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Detection of fluorine with commercial ICPMS is impossible due to the high ionisation potential (IP) of fluorine. A novel approach through the formation of fluorine-containing polyatomic ions [M–F]+ in the plasma allows the successful detection of F at sub ppm levels by ICPMS/MS. Two theories behind [M–F]+ formation have been proposed, yet there is no clear understanding about the mechanism. Here, different metal solutions were tested for the characterisation of plasma processes in the formation of [M–F]+. Three characteristics: high [M–F]+ bond dissociation energy (BDE), low [M–O]+ BDE and low IP were found to be essential to get the highest sensitivity for [M–F]+. It was found that for elements with a higher [M–F]+ BDE than [M–O]+ BDE, the sensitivity decreases linearly with the second IP of the element, meaning that the major process in the plasma is the harvesting of F− by M2+ to form [M–F]+. Barium exhibited the highest sensitivity for [M–F]+. However, the robustness of this approach was questioned due to matrix effects, hence an argument for re-developing negative ion ICPMS/MS was discussed in which detection limits in the sub-ppb range could be reached.

Plasma processes to detect fluorine with ICPMS/MS as [M–F]+: an argument for building a negative mode ICPMS/MS

Plasma processes to detect fluorine with ICPMS/MS as [M–F]⁺: an argument for building a negative mode ICPMS/MS