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Extraction and determination of polybrominated diphenyl ethers in water and urine samples using solidified floating organic drop microextraction along with high performance liquid chromatography

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Abstract

We have developed a method, termed solidification of floating organic drop microextraction (SFOME), for the extraction of polybrominated diphenyl ethers (PBDEs) in water and urine samples, this followed by quantification via HPLC. This method requires very small quantities of organic solvent consumption. It is based on exposing a floating solidified drop of an organic solvent on the surface of aqueous solution in a sealed vial. The organic drop is easily collected with a spatula, molten (at ambient temperature), and then submitted to HPLC. Experimental parameters including extraction solvent and its volume, disperser solvent and its volume, extraction time, ionic strength, stirring speed and extraction temperature were optimized. The enrichment factors of analytes are in the range from 921 to 1,462, and acceptable extraction recoveries (92%–118%) are obtained. The dynamic linear range for five PBDE congeners is in the range of 0.5–75 μg.L−1 and from 5 to 500 μg.L−1 for BDE 209. The correlation coefficients range from 0.9960 to 0.9999. The limits of detection (at S/N = 3) for PBDE congeners vary between 0.01 and 0.04 μg.L−1. This method has been successfully applied to detecting PBDEs in two environmental waters and in human urine.

Under optimized conditions, the enrichment factors of PBDEs by solidification of floating organic drop microextraction were from 921 to 1,462, and extraction recoveries (92%–118%) were obtained. The correlation coefficients ranged from 0.9960 to 0.9999. The limits of detection (at S/N = 3) for PBDE congeners varied between 0.01 and 0.04 μg.L−1.

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References

  1. Dufault C, Poles G, Driscoll LL (2005) Brief postnatal PBDE exposure alters learning and the cholinergic modulation of attention in rats. Toxicol Sci 88:172–180

    Article  CAS  Google Scholar 

  2. Kodavanti PR, Ward TR, Ludewig G, Robertson LW, Birnbaum LS (2005) Polybrominated diphenyl ether (PBDE) effects in rat neuronal cultures: 14C-PBDE accumulation, biological effects, and structure-activity relationships. Toxicol Sci 88:181–192

    Article  CAS  Google Scholar 

  3. Viberg H, Fredriksson A, Eriksson P (2005) Deranged spontaneous behaviour and decrease in cholinergic muscarinic receptors in hippocampus in the adult rat, after neonatal exposure to the brominated flame-retardant, 2,2′,4,4′,5-pentabromodiphenyl ether (PBDE 99). Environ Toxicol Pharmacol 20:283–288

    Article  CAS  Google Scholar 

  4. Fernie KJ, Mayne G, Shutt JL, Pekarik C, Grasman KA, Letcher RJ, Drouillard K (2005) Evidence of immunomodulation in nestling American kestrels (Falco sparverius) exposed to environmentally relevant PBDEs. Environ Pollut 138:485–493

    Article  CAS  Google Scholar 

  5. Nakari T, Pessala P (2005) In vitro estrogenicity of polybrominated flame retardants. Aquat Toxicol 74:272–279

    Article  CAS  Google Scholar 

  6. Tseng LH, Li MH, Tsai SS, Lee CW, Pan MH, Yao WJ, Hsu PC (2008) Developmental exposure to decabromodiphenyl ether (PBDE 209): effects on thyroid hormone and hepatic enzyme activity in male mouse offspring. Chemosphere 70:640–647

    Article  CAS  Google Scholar 

  7. Costa LG, Giordano G (2007) Developmental neurotoxicity of polybrominated diphenyl ether (PBDE) flame retardants. Neurotoxicology 28:1047–1067

    Article  CAS  Google Scholar 

  8. KemmLein S, Herzke D, Law RJ (2003) BFR-governmental testing programme. Environ Int 29:781–792

    Article  CAS  Google Scholar 

  9. Hyötyläinen T, Hartonen K (2002) Determination of brominated flame retardants in environmental samples. Trends Anal Chem 21:13–30

