Development of an interface for the on-line coupling of HPLC and HR-cs-GFAAS for fluorine speciation analysis
Final Report Abstract
PFAS are widely used in manifold applications. Due to their broad fields of applications, they are released into the environment and can be ubiquitously found. Next to their wide distribution in manifold environmental matrices, up to now more than 6000 PFAS substances are available, common target analytical approaches are not sufficient for their analysis. Furthermore, PFAS standards are lacking for valid quantification via LC/ESI-MS. Thus, both is needed: complementary LC/ESI-MS ↔ LC/HR-cs-GFMAS approaches for identification as well as quantification of PFAS substances as well as hot spot screening via EOF sum parameter methods based on HR-cs-GFMAS. Sum parameter methods based on HR-cs-GFMAS are on their way - however, complementary LC/HR-cs-GFMAS methods comprising a species-unspecific response for quantification are still needed. In view of its high sensitivity HR-cs-GFMAS is the most promising tool. Hence, the focal points of this project were: PI) Interface design: Construction of a new interface for the on-line coupling of a HPLC with HR-cs-GFMAS. PII) Fluorine Speciation: Optimization of the developed interface’s parameters for fluorine speciation analysis with test substances and development of a HPLC separation method for several fluorine-containing organic test substances to investigate the species-unspecific response of GFMAS. PIII) Real sample analysis: Development and optimization of water sample preparation as well as sample/species enrichment strategies for fluorinated organic substances and related species with regard to expected low environmental concentrations. Within this project we highlighted the general suitability of HR-cs-GFMAS as a detector for transient signals for HPLC detection. However, the pristine coupling/interface approach via a microdroplet generator was not applicable - thus, a new approach relying on an oven was developed and first promising tests were carried out. However, more investigations for GaF detection are needed. Next to the work package addressing interfacing LC and HR-cs-GFMAS we investigated the species-specific response of several PFAS substances - hence, a HR-cs-GFMAS method optimization was carried out and the species-specific response was almost completely overcome successfully. Within the last work package real sample analysis was addressed: hence sampling approaches including clean up as well as concentration were optimized based on SPE resins. It turned out that PFAS species discrimination takes place on common SPE cartridges. Hence, we developed a new SPE resin stacking approach via the combination of different resin materials and could successfully reduce species discrimination. PFAS analysis is still a challenging task - however, within this project the founding was placed ending up with complementary speciation methods as well as hot spot sum parameter detection approaches - both relying on the powerful tool of HR-cs-GFMAS.
Publications
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Screening method for extractable organically bound fluorine (EOF) in river water samples by means of high-resolutioncontinuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). Analytical and Bioanalytical Chemistry, 2019, 411, 4647-4660
Metzger M., Ley P., Sturm M., Meermann B.
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Determination of organically bound fluorine sum parameters in river water samples—comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Analytical and Bioanalytical Chemistry, 2021, 413, 103-115
Gehrenkemper, L. & Simon, F., Roesch, P., Fischer, E., von der Au, M., Pfeifer, J., Cossmer, A., Wittwer, P., Vogel, C., Simon, F.-G., Meermann, B.
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PFAS-Summenparameteranalytik-Neue analytische Methoden zum Nachweis von per- und polyfluorierten Verbindungen in der Umwelt. GIT-Labor-Fachzeitschrift, 2021, was-00080223
Gehrenkemper, L., Simon, F., & Meermann, B.
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A fast and simple PFAS extraction method utilizing HR-CS-GFMAS for soil samples. Chemosphere, 2022, 295, 133922
Simon, F. & Gehrenkemper, L., von der Au, M., Wittwer, P., Roesch, P., Pfeifer, J., Cossmer, A., Meermann, B.
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Schnelle und einfache Extraktion von PFAS aus Bodenproben: Optimierte EOF-Bestimmung mittels HR-CS-GFMAS. Mitteilungen der Fachgruppe Umweltchemie und Ökotoxikologie, 2022, 28(1), 12-15
Gehrenkemper, L., Simon, F., & Meermann, B.
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Trendbericht Analytische Chemie 2022. Nachrichten aus der Chemie, 2022, 70(6), 52-65
Simon, F., Gehrenkemper, L., von der Au, M., Traub, H., Vogl, J., Meermann, B., ... & Pöthig, A.
