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High-resolution continuum source graphite furnace molecular absorption spectrometry compared with ion chromatography for quantitative determination of dissolved fluoride in river water samples

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Abstract

In addition to beneficial health effects, fluoride can also have adverse effects on humans, animals, and plants if the daily intake is strongly elevated. One main source of fluoride uptake is water, and thus several ordinances exist in Germany that declare permissible concentrations of fluoride in, for example, drinking water, mineral water, and landfill seepage water. Controlling the fluoride concentrations in aqueous matrices necessitate valid and fast analytical methods. In this work an alternative method for the determination of fluoride in surface waters based on high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) was applied. Fluoride detection was made possible by the formation of a diatomic molecule, GaF, and detection of characteristic molecular absorption. On HR-CS-GFMAS parameter optimization, the method was adapted to surface water sample analysis. The influence of potential main matrix constituents such as Na+, Ca2+, Mg2+, and Cl- as well as surface water sampling/storage conditions on the molecular absorption signal of GaF was investigated. Method validation demonstrated a low limit of detection (8.1 μg L-1) and a low limit of quantification (26.9 μg L-1), both sufficient for direct river water sample analysis after 0.45-μm filtration. The optimized HR-CS-GFMAS method was applied for the analysis of real water samples from the rivers Rhine and Moselle. For method validation, samples were also analyzed by an ion chromatography (IC) method. IC and HR-CS-GFMAS results both agreed well. In comparison with IC, HR-CS-GFMAS has higher sample throughput, a lower limit of detection and a lower limit of quantification, and higher selectivity, and is a very suitable method for the analysis of dissolved fluoride in river water.

High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) was applied for the quantitative analysis of dissolved fluoride in river water samples from the Rhine and the Moselle. Fluoride detection was made possible by the addition of Ga for GaF formation and analysis of characteristic molecular absorption at 211.248 nm. Good agreement between HR-CS-GFMAS and ion chromatography (IC) results was obtained. In comparison with IC, HR-CS-GFMAS had a faster sample throughput and lower limit of detection and limit of quantification.

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References

  1. Holleman AF, Wiberg N. Lehrbuch der Anorganischen Chemie. 101st ed. Berlin, New York: Walter de Gruyter; 1995. p. 432.

  2. Holleman AF, Wiberg N. Lehrbuch der Anorganischen Chemie, 101st ed. Berlin, New York: Walter de Gruyter; 1995. Tafel II.

  3. Gleisner H. Fluorine detection in drinking water using HR-CS AAS. Analytik Jena application note LIT_AA_12_10_e. 2010.

  4. Fawell J, Bailey K, Chilton J, Dahi E, Fewtrell L, Magara Y. Fluoride in drinking-water. London: IWA Publishing; 2006.

    Google Scholar 

  5. Edmunds WM, Smedley PL. Groundwater geochemistry and health: an overview. Environ Geochem Health. 1996;113:91–105.

    CAS  Google Scholar 

  6. Federal Institute for Risk Assessment. Information no. 037/2005. 2005.

  7. Standing Committee on the Scientific Evaluation of Dietary Reference Intakes, Dietary Reference Intakes for Calcium, Phosphorus, Magnesium, Vitamin D and Fluoride. Washington: National Academy Press; 1997.

  8. American Academy of Pediatric Dentistry. Guideline on fluoride therapy. Chicago: American Academy of Pediatric Dentistry; 2014.

  9. Haidouti C, Chronopoulou A, Chronopoulos J. Effects of fluoride emissions from industry on the fluoride concentration of soils and vegetation. Biochem Syst Ecol. 1993;21:195–208.

    Article  CAS  Google Scholar 

  10. Trinkwasserverordnung. TrinkwV. 2001.

  11. Deponieverordnung. DepV. 2009.

  12. Mineral- und Tafelwasser-Verordnung. Min/TafelWV. 1984.

  13. German Institute for Standardization. DIN 10304-1: water quality - determination of dissolved anions by liquid chromatography of ions - part 1: determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate. Berlin: Beuth; 2009.

    Google Scholar 

  14. ISO10359-1: water quality - determination of fluoride - part 1: electrochemical probe method for potable and lightly polluted water. 1992.

  15. Ozbek N, Akman S. Method development for the determination of fluorine in water samples via the molecular absorption of strontium monofluoride formed in an electrothermal atomizer. Spectrochim Acta Part B. 2012;69:32–7.

    Article  CAS  Google Scholar 

  16. Butcher DJ. Molecular absorption spectrometry in flames and furnaces: a review. Anal Chim Acta. 2013;804:1–15.

    Article  CAS  Google Scholar 

  17. Ozbek N, Akman S. Determination of fluorine in milk and water via molecular absorption of barium monofluoride by high-resolution continuum source atomic absorption spectrometer. Microchem J. 2014;117:111–5.

    Article  CAS  Google Scholar 

  18. Aramendia M, Florez MR, Piette M, Vanhaecke F, Resano M. Al determination in whole blood samples as AlF via high-resolution continuum source graphite furnace molecular absorption spectrometry: potential application to forensic diagnosis of drowning. J Anal At Spectrom. 2011;26:1964–73.

    Article  CAS  Google Scholar 

  19. Mores S, Monteiro GC, Santos FD, Carasek E, Welz B. Determination of fluorine in tea using high-resolution molecular absorption spectrometry with electrothermal vaporization of the calcium mono-fluoride CaF. Talanta. 2011;85:2681–5.

