Lecture
Dark Side of Atomic Spectrometry: Fluorine and PFAS Analysis Beyond LC–MS
- at -
- ICM Saal 5
- Type: Lecture
Lecture description
J. Feldmann, Graz/A, A. Raab, Graz/A R. Gonzalez de Vega, Graz/A, V. Müller, Graz/A
Liquid chromatography–mass spectrometry (LC–MS/MS and LC–HRMS) is the current gold standard for targeted and non-targeted PFAS analysis. However, even extensive target lists (>40 PFAS) and suspect screening workflows typically explain less than 10% of the total fluorine measured as extractable organofluorine (EOF) in methanolic extracts. This large unidentified fluorine fraction highlights a critical analytical blind spot in PFAS research and the gold standards CIC and HR GFMAS do not agree on the total fluorine concentrations (1).
The absence of a universal fluorine detector is a fundamental limitation of atomic spectrometry. Fluorine’s emission and absorption lines lie in the vacuum ultraviolet (~98 nm), and its high ionization potential (17 eV) prevents direct detection by conventional techniques such as AAS, ICP-OES, and ICP-MS.
Here, we present three complementary atomic spectrometric strategies that enable fluorine determination across a broad range of fluorinated materials, including particulate, polar, and non-polar PTFE. These approaches comprise: (a) ICP-MS/MS detection via BaF⁺ adduct formation (2), (b) negative-ion ICP-MS with fluoride detection (3), (c) high-energy helium-based plasmas with emission detection (AED) and (d) helium atmospheric-pressure glow discharge for liquid sample ionization (4).
The applicability of these methods is demonstrated in environmental case studies involving complex biological matrices, including roe deer (5), bees (6), and whales. The results show that atomic spectrometry, when combined with alternative ionization concepts, can substantially improve fluorine mass balance and provide a powerful complement to molecular mass spectrometry in PFAS research.
References:
1.) A. Al Zbedy et al. Anal. Chim. Acta (2025) 1351, 343855
2.) N.L.A. Jamari et al. J. Anal. At. Spectrom. (2017) 32 (5), 942-950
2) A. Raab et al. J. Anal. At. Spectrom. (2025) 40, 1689-1699.
3.) V. Müller et al. J. Anal At. Spectrom. (2025) 40, 1700-1710.
4.) V. Müller et al. Environ. Poll. (2026) 127685.
5.) V. Müller et al. Environ. Poll. (2025) 126750.
Liquid chromatography–mass spectrometry (LC–MS/MS and LC–HRMS) is the current gold standard for targeted and non-targeted PFAS analysis. However, even extensive target lists (>40 PFAS) and suspect screening workflows typically explain less than 10% of the total fluorine measured as extractable organofluorine (EOF) in methanolic extracts. This large unidentified fluorine fraction highlights a critical analytical blind spot in PFAS research and the gold standards CIC and HR GFMAS do not agree on the total fluorine concentrations (1).
The absence of a universal fluorine detector is a fundamental limitation of atomic spectrometry. Fluorine’s emission and absorption lines lie in the vacuum ultraviolet (~98 nm), and its high ionization potential (17 eV) prevents direct detection by conventional techniques such as AAS, ICP-OES, and ICP-MS.
Here, we present three complementary atomic spectrometric strategies that enable fluorine determination across a broad range of fluorinated materials, including particulate, polar, and non-polar PTFE. These approaches comprise: (a) ICP-MS/MS detection via BaF⁺ adduct formation (2), (b) negative-ion ICP-MS with fluoride detection (3), (c) high-energy helium-based plasmas with emission detection (AED) and (d) helium atmospheric-pressure glow discharge for liquid sample ionization (4).
The applicability of these methods is demonstrated in environmental case studies involving complex biological matrices, including roe deer (5), bees (6), and whales. The results show that atomic spectrometry, when combined with alternative ionization concepts, can substantially improve fluorine mass balance and provide a powerful complement to molecular mass spectrometry in PFAS research.
References:
1.) A. Al Zbedy et al. Anal. Chim. Acta (2025) 1351, 343855
2.) N.L.A. Jamari et al. J. Anal. At. Spectrom. (2017) 32 (5), 942-950
2) A. Raab et al. J. Anal. At. Spectrom. (2025) 40, 1689-1699.
3.) V. Müller et al. J. Anal At. Spectrom. (2025) 40, 1700-1710.
4.) V. Müller et al. Environ. Poll. (2026) 127685.
5.) V. Müller et al. Environ. Poll. (2025) 126750.
