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 - JOUR A1 - Scholl, Juliane A1 - Scharpmann, Philippa A1 - Bagheri, Abbas A1 - Lisec, Jan A1 - Meiers, Emelie A1 - Jaeger, Carsten A1 - Leonhardt, Robert A1 - Haase, Hajo A1 - Koch, Matthias T1 - Beyond the lab: Real-world composition of commercial Li-ion battery electrolytes N2 - This study presents a systematic, characterization of electrolytes from commercial lithium-ion batteries (LIB), encompassing 90 batteries from leading global manufacturers across diverse formats and application sectors. An integrated, complementary mass spectrometric workflow combining LC–MS/MS, GC–MS, and high-resolution MS was employed. To ensure robust structural annotation, molecular identifications were assigned confidence levels following Schymanski et al. (2014). Across all formats, PF6− was confirmed as the dominant Li+ counterion, frequently coexisting with BF4−, PO2F2−, and bis(fluorosulfonyl)imide (FSI−), forming binary and ternary salt systems optimized for both conductivity and safety. Solvent systems revealed the widespread use of propylene carbonate (PC) combined with diverse carbonate mixtures, demonstrating trends in performance optimization specific to cell format. A variety of additives were identified, reflecting a clear shift towards multifunctional, synergistic additive packages and the gradual replacement of fluorinated species with environmentally safer alternatives. Cycling studies demonstrated that electrolyte degradation mechanisms are strongly influenced by electrode composition and additive chemistry, with oxidative degradation pathways dominating. Together, these findings provide rare empirical insight into the evolving formulation strategies of electrolytes in commercial LIB, still employing classic carbonates and LiPF6, but highlighting a trend toward safer, more robust, and sustainable electrolyte architectures by using synergistic multifunctional systems. KW - Mass Spectrometry KW - Lithium-ion batteries KW - Electrolyte degradation PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-656254 DO - https://doi.org/10.1016/j.jpowsour.2026.239739 SN - 0378-7753 VL - 673 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-65625 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 - JOUR A1 - Herter, Sven-Oliver A1 - Haase, Hajo A1 - Koch, Matthias T1 - Semisynthesis of Stable Isotope-Labeled Ergot Alkaloids for HPLC-MS/MS Analysis N2 - Ergot alkaloids (EAs) are prevalent food contaminants affecting cereals, such as rye, wheat, and barley worldwide. To ensure EU safety standards, the six most common EAs: ergometrine, ergotamine, ergosine, ergocornine, ergocristine, and ergocryptine, and their epimers, are quantified using HPLC-MS/MS, as described in the European Standard Method EN 17425:2021. However, this can be challenging and time-consuming in food matrices without appropriate internal standards and highlights the need for more robust and precise analytical tools to support their monitoring. The development of isotope-labeled EAs directly addresses this gap, offering improved accuracy and leading to more consistency across laboratories and consequently to more consumer safety. Therefore, we developed a semisynthetic approach, building upon our previous work where native ergotamine was N6-demethylated to norergotamine and subsequently remethylated using iodomethane (13CD3-I). Herein, we are now able to present the successful synthesis of all of the isotopically labeled priority EAs. These isotope-labeled standards were tested against their native counterparts using HPLC coupled with HR-MS/MS. The chromatographic and mass spectrometric properties of the unlabeled and isotopically labeled EAs match exactly, confirming their successful synthesis and structure. These standards can now be utilized to enhance the accuracy and reliability of EA quantification in food and feed. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Ergot Alkaloids KW - Stable Isotope Dilution Analysis KW - Semisynthesis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639692 DO - https://doi.org/10.1021/acs.jafc.5c03345 SN - 0021-8561 VL - 73 IS - 29 SP - 18412 EP - 18419 PB - American Chemical Society (ACS) AN - OPUS4-63969 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matiushkina, Anna A1 - Abram, Sarah-Luise A1 - Tavernaro, Isabella A1 - Richstein, R. A1 - Reithofer, M. R. A1 - Andresen, Elina A1 - Michaelis, Matthias A1 - Koch, Matthias A1 - Resch-Genger, Ute T1 - Quantifying Citrate Surface Ligands on Iron Oxide Nanoparticles with TGA, CHN Analysis, NMR, and RP-HPLC with UV Detection N2 - Although citrate is frequently used as a surface ligand for nanomaterials (NMs) such as metal, metal