    Article  CAS  Google Scholar 

  20. Ozbek N, Akman S. Molecule formation mechanisms of strontium mono fluoride in high-resolution continuum source electrothermal atomic absorption spectrometry. Anal Sci. 2013;29:741–6.

    Article  CAS  Google Scholar 

  21. Qin ZW, McNee D, Gleisner H, Raab A, Kyeremeh K, Jaspars M, et al. Fluorine speciation analysis using reverse phase liquid chromatography coupled off-line to continuum source molecular absorption spectrometry (CS-MAS): identification and quantification of novel fluorinated organic compounds in environmental and biological samples. Anal Chem. 2012;84:6213–9.

    Article  CAS  Google Scholar 

  22. Heitmann U, Becker-Ross H, Florek S, Huang MD, Okruss M. Determination of non-metals via molecular absorption using high-resolution continuum source absorption spectrometry and graphite furnace atomization. J Anal At Spectrom. 2006;21:1314–20.

    Article  CAS  Google Scholar 

  23. Analytik Jena. Application note. Bestimmung von Nichtmetallen mit der HR-CS AAS. 2011.

  24. Ozbek N, Akman S. Solid sampling determination of total fluorine in baby food samples by high-resolution continuum source graphite furnace molecular absorption spectrometry. Food Chem. 2016;211:180–4.

    Article  CAS  Google Scholar 

  25. Ozbek N, Akman S. Determination of fluorine in milk samples via calcium-monofluoride by electrothermal molecular absorption spectrometry. Food Chem. 2013;138:650–4.

    Article  CAS  Google Scholar 

  26. Ozbek N, Akman S. Determination of fluorine in Turkish wines by molecular absorbance of CaF using a high resolution continuum source atomic absorption spectrometer. LWT Food Sci Technol. 2015;61:112–6.

    Article  CAS  Google Scholar 

  27. Ozbek N, Baltaci H, Baysal A. Investigation of fluorine content in PM2.5 airborne particles of Istanbul, Turkey. Environ Sci Pollut Res. 2016;23:13169–77.

    Article  CAS  Google Scholar 

  28. Venkateswarlu P. Determination of fluoride in bone by aluminum monofluoride molecular absorption spectrometry. Anal Chim Acta. 1992;262:33–40.

    Article  CAS  Google Scholar 

  29. Gleisner H, Einax JW, Morés S, Welz B, Carasek E. A fast and accurate method for the determination of total and soluble fluorine in toothpaste using high-resolution graphite furnace molecular absorption spectrometry and its comparison with established techniques. J Pharm Biomed Anal. 2011;54:1040–6.

    Article  CAS  Google Scholar 

  30. Wurtenberger I, Gust R. A highly sensitive method for in vitro testing of fluorinated drug candidates using high-resolution continuum source molecular absorption spectrometry (HR-CS MAS). Anal Bioanal Chem. 2014;406:3431–42.

    Article  Google Scholar 

  31. Krüger M, Huang MD, Becker-Roß H, Florek S, Ott I, Gust R. Quantification of the fluorine containing drug 5-fluorouracil in cancer cells by GaF molecular absorption via high-resolution continuum source molecular absorption spectrometry. Spectrochim Acta Part B. 2012;69:50–5.

    Article  Google Scholar 

  32. Gleisner H, Welz B, Einax JW. Optimization of fluorine determination via the molecular absorption of gallium mono-fluoride in a graphite furnace using a high-resolution continuum source spectrometer. Spectrochim Acta Part B. 2010;65:864–9.

    Article  Google Scholar 

  33. German Institute for Standardization. DIN 32645: decision limit, detection limit and determination limit. Berlin: Beuth; 1994.

    Google Scholar 

  34. Bermejo P, Barciela J, Pena EM, Bermejo A, Fraga JM, Cocho JA. Determination of selenium in infant formulas whey fractions by SEC-HPLC-HG-ETAAS. J Anal At Spectrom. 2001;16:188–93.

    Article  CAS  Google Scholar 

  35. Ozbek N, Akman S. Method development for the determination of fluorine in toothpaste via molecular absorption of aluminum mono fluoride using a high-resolution continuum source nitrous oxide/acetylene flame atomic absorption spectrophotometer. Talanta. 2012;94:246–50.

    Article  CAS  Google Scholar 

  36. Ozbek N, Akman S. Optimization and application of a slurry sampling method for the determination of total fluorine in fluor using a high-resolution continuum source graphite furnace molecular absorption spectrometer. Food Anal Methods. 2016;9:2925–32.

    Article  Google Scholar 

  37. Dittrich K. Molekülabsorptionsspektrometrie bei Elektrothermischer Verdampfung in einer Graphitrohrküvette II. Bestimmung von Fluoridspuren in Mikrovolumina durch die Molekülabsorption von GaF-Molekülen. Anal Chim Acta. 1978;97:69–80.

    Article  CAS  Google Scholar 

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Acknowledgements

The German Federal Ministry of Transport and Digital Infrastructure (BMVI) is gratefully acknowledged for funding. Manoj Schulz is gratefully acknowledged for his support during the ion chromatography measurements, and Jürgen Pelzer is gratefully acknowledged for supporting us with statistical data assessment with STATISTICA (both from Department G2—Aquatic Chemistry, Federal Institute of Hydrology).

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Correspondence to Björn Meermann.

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Ley, P., Sturm, M., Ternes, T.A. et al. High-resolution continuum source graphite furnace molecular absorption spectrometry compared with ion chromatography for quantitative determination of dissolved fluoride in river water samples. Anal Bioanal Chem 409, 6949–6958 (2017). https://doi.org/10.1007/s00216-017-0647-5

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