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

Nor Laili Azua Jamari, Arne Behrens, Andrea Raab, Eva M. Krupp, Jorg Feldmann

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Abstract

Detection of fluorine with commercial ICPMS is impossible due to fluorine's high ionisation potential (IP). A novel approach through the formation of fluorine-containing polyatomic ions [M-F]+ in the plasma allows the successful detection of F in sub ppm level by ICPMS/MS. Two theories behind [M-F]+ formation have been proposed, yet there is no clear understanding about this mechanism. Here, different metal solutions were tested to study 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, found to be essential to get highest sensitivity of [M-F]+. It was found that for elements with a higher [M-F]+ BDE than [M-O]+ BDE, the sensitivity decreases linearly with the element's second IP, meaning that the major process in the plasma is that M2+ harvests F- in the plasma 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 the negative ion ICPMS/MS was discussed with which detection limits of sub-ppb could be reached.
Original languageEnglish
Pages (from-to)1304-1309
Number of pages6
JournalJournal of Analytical Atomic Spectrometry
Volume33
Issue number8
Early online date16 May 2018
DOIs
Publication statusPublished - 2018

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Fluorine
Ionization potential
Plasmas
Barium
Negative ions
Metals
Ions

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Plasma processes to detect fluorine with ICPMS as M-F+ : an argument for building a negative mode ICPMS/MS. / Jamari, Nor Laili Azua; Behrens, Arne; Raab, Andrea; Krupp, Eva M.; Feldmann, Jorg.

In: Journal of Analytical Atomic Spectrometry, Vol. 33, No. 8, 2018, p. 1304-1309 .

Research output: Contribution to journalArticle

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abstract = "Detection of fluorine with commercial ICPMS is impossible due to fluorine's high ionisation potential (IP). A novel approach through the formation of fluorine-containing polyatomic ions [M-F]+ in the plasma allows the successful detection of F in sub ppm level by ICPMS/MS. Two theories behind [M-F]+ formation have been proposed, yet there is no clear understanding about this mechanism. Here, different metal solutions were tested to study 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, found to be essential to get highest sensitivity of [M-F]+. It was found that for elements with a higher [M-F]+ BDE than [M-O]+ BDE, the sensitivity decreases linearly with the element's second IP, meaning that the major process in the plasma is that M2+ harvests F- in the plasma 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 the negative ion ICPMS/MS was discussed with which detection limits of sub-ppb could be reached.",
author = "Jamari, {Nor Laili Azua} and Arne Behrens and Andrea Raab and Krupp, {Eva M.} and Jorg Feldmann",
note = "NLAJ thanks the Malaysian Government (Grant number: RG12824-10) and National Defence University of Malaysia for financial support throughout the study period, while AB thanks the Erasmus programme of the EU. Special thanks to Swedish Research Council for additional financial support (Grant number: FORMAS 1397306) and also to Samira Al Hinai and Amanda Victor for helping in this project.",
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AU - Krupp, Eva M.

AU - Feldmann, Jorg

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AB - Detection of fluorine with commercial ICPMS is impossible due to fluorine's high ionisation potential (IP). A novel approach through the formation of fluorine-containing polyatomic ions [M-F]+ in the plasma allows the successful detection of F in sub ppm level by ICPMS/MS. Two theories behind [M-F]+ formation have been proposed, yet there is no clear understanding about this mechanism. Here, different metal solutions were tested to study 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, found to be essential to get highest sensitivity of [M-F]+. It was found that for elements with a higher [M-F]+ BDE than [M-O]+ BDE, the sensitivity decreases linearly with the element's second IP, meaning that the major process in the plasma is that M2+ harvests F- in the plasma 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 the negative ion ICPMS/MS was discussed with which detection limits of sub-ppb could be reached.

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