Method of determining of polybrominated diphenyl ethers in fish and fish products by the method of liquid chromatography

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O.N. Timofeeva, I.S. Grinkevich, O.V. Shulyakovskaya


RUE “Scientific practical center of hygiene”, 8 Academicheskaya St., Minsk, 220012, Belarus


The aim of the work was to develop a methodology for determining of polybrominated diphenyl ethers (PBDE) in fish and fish products for the control of impurities content in the food and environmental objects in general. The conditions of chromatography (temperature conditions, the impact of the speed and magnitude of dividing of the gas-carrier stream using a HP-1 capillary columns, the DB-5, HP-50 +, DB-1;) and lipids destructive and non-destructive cleaning methods of extract during the determination of PBDEs. The method of determination of 2,2,4,4-Tetrabromodiphenyl ether (BDE-47), 2,2,4,4,5-pentabromodiphenyl ether (BDE-99) and decabromodiphenyl ether (BDE-209) in fish and fish products by the liquid chromatography with electron detector was suggested. The method of PBDE is based on the extraction of samples with hexane-acetone (3:1), purification of the extract with concentrated sulfuric acid (phase ratio hexane-sulfuric acid – 5:1). The second purification step is carried out by using solid phase extraction cartridges «SiOH-H2SO4/SA» and hexane as the eluent. Gas chromatographic analysis of the determination of BDE-47 and BDE-99 is carried out on low-polar capillary column DB-5 (30 m x0.25 mm x0.25 mum) with the programming of the column temperature. In determining the BDE-209 a DB-1 nonpolar capillary column was used (15 m x 0.25 mm x 0.1 mum) with the column temperature programming.

Calculation of the content of BDE-47 and BDE-99 is carried out with the internal standard (2,2, 3,4,4-pentabromodiphenyl ether (BDE-85)), BDE-209 by absolute calibration. In determining the BDE-209 the calibration matrix was used. The range of concentrations of the calibration solutions for the determination of BDE-47 and BDE-99 is 0.005–0.05 g/cm 3 , for BDE-209 0.05–0.3 g/cm 3 . The technique allows the measurement of BDE-47 and BDE-99 in the range of 0.0002–0.05 mg/kg of the product concerned; BDE-209 – in the range of 0.002–0.3 mg/kg. The metrological characteristics of the method were calculated.

polybrominated diphenyl ethers, 2,2,4,4-Tetrabromodiphenyl ether, 2,2,4,4,5-pentabromodiphenyl ether, decabromodiphenyl ether, fish, fish products, gas-liquid chromatography, electron capture detector
Timofeeva O.N., Grinkevich I.S., Shulyakovskaya O.V. Method of determining of polybrominated diphenyl ethers in fish and fish products by the method of liquid chromatography. Health Risk Analysis. 2016, no. 3, pp. 70–79. DOI: 10.21668/health.risk/2016.3.08.eng
  1. Korenman I.M. Jekstrakcija v analize organicheskih veshhestv [Extraction in the analysis of organic sub-stances]. Moscow: Himija, 1970, 200 p. (in Russian).
  2. Bayen S., Lee H. K., Obbard J. P. Determination of polybrominated diphenyl ethers in marine biological tissues using microwave-assisted extraction. J. of Chromatography A, 2004, no. 1035, pp. 291–294.
  3. Covaci A., Voorspoels S., de Boer J. Determination of brominated flame retardants, with emphasis on po-lybrominated diphenyl ethers (PBDEs) in environmental and human samples. Environment International, 2003, no. 29, pp. 735–756.
  4. Martínez A., Ramil M., Montes R., Hernanz D., Rubi E., Rodriguez I., Cela R. Torrijos. 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. of Chromatography A, 2005, no. 1072, pp. 83–91.
  5. Eljarrat E., de la Cal A., Barceló D. Potential chlorinated and brominated interferences on the polybromi-nated diphenyl ether determinations by gas chromatography – mass spectrometry. J. of Chromatography A, 2003, no. 1008, pp. 181–192.
  6. Rogers E., Petreas M., Park J.-S., Zhao G., Charles M. J. Evaluation of for capillary columns for the analy-sis of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in human serum for epidemiologic studies. J. of Chromatography B, 2004, no. 813, pp. 269–285.
  7. Gensler M., Honikel K.O. Development and evaluation of a methods for the determination of polybromi-nated diphenylethers (PBDE) in food and feed. Tagung Brominated Flame Retardants 2007, Amsterdam, Nieder-lande, 24, 27.04.2007.
  8. Hellstrom T. Brominated flame retardants (PBDE and PBB) in sludge – a problem? VAV, The Svedish Wa-ter and Wastewater Association: Report no. M 113 (eng), 2000, 31 p.
  9. Johnson A., Olson N. Analysis and occurrence of polybrominated diphenyl ethers in Washington State freshwater fish. Arch. Environ. Contam. Toxicol, 2001, no. 41, pp. 339–344.
  10. Król S., Zabiegała B., Namieśnik J. PBDEs in environmental samples: Sampling and analysis. Talanta, 2012, no. 93, pp. 1–17.
  11. Liquori L., Bjørsvik H.R. Extraction, isolation, and purification of analytes from samples of marine ori-gin – A multivariate task. J. of Chromatography B, 2012, no. 910, pp. 46–53.
  12. Bocio A., Llobet J.M., Domingo J.L., Corbella J., Teixido A., Casas C. Polybrominated diphenyl ethers (PBDEs) in foodstuffs: human exposure through the diet. J. Agric. Food Chem, 2003, no. 51, pp. 3191–3195.
  13. Lind Y., Darnerud P.O., Atuma S., Aune M., Becker W., Bjerselius R., Cnattingius S., Glynn A. Poly-brominated diphenyl ethers in breast milk from Uppsala County, Sweden. Environmental Research, 2003, no. 93, pp. 186–194.
  14. Park H.-M., Hong S.-M., Augustin-Camacho M.R., Dirwono W., Lee K.-B. Pressurized liquid extraction for the simultaneous analysis of polychlorinated biphenyls and polybrominated diphenyl ethers from soil by GC-TOF-MS detection. J. of Chromatographic Science, 2009, no. 47, pp. 681–688.
  15. Kolic T.M., Shen L., MacPherson K., Fayez L., Gobran T., Helm P.A., Marvin C.H., Arsenault G., Reiner E.J. The analysis of halogenated flame retardants by GC-HRMS in environmental samples. Journal of Chromato-graphic Science, 2009, no. 47, pp. 83–91.
  16. Toxicological profile for polybrominated biphenyls and polybrominated diphenyl ethers – U.S. Department of health and human services. Public health service. Agency for toxic substances and disease registry, 2004, 619 p.

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