Analytical and Bioanalytical Chemistry

, Volume 396, Issue 3, pp 1311–1320

Development of liquid chromatography atmospheric pressure chemical ionization tandem mass spectrometry for analysis of halogenated flame retardants in wastewater

  • Simon Ningsun Zhou
  • Eric J. Reiner
  • Chris Marvin
  • Paul Helm
  • Nicole Riddell
  • Frank Dorman
  • Michelle Misselwitz
  • Li Shen
  • Patrick Crozier
  • Karen MacPherson
  • Ian D. Brindle
Original Paper


Until recently, atmospheric pressure photoionization (APPI) has typically been used for the determination of non-polar halogenated flame retardants (HFRs) by liquid chromatography (LC) tandem mass spectrometry. In this study, we demonstrated the feasibility of utilizing liquid chromatography atmospheric pressure chemical ionization (APCI) tandem mass spectrometry (LC-APCI-MS/MS) for analysis of 38 HFRs. This developed method offered three advantages: simplicity, rapidity, and high sensitivity. Compared with APPI, APCI does not require a UV lamp and a dopant reagent to assist atmospheric pressure ionization. All the isomers and the isobaric compounds were well resolved within 14-min LC separation time. Excellent instrument detection limits (6.1 pg on average with 2.0 μL injection) were observed. The APCI mechanism was also investigated. The method developed has been applied to the screening of wastewater samples for screening purpose, with concentrations determined by LC-APCI-MS/MS agreeing with data obtained via gas chromatography high resolution mass spectrometry.


LC-APCI-MS/MS for analysis of halogenated flame reterdants


Atmospheric pressure chemical ionization (APCI) Liquid chromatography tandem mass spectrometry (LC-MS/MS) Halogenated flame retardants (HFRs) Wastewater 


