Analytical and Bioanalytical Chemistry

, Volume 409, Issue 1, pp 151–160 | Cite as

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

  • Sara C. CunhaEmail author
  • Cátia Oliveira
  • José O. Fernandes
Research Paper


A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous determination of bisphenol A (BPA) and tetrabromobisphenol A (TBBPA) in different seafood samples was developed and validated. Sample preparation was based on a quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based procedure through an extraction of target analytes with acidified acetonitrile (MeCN) added with inorganic salts (MgSO4, NaCl) followed by a liquid–liquid extraction (LLE) using hexane-tertbutylmethyl ether/hexane-benzene to eliminate matrix co-extracts. The developed method promotes a better removal of interferences than that achieved with the classic QuEChERS procedure. The method was validated following the guidelines of the European Union (EU) for relevant seafood matrices such as fish, mussel, and seaweed. Accuracy (81 % average of recovery), reproducibility (12 % average relative standard deviation for both intra-day and inter-day repeatability), and sensitivity for the target analytes (method detection limits of 0.07 ng/g wet weight (ww) and 0.06 ng/g ww for BPA and TBBPA, respectively) were evaluated for all the matrices studied.

Graphical Abstract

Simultaneous analysis of TBBPA and BPA in seaweeds, mussels and fish


Bisphenol A Tetrabromobisphenol A LC-MS/MS QuEChERS Fish Contaminants 



The research leading to these results has received funding from the European Union Seventh Framework Program (FP7/2007-2013) under the ECsafeSEAFOOD project (grant agreement no. 311820). S.C.C., C.O. and J.O.F. thank REQUIMTE, FCT (Fundação para a Ciência e a Tecnologia) and FEDER through the project UID/QUI/50006/2013 - POCI/01/0145/FEDER/007265 with financial support from FCT/MEC through national funds and cofinanced by FEDER, under the Partnership Agreement PT2020. S.C.C. acknowledges the FCT for the IF/01616/2015 contract.

Compliance with ethical standards

Conflict of interest

The authors declare that there is no conflict of interest.