    Article  Google Scholar 

  10. Cheung KC, Poon BH, Lan CY, Wong MH (2003) Assessment of metal and nutrient concentrations in river water and sediment collected from the cities in the Pearl River Delta, South China. Chemosphere 52:1431–1440

    Article  CAS  Google Scholar 

  11. Zheng GJ, Martin M, Richardson BJ, Yu H, Liu Y, Zhou C, Li J, Hu G, Lam MH, Lam PK (2004) Concentrations of polybrominated diphenyl ethers (PBDEs) in Pearl River Delta sediments. Mar Pollut Bull 49:514–524

    Article  Google Scholar 

  12. Li Y, Hu J, Liu X, Fu L, Zhang X, Wang X (2008) Dispersive liquid-liquid microextraction followed by reversed phase HPLC for the determination of decabrominated diphenyl ether in natural water. J Sep Sci 31:2371–2376

    Article  CAS  Google Scholar 

  13. Pan J, Yang YL, Xu Q, Chen DZ, Xi DL (2007) PCBs, PCNs and PBDEs in sediments and mussels from Qingdao coastal sea in the frame of current circulations and influence of sewage sludge. Chemosphere 66:1971–1982

    Article  CAS  Google Scholar 

  14. Cai ZW, Jiang GB (2006) Determination of polybrominated diphenyl ethers in soil from e-waste recycling site. Talanta 70:88–90

    Article  CAS  Google Scholar 

  15. Päpke O, Fürst P, Herrmann T (2004) Determination of polybrominated diphenylethers (PBDEs) in biological tissues with special emphasis on QC/QA measures. Talanta 63:1203–1211

    Article  Google Scholar 

  16. Akutsu K, Obana H, Okihashi M, Kitagawa M, Nakazawa H, Matsuki Y, Makino T, Oda H, Hori S (2001) GC/MS analysis of polybrominated diphenyl ethers in fish collected from the inland sea of Seto, Japan. Chemosphere 44:1325–1333

    Article  CAS  Google Scholar 

  17. She J, Holden A, Sharp M, Tanner M, Williams-Derry C, Hooper K (2007) Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk from the Pacific Northwest. Chemosphere 67:S307–S317

    Article  CAS  Google Scholar 

  18. Pirard C, De Pauw E (2007) Absorption, disposition and excretion of polybrominated diphenyl ethers (PBDEs) in chicken. Chemosphere 66:320–325

    Article  CAS  Google Scholar 

  19. Serôdio P, Cabral MS, Nogueira JM (2007) Use of experimental design in the optimization of stir bar sorptive extraction for the determination of polybrominated diphenyl ethers in environmental matrices. J Chrom A 1141:259–270

    Article  Google Scholar 

  20. Prieto A, Zuloaga O, Usobiaga A, Etxebarria N, Fernández LA (2008) Use of experimental design in the optimisation of stir bar sorptive extraction followed by thermal desorption for the determination of brominated flame retardants in water samples. Anal Bioanal Chem 390:739–748

    Article  CAS  Google Scholar 

  21. Martínez A, Ramil M, Montes R, Hernanz D, Rubí E, Rodríguez I, Cela Torrijos R (2004) Development of a matrix solid-phase dispersion method for the screening of polybrominated diphenyl ethers and polychlorinated biphenyls in biota samples using gas chromatography with electron-capture detection. J Chrom A 1072:83–91

    Article  Google Scholar 

  22. Wang JX, Jiang DQ, Gu ZY, Yan XP (2006) Multiwalled carbon nanotubes coated fibers for solid-phase microextraction of polybrominated diphenyl ethers in water and milk samples before gas chromatography with electron-capture detection. J Chrom A 1137:8–14

    Article  CAS  Google Scholar 

  23. Bayen S, Lee HK, Obbard JP (2004) Determination of polybrominated diphenyl ethers in marine biological tissues using microwave-assisted extraction. J Chrom A 1035:291–294

    Article  CAS  Google Scholar 

  24. Li YY, Wei GH, Hu J, Liu XJ, Zhao XN, Wang XD (2008) Dispersive liquid–liquid microextraction followed by reversed phase-high performance liquid chromatography for the determination of polybrominated diphenyl ethers at trace levels in landfill leachate and environmental water samples. Anal Chim Acta 615:96–103

