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High-performance thin-layer chromatography coupled with HPLC-DAD/HPLC-MS/MS for simultaneous determination of bisphenol A and nine brominated analogs in biological samples

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Abstract

Bisphenol A (BPA) and its brominated analogs exhibiting bioaccumulation potential, endocrine disruption, and reproductive toxicity have been worldwide detected in water, air, soil, and sediments. But few methods have been proposed for simultaneously determining a variety of these compounds in biological matrices, hindering the further study on their biological transformation/degradation and health risks. In this study, a simple, solvent-saving and sensitive method based on high-performance thin-layer chromatography (HPTLC) for sample pretreatment coupled with high-performance liquid chromatography-diode array detector (HPLC-DAD) (UV = 214 nm)/triple quadrupole mass spectrometry (MS/MS) was developed for determining BPA and its nine brominated analogs in biological samples. The method detection limits (MDLs) and method quantification limits (MQLs) for ten BPA analogs ranged from 0.8 to 685.7 ng g−1 dw (S/N = 3) and 2.7 to 2285.7 ng g−1 dw (S/N = 10), respectively. The recoveries were 64–124% with SD less than 10%. The RSD of intermediate precision was less than 11%, and matrix effects were lower than 19%. Compared with traditional purification procedures, HPTLC largely reduced the workload and procedures for complex biological sample cleanup without inducing decomposition of the analytes. The proposed method exhibited good performance when detecting these ten chemicals in chicken samples from a nearby yard of brominated flame retardant plants, indicating its great potential for investigating their environment level, behavior, and fate in organisms.

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References

  1. Covaci A, Harrad S, Abdallah MAE, Ali N, Law RJ, Herzke D, et al. Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour. Environ Int. 2011;37(2):532–56.

    Article  CAS  PubMed  Google Scholar 

  2. Covaci A, Voorspoels S, Abou-Elwafa Abdallah M, Geens T, Harrad S, Law RJ. Analytical and environmental aspects of the flame retardant tetrabromobisphenol-A and its derivatives. J Chromatogr A. 2009;1216(3):346–63.

    Article  CAS  PubMed  Google Scholar 

  3. Zhu NL, Li A, Wang T, Wang P, Qu GB, Ruan T, et al. Tris(2,3-dibromopropyl) Isocyanurate, hexabromocyclododecanes, and polybrominated diphenyl ethers in mollusks from Chinese Bohai Sea. Environ Sci Technol. 2012;46(13):7174–81. https://doi.org/10.1021/es300776f.

    Article  CAS  PubMed  Google Scholar 

  4. Liu L, Venier M, Salamova A, Hites RA. A novel flame retardant in the Great Lakes atmosphere: 3,3′,5,5′-tetrabromobisphenol A bis(2,3-dibromopropyl) ether. Environ Sci Technol. 2016;3(5):194–9. https://doi.org/10.1021/acs.estlett.6b00138.

    Article  CAS  Google Scholar 

  5. Ali N, Harrad S, Goosey E, Neels H, Covaci A. “Novel” brominated flame retardants in Belgian and UK indoor dust: implications for human exposure. Chemosphere. 2011;83(10):1360–5. https://doi.org/10.1016/j.chemosphere.2011.02.078.

    Article  CAS  PubMed  Google Scholar 

  6. Gauthier LT, Potter D, Hebert CE, Letcher RJ. Temporal trends and spatial distribution of non-polybrominated diphenyl ether flame retardants in the eggs of colonial populations of Great Lakes herring gulls. Environ Sci Technol. 2008;43(2):312–7. https://doi.org/10.1021/es801687d.

    Article  CAS  Google Scholar 

  7. Liu L, Liu A, Zhang Q, Shi J, He B, Yun Z, et al. Determination of tetrabromobisphenol-A/S and their main derivatives in water samples by high performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry. J Chromatogr A. 2017;1497:81–6. https://doi.org/10.1016/j.chroma.2017.03.040.

