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Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction

Abstract

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.

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References

  1. Abb, M., Stahl, B., & Lorenz, W. (2011). Analysis of brominated flame retardants in house dust. Chemosphere, 85(11), 1657–1663.

    CAS  Article  Google Scholar 

  2. Abdallah, M. A.-E., & Harrad, S. (2009). Personal exposure to HBCDs and its degradation products via ingestion of indoor dust. Environment International, 35(6), 870–876.

    CAS  Article  Google Scholar 

  3. Abdallah, M. A.-E., Ibarra, C., Neels, H., Harrad, S., & Covaci, A. (2008). Comparative evaluation of liquid chromatography-mass spectrometry versus gas chromatography-mass spectrometry for the determination of hexabromocyclododecanes and their degradation products in indoor dust. Journal of Chromatography A, 1190(1–2), 333–341.

    Article  Google Scholar 

  4. An, T., Zhang, D., Li, G., Mai, B., & Fu, J. (2011). On-site and off-site atmospheric PBDEs in an electronic dismantling workshop in south China: Gas-particle partitioning and human exposure assessment. Environmental Pollution, 159(12), 3529–3535.

    CAS  Article  Google Scholar 

  5. Bai, Y. M., Sun, P., Zhang, M. Q., Zhao, G., Yang, Z. Y., & Shao, Y. H. (2003). Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface. Electrochimica Acta, 48(23), 3447–3453.

    CAS  Article  Google Scholar 

  6. Birnbaum, L. S., & Staskal, D. F. (2004). Brominated flame retardants: Cause for concern? Environmental Health Perspectives, 112(1), 9–17.

    CAS  Article  Google Scholar 

  7. Chu, S., Haffner, G. D., & Letcher, R. J. (2005). Simultaneous determination of tetrabromobisphenol A, tetrachlorobisphenol A, bisphenol A and other halogenated analogues in sediment and sludge by high performance liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography A, 1097(1–2), 25–32.

    CAS  Article  Google Scholar 

  8. Covaci, A., Voorspoels, S., Abdallah, M. A.-E., Geens, T., Harrad, S., & Law, R. J. (2009). Analytical and environmental aspects of the flame retardant tetrabromobisphenol-A and its derivatives. Journal of Chromatography A, 1216(3), 346–363.

    CAS  Article  Google Scholar 

  9. Covaci, A., Voorspoels, S., & de Boer, J. (2003). Determination of brominated flame retardants, with emphasis on polybrominated diphenyl ethers (PBDEs) in environmental and human samples—a review. Environment International, 29(6), 735–756.

    CAS  Article  Google Scholar 

  10. Covaci, A., Voorspoels, S., Ramos, L., Neels, H., & Blust, R. (2007). Recent developments in the analysis of brominated flame retardants and brominated natural compounds. Journal of Chromatography A, 1153(1–2), 145–171.

    CAS  Article  Google Scholar 

  11. Davis, J. W., Gonsior, S. J., Markham, D. A., Friederich, U., Hunziker, R. W., & Ariano, J. M. (2006). Biodegradation and product identification of [C-14]hexabromocyclododecane in wastewater sludge and freshwater aquatic sediment. Environmental Science and Technology, 40(17), 5395–5401.

    CAS  Article  Google Scholar 

  12. de Wit, C. A. (2002). An overview of brominated flame retardants in the environment. Chemosphere, 46(5), 583–624.

    Article  Google Scholar 

  13. Dodder, N. G., Strandberg, B., & Hites, R. A. (2002). Concentrations and spatial variations of polybrominated diphenyl ethers and several organochlorine compounds in fishes from the northeastern United States. Environmental Science and Technology, 36(2), 146–151.

    CAS  Article  Google Scholar 

  14. Evenset, A., Christensen, G. N., Carroll, J., Zaborska, A., Berger, U., Herzke, D., et al. (2007). Historical trends in persistent organic pollutants and metals recorded in sediment from Lake Ellasjoen, Bjornoya, Norwegian Arctic. Environmental Pollution, 146(1), 196–205.

    CAS  Article  Google Scholar 

  15. Gao, S. T., Wang, J. Z., Yu, Z. Q., Guo, Q. R., Sheng, G. Y., & Fu, J. M. (2011). Hexabromocyclododecanes in surface soils from e-waste recycling areas and industrial areas in South China: Concentrations, diastereoisomer- and enantiomer-specific profiles, and inventory. Environmental Science and Technology, 45(6), 2093–2099.

