TY - JOUR A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Wittwer, Philipp A1 - Huthwelker, T. A1 - Borca, C. A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Piechotta, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Taking a Look at the Surface: µ-XRF Mapping and Fluorine K-edge µ-XANES Spectroscopy of Organofluorinated Compounds in Environmental Samples and Consumer Products N2 - For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples. KW - PFAS KW - XRF KW - LC-MS/MS KW - XANES KW - Fluoride KW - Soil PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576109 DO - https://doi.org/10.1039/D3EM00107E SN - 2050-7887 SP - 1 EP - 12 PB - Royal Society of Chemistry AN - OPUS4-57610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schünemann, Pia T1 - Seasonal PFAS monitoring in surface water via complementary EOF (HR-CS-GFMAS) and target analytics N2 - The aim of this study was to investigate seasonal shifts in PFAS contamination. Therefore, samples were collected from the River Spree to measure the level of extractable organically bound fluorine (EOF). This was achieved by employing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS), a method for EOF surface water analysis first described by Metzger et al.. Complementary target-screenings were performed for a small set of relevant PFAS to achieve a more detailed look into the PFAS contamination over time and space and into the identifiable fraction of the EOF. Furthermore, hot spots of relevant PFAS pollution were identified in the river system. T2 - PFAS - Vermeidbar, Ersetzbar, Unverzichtbar?! CY - Berlin, Germany DA - 07.04.2025 KW - PFAS KW - HR-CS-GFMAS KW - Environmental Analysis PY - 2025 AN - OPUS4-63137 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schünemann, Pia T1 - Seasonal PFAS monitoring in surface water via complementary EOF (HR-CS-GFMAS) and target analytics N2 - The aim of this study was to investigate seasonal shifts in PFAS contamination. Therefore, samples were collected from the River Spree to measure the level of extractable organically bound fluorine (EOF). This was achieved by employing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS), a method for EOF surface water analysis first described by Metzger et al.. Complementary target-screenings were performed for a small set of relevant PFAS to achieve a more detailed look into the PFAS contamination over time and space and into the identifiable fraction of the EOF. Furthermore, hot spots of relevant PFAS pollution were identified in the river system. T2 - Anakon 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - PFAS KW - HR-CS-GFMAS KW - Environmental Analysis PY - 2025 AN - OPUS4-63136 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sommerfeld, Thomas A1 - Riedel, Juliane A1 - Lisec, Jan A1 - Mauch, Tatjana A1 - Richter, Silke A1 - Koch, Matthias T1 - Development of a certified reference material for per- and polyfluoroalkyl substances (PFAS) in textiles N2 - Per- and polyfluoroalkyl substances (PFASs) are a large group of emerging organic pollutants that contaminate the environment, food, and consumer products. Textiles and other outdoor products are a major source of PFAS exposure due to their water-repellent impregnations. Determination of PFASs in textiles is increasingly important for enhancing their contribution to the circular economy. While maximum levels and restrictions exist for certain key compounds under the Stockholm Convention on Persistent Organic Pollutants and the REACH regulation, certified reference materials (CRMs) are not currently available. To address this issue, the first CRM for determining PFASs in outdoor textiles (BAM-B003) was developed. It fully complies with the requirements of ISO 17034 and ISO 33405. This work presents the entire process of CRM development process, including preparation, a homogeneity study, a stability study, and value assignment. Certification was based on an in-house study at BAM using liquid chromatography tandem mass spectrometry (LC–MS/MS) with stable isotope dilution analysis (SIDA). The certified mass fractions of 18 PFASs range widely from 0.46 to 69 µg/kg, with a prevalence of PFOA (69 µg/kg), PFOS (41 µg/kg) and PFHxA (35 µg/kg) exceeding legal limits. BAM-B003 is intended for analytical quality control and contributes to improving the chemical safety of textiles and strengthening the circular economy. KW - Reference Material