    Article  CAS  PubMed  Google Scholar 

  8. Liu A, Shi J, Qu G, Hu L, Ma Q, Song M, et al. Identification of emerging brominated chemicals as the transformation products of tetrabromobisphenol A (TBBPA) derivatives in soil. Environ Sci Technol. 2017. https://doi.org/10.1021/acs.est.7b01071.

  9. Liu A, Qu G, Yu M, Liu Y, Shi J, Jiang G. Tetrabromobisphenol-A/S and nine novel analogs in biological samples from the Chinese Bohai Sea: implications for trophic transfer. Environ Sci Technol. 2016;50(8):4203–11. https://doi.org/10.1021/acs.est.5b06378.

    Article  CAS  PubMed  Google Scholar 

  10. Liu A, Qu G, Zhang C, Gao Y, Shi J, Du Y, et al. Identification of two novel brominated contaminants in water samples by ultra-high performance liquid chromatography-Orbitrap fusion Tribrid mass spectrometer. J Chromatogr A. 2015;1377:92–9. https://doi.org/10.1016/j.chroma.2014.12.038.

    Article  CAS  PubMed  Google Scholar 

  11. Hites RA. Polybrominated diphenyl ethers in the environment and in people: a meta-analysis of concentrations. Environ Sci Technol. 2004;38(4):945–56.

    Article  CAS  PubMed  Google Scholar 

  12. Letcher RJ, Chu S. High-sensitivity method for determination of tetrabromobisphenol-S and tetrabromobisphenol-A derivative flame retardants in Great Lakes herring gull eggs by liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry. Environ Sci Technol. 2010;44(22):8615–21. https://doi.org/10.1021/es102135n.

    Article  CAS  PubMed  Google Scholar 

  13. Tian Y, Liu A, Qu G, Liu C, Chen J, Handberg E, et al. Silver ion post-column derivatization electrospray ionization mass spectrometry for determination of tetrabromobisphenol A derivatives in water samples. RSC Adv. 2015;5(23):17474–81. https://doi.org/10.1039/C4RA16166A.

    Article  CAS  Google Scholar 

  14. Qu G, Shi J, Wang T, Fu J, Li Z, Wang P, et al. Identification of tetrabromobisphenol A diallyl ether as an emerging neurotoxicant in environmental samples by bioassay-directed fractionation and HPLC-APCI-MS/MS. Environ Sci Technol. 2011;45(11):5009–16. https://doi.org/10.1021/Es2005336.

    Article  CAS  PubMed  Google Scholar 

  15. Zhang H, Bayen S, Kelly BC. Co-extraction and simultaneous determination of multi-class hydrophobic organic contaminants in marine sediments and biota using GC-EI-MS/MS and LC-ESI-MS/MS. Talanta. 2015;143:7–18. https://doi.org/10.1016/j.talanta.2015.04.084.

    Article  CAS  PubMed  Google Scholar 

  16. Deceuninck Y, Bichon E, Durand S, Bemrah N, Zendong Z, Morvan ML, et al. Development and validation of a specific and sensitive gas chromatography tandem mass spectrometry method for the determination of bisphenol A residues in a large set of food items. J Chromatogr A. 2014;1362:241–9. https://doi.org/10.1016/j.chroma.2014.07.105.

    Article  CAS  PubMed  Google Scholar 

  17. Cunha SC, Oliveira C, Fernandes JO. Development of QuEChERS-based extraction and liquid chromatography-tandem mass spectrometry method for simultaneous quantification of bisphenol A and tetrabromobisphenol A in seafood: fish, bivalves, and seaweeds. Anal Bioanal Chem. 2017;409(1):151–60. https://doi.org/10.1007/s00216-016-9980-3.

    Article  CAS  PubMed  Google Scholar 

  18. Abdallah MA, Harrad S, Covaci A. Isotope dilution method for determination of polybrominated diphenyl ethers using liquid chromatography coupled to negative ionization atmospheric pressure photoionization tandem mass spectrometry: validation and application to house dust. Anal Chem. 2009;81(17):7460–7.