  1. 1.
    Watson RA, Nowara GB, Hartmann K, Green BS, Tracey SR, Carte CG. Marine foods sourced from farther as their use of global ocean primary production increases. Nature Commun. 2015;6:7365.CrossRefGoogle Scholar
  2. 2.
    Norman-network. 2016. Accessed July 2016.
  3. 3.
    Geissen V, Mol H, Klumpp E, Umlauf G, Nadal M, Ploeg MV, et al. Emerging pollutants in the environment: a challenge for water resource management. Int Soil Water Conserv Res. 2015;3:57–65.CrossRefGoogle Scholar
  4. 4.
    Chu S, 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;1097:25–32.CrossRefGoogle Scholar
  5. 5.
    Harrison EZ, Oakes SR, Hysell M, Hay A. Organic chemicals in sewage sludges. Sci Total Environ. 2006;367:481–97.CrossRefGoogle Scholar
  6. 6.
    Flint S, Markle T, Thompson S, Wallace E. Bisphenol A exposure, effects, and policy: a wildlife perspective. J Environ Manag. 2012;104:19–34.CrossRefGoogle Scholar
  7. 7.
    Cunha SC, Almeida C, Mendes E, Fernandes JO. Simultaneous determination of bisphenol A and bisphenol B in beverages and powdered infant formula by dispersive liquid–liquid micro-extraction and heart-cutting multidimensional gas chromatography-mass spectrometry. Food Addit Contam. 2011;28:513–28.CrossRefGoogle Scholar
  8. 8.
    Cunha SC, Cunha C, Ferreira AR, Fernandes JO. Determination of bisphenol A and bisphenol B in canned seafood combining QuEChERS extraction with dispersive liquid–liquid microextraction followed by gas chromatography-mass spectrometry. Anal Bioanal Chem. 2012;404:2453–63.CrossRefGoogle Scholar
  9. 9.
    Cunha SC, Fernandes JO. Assessment of bisphenol A and bisphenol B in canned vegetables and fruits by gas chromatography mass spectrometry after QuEChERS and dispersive liquid–liquid microextraction. Food Control. 2013;33:549–55.CrossRefGoogle Scholar
  10. 10.
    Chen D, Kannan K, Tan H, Zheng Z, Feng YL, Wu Y, et al. Bisphenol analogues other than BPA: environmental occurrence, human exposure, and toxicity—a review. Environ Sci Technol. 2016;50:5438–53.CrossRefGoogle Scholar
  11. 11.
    Liao C, Kannan K. Concentrations and profiles of bisphenol A and other bisphenol analogues in foodstuffs from the United States and their implications for human exposure. J Agric Food Chem. 2013;61:4655–62.CrossRefGoogle Scholar
  12. 12.
    Liao C, Kannan K. A survey of bisphenol A and other bisphenol analogues in foodstuffs from nine cities in China. Food Addit Contam. 2014;31:319–29.CrossRefGoogle Scholar
  13. 13.
    Crain DA, Eriksen M, Iguchi T, Jobling S, Laufer H, LeBlanc GA, et al. An ecological assessment of bisphenol A: evidence from comparative biology. Reprod Toxicol. 2007;24:225–39.CrossRefGoogle Scholar
  14. 14.
    Rhee J, Kim BM, Lee CJ, Yoon YD, Lee YM, Lee JS. Bisphenol A modulates expression of sex differentiation genes in the self-fertilizing fish, Kryptolebias marmoratus. Aquat Toxicol. 2011;104:218–29.CrossRefGoogle Scholar
  15. 15.
    Canada Report (2013) Ethanol, 2,2'-[(1-methylethylidene)bis[(2,6-dibromo-4,1-phenylene)oxy]]bis chemical abstracts service registry number 4162-45-2 and benzene, 1,1'-(1-methylethylidene)bis[3,5-dibromo-4-(2- propenyloxy)-chemical abstracts service registry number 25327-89-3, Environment Canada Health Canada November 2013.Google Scholar
  16. 16.
    Li Y, Zhou Q, Wang Y, Xie X. Fate of tetrabromobisphenol A and hexabromocyclododecane brominated flame retardants in soil and uptake by plants. Chemosphere. 2011;82:204–9.CrossRefGoogle Scholar
  17. 17.
    Harrad S, Abdallah MAE, Rose NL, Turner SD, Davidson TA. Current-use brominated flame retardants in water, sediment, and fish from English lakes. Environ Sci Technol. 2009;43:9077–83.CrossRefGoogle Scholar
  18. 18.
    Sellström U, Jansson B. Analysis of tetrabromobisphenol A in a product and environmental samples. Chemosphere. 1995;31:3085–92.CrossRefGoogle Scholar
  19. 19.
    Cariou R, Antignac JP, Zalko D, Berrebi A, Cravedi JP, Maume D, et al. Exposure assessment of French women and their newborns to tetrabromobisphenol A: occurrence measurements in maternal adipose tissue, serum, breast milk, and cord serum. Chemosphere. 2008;73:1036–41.CrossRefGoogle Scholar
  20. 20.
    Cruz R, Cunha SC, Casal S. Brominated flame retardants and seafood safety: a review. Environ Int. 2015;77:116–31.CrossRefGoogle Scholar
  21. 21.
    Ashizuka Y, Nakagawa R, Hori T, Yasutake D, Tobiishi K, Sasaki K. Determination of brominated flame retardants and brominated dioxins in fish collected from three regions of Japan. Mol Nutr Food Res. 2008;52:273–83.CrossRefGoogle Scholar
  22. 22.
    Van der Ven LT, Van de Kuil T, Verhoef A, Verwer CM, Lilienthal H, Leonards PE, et al. Endocrine effects of tetrabromobisphenol A (TBBPA) in Wistar rats as tested in a one-generation reproduction study and a subacute toxicity study. Toxicology. 2008;245:76–89.CrossRefGoogle Scholar
  23. 23.
