Flow injection analysis of fluoride: optimization of experimental conditions and non-linear calibration using artificial neural networks

This paper deals with the application of artificial neural networks (ANNs) to two common problems in spectroscopy: optimization of experimental condit ions and non-linear calibration of the result, with particular reference to the determination of fluoride by flow injection analysis (FIA). The FIA sy stem was based on the formation of a blue ternary complex between zirconium (iv), p-methyldibromoarsenazo and F- with the maximum absorption wavelength at 635 nm. First, optimization in terms of sensitivity and sampling rate w as carried out by using jointly a central composite design and ANNs, and a neural network with a 3-7-1 structure was confirmed to be able to provide t he maximum performance. Second, the relationship between the concentration of fluoride and its absorbance was modeled by ANNs. In this process, cross- validation and leave-k-out were used. The results showed that good predicti on was attained in the 1-4-1 neural net. The trained networks proved to be very powerful in both applications. The proposed method was successfully ap plied to the determination of free fluoride in tea and toothpaste with reco veries between 96 and 101%.