Novel non-targeted analysis of perfluorinated compounds using fluorine-specific detection regardless of their ionisability (HPLC-ICPMS/MS-ESI-MS)

Nor Laili Azua Jamari, Jan Frederik Dohmann, Andrea Raab, Eva M. Krupp, Joerg Feldmann (Corresponding Author)

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Although perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out, there is a plethora of per- or polyfluoroalkyl substances (PFAS) generated and only a small number of these compounds are currently being monitored in environmental and biological sample using molecular mass spectrometry (MS). Total fluorine determination has revealed that a substantial amount of fluorinated organic compounds has not been identified. Due to the small mass deficiency of fluorine, it is not an easy task to screen successfully all fluorinated compounds including those which are not easy ionisable, hence a novel fluorine-specific detector is needed. Here, inductively-coupled plasma mass spectrometry (ICPMS) was used for the first time for the detection of PFAS, by using the novel approach to transfer F- into a detectable [BaF]+ in the argon plasma. A reverse phase-high performance liquid chromatography (RP-HPLC) method was developed and then online coupled to ICPMS/MS for the fluorine-specific detection and simultaneously to electrospray MS (ESI-MS) to separate perfluorinated carboxylic acids (PFCA) and perfluorooctanesulfonic acid (PFOS). The calibration was linear and was element-specific with detection limits of 0.49 mg F L-1 under gradient elution method. As a proof of concept, PFCA standards in methanol were not fully neutralised to force the esterification and those solutions were measured using HPLC-ICPMS/MS-ESI-MS. The methyl esters were not detectable by ESI-MS but by ICPMS/MS. This illustrates that the undetectable fluorine-containing compounds were detected and quantified by the element-specific detection of ICPMS/MS. The analysis of spiked river water at a sub-ppb level gave acceptable recovery using a SPE-based preconcentration method. Since ICPMS/MS method is element-specific detection, all non-fluorinated compounds interfering in ESI-MS were eliminated. Hence, HPLC-ICPMS/MS can be used as a non-targeted method of fluorinated compounds which may help the identification of novel fluorinated compounds in environmental and biological samples and helps with mining the ESI-MS data.
Original languageEnglish
Pages (from-to)22-31
Number of pages10
JournalAnalytica Chimica Acta
Volume1053
Early online date20 Nov 2018
DOIs
Publication statusPublished - 11 Apr 2019

Fingerprint

Fluorine Compounds
Inductively coupled plasma mass spectrometry
Electrospray Ionization Mass Spectrometry
fluorine
Tandem Mass Spectrometry
Mass spectrometry
mass spectrometry
High Pressure Liquid Chromatography
plasma
Fluorine
perfluorooctanoic acid
Carboxylic Acids
Mass Spectrometry
analysis
detection
Argon
Esterification
Rivers
Calibration
Methanol

Keywords

  • non-target method
  • ICPMS/MS
  • polyatomic ion [BaF]+
  • perfluoroalkyl substances
  • Polyatomic ion [BaF]
  • Perfluoroalkyl substances
  • Non-target method
  • Polyatomic ion [BaF] +
  • Polyatomic ion [BaF](+)
  • CHROMATOGRAPHY
  • WATER

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Spectroscopy
  • Environmental Chemistry