    Meerts IATM, Van Zanden JJ, Luijks EAC, Van Leewen-Bol I, Marsh G, Jakobsson E, et al. Potent competitive interactions of some brominated flame retardants and related compounds with human transthyretin in vitro. Toxicol Sci. 2000;56:95–104.CrossRefGoogle Scholar
  24. 24.
    Covaci A, Voorspoels A, Abdallah MAE, Geens T, Harrad S, Law RJ. Analytical and environmental aspects of the flame retardant tetrabromobisphenol A and its derivatives. J Chromatogr A. 2009;1216:346–63.CrossRefGoogle Scholar
  25. 25.
    Webster L, Walsham P, Russell M, Neat F, Phillips L, Dalgarno E, et al. Halogenated persistent organic pollutants in Scottish deep water fish. J Environ Monit. 2009;11:406–17.CrossRefGoogle Scholar
  26. 26.
    Dam GT, Pardo O, Traag W, van der Lee M, Peters R. Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish. J Chromatogr B. 2012;898:101–10.CrossRefGoogle Scholar
  27. 27.
    Fernandes A, Dicks P, Mortimer D, Gem M, Smith F, Driffield M, et al. Brominated and chlorinated dioxins, PCBs and brominated flame retardants in Scottish shellfish: methodology, occurrence, and human dietary exposure. Molec Nutr Food Res. 2008;52:238–49.CrossRefGoogle Scholar
  28. 28.
    Wei X, Huang Y, Wong MH, Giesy JP, Wong CKC. Assessment of risk to humans of bisphenol A in marine and freshwater fish from Pearl River delta, China. Chemosphere. 2011;85:122–8.CrossRefGoogle Scholar
  29. 29.
    Staniszewska M, Falkowska L, Grabowski P, Kwaśniak J, Mudrak-Cegiołka S, Reindl AR, et al. Bisphenol A, 4-tert-octylphenol, and 4 nonylphenol in the Gulf of Gdańsk (Southern Baltic). Arch Environ Contam Toxicol. 2014;67:335–47.CrossRefGoogle Scholar
  30. 30.
    Lankova D, Kockovska M, Lacina O, Kalachova K, Pulkrabova J, Hajslova J. Rapid and simple method for determination of hexabromocyclododecanes and other LC-MS-MS amenable brominated flame retardants in fish. Anal Bioanal Chem. 2013;405:7829–39.CrossRefGoogle Scholar
  31. 31.
    EFSA Panel on Food contact materials, enzymes, flavourings, and processing aids CEF. Scientific opinion on the risks to public health related to the presence of bisphenol A (BPA) in foodstuffs – Part 1: exposure assessment. EFSA J. 2015;13(1):3978.CrossRefGoogle Scholar
  32. 32.
    European Union Decision 2002/657/EC. Off J Eur Commun. 2002;L221:8–36.Google Scholar
  33. 33.
    Yang S, Xu F, Zheng B, Wu F, Wang S. Multi-biomarker responses upon exposure to tetrabromobisphenol A in the freshwater fish Carassius auratus. Aquatic Toxicol. 2013;142:248–56.CrossRefGoogle Scholar
  34. 34.
    Canesi L, Fabbri E. Environmental effects of BPA: focus on aquatic species. Dose–Response Int J. 2015;1–14Google Scholar
  35. 35.
    European Standard Method EN 15662.2008. Foods of plant origin – Determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and cleanup by dispersive SPE – QuEChERS-method.Google Scholar
  36. 36.
    Dussault EB, Balakrishnan VK, Solomon KR, Sibley PK. Matrix effects on mass spectrometric determinations of four pharmaceuticals and personal care products in water, sediments, and biota. Can J Chem. 2009;87:662–72.CrossRefGoogle Scholar
  37. 37.
    Remberger M, Lilja K, Kaj L, Viktor T, Brorström-Lundén E (2011) Results from the Swedish National Screening Programme 2009 Subreport 3: UV-filters. IVL Swedish Environmental Research Institute Ltd.Google Scholar
  38. 38.
    Sanco document no. 12571/2013. Method validation and quality control procedures for pesticide residues analysis in food and feed.Google Scholar
  39. 39.
    Commission Recommendation 2014/118/EU. Commission recommendation of March 3 (2014) on the monitoring of traces of brominated flame retardants in food.Google Scholar
  40. 40.
    EFSA. European Food Safety Authority scientific opinion on tetrabromobisphenol A (TBBPA) and its derivatives in food. EFSA J. 2011;9:2477.CrossRefGoogle Scholar
  41. 41.
    Podlipna D, Cichna-Markl M. Determination of bisphenol A in canned fish by sol–gel immunoaffinity chromatography, HPLC and fluorescence detection. Eur Food Res Tecnol. 2007;224:629–34.CrossRefGoogle Scholar
  42. 42.
    Thomson BM, Grounds PR. Bisphenol A in canned foods in New Zealand: an exposure assessment. Food Addit Contam. 2005;22:65–72.CrossRefGoogle Scholar
  43. 43.
    Munguía-López EM, Gerardo-Lugo S, Peralta E, Bolumen S, Soto-Valdez H. Migration of bisphenol A (BPA) from can coatings into a fatty-food simulant and tuna fish. Food Addit Contam. 2005;22:892–8.CrossRefGoogle Scholar
  44. 44.
    Lim DS, Kwack SJ, Kim K, Kim HS, Lee BM. Risk assessment of bisphenol A migrated from canned foods in Korea. J Toxicol Environ Health A. 2009;72:1327–35.CrossRefGoogle Scholar
  45. 45.
    Commission Regulation (EU) no. 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food. Available at: Accessed: xxxx.

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Sara C. Cunha
    • 1
    Email author
  • Cátia Oliveira
    • 1
  • José O. Fernandes
    • 1
  1. 1.LAQV-REQUIMTE, Laboratory of Bromatology and Hydrology, Faculty of PharmacyUniversity of PortoPortoPortugal

Personalised recommendations