oxide, and lanthanide-based NMs in hydrophilic environments due to its biocompatibility and simple replacement by other more strongly binding ligands in postsynthetic surface modification reactions, its quantification on NM surfaces has rarely been addressed. Here, we present a multimethod approach for citrate quantification on iron oxide nanoparticles (IONPs) broadly applied in the life and material sciences. Methods explored include thermogravimetric (TGA) and elemental (CHN) analysis, providing citrate-nonspecific information on the IONP coating, simple photometry, and citrate-selective reversed-phase high-performance liquid chromatography (RP-HPLC) with absorption (UV) detection and quantitative nuclear magnetic resonance spectroscopy (qNMR). Challenges originating from the strongly absorbing magnetic NM and paramagnetic iron species interfering with optical and NMR Methods were overcome by suitable sample preparation workflows. Our multimethod approach to citrate quantification highlights the advantages of combining specific and unspecific methods for characterizing NM Surface chemistry and method cross-validation. It also demonstrates that chemically nonselective measurements can favor an overestimation of the amount of a specific surface ligand by signal contributions from molecules remaining on the NM surface, e.g., from particle synthesis, such as initially employed ligands and/or surfactants. Our results emphasize the potential of underexplored selective RPHPLC for quantifying ligands on NMs, which does not require a multistep sample preparation workflow such as qNMR for many NMs and provides a higher sensitivity. These findings can pave the road to future applications of versatile HPLC methods in NM characterization. KW - Advanced material KW - Functional group KW - Iron oxide KW - Ligand KW - Nano KW - Particle KW - Quantification KW - Surface analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648632 DO - https://doi.org/10.1021/acs.analchem.5c03024 SN - 0003-2700 VL - 97 IS - 36 SP - 19627 EP - 19634 PB - American Chemical Society (ACS) CY - Washington, DC AN - OPUS4-64863 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meiers, Emelie A1 - Scholl, Juliane A1 - Droas, Morten A1 - Vogel, Christian A1 - Leube, Peter A1 - Sommerfeld, Thomas A1 - Bagheri, A. A1 - Adam, Christian A1 - Seubert, A. A1 - Koch, Matthias T1 - Development and evaluation of analytical strategies for the monitoring of per- and polyfluoroalkyl substances from lithium-ion battery recycling materials N2 - Per- and polyfluoroalkyl substances (PFAS) are well-known as “forever chemicals” and persistent pollutants released by different anthropogenic sources. The potential release of PFAS from accumulating electronic waste and lithium-ion battery (LIB) recycling activities has gained increasing attention in the past years. This creates a need for analytical methods tailored for the determination of PFAS out of environmental matrices related to the named activities or directly out of the concerned materials. In this work, analytical strategies for the monitoring of PFAS in LIB recycling materials were explored for a group of legacy perfluoro sulfonic- and carbonic acids (PFSA and PFCA) and of fluorinated sulfonylimides suspected to be LIB electrolyte ingredients. These analytical strategies comprehend PFAS target approaches with a herein optimized liquid chromatography tandem mass spectrometry (LC–MS/MS) method equipped with a HILIC (hydrophilic interaction liquid chromatography) column in combination with the TOP (total oxidizable precursor) assay and an adapted sample preparation method for high-matrix LIB recycling materials. The validated target method was applied to a set of LIB recycling materials: end-of-life batteries, black masses from hydrometallurgical recycling, and gas absorption solutions from thermal treatment of black masses as part of the recycling procedure. Investigation results show that the LIB industry can be connected to the release of both “LIB”-PFAS, such as the target sulfonylimides, and “already-legacy” PFAS, like the PFSA and PFCA. Especially, the presence of trifluoroacetic acid (TFA) as an emerging pollutant in every investigated LIB material type underlines the threat of PFAS emissions from LIB waste and recycling activities. KW - Per- and polyfluoroalkyl substances (PFAS) KW - Battery PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647015 DO - https://doi.org/10.1007/s00216-025-06165-8 SN - 1618-2642 VL - 417 SP - 6567 EP - 6583 PB - Springer Science and Business Media LLC AN - OPUS4-64701 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herter, Sven-Oliver A1 - Koch, Matthias A1 - Haase, Hajo T1 - First Synthesis of