Analytical and Bioanalytical Chemistry

, Volume 396, Issue 2, pp 865–875 | Cite as

Development of analytical procedures for trace-level determination of polybrominated diphenyl ethers and tetrabromobisphenol A in river water and sediment

  • Pierre LabadieEmail author
  • Khawla Tlili
  • Fabrice Alliot
  • Catherine Bourges
  • Annie Desportes
  • Marc Chevreuil
Original Paper


The aim of this work was to develop procedures for the simultaneous determination of selected brominated flame retardants (BFRs) in river water and in river bed sediment. The target analytes were polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA). To determine dissolved BFRs, a novel mixed-mode solid-phase extraction procedure was developed by combining a hydrophobic sorbent (C18) with a silica-based anion exchange sorbent, so as to overcome the negative artefact induced by dissolved organic carbon. Extraction recoveries exceeded 73% for most analytes, except for BDE-183 and BDE-209 (57%). As regards suspended sediment and river bed sediment, extraction was carried out by means of ultrasonication (recoveries: 73–94%). These procedures, combined to gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS), enabled the determination of BFRs at trace level: 3-160 pg L−1 in river water, 5–145 pg g−1 in bed sediment. These methods were applied to the determination of PBDEs and TBBPA in a suburban river (near Paris, France). PBDEs were systematically detected in the water column (ΣBDEs, 2,300–4,300 pg L−1); they partitioned between the dissolved and particulate phases and BDE-209 was the dominant congener, followed by BDE-99 and BDE-47. TBBPA was detected in the dissolved phase only (<35–68 pg L−1). All selected BFRs were ubiquitous in bed sediments and levels ranged from 3,100 to 15,100 pg g−1 and from 70 to 280 pg g−1 (dry weight), for ΣBDEs and TBBPA, respectively.


Polybrominated diphenyl ethers Tetrabromobisphenol A Solid-phase extraction River water Sediment 



This work was funded by the Piren Seine programme ( The authors also wish to acknowledge the Ile-de-France Regional Council for providing PhD funding for K. Tlili (R2DS grant). We are grateful to Ms J. Martin and Dr J. Garnier (UMR 7619 Sisyphe, Paris) who carried out DOC determination. Reference sediment BROC-02 was kindly provided by Dr M. Lohman and P. Korytar (Wageningen UR, The Netherlands).