    Article  CAS  PubMed  Google Scholar 

  19. Liu J, Wang Y, Jiang B, Wang L, Chen J, Guo H, et al. Degradation, metabolism, and bound-residue formation and release of tetrabromobisphenol A in soil during sequential anoxic–oxic incubation. Environ Sci Technol. 2013;47(15):8348–54. https://doi.org/10.1021/es4014322.

    Article  CAS  PubMed  Google Scholar 

  20. Li F, Wang J, Nastold P, Jiang B, Sun F, Zenker A, et al. Fate and metabolism of tetrabromobisphenol A in soil slurries without and with the amendment with the alkylphenol degrading bacterium Sphingomonas sp strain TTNP3. Environ Pollut. 2014;193:181–8. https://doi.org/10.1016/j.envpol.2014.06.030.

    Article  CAS  PubMed  Google Scholar 

  21. Liu A, Shi J, Qu G, Hu L, Ma Q, Song M, et al. Identification of emerging brominated chemicals as the transformation products of tetrabromobisphenol A (TBBPA) derivatives in soil. Environ Sci Technol. 2017;51(10):5434–44. https://doi.org/10.1021/acs.est.7b01071.

    Article  CAS  PubMed  Google Scholar 

  22. Fini J-B, Riu A, Debrauwer L, Hillenweck A, Le Mevel S, Chevolleau S, et al. Parallel biotransformation of tetrabromobisphenol A in Xenopus laevis and mammals: Xenopus as a model for endocrine perturbation studies. Toxicol Sci. 2012;125(2):359–67. https://doi.org/10.1093/toxsci/kfr312.

    Article  CAS  PubMed  Google Scholar 

  23. Hou X, Yu M, Liu A, Li Y, Ruan T, Liu J, et al. Biotransformation of tetrabromobisphenol A dimethyl ether back to tetrabromobisphenol A in whole pumpkin plants. Environ Pollut. 2018;241:331–8. https://doi.org/10.1016/j.envpol.2018.05.075.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Han SK, Yamasaki T, Yamada K-I. Photodecomposition of tetrabromobisphenol A in aqueous humic acid suspension by irradiation with light of various wavelengths. Chemosphere. 2016;147:124–30. https://doi.org/10.1016/j.chemosphere.2015.12.072.

    Article  CAS  PubMed  Google Scholar 

  25. Wang S, Cao S, Wang Y, Jiang B, Wang L, Sun F, et al. Fate and metabolism of the brominated flame retardant tetrabromobisphenol A (TBBPA) in rice cell suspension culture. Environ Pollut. 2016;214:299–306. https://doi.org/10.1016/j.envpol.2016.04.037.

    Article  CAS  PubMed  Google Scholar 

  26. Köppen R, Becker R, Jung C, Piechotta C, Nehls PI. Investigation of extraction procedures and HPLC-DAD/MS for the determination of the brominated flame retardant tetrabromobisphenol A bis(2,3-dibromopropylether) in environmental samples. Anal Bioanal Chem. 2006;384(7–8):1485–92.

    Article  CAS  PubMed  Google Scholar 

  27. Shi T, Chen S, Luo X, Zhang X, Tang C, Luo Y, et al. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere. 2009;74(7):910–6.

    Article  CAS  PubMed  Google Scholar 

  28. Nyholm JR, Norman A, Norrgren L, Haglund P, Andersson PL. Maternal transfer of brominated flame retardants in zebrafish (Danio rerio). Chemosphere. 2008;73(2):203–8. https://doi.org/10.1016/j.chemosphere.2008.04.033.

    Article  CAS  PubMed  Google Scholar 

  29. Law RJ, Bersuder P, Allchin CR, Barry J. 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. Environ Sci Technol. 2006;40(7):2177–83. https://doi.org/10.1021/es052416o.

