An Improved Methodology for Determination of Fluorine in Biological Samples Using High-Resolution Molecular Absorption Spectrometry via Gallium Fluorine Formation in a Graphite Furnace

Abstract

Nowadays growing attention is paid to the control of fluorine content in samples of biological origin as it is present in the form of various biologically active organic compounds. Due to the chemically-rich matrix of biological tissues, the determination of fluorine becomes a very difficult task. Furthermore, a required complex sample preparation procedure makes the determination of the low contents of F by ion chromatography UV-Vis or ion-selective electrodes not possible. High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) seems to be the best option for this purpose due to its high robustness to matrix interferences, especially in the presence of carefully selected modifiers. In this work the possibility of quantitative F determination in water and animal tissues was examined by measuring the molecular absorption of gallium monofluoride (GaF) at 211.248 nm with the use of a commercially available HR-CS GF MAS system. Experimental conditions for the sensitive and precise determination of fluorine were optimized, including the time/temperature program as well as addition of gallium and modifier mixture in combined mode. Under these conditions the fluoride present in the sample was stabilized up to 600 °C, and the optimum vaporization temperature for GaF was 1540 °C. Palladium and zirconium deposited onto the graphite surface served as solid modifiers; sodium acetate and ruthenium modifiers were added directly to the sample. The limit of detection and the characteristic mass of the method were 0.43 μg/L and 8.7 pg, respectively. The proposed procedure was validated by the use of certified reference materials (CRMs) of lake water and animal tissue; the acceptable recovery was obtained, proving that it can be applied for samples with a similar matrix.