TY - JOUR A1 - Kotthoff, Lisa A1 - O’Callaghan, S.-L. A1 - Lisec, Jan A1 - Schwerdtle, T. A1 - Koch, Matthias T1 - Structural annotation of electro- and photochemically generated transformation products of moxidectin using high-resolution mass spectrometry N2 - Moxidectin (MOX) is a widely used anthelmintic drug for the treatment of internal and external parasites in food-producing and companion animals. Transformation products (TPs) of MOX, formed through metabolic degradation or acid hydrolysis, May pose a potential environmental risk, but only few were identified so far. In this study, we therefore systematically characterized electro- and photochemically generatedMOX TPs using high-resolution mass spectrometry (HRMS). Oxidative electrochemical (EC) TPs were generated in an electrochemical reactor and photochemical (PC) TPs by irradiation with UV-C light. Subsequent HRMS measurements were performed to identify accuratemasses and deduce occurring modification reactions of derived TPs in a suspected target analysis. In total, 26 EC TPs and 59 PC TPs were found. The main modification reactions were hydroxylation, (de-)hydration, and derivative formation with methanol for EC experiments and isomeric changes, (de-)hydration, and changes at the methoxime moiety for PC experiments. In addition, several combinations of different modification reactions were identified. For 17 TPs, we could predict chemical structures through interpretation of acquired MS/MS data. Most modifications could be linked to two specific regions of MOX. Some previously described metabolic reactions like hydroxylation or O-demethylation were confirmed in our EC and PC experiments as reaction type, but the corresponding TPs were not identical to known metabolites or degradation products. The obtained knowledge regarding novel TPs and reactions will aid to elucidate the degradation pathway of MOX which is currently unknown. KW - Moxidectin KW - Transformation products KW - Electrochemical Reactor PY - 2020 DO - https://doi.org/10.1007/s00216-020-02572-1 VL - 412 IS - 13 SP - 3141 EP - 3152 PB - Springer AN - OPUS4-50721 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Knoche, Lisa A1 - Lisec, Jan A1 - Koch, Matthias T1 - Analysis of electrochemical and liver microsomal transformation products of lasalocid by LC/HRMS N2 - Rationale: Lasalocid (LAS), an ionophore, is used in cattle and poultry farming as feed additive for its antibiotic and growth-promoting properties. Literature on transformation products (TP) resulting from LAS degradation is limited. So far, only hydroxylation is found to occur as the metabolic reaction during the LAS degradation. To investigate potential TPs of LAS, we used electrochemistry (EC) and liver microsome (LM) assays to synthesize TPs, which were identified using liquid chromatography high-resolution mass spectrometry (LC/HRMS). Methods: Electrochemically produced TPs were analyzed online by direct coupling of the electrochemical cell to the electrospray ionization (ESI) source of a Sciex Triple-TOF high resolution mass spectrometer. Then, EC-treated LAS solution was collected and analyzed offline using LC/HRMS to confirm stable TPs and improve their annotation with a chemical structure due to informative MS/MS spectra. In a complementary approach, TPs formed by rat and human microsomal incubation were investigated using LC/HRMS. The resulting data were used to investigate LAS modification reactions and elucidate the chemical structure of obtained TPs. Results: The online measurements identified a broad variety of TPs, resulting from modification reactions like (de-)hydrogenation, hydration, methylation, oxidation as well as adduct formation with methanol. We consistently observed different ion complexations of LAS and LAS-TPs (Na+; 2Na+ K+; NaNH4 +; KNH4 +). Two stable methylated EC-TPs were found, structurally annotated, and assigned to a likely modification reaction. Using LM incubation, seven TPs were formed, mostly by oxidation/hydroxylation. After the identification of LM-TPs as Na+-complexes, we identified LM-TPs as K+-complexes. Conclusion: We identified and characterized TPs of LAS using EC- and LM-based methods. Moreover, we found different ion complexes of LAS-based TPs. This knowledge, especially the different ion complexes, may help elucidate the metabolic and environmental degradation pathways of LAS. KW - Mass Spectrometry KW - Electrochemistry KW - ECR KW - Lasalocid KW - Ionophore KW - Transformation products PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-553919 DO - https://doi.org/10.1002/rcm.9349 VL - 36 IS - 18 SP - 1 EP - 10 PB - Wiley online library AN - OPUS4-55391 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Temgoua, Ranil C. T. T1 - Mimicking Environmental Degradation of Carbendazim Pesticide by EC-MS N2 - Currently, there is a growing interest in the study of environmental degradation pathways of organic contaminants such as pesticides, with the objective to better understand their potential risk for environmental systems and living organisms. In this context, DFT (conceptual density functional theory) and predictive methods may systematically be used to simplify and accelerate the elucidation of environmental degradation. We report herein the electrochemical behavior/degradation of the carbendazim (CBZ) fungicide widely used to treat cereal and fruit crops. Oxidative degradation of CBZ was studied using an electrochemical flow-through cell directly coupled to a mass spectrometer for rapid identification of CBZ degradation products. The structural elucidation of CBZ oxidation products was based on retention time, accurate mass, isotopic distribution and fragmentation pattern by using LC-HRMS an LC-HRMS2. The most important chemical reactions found to occur in the transformation of CBZ were hydrolysis and hydroxylation. EC-LC-MS and EC-MS analysis has made it possible to highlight the identification of degradation products of CBZ. In addition to previously known transformation products common to those observed during environmental degradation (monocarbomethoxyguanidine, benzimidazole-isocyanate, 2-aminobenzimidazole, hydroxy-2-aminobenzimidazole, hydroxycarbendazim, CBZ-CBZ dimer), two new degradation products were identified in this work: a quinone imine and a nitrenium ion. Electrochemistry mass spectrometry hyphenated techniques represent an accessible, rapid and reliable tool to elucidate the oxidative degradation of CBZ, including reactive degradation products and conjugates. T2 - 36th Topical Meeting of the International Society of Electrochemistry CY - Šibenik, Croatia DA - 26.05.2024 KW - Electrochemistry KW - Mass Spectrometry KW - Emerging pollutants KW - Transformation products PY - 2024 AN - OPUS4-61062 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Temgoua, Ranil C. T. T1 - Hyphenated Electrochemistry-Liquid Chromatography-Mass Spectrometry (EC-LC-MS) N2 - The coupling of electrochemistry with mass spectrometry (EC-MS) represents a revolutionary approach for studying redox-active compounds, which constitute over 90% of known chemical entities. This poster demonstrates the versatility of EC-MS as a rapid and environmentally friendly alternative to traditional in-vivo and in-vitro methods. Our focus encompasses three key applications: Simulation of drug metabolism pathways, investigation of environmental xenobiotic degradation/fate (eFate), and green synthesis of analytical standards. T2 - 56th annual conference of the DGMS (Deutschen Gesellschaft für Massenspektrometrie) CY - Göttingen, Germany DA - 04.03.2025 KW - Electrochemistry KW - Mass Spectrometry KW - Emerging pollutants KW - Transformation products PY - 2025 AN - OPUS4-63517 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 - 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 - 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 -