Determination of fluorine in herbs and water samples by molecular absorption spectrometry after preconcentration on nano-TiO ₂ using ultrasound-assisted dispersive micro solid phase extraction

Abstract

This work presents ultrasound-assisted dispersive micro solid phase extraction (USA DMSPE) for preconcentration of fluorine (F) in water and herb samples. TiO ₂ nanoparticles (NPs) were used as an adsorbent. The determination with slurry sampling was performed via molecular absorption of calcium monofluoride (CaF) at 606.440 nm using a high-resolution continuum source electrothermal absorption spectrometry (HR-CS ET MAS). Several factors influencing the efficiency of the preconcentration technique, such as the amount of TiO ₂, pH of sample solution, ultrasonication and centrifugation time and TiO ₂ slurry solution preparation before injection to HR-CS ET MAS, were investigated in detail. The conditions of detection step (wavelength, calcium amount, pyrolysis and molecule-forming temperatures) were also studied. After extraction, adsorbent with the analyte was mixed with 200 μL of H ₂O to prepare a slurry solution. The concentration limit of detection was 0.13 ng mL ⁻¹. The achieved preconcentration factor was 7. The relative standard deviations (RSDs, %) for F in real samples were 3–15%. The accuracy of this method was evaluated by analyses of certified reference materials after spiking: INCT-MPH-2 (Mixed Polish Herbs), INCT-SBF-4 (Soya Bean Flour), ERM-CAO11b (Hard Drinking Water) and TMDA-54.5 (Lake Ontario Water). The measured F contents in reference materials were in satisfactory agreement with the added amounts, and the recoveries were found to be 97–109%. Under the developed extraction conditions, the proposed method has been successfully applied for the determination of F in real water samples (lake, sea, tap water) and herbs.