Cite this

@article{3e7c643ddd6244468c2a097aadbc4673,
title = "Novel non-targeted analysis of perfluorinated compounds using fluorine-specific detection regardless of their ionisability (HPLC-ICPMS/MS-ESI-MS)",
abstract = "Although perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out, there is a plethora of per- or polyfluoroalkyl substances (PFAS) generated and only a small number of these compounds are currently being monitored in environmental and biological sample using molecular mass spectrometry (MS). Total fluorine determination has revealed that a substantial amount of fluorinated organic compounds has not been identified. Due to the small mass deficiency of fluorine, it is not an easy task to screen successfully all fluorinated compounds including those which are not easy ionisable, hence a novel fluorine-specific detector is needed. Here, inductively-coupled plasma mass spectrometry (ICPMS) was used for the first time for the detection of PFAS, by using the novel approach to transfer F- into a detectable [BaF]+ in the argon plasma. A reverse phase-high performance liquid chromatography (RP-HPLC) method was developed and then online coupled to ICPMS/MS for the fluorine-specific detection and simultaneously to electrospray MS (ESI-MS) to separate perfluorinated carboxylic acids (PFCA) and perfluorooctanesulfonic acid (PFOS). The calibration was linear and was element-specific with detection limits of 0.49 mg F L-1 under gradient elution method. As a proof of concept, PFCA standards in methanol were not fully neutralised to force the esterification and those solutions were measured using HPLC-ICPMS/MS-ESI-MS. The methyl esters were not detectable by ESI-MS but by ICPMS/MS. This illustrates that the undetectable fluorine-containing compounds were detected and quantified by the element-specific detection of ICPMS/MS. The analysis of spiked river water at a sub-ppb level gave acceptable recovery using a SPE-based preconcentration method. Since ICPMS/MS method is element-specific detection, all non-fluorinated compounds interfering in ESI-MS were eliminated. Hence, HPLC-ICPMS/MS can be used as a non-targeted method of fluorinated compounds which may help the identification of novel fluorinated compounds in environmental and biological samples and helps with mining the ESI-MS data.",
keywords = "non-target method, ICPMS/MS, polyatomic ion [BaF]+, perfluoroalkyl substances, Polyatomic ion [BaF], Perfluoroalkyl substances, Non-target method, Polyatomic ion [BaF] +, Polyatomic ion [BaF](+), CHROMATOGRAPHY, WATER",
author = "{Azua Jamari}, {Nor Laili} and Dohmann, {Jan Frederik} and Andrea Raab and Krupp, {Eva M.} and Joerg Feldmann",
note = "NLAJ thanks the Malaysian Government (Grant number: RG12824-10) and the National Defence University of Malaysia for financial support throughout the study period, while JFD thanks the Erasmus program of the EU. Special thanks to the Swedish Research Council (Grant number: FORMAS 1397306) for additional financial support in this project.",
year = "2019",
month = "4",
day = "11",
doi = "10.1016/j.aca.2018.11.037",
language = "English",
volume = "1053",
pages = "22--31",
journal = "Analytica Chimica Acta",
issn = "0003-2670",
publisher = "Elsevier",

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TY - JOUR

T1 - Novel non-targeted analysis of perfluorinated compounds using fluorine-specific detection regardless of their ionisability (HPLC-ICPMS/MS-ESI-MS)

AU - Azua Jamari, Nor Laili

AU - Dohmann, Jan Frederik

AU - Raab, Andrea

AU - Krupp, Eva M.

AU - Feldmann, Joerg

N1 - NLAJ thanks the Malaysian Government (Grant number: RG12824-10) and the National Defence University of Malaysia for financial support throughout the study period, while JFD thanks the Erasmus program of the EU. Special thanks to the Swedish Research Council (Grant number: FORMAS 1397306) for additional financial support in this project.