    CAS  Article  Google Scholar 

  16. Gerecke, A. C., Giger, W., Hartmann, P. C., Heeb, N. V., Kohler, H.-P. E., Schmid, P., et al. (2006). Anaerobic degradation of brominated flame retardants in sewage sludge. Chemosphere, 64(2), 311–317.

    CAS  Article  Google Scholar 

  17. Han, C., Chen, X., Xie, W., Zhu, Z., Liu, C., Chen, F., et al. (2010). Determination of hexabromocyclododecane diastereoisomers in Sargassum fusiforme and comparison of the extraction efficiency of ultrasonication, microwave-assisted extraction, Soxhlet extraction and pressurised liquid extraction. Journal of Separation Science, 33(21), 3319–3325.

    CAS  Article  Google Scholar 

  18. Haukås, M., Hylland, K., Berge, J. A., Nygård, T., & Mariussen, E. (2009). Spatial diastereomer patterns of hexabromocyclododecane (HBCD) in a Norwegian fjord. Science of the Total Environment, 407(22), 5907–5913.

    Article  Google Scholar 

  19. Hiebl, J., & Vetter, W. (2007). Detection of hexabromocyclododecane and its metabolite pentabromocyclododecene in chicken egg and fish from the official food control. Journal of Agricultural and Food Chemistry, 55(9), 3319–3324.

    CAS  Article  Google Scholar 

  20. Hoh, E., & Hites, R. A. (2005). Brominated flame retardants in the atmosphere of the east-central United States. Environmental Science and Technology, 39(20), 7794–7802.

    CAS  Article  Google Scholar 

  21. Hyotylainen, T., & Hartonen, K. (2002). Determination of brominated flame retardants in environmental samples. TrAC Trends in Analytical Chemistry, 21(1), 13–30.

    CAS  Article  Google Scholar 

  22. Johari, G. P. (1968). Dielectric constants, densities, and viscosities of acetone-1-propanol and acetone-n-hexane mixtures at 25 °C. Journal of Chemical and Engineering Data, 13(4), 541–543.

    CAS  Article  Google Scholar 

  23. Johnson-Restrepo, B., Adams, D. H., & Kannan, K. (2008). Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) in tissues of humans, dolphins, and sharks from the United States. Chemosphere, 70(11), 1935–1944.

    CAS  Article  Google Scholar 

  24. Kajiwara, N., Noma, Y., & Takigami, H. (2011). Brominated and organophosphate flame retardants in selected consumer products on the Japanese market in 2008. Journal of Hazardous Materials, 192(3), 1250–1259.

    CAS  Article  Google Scholar 

  25. Kemmlein, S., Herzke, D., & Law, R. J. (2009). Brominated flame retardants in the European chemicals policy of REACH-Regulation and determination in materials. Journal of Chromatography A, 1216(3), 320–333.

    CAS  Article  Google Scholar 

  26. Law, R. J., Bersuder, P., Allchin, C. R., & Barry, J. (2006). Levels of the flame retardants hexabromocyclododecane and tetrabromobisphenol A in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the UK, with evidence for an increase in HBCD concentrations in recent years. Environmental Science and Technology, 40(7), 2177–2183.

    CAS  Article  Google Scholar 

  27. Law, R. J., Bersuder, P., Barry, J., Wilford, B. H., Allchin, C. R., & Jepson, P. D. (2008). A significant downturn in levels of hexabromocyclododecane in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the UK: An update to 2006. Environmental Science and Technology, 42(24), 9104–9109.

    CAS  Article  Google Scholar 

  28. Mechlińska, A., Wolska, L., & Namiesńik, J. (2012). Removal of sulfur from a solvent extract. TrAC Trends in Analytical Chemistry, 31, 129–133.

    Article  Google Scholar 

  29. Meng, X. Z., Duan, Y. P., Yang, C., Pan, Z. Y., Wen, Z. H., & Chen, L. (2011). Occurrence, sources, and inventory of hexabromocyclododecanes (HBCDs) in soils from Chongming Island, the Yangtze River Delta (YRD). Chemosphere, 82(5), 725–731.

    CAS  Article  Google Scholar 

  30. Morris, S., Allchin, C. R., Zegers, B. N., Haftka, J. H., Boon, J. P., Belpaire, C., et al. (2004). Distribution and fate of HBCD and TBBPA brominated flame retardants in north sea estuaries and aquatic food webs. Environmental Science and Technology, 38(21), 5497–5504.