KW - PFAS KW - Textiles PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641040 DO - https://doi.org/10.1007/s00216-025-06098-2 SN - 1618-2642 SP - 1 EP - 9 PB - Springer Science and Business Media LLC AN - OPUS4-64104 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Herter, Sven-Oliver T1 - New PFAS Reference Materials for Environment and Circular Economy N2 - Per- and polyfluorinated alkyl substances (PFAS) are a group of synthetic compounds that have been used in various industrial and consumer products for decades. Their wide range of applications is due to water- and oil-repellent properties, as well as their chemical and thermal stability. However, the use of PFAS has raised concerns due to their persistence in environment and their adverse health effects, leading to regulations aimed at controlling their use and minimizing exposure. Substances such as PFOS, PFHxS, and PFOA are listed in the Stockholm Convention on Persistent Organic Pollutants (POP Regulation, EU 2019/1021). Maximum values have been set for PFAS in environmental matrices such as soil and water, but also for textiles as a relevant area of circular economy and part of the current German standardization roadmap “Circular Economy”. Reliable PFAS analysis requires an increasing global demand for certified reference materials (CRM). However, CRMs for PFAS in soils and textiles are rare or currently not available. To improve the metrological infrastructure and support PFAS measurements, two CRMs for PFAS in soil (BAM-U027) and PFAS in textiles (BAM-B003) based on ISO 17034 and ISO 33405 were developed. This poster provides an overview of the different steps for preparation and characterization of the two candidate materials. The assignment of the certified mass fractions for relevant PFAS targets (18 PFAS targets for BAM-B003) is based isotope dilution HPLC-MS/MS at three independent workplaces. The results of the BAM in-house study on BAM-U027 were supported by an interlaboratory comparison study. T2 - 16th International Symposium on Biological and Environmental Reference Materials CY - Halifax, Nova Scotia, Canada DA - 01.06.2025 KW - Certified Reference Material KW - PFAS KW - Circular Economy KW - Textiles KW - Quality assurance PY - 2025 AN - OPUS4-63404 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Koch, Matthias T1 - PFAS-Analytik – Ein Überblick N2 - Die Gruppe der PFAS (Per- und polyfluorierte Alkylsubstanzen) mit mehr als 10.000 Substanzen stellt ein zunehmendes Problem bei der Bewertung und Entsorgung belasteter Abfälle dar. Die zuverlässige PFAS-Analytik stellt hier aufgrund der Vielzahl an Einzelparametern mit zum Teil sehr großen Konzentrationsunterschieden eine komplexe Herausforderung dar. Der Vortrag gibt zunächst einen Überblick über grundlegende Anforderungen an die LC-MS/MS Analytik von PFAS-Targetsubstanzen. Am Beispiel eines von BAM und SenMVKU organisierten Ringversuches 2024 zur Bestimmung von PFAS in Bodenproben (Feststoffe und Eluate) wird auf spezifische Fragestellungen zur PFAS-Analytik eingegangen. Zur Verbesserung von Richtigkeit und Vergleichbarkeit ist die Einhaltung von Normvorgaben und die Anwendung von Qualitätssicherungsmaßnahmen unerlässlich. Hierzu gehören u.a. die Verwendung zuverlässiger Kalibrierstandards, die Kalibrierung mit definierten n-Isomeren, die Quantifizierung der Summe aus n-/br-Isomeren, der Einsatz isotopenmarkierter interner Standards für die LC-MS/MS Analyse, die Verwendung von Matrix-Referenzmaterialien sowie die Teilnahme an Ringversuchen. T2 - Schaffung von Laborkapazitäten zur Untersuchung PFAS-belasteter Abfälle CY - Potsdam, Germany DA - 11.09.2024 KW - PFAS KW - Ringversuch KW - Qualitätssicherung KW - Referenzmaterial PY - 2024 AN - OPUS4-61014 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schünemann, Pia T1 - Spatiotemporal monitoring of River Spree N2 - Per- and polyfluoroalkyl substances (PFAS) are known for their high chemical stability and persistence. They have the potential to bioaccumulate in organisms. Moreover, PFAS are environmental contaminants of concern due to their ubiquitous appearance in the environment. Consequently, there is a demand to develop and optimize new methods for analyzing these substances. In this project a comprehensive investigation of the pollution situation of the entire River Spree was performed. The sum parameter approach (extractable organic fluorine, EOF) is used