    Article  CAS  Google Scholar 

  25. Rezaei F, Bidari A, Birjandi AP, Milani Hosseini MR, Assadi Y (2008) Development of a dispersive liquid-liquid microextraction method for the determination of polychlorinated biphenyls in water. J Hazard Mater 158:621–627

    Article  CAS  Google Scholar 

  26. Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S (2006) Determination of organic compounds in water using dispersive liquid-liquid microextraction. J Chrom A 1116:1–9

    Article  CAS  Google Scholar 

  27. Berijani S, Assadi Y, Anbia M, Milani Hosseini MR, Aghaee E (2006) Dispersive liquid-liquid microextraction combined with gas chromatography-flame photometric detection: very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. J Chrom A 1123:1–9

    Article  CAS  Google Scholar 

  28. Naseri MT, Hosseini MR, Assadi Y, Kiani A (2008) Rapid determination of lead in water samples by dispersive liquid-liquid microextraction coupled with electrothermal atomic absorption spectrometry. Talanta 75:56–62

    Article  CAS  Google Scholar 

  29. Shokoufi N, Shemirani F, Assadi Y (2007) Fiber optic-linear array detection spectrophoto- metry in combination with dispersive liquid-liquid microextraction for simultaneous preconcentration and determination of palladium and cobalt. Anal Chim Acta 597:349–356

    Article  CAS  Google Scholar 

  30. Lv LL, Xu H, Song D, Cui Y, Hu S, Zhang G (2010) Analysis of volatile aldehyde biomarkers in human blood by derivatization and dispersive liquid-liquid microextraction based on solidification of floating organic droplet method by high performance liquid chromatography. J Chrom A 1217:2365–2370

    Article  CAS  Google Scholar 

  31. Khalili Zanjani MR, Yamini Y, Shariati S, Jönsson JA (2007) A new liquid-phase microextraction method based on solidification of floating organic drop. Anal Chim Acta 585:286–293

    Article  CAS  Google Scholar 

  32. Khalili-Zanjani MR, Yamini Y, Yazdanfar N, Shariati S (2008) Extraction and determination of organophosphorus pesticides in water samples by a new liquid phase microextraction gas chromatography-flame photometric detection. Anal Chim Acta 606:202–208

    Article  CAS  Google Scholar 

  33. Chang C, Huang S (2010) Determination of the sterod hormone levels in water samples by dispersive liquid-liquid microextraction with solidification of a floating organic drop followed by high performance liquid chromatography. Anal Chim Acta 662:39–43

    Article  CAS  Google Scholar 

  34. Li YY, Wei GH, Wang XD (2007) Determination of decabromodiphenyl ether in water samples by single-drop microextraction and RP-HPLC. J Sep Sci 30:2698–2702

    Article  CAS  Google Scholar 

  35. Cortazar E, Zuloaga O, Sanz J, Raposo JC, Etxebarria N, Fernández LA (2002) Multisimplex optimization of the solid-phase microextraction gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and phthalates from water samples. J Chrom A 978:165–175

    Article  CAS  Google Scholar 

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Acknowledgements

This work was jointly funded by “Xinmiao Talent” Project of Zhejiang Province (2010R413061), Public Benefit Project of Zhejiang Province (2011C23112, 2011C37006), National Natural Science Foundation of China (21077079), Key Project of Wenzhou City (20082780125, Z090921421), and International Cooperation Project of Wenzhou Science and Technology Bureau (H20090079, H20100053, H20100054).

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Correspondence to Xuedong Wang or Huili Wang.

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Liu, H., Zhang, M., Wang, X. et al. Extraction and determination of polybrominated diphenyl ethers in water and urine samples using solidified floating organic drop microextraction along with high performance liquid chromatography. Microchim Acta 176, 303–309 (2012). https://doi.org/10.1007/s00604-011-0713-1

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  • DOI: https://doi.org/10.1007/s00604-011-0713-1

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