  1. 1.
    de Wit CA (2002) Chemosphere 46:583–624CrossRefGoogle Scholar
  2. 2.
    Covaci A, Voorspoels S, Ramos L, Neels H, Blust R (2007) J Chromatogr A 1153:145–171CrossRefGoogle Scholar
  3. 3.
    Kolic TM, Shen L, MacPherson K, Fayez L, Gobran T, Helm PA, Marvin CH, Arsenault G, Reiner EJ (2009) J Chromatogr Sci 47:83–91Google Scholar
  4. 4.
    Covaci A, Voorspoels S, de Boer J (2003) Environ Int 29:735–756CrossRefGoogle Scholar
  5. 5.
    Law RJ, Kohler M, Heeb NV, Gerecke AC, Schmid P, Voorspoels S, Covaci A, Becher G, Janak K, Thomsen C (2005) Environ Sci Technol 39:281A–287ACrossRefGoogle Scholar
  6. 6.
    Budakowski W, Tomy G (2003) Rapid Commun Mass Spectrom 17:1399–1404CrossRefGoogle Scholar
  7. 7.
    Morris S, Allchin CR, Zegers BN, Haftka JJH, Boon JP, Belpaire C, Leonards PEG, Van Leeuwen SPJ, De Boer J (2004) Environ Sci Technol 38:5497–5504CrossRefGoogle Scholar
  8. 8.
    Saint-Louis R, Pelletier E (2004) Analyst 129:724–730CrossRefGoogle Scholar
  9. 9.
    Suzuki S, Hasegawa A (2006) Analyt Sci 22:469–474CrossRefGoogle Scholar
  10. 10.
    Tollback J, Crescenzi C, Dyremark E (2006) J Chromatogr A 1104:106–112CrossRefGoogle Scholar
  11. 11.
    Koppen R, Becker R, Jung C, Piechotta C, Nehls I (2006) Analyt Bioanalyt Chem 384:1485–1492CrossRefGoogle Scholar
  12. 12.
    Debrauwer L, Riu A, Jouahri M, Rathahao E, Jouanin I, Antignac JP, Cariou R, Le Bizec B, Zalko D (2005) J Chromatogr A 1082:98–109CrossRefGoogle Scholar
  13. 13.
    Morris S, Bersuder P, Allchin CR, Zegers B, Boon JP, Leonards PEG, de Boer J (2006) TrAC. Trends Anal Chem 25:343–349CrossRefGoogle Scholar
  14. 14.
    Riu A, Zalko D, Debrauwer L (2006) Rapid Commun Mass Spectrom 20:2133–2142CrossRefGoogle Scholar
  15. 15.
    Lagalante AF, Oswald TD (2008) Analyt Bioanalyt Chem 391:2249–2256CrossRefGoogle Scholar
  16. 16.
    Riu A, Cravedi JP, Debrauwer L, Garcia A, Canlet C, Jouanin I, Zalko D (2008) Environ Int 34:318–329CrossRefGoogle Scholar
  17. 17.
    Long M, Dorman FL, Lake R, Kowalski J, Wittrig RE (2008) In: 32nd International Symposium on HPLC, Baltimore, MarylandGoogle Scholar
  18. 18.
    Janak K, Covaci A, Voorspoels S, Becher G (2005) Environ Sci Technol 39:1987–1994CrossRefGoogle Scholar
  19. 19.
    Tomy GT, Halldorson T, Danell R, Law K, Arsenault G, Alaee M, MacInnis G, Marvin CH (2005) Rapid Commun Mass Spectrom 19:2819–2826CrossRefGoogle Scholar
  20. 20.
    Marvin CH, Tomy GT, Alaee M, MacInnis G (2006) Chemosphere 64:268–275CrossRefGoogle Scholar
  21. 21.
    Cariou R, Antignac JP, Marchand P, Berrebi A, Zalko D, Andre F, Le Bizec B (2005) J Chromatogr A 1100:144–152CrossRefGoogle Scholar
  22. 22.
    Hayama T, Yoshida H, Onimaru S, Yonekura S, Kuroki H, Todoroki K, Nohta H, Yamaguchi M (2004) J Chromatogr B Analyt Technol Biomed Life Sci 809:131–136CrossRefGoogle Scholar
  23. 23.
    Berger U, Herzke D, Sandanger TM (2004) Anal Chem 76:441–452CrossRefGoogle Scholar
  24. 24.
    Chu SG, Haffner GD, Letcher RJ (2005) J Chromatogr A 1097:25–32CrossRefGoogle Scholar
  25. 25.
    Cai SS, Hanold KA, Syage JA (2007) Anal Chem 79:2491–2498CrossRefGoogle Scholar
  26. 26.
    Raffaelli A (2007) Advances in LC-MS instrumentation. Elsevier, AmsterdamGoogle Scholar
  27. 27.
    Raffaelli A (2007) In: Cappiello A (ed) Advances in LC-MS Instrumentation, vol. 72. Elsevier, Amsterdam, pp 14–16Google Scholar
  28. 28.
    Stapleton HM, Allen JG, Kelly SM, Konstantinov A, Klosterhaus S, Watkins D, McClean MD, Webster TF (2008) Environ Sci Technol 42:6910–6916CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Simon Ningsun Zhou
    • 1
    • 2
  • Eric J. Reiner
    • 2
  • Chris Marvin
    • 3
  • Paul Helm
    • 4
  • Nicole Riddell
    • 5
  • Frank Dorman
    • 6
    • 7
  • Michelle Misselwitz
    • 6
  • Li Shen
    • 1
    • 2
  • Patrick Crozier
    • 2
  • Karen MacPherson
    • 2
  • Ian D. Brindle
    • 1
  1. 1.Department of ChemistryBrock UniversitySt. CatharinesCanada
  2. 2.Ontario Ministry of the EnvironmentLaboratory Services BranchTorontoCanada
  3. 3.Environment CanadaNational Water Research InstituteBurlingtonCanada
  4. 4.Ontario Ministry of the EnvironmentEnvironmental Monitoring and Reporting BranchTorontoCanada
  5. 5.Wellington LaboratoriesGuelphCanada
  6. 6.Restek CorporationBellefonteUSA
  7. 7.Juniata College Department of ChemistryHuntingdonUSA

Personalised recommendations