to monitor a broad spectrum of PFAS in surface water. Herein, high resolution-continuum source-graphite furnace molecular adsorption spectrometry (HR-CS-GFMAS) is employed for fast and sensitive measurements. The occurrence and fate of PFAS are detected with complementary target and non-target screening. Hot spots as well as seasonal aspects with influence on the pollution situation on the river were detected. Moreover, the correlation to other organic pollutants was investigated via statistical analysis. The question arises if routine organic trace substance monitoring can provide information about PFAS contamination. T2 - 3rd Fluorine Summer School and Conference of the CRC 1349 CY - Berlin, Germany DA - 06.10.2025 KW - PFAS KW - HR-CS-GFMAS KW - Environmental Analysis PY - 2025 AN - OPUS4-64564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Riedel, Juliane A1 - Mauch, Tatjana A1 - Koch, Matthias T1 - CRM BAM-B003 eCerto data file N2 - Data file (RData) containing measurement data recorded during the production process of the Certified Reference Material BAM-B003 containing per- and polyfluoroalkyl substances (PFAS) in textiles. The data can be most conveniently openend using the Shiny-App eCerto which is accessible at https://www.bam.de/eCerto. KW - Certified reference material KW - Mass spectrometry KW - PFAS PY - 2025 DO - https://doi.org/10.5281/zenodo.15907581 PB - Zenodo CY - Geneva AN - OPUS4-64544 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Transformation of fluorinated electrolytes from lithium-ion batteries N2 - Lithium-ion battery (LiB) operation remains challenging, particularly in terms of safety, cycling stability, capacity rates and high-voltage applications. Although the electrolytes of LiBs account for 10-15% of the total battery weight, they are still an underestimated part. Data suggest that the composition of electrolytes offers great potential to deal with all these issues. In particular, fluorinated electrolyte solvents or even fluorinated additives offer several advantages due to the strength of the C-F bond, providing chemical and oxidative stability and increased electronegativity, exhibiting flame retardant properties and facilitating anode-mediated degradation, resulting in a LiF-rich and more stable solid electrolyte interphase (SEI), enabling more efficient surface passivation. Therefore, studies suggest that fluorinated equivalents, as well as entirely new compounds, are promising for solving battery-related problems. But what happens to fluorinated organic compounds (FOCs) during usage? And what are the new potential risks associated with their release into the environment? The environmental and application-specific fate of FOCs is investigated by a selection of different fluorinated electrolytes, the application of various simulation methods, including the TOP (Total Oxidizable Precursor) Assay, electrochemistry, photo-induced degradation, and cycling of FOC-prepared self-assembled coin cells. Gas chromatography and liquid chromatography coupled with high resolution mass spectrometry (GC/LC-HRMS) are used to identify transformation products (TP). T2 - Tag der Chemie 2023 CY - Berlin, Germany DA - 05.07.2023 KW - Transformation products KW - Lithium-ion batteries KW - PFAS KW - TP KW - Batteries PY - 2023 AN - OPUS4-58265 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Fluorinated Additives used in LiBs: Forever Chemicals of Tomorrow? N2 - Fluorinated organic compounds (FOCs) are a type of man-made chemicals characterized by their robust carbon-fluorine bonds, which contribute to their chemical stability and resistance to degradation. This durability makes them valuable in various applications, such as lithium-ion batteries (LiBs) [1-3], could have a significant impact on the environment, but this potential has not yet been fully considered. This study examines the environmental impact of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their role in enhancing the performance of LiBs[4, 5]. In order to achieve this, a number of laboratory simulation methods were employed, including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were employed for the identification of transformation products (TPs) and the prediction of their molecular formulae. Notwithstanding their structural similarities, TPFPB and TPFPP exhibited distinct differences in their electrochemical behavior and degradation pathways. TPFPB