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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)

Metzger, Matthias, Ley, Philip, Sturm, Manfred, Meermann, Björn
Analytical and bioanalytical chemistry 2019 v.411 no.19 pp. 4647-4660
bioaccumulation, detection limit, fluorides, fluorine, high performance liquid chromatography, organic matter, perfluorocarbons, physical properties, physicochemical properties, pollution, quantitative analysis, risk, river water, rivers, screening, solid phase extraction, spectroscopy, surface water, toxicity, Netherlands
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. Graphical abstract 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.