PY - 2019/4/11

Y1 - 2019/4/11

N2 - Although perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out, there is a plethora of per- or polyfluoroalkyl substances (PFAS) generated and only a small number of these compounds are currently being monitored in environmental and biological sample using molecular mass spectrometry (MS). Total fluorine determination has revealed that a substantial amount of fluorinated organic compounds has not been identified. Due to the small mass deficiency of fluorine, it is not an easy task to screen successfully all fluorinated compounds including those which are not easy ionisable, hence a novel fluorine-specific detector is needed. Here, inductively-coupled plasma mass spectrometry (ICPMS) was used for the first time for the detection of PFAS, by using the novel approach to transfer F- into a detectable [BaF]+ in the argon plasma. A reverse phase-high performance liquid chromatography (RP-HPLC) method was developed and then online coupled to ICPMS/MS for the fluorine-specific detection and simultaneously to electrospray MS (ESI-MS) to separate perfluorinated carboxylic acids (PFCA) and perfluorooctanesulfonic acid (PFOS). The calibration was linear and was element-specific with detection limits of 0.49 mg F L-1 under gradient elution method. As a proof of concept, PFCA standards in methanol were not fully neutralised to force the esterification and those solutions were measured using HPLC-ICPMS/MS-ESI-MS. The methyl esters were not detectable by ESI-MS but by ICPMS/MS. This illustrates that the undetectable fluorine-containing compounds were detected and quantified by the element-specific detection of ICPMS/MS. The analysis of spiked river water at a sub-ppb level gave acceptable recovery using a SPE-based preconcentration method. Since ICPMS/MS method is element-specific detection, all non-fluorinated compounds interfering in ESI-MS were eliminated. Hence, HPLC-ICPMS/MS can be used as a non-targeted method of fluorinated compounds which may help the identification of novel fluorinated compounds in environmental and biological samples and helps with mining the ESI-MS data.

AB - Although perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out, there is a plethora of per- or polyfluoroalkyl substances (PFAS) generated and only a small number of these compounds are currently being monitored in environmental and biological sample using molecular mass spectrometry (MS). Total fluorine determination has revealed that a substantial amount of fluorinated organic compounds has not been identified. Due to the small mass deficiency of fluorine, it is not an easy task to screen successfully all fluorinated compounds including those which are not easy ionisable, hence a novel fluorine-specific detector is needed. Here, inductively-coupled plasma mass spectrometry (ICPMS) was used for the first time for the detection of PFAS, by using the novel approach to transfer F- into a detectable [BaF]+ in the argon plasma. A reverse phase-high performance liquid chromatography (RP-HPLC) method was developed and then online coupled to ICPMS/MS for the fluorine-specific detection and simultaneously to electrospray MS (ESI-MS) to separate perfluorinated carboxylic acids (PFCA) and perfluorooctanesulfonic acid (PFOS). The calibration was linear and was element-specific with detection limits of 0.49 mg F L-1 under gradient elution method. As a proof of concept, PFCA standards in methanol were not fully neutralised to force the esterification and those solutions were measured using HPLC-ICPMS/MS-ESI-MS. The methyl esters were not detectable by ESI-MS but by ICPMS/MS. This illustrates that the undetectable fluorine-containing compounds were detected and quantified by the element-specific detection of ICPMS/MS. The analysis of spiked river water at a sub-ppb level gave acceptable recovery using a SPE-based preconcentration method. Since ICPMS/MS method is element-specific detection, all non-fluorinated compounds interfering in ESI-MS were eliminated. Hence, HPLC-ICPMS/MS can be used as a non-targeted method of fluorinated compounds which may help the identification of novel fluorinated compounds in environmental and biological samples and helps with mining the ESI-MS data.

KW - non-target method

KW - ICPMS/MS

KW - polyatomic ion [BaF]+

KW - perfluoroalkyl substances

KW - Polyatomic ion [BaF]

KW - Perfluoroalkyl substances

KW - Non-target method

KW - Polyatomic ion [BaF] +

KW - Polyatomic ion [BaF](+)

KW - CHROMATOGRAPHY

KW - WATER

UR - http://www.scopus.com/inward/record.url?scp=85057420468&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/novel-nontargeted-analysis-perfluorinated-compounds-using-fluorinespecific-detection-regardless-ioni

U2 - 10.1016/j.aca.2018.11.037

DO - 10.1016/j.aca.2018.11.037

M3 - Article

VL - 1053

SP - 22

EP - 31

JO - Analytica Chimica Acta

JF - Analytica Chimica Acta

SN - 0003-2670

ER -