was readily transformed via hydroxylation and hydrolysis, resulting in a diverse range of 49 TPs. In total, 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded only under extreme conditions, highlighting the need to develop new conditioning protocols for EC. Overall, the simulation experiments produced 9 structurally unique compounds, including 7 previously unidentified partially defluorinated byproducts. This study emphasizes the potential hazards linked to the use of FOCs in lithium-ion batteries and enhances our understanding of the complex environmental interactions of these compounds. T2 - Adlershofer Forschungsforum 2024 CY - Berlin, Germany DA - 11.11.2024 KW - PFAS KW - Lithium-ion batteries KW - Fluorinated Compounds KW - Simulation methods KW - Liquid chromatography/ QTOF-MS KW - Gas chromatography/ QTOF-MS KW - Electrochemistry KW - Photochemistry KW - Top-Assay PY - 2024 AN - OPUS4-61681 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane A1 - Meiers, Emelie T1 - Bestimmung von Trifluoressigsäure (TFA) in Acker- und Grünlandböden N2 - Aufgrund ihrer Persistenz, Mobilität und Toxizität haben per- und polyfluorierte Alkylverbindungen (PFAS) zunehmend an Aufmerksamkeit und Relevanz gewonnen. Mit der PFAS-Belastung von Umweltmatrices ist auch der Bedarf an analytischen Methoden gestiegen. Trifluoressigsäure (TFA) gehört als kürzeste perfluorierte Carbonsäure zur Gruppe der PFAS und gilt als emerging pollutant, dessen Gehalte in der Umwelt zukünftig eine stärkere Überwachung erfordern. Im Vortrag wird zunächst auf die Entwicklung einer sensitiven Analysenmethode zur Bestimmung von TFA in Böden mittels HPLC-MS/MS eingegangen. Anschließend werden die TFA-Ergebnisse von 100 ausgewählten Acker- und Grünlandproben aus Deutschland vorgestellt und diskutiert. T2 - PFAS-Länderaustausch – Erfassung und Erstbewertung PFAS-relevanter Flächen CY - Online meeting DA - 18.11.2024 KW - PFAS KW - LC-MS/MS KW - HILIC KW - TFA KW - Boden PY - 2024 AN - OPUS4-61684 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholl, Juliane A1 - Meiers, Emelie A1 - Mauch, Tatjana A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Weinfurtner, Karlheinz A1 - Haase, Hajo A1 - Koch, Matthias T1 - Approaches towards sensitive and reliable determination of trifluoroacetic acid (TFA) from German grass- and farmland soils N2 - In light of the emerging threat of environmental contamination from per- and polyfluoroalkyl substances (PFAS), there is a growing need for analytical techniques that can be applied to a range of environmental matrices, including water, air, plant, and soil samples. Trifluoroacetic acid (TFA) is a member of the PFAS class, representing the shortest perfluorinated carboxylic acid and is an emerging pollutant whose environmental levels are expected to increase in the future. Soil matrices represent the interface between plant and ecosystem uptake of TFA, but contamination is poorly understood, largely due to a lack of uniform TFA determination methods. This study compares six ways of determining TFA in soils and highlights their limitations. We present a validated sample preparation method with high recoveries (104 %), low LOD (0.015 ng/g) and LOQ (0.045 ng/g). This approach includes isotope dilution analysis with hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry (HILIC-MS/MS) detection. The method was applied to quantify the TFA content in 100 soil samples from grassland and farmland across Germany. The results indicate the ubiquity of TFA, accompanied by elevated contamination levels in certain locations. An analysis of variance revealed no correlation with collection site and designation purpose. However, a low correlation was observed with dry bulk density. KW - PFAS KW - Extraction methods KW - HILIC-MS/M KW - Emerging pollutant KW - German soil protection PY - 2025 DO - https://doi.org/10.1016/j.chemosphere.2025.144496 SN - 0045-6535 VL - 382 SP - 1 EP - 11 PB - Elsevier CY - Amsterdam AN - OPUS4-63499 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Scholl, Juliane A1 - Bagheri, Abbas A1 - Meiers, Emelie A1 - Lisec, Jan A1 - Russo, Francesco A1 - Haase, Hajo A1 - Koch, Matthias T1 - Unveiling Aging Mechanisms of Electrolytes in Commercial End-of-Life Lithium-Ion Batteries N2 - In this study, 77 end-of-life (EOL) commercial lithium-ion batteries (LIBs) of different formats were systematically analyzed to investigate electrolyte