    Article  CAS  PubMed  Google Scholar 

  30. Qu G, Liu A, Hu L, Liu S, Shi J, Jiang G. Recent advances in the analysis of TBBPA/TBBPS, TBBPA/TBBPS derivatives and their transformation products. TrAC-Trend Anal Chem. 2016;83(Part B):14–24. https://doi.org/10.1016/j.trac.2016.06.021.

    Article  CAS  Google Scholar 

  31. Zhong Y, Li D, Mao Z, Huang W, Peng PA, Chen P, et al. Kinetics of tetrabromobisphenol A (TBBPA) reactions with H2SO4, HNO3 and HCl: implication for hydrometallurgy of electronic wastes. J Hazard Mater. 2014;270:196–201. https://doi.org/10.1016/j.jhazmat.2014.01.032.

    Article  CAS  PubMed  Google Scholar 

  32. Patel AA, Amin AA, Patwari AH, Shah MB. Validated high performance thin layer chromatography method for simultaneous determination of quercetin and gallic acid in Leea indica. Rev Bras Farmacogn. 2017;27(1):50–3. https://doi.org/10.1016/j.bjp.2016.05.017.

    Article  CAS  Google Scholar 

  33. Guzelmeric E, Ristivojević P, Vovk I, Milojković-Opsenica D, Yesilada E. Quality assessment of marketed chamomile tea products by a validated HPTLC method combined with multivariate analysis. J Pharm Biomed Anal. 2017;132:35–45. https://doi.org/10.1016/j.jpba.2016.09.030.

    Article  CAS  PubMed  Google Scholar 

  34. Dawan P, Satarpai T, Tuchinda P, Shiowatana J, Siripinyanond A. A simple analytical platform based on thin-layer chromatography coupled with paper-based analytical device for determination of total capsaicinoids in chilli samples. Talanta. 2017;162:460–5. https://doi.org/10.1016/j.talanta.2016.10.077.

    Article  CAS  PubMed  Google Scholar 

  35. Guzelmeric E, Vovk I, Yesilada E. Development and validation of an HPTLC method for apigenin 7-O-glucoside in chamomile flowers and its application for fingerprint discrimination of chamomile-like materials. J Pharm Biomed Anal. 2015;107:108–18. https://doi.org/10.1016/j.jpba.2014.12.021.

    Article  CAS  PubMed  Google Scholar 

  36. Loescher CM, Morton DW, Razic S, Agatonovic-Kustrin S. High performance thin layer chromatography (HPTLC) and high performance liquid chromatography (HPLC) for the qualitative and quantitative analysis of Calendula officinalis—advantages and limitations. J Pharm Biomed Anal. 2014;98:52–9. https://doi.org/10.1016/j.jpba.2014.04.023.

    Article  CAS  PubMed  Google Scholar 

  37. Renger B, Végh Z, Ferenczi-Fodor K. Validation of thin layer and high performance thin layer chromatographic methods. J Chromatogr A. 2011;1218(19):2712–21.

    Article  CAS  PubMed  Google Scholar 

  38. Ferenczifodor K, Renger B, Végh Z. The frustrated reviewer—recurrent failures in manuscripts describing validation of quantitative TLC/HPTLC procedures for analysis of pharmaceuticals. J Planar Chromat. 2010;23(3):173–9.

    Article  CAS  Google Scholar 

  39. Witos YA, Milz B, Spangenberg B. Two-dimensional thin-layer chromatography of 17α-ethinylestradiol on RP-18 W plate, detected by effect-directed analysis using the YES test. J Planar Chromat. 2017;30(2):136–41. https://doi.org/10.1556/1006.2017.30.2.8.

    Article  CAS  Google Scholar 

  40. Kokotkiewicz A, Migas P, Stefanowicz J, Luczkiewicz M, Krauze-Baranowska M. Densitometric TLC analysis for the control of tropane and steroidal alkaloids in Lycium barbarum. Food Chem. 2017;221:535–40. https://doi.org/10.1016/j.foodchem.2016.11.142.

