Ten blank measurements for the aqueous solution gave an average and standard deviation of Aint = 0.0046 ± 0.0009, whereas the values for the acid digestion and the alkaline solubilization were Aint = 0.0045 ± 0.0011, and Aint = 0.0043 ± 0.0001, respectively. These values clearly demonstrate that there was no detectable amount of fluorine leaching from the PTFE vessels during the digestion or solubilization processes.
For validation purposes a Tea Reference Material (NCS-ZC73014) with a certified value of 57 ± 15 μg g−1 F was subject to a microwave-assisted acid digestion and also solubilized using TMAH (refer to Section 2). The result obtained with the former sample pretreatment was 51 ± 12 μg g−1 F, and with the latter one 56 ± 6 μg g−1 F. Both values were not significantly different from the certified vale on a 95% confidence level.
The sensitivity obtained at the CaF molecular absorption band head at 606.440 nm is more than two orders of magnitude lower than that reported by Heitmann et al. [27] and Gleisner et al. [28] and [29] for the GaF line at 211.248 nm. This, however, was not considered a disadvantage, as the sensitivity obtained at the former line perfectly served the purpose, avoiding the need for excessive dilution. In addition, the relatively high blank value reported by Gleisner et al. [28] and [29] also was not observed in this work.
3.5. Analysis of tea samples
Ten tea samples from different parts of the world have been acquired and brought into solution using both an acid digestion and an alkaline solubilization, and also preparing a conventional tea infusion, as described in Section 2. The results are presented in Table 4, and there is no significant difference between the results obtained with the two digestion/solubilization procedures on a 95% confidence level. The fluorine content in the different tea samples was between 42 μg g−1 and 87 μg g−1, but with no detectable tendency for the different brands of tea. According to expectation, the infusions had lower fluoride content with an extraction rate between 48% and 74% of the total content. Nevertheless, tea might be a significant source of fluorine in countries with a high consumption of this beverage.
Table 4.
Values obtained for fluorine in tea samples using HR-CS ETV MAS of the CaF molecule at 606.440 nm, using acid digestion, alkaline solubilization and regular infusion.
Sample Acid digestion (μg g−1) Alkaline solubilization (μg g−1) Infusion (μg g−1) Extraction to infusion (%)
Darjeeling FOP 59 ± 11 60 ± 12 37 ± 8 62
Longjing tea 47 ± 15 44 ± 15 27 ± 10 59
Earl Gray 67 ± 12 67 ± 14 49 ± 15 73
Darjeeling 76 ± 9 79 ± 11 40 ± 13 52
White tea 42 ± 7 45 ± 12 21 ± 11 48
Green tea with passion fruit 63 ± 12 64 ± 10 47 ± 17 74
Green tea with lemon 64 ± 17 67 ± 14 39 ± 13 59
Black tea 1 50 ± 13 49 ± 13 26 ± 13 52
Black tea 2 85 ± 19 87 ± 16 55 ± 17 65
Mate tea 50 ± 11 49 ± 9 29 ± 10 59
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4. Conclusion
A simple procedure has been developed for the determination of fluorine in tea using the molecular absorption of CaF after electrothermal vaporization in a graphite tube furnace. The great advantage is that only calcium has to be added in a 20-fold molar excess over fluorine as the molecule-forming agent, and no other modifier was necessary. The only disadvantage is that the graphite tubes last for only about 100 determinations due to the well-known reaction of calcium with graphite under the formation of a carbide, which decomposes upon the addition of water. The sensitivity of the proposed method is lower than that described for the GaF molecular absorption, but it perfectly served the purpose, and the CaF absorption line at 606.440 nm might well be applicable for the determination of fluorine in other types of samples in case the analyte concentration is high enough.
Acknowledgements
The authors are grateful to Concelho Nacional de Desenvolvimento Científico e Tecnológico do Brasil (CNPq) for financial support and research scholarships. The authors are also grateful to Analytik Jena for the loan of the contrAA 700 high-resolution continuum source atomic absorption spectrometer.