degradation mechanisms and the influence of pristine electrolyte composition on aging. Comprehensive chemical characterization employed targeted and non-targeted mass spectrometry (MS), combining liquid and gas chromatography (LC-MS/MS, GC-MS) with high-resolution MS (HRMS). This approach identified confirmed pristine components and complex degradation products. Commercial rechargeable pouch and cylindrical cells often deviated from conventional research model systems, using mixed lithium salt anions, ionic liquids (ILs), and high concentrations of triflates, triflimides, and bis(fluorosulfonyl)imide (FSI), functioning as solvents, salts, or additives. Specific IL degradation products and previously unreported pathways were proposed. A novel series of oligomerization products from propylene carbonate (PC) was also identified. In contrast, non-rechargeable coin cells showed prevalent use of per- and polyfluoroalkyl substances (PFAS) in their original electrolytes. Distinct PFAS degradation mechanisms were proposed for the first time. The absence of carbonate oligomers and lithium salt-derived products in coin cells, alongside standard carbonates, suggests lithium counterion coordination critically influences Lewis acid-catalyzed degradation. These findings provide new insight into real-world LIB aging, highlighting differences between commercial devices and model systems. KW - Mass Spectrometry KW - PFAS KW - Electrolyte degradation KW - Transformation products KW - Battery aging PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641059 DO - https://doi.org/10.2139/ssrn.5395937 SP - 1 EP - 15 PB - Elsevier BV AN - OPUS4-64105 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholl, Juliane A1 - Lisec, Jan A1 - Bagheri, Abbas A1 - Meiers, Emelie A1 - Russo, Francesco Friedrich A1 - Haase, Hajo A1 - Koch, Matthias T1 - Unveiling aging mechanisms of electrolytes in commercial end-of-life lithium-ion batteries N2 - In this study, 77 end-of-life (EOL) commercial lithium-ion batteries (LIBs) of various formats were systematically analyzed to investigate electrolyte degradation and the influence of pristine electrolyte compositions on aging behavior. Comprehensive chemical characterization was conducted using targeted and non-targeted mass spectrometry (MS), employing LC-MS/MS, GC-MS, and high-resolution MS (HRMS). This integrated approach enabled the identification of confirmed pristine components and complex degradation products. The results show that rechargeable pouch and cylindrical cells often deviate from conventional model systems, containing mixed lithium salt anions, ionic liquids (ILs), and high concentrations of triflates, triflimides, and bis(fluorosulfonyl)imide (FSI). These function as solvents, salts, or safety-enhancing additives. Specific IL degradation products were identified, and hypotheses formulated on previously unreported pathways. Furthermore, a novel series of oligomerization products of propylene carbonate (PC) was detected. In contrast, non-rechargeable coin cells revealed widespread use of per- and polyfluoroalkyl substances (PFAS) in their original electrolytes. Based on ex situ analyses, hypothetical PFAS degradation mechanisms are proposed here for the first time. The absence of carbonate oligomers and lithium salt-derived products, alongside the presence of standard carbonates, indicates lithium counterion coordination as a key factor in Lewis acid-catalyzed degradation. This study offers valuable insights into real-world battery aging. KW - Transformation products KW - Lithium-ion batteries KW - Fluorinated Compounds KW - Gas chromatography/ QTOF-MS KW - HILIC-LC-MS/MS KW - PFAS KW - Electrochemistry PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644991 DO - https://doi.org/10.1016/j.jpowsour.2025.238613 SN - 0378-7753 VL - 661 SP - 1 EP - 10 PB - Elsevier B.V. AN - OPUS4-64499 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Fate of fluorinated electrolytes used in lithium-ion batteries N2 - The use of per- and polyfluorinated alkyl substances (PFAS), which are very persistent and cannot be completely degraded in the environment, is a well-known problem worldwide. In contrast, fluorinated organic compounds used as electrolytes in lithium-based batteries (LiBs) have been less studied. Despite their increasing use in LiBs due to beneficial properties, such as improving safety, cycling performance, or even enabling