    CAS  Article  Google Scholar 

  31. Morris, S., Bersuder, P., Allchin, C. R., Zegers, B., Boon, J. P., Leonards, P. E. G., et al. (2006). Determination of the brominated flame retardant, hexabromocyclodocane, in sediments and biota by liquid chromatography-electrospray ionisation mass spectrometry. TrAC Trends in Analytical Chemistry, 25(4), 343–349.

    CAS  Article  Google Scholar 

  32. Pulkrabová, J., Hajšlová, J., Poustka, J., & Kazda, R. (2007). Fish as biomonitors of polybrominated diphenyl ethers and hexabromocyclododecane in Czech aquatic ecosystems: pollution of the Elbe river basin. Environmental Health Perspectives, 115(Suppl 1), 28–34.

    Article  Google Scholar 

  33. Sellström, U., & Jansson, B. (1995). Analysis of tetrabromobisphenol A in a product and environmental-samples. Chemosphere, 31(4), 3085–3092.

    Article  Google Scholar 

  34. Strandberg, B., Dodder, N. G., Basu, I., & Hites, R. A. (2001). Concentrations and spatial variations of polybrominated diphenyl ethers and other organohalogen compounds in Great Lakes air. Environmental Science and Technology, 35(35), 1078–1083.

    CAS  Article  Google Scholar 

  35. Takigami, H., Suzuki, G., Hirai, Y., & Sakai, S. (2009). Brominated flame retardants and other polyhalogenated compounds in indoor air and dust from two houses in Japan. Chemosphere, 76(2), 270–277.

    CAS  Article  Google Scholar 

  36. van Leeuwen, S. P. J., & de Boer, J. (2008). Advances in the gas chromatographic determination of persistent organic pollutants in the aquatic environment. Journal of Chromatography A, 1186(1–2), 161–182.

    Article  Google Scholar 

  37. Wu, J. P., Luo, X. J., Zhang, Y., Luo, Y., Chen, S. J., Mai, B. X., et al. (2008). Bioaccumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in wild aquatic species from an electronic waste (e-waste) recycling site in South China. Environment International, 34(8), 1109–1113.

    CAS  Article  Google Scholar 

  38. Xiong, J., An, T., Zhang, C., & Li, G. (2015). Pollution profiles and risk assessment of PBDEs and phenolic brominated flame retardants in water environments within a typical electronic waste dismantling region. Environmental Geochemistry and Health, 37(3), 457–473.

    CAS  Article  Google Scholar 

  39. Xiong, J., Li, G., An, T., Zhang, C., & Wei, C. (2016). Emission patterns and risk assessment of polybrominated diphenyl ethers and bromophenols in water and sediments from the Beijiang River, South China. Environmental Pollution, 219, 596–603.

    CAS  Article  Google Scholar 

  40. Zhang, X. L., Luo, X. J., Chen, S. J., Wu, J. P., & Mai, B. X. (2009). Spatial distribution and vertical profile of polybrominated diphenyl ethers, tetrabromobisphenol A, and decabromodiphenylethane in river sediment from an industrialized region of South China. Environmental Pollution, 157(6), 1917–1923.

    CAS  Article  Google Scholar 

  41. Zhong, Y., Peng, P. A., & Huang, W. L. (2012). Transformation of tetrabromobisphenol A in the presence of different solvents and metals. Chemosphere, 87(10), 1141–1148.

    CAS  Article  Google Scholar 

  42. Zhong, Y., Peng, P. A., Yu, Z. Q., & Deng, H. P. (2010). Effects of metals on the transformation of hexabromocyclododecane (HBCD) in solvents: Implications for solvent-based recycling of brominated flame retardants. Chemosphere, 81(1), 72–78.

    CAS  Article  Google Scholar 

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Acknowledgements

This study was supported financially by National Natural Science Foundation of China (Nos. 41120134006 and 41473107). This is contribution No. IS-2392 from GIGCAS.

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Correspondence to Yin Zhong.

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Zhong, Y., Li, D., Zhu, X. et al. Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction. Environ Geochem Health 40, 1955–1964 (2018). https://doi.org/10.1007/s10653-017-9979-5

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Keywords

  • DecaBDE
  • TBBPA
  • HBCD
  • Soxhlet extraction
  • Acetone