Analytical and Bioanalytical Chemistry

, Volume 391, Issue 6, pp 2249–2256 | Cite as

Analysis of polybrominated diphenyl ethers (PBDEs) by liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS): application to house dust

  • Anthony F. Lagalante
  • Timothy D. Oswald
Original Paper


Eight polybrominated diphenyl ether (PBDE) congeners of primary interest to the US EPA were separated using reverse-phase liquid chromatography on an octadecylsilane column. BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209 were baseline-resolved under isocratic conditions in 92:8 methanol/water (v/v). Negative-ion atmospheric pressure photoionization (NI-APPI) with a toluene dopant produced precursor ions corresponding to [M–Br+O] for the eight congeners studied. Each congener was quantified by tandem mass spectrometry through a unique multiple reaction monitoring (MRM) transition. On-column limits of detection were between 2.4 and 27.8 pg for the eight congeners studied, with an intra-day method precision of 9%. The LC/NI-APPI/MS/MS method was validated for the analysis of the eight PBDE congeners in NIST SRM 2585 (Organics in House Dust). Pressurized liquid extraction (PLE) with subsequent LC/NI-APPI/MS/MS analysis afforded quantitative recovery for all eight PBDE congeners with recoveries ranging from 92.7 to 113%. The liquid-phase separation of the LC/NI-APPI/MS/MS method is not prone to the thermal degradation issues that plague splitless GC based analyses of highly brominated PBDEs such as BDE-209.


Negative-ion atmospheric pressure photoionization (NI-APPI) Liquid chromatography tandem mass spectrometry (LC/MS/MS) Dust Polybrominated diphenyl ethers (PBDEs) Pressurized liquid extraction (PLE) 



We are grateful to Michelle Schantz at NIST for providing SRM 2585. This material is based upon work supported by the National Science Foundation under grant numbers CHE-0718530 and CHE-0619394.