  1. 1.
    de Wit C (2002) Chemosphere 46:583–624CrossRefGoogle Scholar
  2. 2.
    Covaci A, Voorspoels S, Abou-Elwaf Abdallah M, Geens T, Harrad S, Law RJ (2009) J Chrom A 1216:346–363CrossRefGoogle Scholar
  3. 3.
    Kitamura S, Jinno N, Ohta S, Kuroki H, Fujimoto N (2002) Biophys Res Commun 293:554–559CrossRefGoogle Scholar
  4. 4.
    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
  5. 5.
    Suzuki S, Hasegawa A (2006) Anal Sci 22:469–474CrossRefGoogle Scholar
  6. 6.
    Sambe H, Hoshina K, Hosoya K, Haginaka J (2006) J Chrom A 1134:16–23CrossRefGoogle Scholar
  7. 7.
    Alaee M, Arias P, Sjödin A, Bergman Å (2003) Environ Internat 29:683–689CrossRefGoogle Scholar
  8. 8.
    Law R, Herzke D, Harrad S, Morris S, Bersuder P, Allchin CR (2008) Chemosphere 73:223–241CrossRefGoogle Scholar
  9. 9.
    Decision No 2455/2001/EC of the European Parliament and of the Council of 20, November 2001, establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC. Official Journal of the European Communities, 15.12.2001, L 331/2Google Scholar
  10. 10.
    Cetin B, Odabasi M (2007) Environ Sci Technol 41:785–791CrossRefGoogle Scholar
  11. 11.
    Booij K, Zegers BN, Boon JP (2002) Chemosphere 46:683–688CrossRefGoogle Scholar
  12. 12.
    Carroll J, Savinov V, Savinova T, Dahle S, McCrea R, Muir DCG (2008) Environ Sci Technol 42:69–74CrossRefGoogle Scholar
  13. 13.
    Wurl O, Lam PKS, Obbard JP (2006) Chemosphere 65:1660–1666CrossRefGoogle Scholar
  14. 14.
    Guan YF, Wang JZ, Ni HG, Zeng EY (2007) Environ Sci Technol 41:6007–6013CrossRefGoogle Scholar
  15. 15.
    Luo X, Yu M, Mai B, Chen S (2008) Chin Sci Bull 53:493–500CrossRefGoogle Scholar
  16. 16.
    Oros DR, Hoover D, Rodigari F, Crane D, Sericano J (2005) Environ Sci Technol 39:33–41CrossRefGoogle Scholar
  17. 17.
    Streets SS, Henderson SA, Stoner AD, Carlson DL, Simicik MF, Swackhamer DL (2006) Environ Sci Technol 40:7263–7269CrossRefGoogle Scholar
  18. 18.
    Ikonomou MG, Rayne S, Fischer M, Fernandez MP, Cretney W (2002) Chemosphere 46:649–66CrossRefGoogle Scholar
  19. 19.
    Covaci Q, Voorspoels S, de Boer J (2003) Environ Int 29:735–756CrossRefGoogle Scholar
  20. 20.
    Saint-Louis R, Pelletier E (2004) Analyst 129:724–730CrossRefGoogle Scholar
  21. 21.
    Liu X, Li J, Zhao Z, Zhang W, Lin K, Huang C, Wang X (2009) J Chrom A 1216:2220–2226CrossRefGoogle Scholar
  22. 22.
    Tian MK, Feng XL (2008) Chin J Chem 26:1251–1256CrossRefGoogle Scholar
  23. 23.
    Polo M, Llompart M, Garcia-Jares C, Gomez-Noya G, Bollain MH, Cela R (2006) J Chrom A 1124:11–21CrossRefGoogle Scholar
  24. 24.
    de la Cal A, Kuster M, Lopez de Alda M, Eljarrat E, Barceló D (2008) Talanta 76:327–332CrossRefGoogle Scholar
  25. 25.
    Li M, Lei N, Gong C, Yu Y, Lam K, Lam M, Yu H, Lam P (2009) Anal Chim Acta 633:197–203CrossRefGoogle Scholar
  26. 26.
    Blanco E, Casais MC, Mejuto MC, Cela R (2005) J Chrom A 1071:205–211CrossRefGoogle Scholar
  27. 27.
    Font G, Mañies J, Moltó JC, Picó Y (1996) J Chrom A 733:449–471CrossRefGoogle Scholar
  28. 28.
    Li N, Lee HK (2000) Anal Chem 72:5272–5279CrossRefGoogle Scholar
  29. 29.
    Otaka H, Shimono H, Hashimoto S (2004) Anal Bioanal Chem 378:1854–1860CrossRefGoogle Scholar
  30. 30.
    Lepom P, Brown B, Hanke G, Loos R, Quevauviller P, Wollgast J (2009) J Chrom A 1216:302–315CrossRefGoogle Scholar
  31. 31.
    van Leeuwen SPJ, Van Cleuvenbergen R, Abalos M, Pasini AL, Eriksson U, Cleemann M, Hajslova J, de Boer J (2006) TrAC 25:397–409Google Scholar
  32. 32.
    Bercaru O, Ulberth F, Emons H, Vandecasteele C (2006) Anal Bioanal Chem 384:1207–1213CrossRefGoogle Scholar
  33. 33.
    Xie Z, Ebinghaus R, Lohmann R, Heemken O, Caba A, Püttmann W (2007) Anal Chim Acta 584:333–342CrossRefGoogle Scholar
  34. 34.
    Currie LA (1999) Anal Chim Acta 391:127–134CrossRefGoogle Scholar
  35. 35.
    WHO/IPCS, Environmental Health Criteria 172. Tetrabromobisphenol A and Derivatives, World Health Organization, Geneva, Switzerland (1995)Google Scholar
  36. 36.
    Li N, Lee HK (2001) J Chrom A 921:255–263CrossRefGoogle Scholar
  37. 37.
    Gómez-Belínchón JI, Grimalt JO, Albaigés J (1988) Environ Sci Technol 22:677–685CrossRefGoogle Scholar
  38. 38.
    Bonifazi R, Pierini E, Bruner E (1997) Chroma 44:595–600CrossRefGoogle Scholar
  39. 39.
    Jano P (2003) J Chrom A 983:1–18CrossRefGoogle Scholar
  40. 40.
    Kuramochi H, Kawamoto K, Sakai SI (2008) J Environ Monit 10:206–210CrossRefGoogle Scholar
  41. 41.
    Salgado-Petinal C, Llompart M, García-Jares C, García-Chao M, Cela R (2006) J Chrom A 1124:139–147CrossRefGoogle Scholar
  42. 42.
    Guan YF, Sojinu OSS, Li SM, Zeng EY (2009) Environ Pol 157:2166–2172CrossRefGoogle Scholar
  43. 43.
    Zhang XL, Luo XJ, Chen SJ, Wu JP, Mai BX (2009) Environ Pol 157:1917–1923CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Pierre Labadie
    • 1
    Email author
  • Khawla Tlili
    • 1
  • Fabrice Alliot
    • 2
  • Catherine Bourges
    • 2
  • Annie Desportes
    • 2
  • Marc Chevreuil
    • 2
  1. 1.UMR 7619 Sisyphe, CNRS/UPMCUniversité Pierre et Marie CurieParis Cedex 05France
  2. 2.Laboratoire Hydrologie et Environnement EPHE, UMR 7619 Sisyphe, CNRS/UPMCUniversité Pierre et Marie CurieParis Cedex 05France

Personalised recommendations