Ergotamine-13CD3 and Ergotaminine-13CD3 from Unlabeled Ergotamine N2 - Ergot alkaloids (EAs) formed by Claviceps fungi are one of the most common food contaminants worldwide, affecting cereals such as rye, wheat, and barley. To accurately determine the level of contamination and to monitor EAs maximum levels set by the European Union, the six most common EAs (so-called priority EAs) and their corresponding epimers are quantified using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The quantification of EAs in complex food matrices without appropriate internal tandards is challenging but currently carried out in the standard method EN 7425:2021 due to their commercial unavailability. To address the need for isotopically labeled EAs, we focus on two semi-synthetic approaches for the synthesis of these reference standards. Therefore, we investigate the feasibility of the N6-demethylation of native ergotamine to yield norergotamine, which can subsequently be remethylated with an isotopically labeled methylating reagent, such as iodomethane (13CD3-I), to yield isotopically labeled ergotamine and its C8-epimer ergotaminine. Testing the isotopically labeled ergotamine/-inine against native ergotamine/-inine with HPLC coupled to high-resolution HR-MS/MS proved the structure of ergotamine-13CD3 and ergotaminine-13CD3. Thus, for the first time, we can describe their synthesis from unlabeled, native ergotamine. Furthermore, this approach is promising as a universal way to synthesize other isotopically labeled EAs. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Standards KW - Organic Synthesis KW - Isotope PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600167 DO - https://doi.org/10.3390/toxins16040199 VL - 16 IS - 4 SP - 1 EP - 12 PB - MDPI AN - OPUS4-60016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Lisec, Jan A1 - Koch, Matthias T1 - Changes in Black Truffle (Tuber melanosporum) Aroma during Storage under Different Conditions N2 - The enticing aroma of truffles is a key factor for their culinary value. Although all truffle species tend to be pricy, the most intensely aromatic species are the most sought after. Research into the aroma of truffles encompasses various disciplines including chemistry, biology, and sensory science. This study focusses on the chemical composition of the aroma of black truffles (Tuber melanosporum) and the changes occurring under different storage conditions. For this, truffle samples were stored under different treatments, at different temperatures, and measured over a total storage time of 12 days. Measurements of the truffle aroma profiles were taken with SPME/GC–MS at regular intervals. To handle the ample data collected, a systematic approach utilizing multivariate data analysis techniques was taken. This approach led to a vast amount of data which we made publicly available for future exploration. Results reveal the complexity of aroma changes, with 695 compounds identified, highlighting the need for a comprehensive understanding. Principal component analyses offer initial insights into truffle composition, while individual compounds may serve as markers for age (formic acid, 1-methylpropyl ester), freshness (2-Methyl-1-propanal; 1-(methylthio)-propane), freezing (tetrahydrofuran), salt treatment (1-chloropentane), or heat exposure (4-hydroxy-3-methyl-2-butanone). This research suggests that heat treatment or salt contact significantly affects truffle aroma, while freezing and cutting have less pronounced effects in comparison. The enrichment of compounds showing significant changes during storage was investigated with a metabolomic pathway analysis. The involvement of some of the enriched compounds on the pyruvate/glycolysis and sulfur pathways was shown. KW - Mass Spectrometry KW - Metabolomics KW - Tuber melanosporum KW - Truffle Aroma PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601731 DO - https://doi.org/10.3390/jof10050354 VL - 10 IS - 5 SP - 1 EP - 22 PB - MDPI AN - OPUS4-60173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholl, Juliane A1 - Lisec, Jan A1 - Haase, Hajo A1 - Koch, Matthias T1 - Identification of transformation products from fluorinated lithium-ion battery additives TPFPB and TPFPP: forever chemicals of tomorrow? N2 - AbstractFluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon–fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs. KW - Mass Spectrometry KW - LiBs KW - POPs KW - Transformation products KW - Electrochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611339 DO - https://doi.org/10.1007/s00216-024-05526-z SP - 1 EP - 15 PB - Springer Science and Business Media LLC AN - OPUS4-61133 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 -