The use of microwave-induced plasma optical emission spectrometry for fluorine determination and its application to tea infusions.

This study presents a novel method for fluorine quantification determination by microwave-induced plasma optical emission spectrometry (MIP-OES). Due to the low temperature of this plasma, atomic emission of fluorine could not be measured, instead CaF molecular emissions were measured by using a calcium solution mixed in the spray chamber with the sample using a T-piece. Several wavelengths were studied to find the best signal to noise ratio for fluorine determination and 530.45 nm was chosen. The limit of detection for the determination of fluorine via CaF using MIP-OES was 1.1 mg L-1. A linear response was observed over two orders of magnitude (R2 = 0.998). The developed method was applied to ten tea infusion samples from the UK and Saudi Arabia. The results were not significantly different (paired Student's t-test, p = 0.97) to the results obtained using the reference method, high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GF MAS). The total fluorine in the tea infusions varied between 2.7 and 7.8 mg L-1; all of which were above the WHO recommended level of fluoride (0.8-1.5 mg L-1) in drinking water. This method can potentially be used for total fluorine determination and might be useful for fluorine speciation analysis when coupled with HPLC.

The use of high resolution graphite furnace molecular absorption spectrometry (HR -MAS) for total fluorine determination in extractable organofluorines (EOF).

The determination of total fluorine content using high-resolution graphite furnace continuum source molecular absorption spectrometry (HR- MAS) has been employed in a variety of samples for over 10 years. However, most of the samples analysed by HR- MAS are rich in fluoride, with negligible levels of organic fluorinated species. With an increase in concern surrounding per- and polyfluoroalkyl substances (PFASs), new methods to measure total fluorine of organofluorine using different techniques have been developed. However, no studies focused on PFASs behaviour in HR-MAS have been performed. As these compounds encompass a wide range of different structures, boiling points, decomposition temperatures and matrix interactions, a loss of accuracy can occur when an aqueous external calibration is performed using only one compound. To overcome this issue, an investigation into permanent modifiers for the graphite furnace was performed. After optimisation similar sensitivity for different PFCA was achieved when 400 µg of W was used as a permanent modifier together with an optimised temperature program. The relative deviation between the different PFCA standard slopes relative to the PFOA slope was lower than 15%. The instrumental limit of detection and quantification (LOD and LOQ, respectively) of total fluorine as total PFCA was 0.1 mg L-1 and 0.3 mg L-1, respectively, while the method LOD and LOQ (using solid phase extraction) was 0.3 µg L-1 and 1.0 µg L-1, respectively. The developed method gave satisfactory recoveries for the spiked PFCA into seawater, river water and effluent using PFOA calibration standards. The optimised method is useful for measuring extractable organofluorines (EOF) when only ionic PFASs such as PFCA are expected. When other organofluorines are expected, the results using HR GF-MAS should be taken with caution.