    Article  CAS  PubMed  Google Scholar 

  41. Qu G, Liu A, Wang T, Zhang C, Fu J, Yu M, et al. Identification of tetrabromobisphenol A allyl ether and tetrabromobisphenol A 2,3-dibromopropyl ether in the ambient environment near a manufacturing site and in mollusks at a coastal region. Environ Sci Technol. 2013;47(9):4760–7. https://doi.org/10.1021/es3049916.

    Article  CAS  PubMed  Google Scholar 

  42. George KW, Haeggblom MM. Microbial O-methylation of the flame retardant tetrabromobisphenol-A. Environ Sci Technol. 2008;42(15):5555–61. https://doi.org/10.1021/es800038q.

    Article  CAS  PubMed  Google Scholar 

  43. Nakao T, Akiyama E, Kakutani H, Mizuno A, Aozasa O, Akai Y, et al. Levels of tetrabromobisphenol A, tribromobisphenol A, dibromobisphenol A, monobromobisphenol A, and bisphenol A in Japanese breast milk. Chem Res Toxicol. 2015;28(4):722–8. https://doi.org/10.1021/tx500495j.

    Article  CAS  PubMed  Google Scholar 

  44. Liu A, Shen Z, Tian Y, Shi R, Liu Y, Zhao Z, et al. Thin-layer chromatography coupled with high performance liquid chromatography for determining tetrabromobisphenol A/S and their derivatives in soils. J Chromatogr A. 2017;1526(Supplement C):151–6. https://doi.org/10.1016/j.chroma.2017.10.045.

    Article  CAS  PubMed  Google Scholar 

  45. Abou-Elwafa AM. Environmental occurrence, analysis and human exposure to the flame retardant tetrabromobisphenol-A (TBBP-A)—a review. Environ Int. 2016;94:235–50. https://doi.org/10.1016/j.envint.2016.05.026.

    Article  CAS  Google Scholar 

  46. Akiyama E, Kakutani H, Nakao T, Motomura Y, Takano Y, Sorakubo R, et al. Facilitation of adipocyte differentiation of 3T3-L1 cells by debrominated tetrabromobisphenol A compounds detected in Japanese breast milk. Environ Res. 2015;140:157–64. https://doi.org/10.1016/j.envres.2015.03.035.

    Article  CAS  PubMed  Google Scholar 

  47. Chu SG, Haffner GD, Letcher RJ. 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. J Chromatogr A. 2005;1097(1–2):25–32. https://doi.org/10.1016/j.chroma.2005.08.007.

    Article  CAS  PubMed  Google Scholar 

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Funding

This work was supported by the National Natural Science Foundation of China (21707148), the China Postdoctoral Science Foundation (2016M602210 and 2018T110715) and the Open Fund supported by the State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (KF2016-12).

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Authors and Affiliations

  1. CAS Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, Shandong, China

    Aifeng Liu, Zhaoshuang Shen, Mengmeng Xu, Zongshan Zhao & Xiangfeng Liang

  2. Research Center for Analytical Sciences, College of Sciences, Northeastern University, Shenyang, 110819, Liaoning, China

    Li Yuan

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  1. Aifeng Liu
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  2. Zhaoshuang Shen
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  3. Li Yuan
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Correspondence to Zongshan Zhao.

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All procedures performed in studies involving animals were in accordance with the ethical standards of the care and use of animals in china. The studies have been approved by the Academic Committee (Ethics Committee) of Qingdao Institute of Bioenergy and Bioprocess Technology, China Academy of Sciences.

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Liu, A., Shen, Z., Yuan, L. et al. High-performance thin-layer chromatography coupled with HPLC-DAD/HPLC-MS/MS for simultaneous determination of bisphenol A and nine brominated analogs in biological samples. Anal Bioanal Chem 411, 725–734 (2019). https://doi.org/10.1007/s00216-018-1492-x

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