  1. 1.
    La Guardia MJ, Hale RC, Harvey E (2006) Environ Sci Technol 40:6267–6254CrossRefGoogle Scholar
  2. 2.
    Sjödin A, Jokobsson E, Kierkegaard A, Marsh G, Sellström U (1998) J Chromatogr A 822:83–89CrossRefGoogle Scholar
  3. 3.
    Hale RC, La Guardia MJ, Harvey E, Mainor TM (2002) Chemosphere 46:729–735CrossRefGoogle Scholar
  4. 4.
    Renner R (2004) Environ Sci Technol 38:14AGoogle Scholar
  5. 5.
    BSEF (2001) Major brominated flame retardants volume estimates. Bromine Science and Environmental Forum, Brussels (see, last accessed 28 April 2008)
  6. 6.
    Stapleton H, Letcher R, Baker J (2002) Organohal Compd 58:201–204Google Scholar
  7. 7.
    Alaee M, Wenning RJ (2002) Chemosphere 46:579–796CrossRefGoogle Scholar
  8. 8.
    de Wit CA (2002) Chemosphere 46:583–624CrossRefGoogle Scholar
  9. 9.
    Lectcher R, Behnisch P (2003) Environ Int 29:663–885CrossRefGoogle Scholar
  10. 10.
    Benedict RT, Stapleton HM, Letcher RJ, Mitchelmore CL (2007) Chemosphere 69:987–993CrossRefGoogle Scholar
  11. 11.
    Betts KS (2004) Environ Sci Technol 38:50A–51ACrossRefGoogle Scholar
  12. 12.
    Gouin T, Harner T, Daly GL, Wania F, Mackay D, Jones KC (2005) Atmos Environ Part A 39:151–166Google Scholar
  13. 13.
    Mazdai A, Dodder NG, Abernathy MP, Hites RA, Bigsby RM (2003) Environ Health Perspect 111:1249–1252Google Scholar
  14. 14.
    Petreas M, She J, Brown R, Winkler J, Winham G, Rogers E, Zhao G, Bhatia R, Charles MJ (2003) Environ Health Perspect 111:1175–1179Google Scholar
  15. 15.
    Sellström U, De Wit CA, Lundgren N, Tysklind M (2005) Environ Sci Technol 39:9064–9070CrossRefGoogle Scholar
  16. 16.
    Thuresson K, Höglund P, Hagmar L, Sjödin A, Bergman A, Jakobsson E (2006) Environ Health Perspect 114:176–181Google Scholar
  17. 17.
    Bocio A, Llobet JM, Domingo JL, Corbella J, Teixidó A, Casas C (2003) J Agric Food Chem 51:3191–3195CrossRefGoogle Scholar
  18. 18.
    Schecter AN, Päpke O, Harris RT, Tung KC, Musumba A, Olson J, Birnbaum L (2006) Environ Health Perspect 114:1515–1520CrossRefGoogle Scholar
  19. 19.
    Schecter A, Päpke O, Tung K, Staskal D, Birnbaum L (2004) Environ Sci Technol 38:5306–5311CrossRefGoogle Scholar
  20. 20.
    Allen JG, McClean MD, Stapleton HM, Nelson JW, Webster TF (2007) Environ Sci Technol 41:4574–4579CrossRefGoogle Scholar
  21. 21.
    Stapleton HM, Dodder NG, Offenberg JH, Schantz MM, Wise SA (2005) Environ Sci Technol 39:925–931CrossRefGoogle Scholar
  22. 22.
    Jones-Otazo HA, Clarke JP, Diamond ML, Archbold JA, Ferguson G, Harner T, Richardson GM, Ryan JJ, Wilford B (2005) Environ Sci Technol 39:5121–5530CrossRefGoogle Scholar
  23. 23.
    Stapleton HM, Harner T, Shoeib M, Keller JM, Schantz MM, Leigh SD, Wise SA (2006) Anal Bioanal Chem 384:791–800CrossRefGoogle Scholar
  24. 24.
    Harrad S, Hazrati S, Ibarra C (2006) Environ Sci Technol 40:4633–4638CrossRefGoogle Scholar
  25. 25.
    Tan J, Cheng SM, Loganath A, Chong YS, Obbard JP (2007) Chemosphere 66:985–992CrossRefGoogle Scholar
  26. 26.
    Karlsson M, Julander A, van Bavel B, Hardel L (2007) Environ Int 33:62–69CrossRefGoogle Scholar
  27. 27.
    Wu N, Herrmann T, Paepke O, Tickner J, Hale R, Harvey E, La Guardia MJ, McClean MD, Webster TF (2007) Environ Sci Technol 41:1584–1589CrossRefGoogle Scholar
  28. 28.
    Schecter A, Päpke O, Joseph JE, Tung K (2005) J Toxicol Environ Health 68:501–513CrossRefGoogle Scholar
  29. 29.
    Tulve NS, Suggs JC, McCurdy T, Cohen Hubal EA, Moya J (2002) J Expo Anal Environ Epidemiol 12:259–264CrossRefGoogle Scholar
  30. 30.
    Covaci A, Voorspoels S, Ramos L, Neels H, Blust R (2007) J Chromatogr A 1153:145–171CrossRefGoogle Scholar
  31. 31.
    Stapleton HM (2006) Anal Bioanal Chem 386:807–817CrossRefGoogle Scholar
  32. 32.
    Björklund J, Tollbäck P, Östman C (2003) J Mass Spectrom 38:394–400CrossRefGoogle Scholar
  33. 33.
    Ackerman LK, Wilson GR, Simonich SL (2007) Anal Chem 77:1979–1987CrossRefGoogle Scholar
  34. 34.
    Regueiro J, Llompart M, Garcia-Jares C, Cela R (2007) Anal Bioanal Chem 388:1095–1107CrossRefGoogle Scholar
  35. 35.
    Björklund J, Tollbäck P, Hiärne C, Dyremark E, Östman C (2004) J Chromatogr A 1041:201–210CrossRefGoogle Scholar
  36. 36.
    Rogers E, Petreas M, Park J, Zhao G, Charles MJ (2004) J Chromatogr B 813:269–285CrossRefGoogle Scholar
  37. 37.
    Covaci A, de Boer J, Ryan JJ, Voorspoels S, Schepens P (2002) Anal Chem 74:790–798CrossRefGoogle Scholar
  38. 38.
    Worall K, Newton A, Van Bavel B, Pettersson A, Linstrom G, Reiner E, Macpherson K, Kolic T, Ordsmith N, Catterall S (2004) Organohalog Compd 66:186–190Google Scholar
  39. 39.
    Schummler M, Brandl F, Mäurer A, van Eldik R (2005) J Chromatogr A 1064:39–51CrossRefGoogle Scholar
  40. 40.
    Pohlein M, Llopis AS, Wolf M, Van Eldik R (2005) J Chromatogr A 1066:111–117CrossRefGoogle Scholar
  41. 41.
    Debrauwer L, Riu A, Jouahri M, Rathahao E, Jouanin I, Antignac J, Cariou R, Le Bizec B, Zalko D (2005) J Chromatogr A 1082:98–109CrossRefGoogle Scholar
  42. 42.
    Cariou R, Antignac J, Debrauwer L, Maume D, Fabrice M, Zalko D, Le Bizec B, Andre F (2006) J Chromatogr Sci 44:489–497Google Scholar
  43. 43.
    Basso E, Marotta E, Seraglia R, Tubaro M, Traldi P (2003) J Mass Spectrom 38:1113–1115CrossRefGoogle Scholar
  44. 44.
    Riu A, Zalko D, Debrauwer L (2006) Rapid Commun Mass Spectrom 20:2133–2142CrossRefGoogle Scholar
  45. 45.
    Short LC, Cai S, Syage JA (2007) J Am Soc Mass Spectrom 18:589–599CrossRefGoogle Scholar
  46. 46.
    Robb DB, Blades MW (2005) J Am Soc Mass Spectrom 16:1275–1290CrossRefGoogle Scholar
  47. 47.
    Kauppila TJ, Kotiaho T, Kostiainen R, Bruins AP (2004) J Am Soc Mass Spectrom 15:203–211CrossRefGoogle Scholar
  48. 48.
    Gómara B, Herrero L, González MJ (2007) Anal Chim Acta 597:121–128CrossRefGoogle Scholar
  49. 49.
    Stapleton H, Keller JM, Schantz MM, Kucklick JR, Leigh SD, Wise SA (2007) Anal Bioanal Chem 387:2365–2379CrossRefGoogle Scholar
  50. 50.
    De Boer J, Cofino WP (2002) Chemosphere 46:625–633CrossRefGoogle Scholar
  51. 51.
    Thomsen C, Leknes H, Lundanes E, Becher G (2001) J Chromatogr A 923:299–304CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  1. 1.Department of ChemistryVillanova UniversityVillanovaUSA

Personalised recommendations