high-voltage applications, there is little data on their distribution, transformation, and fate in the environment. To fill this gap, fluorine-containing electrolyte components are studied in oxidative and reductive transformation processes. The identified transformation products (TP) will be determined in relevant environmental matrices and LiBs. T2 - ANAKON 2023 CY - Vienna, Austria DA - 11.04.2023 KW - Transformation products KW - Lithium-ion batteries KW - PFAS KW - TP KW - Batteries PY - 2023 AN - OPUS4-57502 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Degradation and Impact of Fluorinated electrolytes from Lithium-Ion Batteries N2 - Lithium-based batteries (LiBs) have become increasingly important in modern society, as cutting-edge portable energy storage systems and as a crucial component in the energy revolution. However, they still face challenges such as safety concerns, capacity degradation, and the ever-growing demand for higher energy density. To address these issues, researchers have turned their attention to fluorinated organic compounds (FOCs) as part of LiBs electrolytes. These substances, closely related to per- and polyfluorinated alkyl substances (PFAS), have shown great potential in optimizing LiBs. Specifically, their strong fluorine-carbon bond offers enhanced oxidative and chemical resistance. Nevertheless, their environmental impact is a cause for concern. Fluorinated organics can persist in the environment or can lead to the formation of persistent end-products, which accumulate and contribute to global health problems. To study the fate of fluorinated organic electrolytes in different environmental and application scenarios, a range of simulation methods are employed, including the TOP (Total Oxidizable Precursor) Assay, electrochemistry, photo-induced degradation, and cycling of self-assembled coin cells prepared with FOCs. Transformation products (TP) are identified using gas chromatography and liquid chromatography coupled with high resolution mass spectrometry (GC/LC-HRMS). T2 - 23. Norddeutsches Doktorandenkolloquium CY - Berlin, Germany DA - 05.10.2023 KW - Transformation products KW - Lithium-ion batteries KW - PFAS KW - TP KW - Batteries KW - Electrolytes PY - 2023 AN - OPUS4-58511 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Forever Chemicals of Tomorrow? Fate of Fluorinated Li-Ion Battery Additives N2 - Fluorinated organic compounds (FOCs) are a category of anthropogenic chemicals distinguished by their resilient carbon-fluorine bonds, which confer significant chemical stability and resistance to degradation. This durability makes them valuable in various applications, particularly in lithium-ion batteries (LiBs) [1,2]. However, the environmental implications of these compounds have not been thoroughly investigated. This study focuses on the environmental impact of two fluorinated aromatic compounds: tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), specifically regarding their roles in enhancing LiB performance [3,4]. To assess their environmental fate, we employed a range of laboratory simulation techniques generating transformation products (TPs), including total oxidizable precursor assays, electrochemistry (EC), Fenton reactions, UV-C irradiation, and hydrolysis. We utilized liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry to identify TPs and predict their molecular formulas. Despite their structural similarities, TPFPB and TPFPP displayed differences in electrochemical behavior and degradation pathways. TPFPB underwent significant transformation through hydroxylation and hydrolysis, yielding a diverse array of 49 TPs, including 28 newly identified compounds, including oligomers and minor levels of highly toxic dioxins. In contrast, TPFPP underwent degradation only at extreme conditions, highlighting the necessity for new conditioning protocols in electrochemistry. Overall, our simulation experiments revealed 9 structurally unique compounds, including 7 previously unidentified partially defluorinated byproducts. This study underscores the potential environmental hazards associated with the use of FOCs in lithium-ion batteries and enhances our understanding of the complex interactions these compounds have with the environment. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - High Resolution Mass Spectrometry (HRMS) KW - Lithium-Ion Batteries KW - Simulation methods KW - PFAS KW - Electrochemistry KW - Photochemistry KW - TOP assay PY - 2025 AN - OPUS4-62805 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Fluorinated Additives used in LiBs - Forever Chemicals of Tomorrow? N2 - Lithium-ion batteries (LiBs) are increasingly crucial in modern society, serving as advanced portable energy storage systems and playing a vital role in the energy revolution. Despite their importance, challenges such as safety risks, capacity decline, and the need for higher energy density persist. Researchers are exploring the use of fluorinated organic compounds (FOCs) in LiBs electrolytes as a potential solution [1-3]. These compounds, similar to per- and polyfluorinated alkyl substances (PFAS), offer improved oxidative and chemical resistance due to their strong fluorine-carbon bond. However, concerns over their environmental impact remain, as FOCs could persist in the environment or create harmful degradation products, which accumulate and contribute to global health problems. To investigate the environmental fate of two structurally similar and prominent FOCs found in electrolytes, various methods are used to simulate transformation products (TPs). These methods include the TOP (total oxidizable precursor) assay, the Fenton reaction, electrochemistry, photoinduced degradation, and hydrolysis. TPs are identified using gas chromatography and liquid chromatography coupled with high resolution mass spectrometry (GC- and LC-HRMS). First results of this TP screening will be presented. T2 - ISC 2024 CY - Liverpool, GB DA - 06.10.2024 KW - Transformation products KW - Lithium-ion batteries KW - Fluorinated Compounds KW - Gas chromatography/ QTOF-MS KW - Liquid chromatography/ QTOF-MS KW - PFAS PY - 2024 AN - OPUS4-61341 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Scholl, Juliane T1 - Reliable Determination of TFA from German Grass- and Farmland Soils N2 - In light of the growing environmental contamination by per- and polyfluoroalkyl substances (PFAS), there is an increasing need for analytical methods capable of detecting these substances in diverse environmental matrices, including water, air, plant, and soil samples. Trifluoroacetic acid (TFA) is a member of the large PFAS class [1], representing the shortest perfluorinated carboxylic acid and an emerging pollutant with projected environmental levels that are anticipated to continue rising in the future [2,3]. Soil matrices represent the interface between plant and ecosystem uptake of TFA, yet contamination pathways remain poorly understood, largely due to a lack of sensitive/reliable TFA determination methods. Since TFA as ultra short-chain PFAS has different properties (e.g. acidity) in comparison to long-chain PFAS, selective methods are required for its determination. This study compares six distinct approaches for TFA determination in soil and presents an optimized and validated sample preparation method including isotope dilution analysis and subsequent HILIC-LC-MS/MS detection. The method was employed to quantify TFA concentrations in 100 soil samples obtained from grassland and agricultural locations across Germany. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - PFAS KW - Emerging pollutant KW - German soil protection KW - Extraction methods KW - HILIC-LC-MS/MS PY - 2025 AN - OPUS4-62797 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Junge, Florian A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Gehrenkemper, Lennart A1 - Zoister, Christian A1 - Nickl, Philip A1 - Koch, Matthias A1 - Meermann, Björn A1 - Haag, Rainer T1 - Adsorber Charge Dominates over Hydrophobic or Fluorophilic Functionalization in Influencing Adsorption of PFCA onto Polystyrene Resins N2 - A systematic series of industrial-relevant polystyrene-based anion exchange resins that are functionalized with hydro- or fluorocarbon chains are compared regarding their adsorption behavior toward perfluorocarboxylic acids (PFCA) in respect to their charge, chain length, and type of chain. The results clearly show the dominance of electrostatic interactions in the adsorption process as uncharged adsorber materials showed no adsorption at all. In contrast, the charged adsorber materials showed in general a PFCA removal of 80% to 30% over the experiment depending on effluent fraction. Unexpectedly, for perfluorobutanoic acid (PFBA) the highest removal rate is found with consistently >90%. Despite observing significant