr(VI). T2 - 6th Conference on Diffusive Gradients in Thin Films CY - Vienna, Austria DA - 17.09.2019 KW - Fertilzer KW - Pollutant KW - Chromium KW - Diffusive gradients in thin films (DGT) KW - XANES spectroscopy PY - 2019 AN - OPUS4-49058 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Veh, G. A1 - Lützow, N. A1 - Tamm, J. A1 - Luna, L. V. A1 - Hugonnet, R. A1 - Vogel, Kristin A1 - Geertsema, M. A1 - Clague, J. J. A1 - Korup, O. T1 - Less extreme and earlier outbursts of ice-dammed lakes since 1900 N2 - Episodic failures of ice-dammed lakes have produced some of the largest floods in history, with disastrous consequences for communities in high mountains. Yet, estimating changes in the activity of ice-dam failures through time remains controversial because of inconsistent regional flood databases. Here, by collating 1,569 ice-dam failures in six major mountain regions, we systematically assess trends in peak discharge, volume, annual timing and source elevation between 1900 and 2021. We show that extreme peak flows and volumes (10 per cent highest) have declined by about an order of magnitude over this period in five of the six regions, whereas median flood discharges have fallen less or have remained unchanged. Ice-dam floods worldwide today originate at higher elevations and happen about six weeks earlier in the year than in 1900. Individual ice-dammed lakes with repeated outbursts show similar negative trends in magnitude and earlier occurrence, although with only moderate correlation to glacier thinning8. We anticipate that ice dams will continue to fail in the near future, even as glaciers thin and recede. Yet widespread deglaciation, projected for nearly all regions by the end of the twenty-first century9, may bring most outburst activity to a halt. KW - Outburst floods KW - Bayesian hierachical modelling KW - Trends in extreme events PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-570529 DO - https://doi.org/10.1038/s41586-022-05642-9 VL - 614 IS - 7949 SP - 701 EP - 707 AN - OPUS4-57052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian A1 - Wittwer, Philipp A1 - Roesch, Philipp A1 - Simon, Franz-Georg T1 - Per- and polyfluoroalkyl substances (PFAS) in sewage sludge and wastewater-based fertilizers and future PFAS remediation N2 - Per- and polyfluoroalkyl substances (PFAS) are a group of anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. As a result of the perpetual use of PFAS containing products, effluents and sewage sludge from wastewater treatment plants (WWTPs) have been observed to be an important pathway for PFAS into the environment. In Germany, phosphorus and other nutrients from sewage sludge and wastewater should be recycled in WWTPs of cities with a large population. However, it is not clear if PFAS contamination from wastewater and sewage sludge end up in novel wastewater-based fertilizers. Normally, PFAS are analyzed using PFAS protocols typically with liquid chromatography tandem mass spectrometry (LC-MS/MS) quantification. To get a better overview of the amount of “total PFAS,” we applied sum parameter methods based on combustion ion chromatography (CIC) to screen the PFAS contaminations in various sewage sludge and wastewater-based fertilizers. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. T2 - Seminar of Ben-Gurion University CY - Midreshet Ben-Gurion, Israel DA - 02.11.2022 KW - PFAS KW - Sewage sludge KW - XANES spectroscopy PY - 2022 AN - OPUS4-56166 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Investigation of per and polyfluoroalkyl substances (PFAS) in soils and groundwater through fluorine K-edge XANES spectroscopy – potential for collaboration N2 - Per- and polyfluoroalkyl substances (PFAS) are a group of anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination. In this presentation the advantages of fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy for various environment samples are shown. T2 - SESAME-Germany Info Day CY - Hamburg, Germany DA - 21.04.2023 KW - Soil KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Synchotron KW - X-ray absorption near-edge structure (XANES) spectroscopy PY - 2023 AN - OPUS4-57365 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Capitain, C. A1 - Simon, Fabian Michael A1 - Roesch, Philipp A1 - Bugsel, B. A1 - Zwiener, C. T1 - Non-extractable PFAS in functional textiles − Characterization by complementary methods: oxidation, hydrolysis, and fluorine sum parameters N2 - Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from