Development of quantitative non-target analysis approaches for fluorinated substances in environmental samples using complementary HPLC/PARCI-MS and HPLC/ESI-MS

• Applicant: Dr. Fabian Simon
• Subject Area: Analytical Chemistry
• Term: since 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 539566218

This project aims to combine non-target analysis (NTA) based on high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) with elemental fluorine speciation analysis based on high performance liquid chromatography- plasma-assisted reaction chemical ionization-mass spectrometry (HPLC-PARCI-MS) for the identification and quantification of (unknown) organofluorines in environmental samples. Furthermore, sample preparation strategies and automated software tools for data analysis will be developed and tested for their suitability in routine analysis. Per- and polyfluoroalkyl substances (PFASs) compromise persistent, bioaccumulative, and toxic properties and are hence, environmental contaminants of emerging concern. Thus, procedures for identifying potential sources of the entrance of these compounds into the environment, identification of new organofluorine species, and closing mass balances need urgent development. The intrinsic fluorine tag appears in a sizable fraction of these and other xenobiotics, making elemental speciation desirable for quantitative NTA in these areas. Current non-target approaches based on ESI-HRMS suffer from a lack of data mining algorithms for identification of PFASs with low fluorine mass percentages. Furthermore, low ionization efficiencies of the compounds hamper detection limits. Hence, the proposed combination of simultaneous HPLC-ESI-MS and HPLC-PARCI-MS via split-stream coupling is a promising approach for environmental PFAS monitoring. Furthermore, it could serve as an important analytical procedure to set up limiting values in compliance with the desired PFAS ban of the European Union. Hence, for the development of reliable analytical procedures, the following research goals will be tackled within this application: 1. development of high-throughput sample preparation procedures for PARCI-MS bulk analysis, 2. optimization and validation of workflows for non-target organofluorine analysis via HPLC-PARCI-MS based on BaF+ afterglow ionization, 3. coupling of simultaneous HPLC-ESI-MS and HPLC-PARCI-MS for quantitative non-target analysis of organofluorines, and 4. application of the developed procedures to environmental sample analysis.

• DFG Programme: WBP Fellowship
• International Connection: USA
• Host: Professor Kaveh Jorabchi