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Screening method for extractable organically bound fluorine (EOF) in river water samples by means of high-resolution–continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS)

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Abstract

The introduction of fluorine into organic molecules leads to new chemical/physical properties. Especially in the field of pharmaceutical as well as technical applications, fluorinated organic substances gain in importance. The OECD identified and categorized 4730 per- and polyfluoroalkyl substances-related CAS numbers. Thus, an increasing release of fluorinated compounds into the environment is expected. In particular, perfluorinated compounds often show higher environmental stability leading to the risk of bioaccumulation. Polyfluorinated compounds undergo decomposition; thus, further possible fluorine species occur, which may exhibit different toxic/chemical properties. However, current target methods based on, e.g., HPLC/MS-MS, are not applicable for a comprehensive screening of fluorinated substances as well as assessment of pollution. Thus, within this work, a sum parameter method for quantitative determination of extractable organically bound fluorine (EOF) in surface waters was developed. The method is based on solid-phase extraction (SPE) for extraction of fluorinated compounds as well as separation of interfering inorganic fluoride in combination with high-resolution–continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) for organic fluorine quantification. Upon optimization of the SPE procedure (maximum concentration of extractable organic fluorine), enrichment factors of about 1000 were achieved, allowing for highly sensitive fluorine detection. HR-CS GF MAS allows for selective fluorine detection upon in situ formation of a diatomic molecule (“GaF”). Next to a species-unspecific response, limits of detection in the low nanogram per liter range (upon enrichment) were achieved. Upon successful method development, surface water samples (rivers Moselle and Rhine) were analyzed. Furthermore, a sampling campaign along the river Rhine (from the south—close to the French border; to the north—close to The Netherlands border) was conducted. EOF values in the range of about 50–300 ng/L were detected. The developed method allows for a fast and sensitive as well as selective/screening detection of organically bound fluorine (EOF) in surface water samples, helping to elucidate pollution hotspots as well as discharge routes.

A solid phase extraction (SPE) HR-CS GF MAS screening method was developed for the quantitative analysis/screening of extractable organically bound fluorine (EOF) in river water samples. Highly sensitive EOF analysis (low ppq range) was obtained upon SPE and HR-CS GF MAS analysis. Sampling campaign along the river Rhine was conducted.

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Funding

The German Research Foundation (DFG - Deutsche Forschungsgemeinschaft; reference number: ME 3685/4-1, project number: 358057020) and the German Federal Ministry of Transport and Digital Infrastructure (BMVI) are gratefully acknowledged for funding.

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Authors and Affiliations

  1. Department G2 - Aquatic Chemistry, Federal Institute of Hydrology, Am Mainzer Tor 1, 56068, Koblenz, Germany

    Matthias Metzger, Manfred Sturm & Björn Meermann

  2. Department of Ecology, Environment and Plant Sciences, Stockholm University, Svante Arrhenius väg 20 A, 114 18, Stockholm, Sweden

    Philip Ley

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  1. Matthias Metzger
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  2. Philip Ley
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  4. Björn Meermann
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Correspondence to Björn Meermann.

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Published in the topical collection Young Investigators in (Bio-)Analytical Chemistry with guest editors Erin Baker, Kerstin Leopold, Francesco Ricci, and Wei Wang.

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Metzger, M., Ley, P., Sturm, M. et al. Screening method for extractable organically bound fluorine (EOF) in river water samples by means of high-resolution–continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). Anal Bioanal Chem 411, 4647–4660 (2019). https://doi.org/10.1007/s00216-019-01698-1

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  • DOI: https://doi.org/10.1007/s00216-019-01698-1

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