benefits in the adsorption of PFCA for fluoroalkylated adsorbers in comparison to their non-fluorinated counterparts, this effect of fluoroalkylation is comparatively small and can not be clearly attributed to fluorophilic interactions between the fluoroalkyl chains. These findings help clarifying that the introduction of fluorocarbon moieties in adsorber materials is not necessary in order to remove fluorocarbon molecules from the environment. KW - PFAS KW - Remediation KW - Adsorption KW - Fluorophilic interactions PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601883 DO - https://doi.org/10.1002/admi.202400199 SN - 2196-7350 SP - 1 EP - 10 PB - John Wiley & Sons CY - Hoboken, New Jersey, USA AN - OPUS4-60188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoque, Maroof Arshadul A1 - Sommerfeld, Thomas A1 - Lisec, Jan A1 - Das, Prasenjit A1 - Prinz, Carsten A1 - Heinekamp, Christian A1 - Stolar, Tomislav A1 - Etter, Martin A1 - Rosenberger, David A1 - George, Janine A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska T1 - Mechanochemically Synthesized Covalent Organic Framework Effectively Captures PFAS Contaminants N2 - Per‐ and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants that pose significant health risks, prompting urgent efforts to develop effective removal methods and adsorbers. Covalent organic frameworks (COFs) are metal‐free adsorbers with high stability and tunable porosity. A highly crystalline COF is synthesised mechanochemically using 1,3,5‐tris(4‐aminophenyl)benzene (TAPB) and 1,3,5‐triformylbenzene (TFB). The formation dynamics are monitored in real time with time‐resolved in situ synchrotron X‐ray diffraction. The TAPB‐TFB COF demonstrates good efficiency in eliminating PFAS from water. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are effectively extracted, and most of the adsorption occurred within the first 10 min. Additionally, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and DFT calculations are employed to elucidate the molecular interactions between PFAS and the COF framework. The rapid and efficient removal of PFAS makes TAPB‐TFB COF a promising material for water treatment applications. KW - COFs KW - Ball-milling KW - PFAS PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648712 DO - https://doi.org/10.1002/smll.202509275 SN - 1613-6810 VL - 21 IS - 44 SP - 1 EP - 8 PB - Wiley CY - Weinheim AN - OPUS4-64871 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoque, Maroof Arshadul T1 - Mechanochemically synthesized COF for PFAS adsorption N2 - Since the 1950s, per- and polyfluoroalkyl substances (PFAS) have been widely used in a range of consumer products, including clothing, paints, cookware and fast-food packaging. Properties such as high thermal resistance and water and oil repellency contribute to their wide usage. After decades of production, these substances have eventually found their way into our drinking water. Given the adverse effects of PFAS molecules on human health, the removal of these substances from our drinking water is a matter of urgency.1 This study employs the use of materials known as covalent organic frameworks (COFs) to adsorb PFAS molecules from an aqueous medium. COFs are crystalline, highly porous, two- or three-dimensional polymers with tunable topology and functionalities.² For the purposes of this study, a COF was synthesised using 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 1,3,5-triformylbenzene (TFB) via a mechanochemical process. Mechanochemistry represents a green synthesis method that uses mechanical energy to initiate chemical reactions, as opposed to using harmful solvents and heat.3 Adsorption tests were carried out to test the effectiveness of the material in question against PFAS. The COF was exposed to a solution of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid PFOS). Following a 13-hour period, it was observed that 90% of PFOA and 99% of PFOS had been adsorbed by the COF. Most of the adsorption appeared to have occurred within the first 10 minutes of exposure. It can therefore be concluded that the TAPB-TFB COF is a promising material for the adsorption of PFAS molecules. T2 - Adlershofer Forschungsforum 2024 CY - Berlin, Germany DA - 11.11.2024 KW - Covalent organic framework KW - Mechanochemistry KW - PFAS KW - In situ Xray diffraction PY - 2024 AN - OPUS4-61808 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -