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Single sample preparation for brominated flame retardants in fish and shellfish with dual detection: GC-MS/MS (PBDEs) and LC-MS/MS (HBCDs)

  • Tamara Tavoloni
  • Arianna Stramenga
  • Tommaso Stecconi
  • Melania Siracusa
  • Simone Bacchiocchi
  • Arianna PiersantiEmail author
Research Paper
First Online:

Abstract

An analytical method for the simultaneous determination of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in fish, shellfish and muscle of terrestrial animals was developed as an extension of a previously validated method for PBDE analysis. A single sample preparation based on QuEChERS-like extraction and a two-step clean-up, followed by a dual instrumental detection, was implemented. GC-MS/MS was used for PBDEs and LC-MS/MS for HBCDs. The method allows the quantification of fifteen PBDEs (28, 47, 49, 66, 77, 85, 99, 100, 138, 153, 154, 183, 197, 206, 209) and three HBCD isomers (α, β and γ), reaching 10 pg/g LOQs for all the analytes except BDE 206 and 209 (100 pg/g LOQ). The validated method was applied to the analysis of 12 fish and shellfish species (sole, spiny dogfish, smooth-hound, mackerel, swordfish, grey mullet, cod, anchovy, red mullet, Atlantic horse mackerel, tuna fish and mussel) collected in central Italian markets accounting for a total of 44 samples. Generally, ΣPBDEs showed higher concentration than ΣHBCDs except in the case of mussels in which ΣHBCDs > ΣPBDEs. Cod and smooth-hound are the least contaminated species among those analysed in the present study, whereas the highest brominated flame retardant (BFR) levels were found in spiny dogfish samples. The measured contamination levels were generally comparable to or lower than those already published in European studies. Literature data for HBCDs in European fish and shellfish were hard to find; therefore, PBDE and HBCD levels were also compared with European Environmental Quality Standard (EQS) in biota (Directive 2013/39/EU). EQSs for HBCDs are six orders of magnitude higher than those for PBDEs; therefore, while no exceedance was observed for the first, almost all the samples analysed for PBDEs were above EQSs. The presented preliminary data on PBDEs and HBCDs are among the first published in marine fish and shellfish commercialised in Central Italy.

Graphical abstrac

Keywords

BFRs Analytical method Triple quadrupole mass spectrometry Chromatography Fish Shellfish 
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Notes

Acknowledgements

The authors gratefully acknowledge Carmela Lestingi for proof reading.

Funding information

Funding was from the Italian Health Ministry (Ricerca Corrente IZSUM 05 2015 - “Sviluppo di un metodo multiclasse per la determinazione di ritardanti di fiamma bromurati (PBDEs e HBCDDs): definizione dei livelli di contaminazione nei prodotti ittici.”).

Compliance with ethical standards

Conflict of interest

The authors declare they have no conflict of interest.

Supplementary material

216_2019_2250_MOESM1_ESM.pdf (161 kb)
ESM 1 (PDF 161 kb)

References

  1. 1.
    de Wit CA. An overview of brominated flame retardants in the environment. Chemosphere. 2002;46:583–624.CrossRefGoogle Scholar
  2. 2.
    Alaee M, Arias P, Sjödin A, Bergman A. An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release. Environ Int. 2003;29:683–9.CrossRefGoogle Scholar
  3. 3.
    EFSA Panel on Contaminants in the Food Chain (CONTAM). Scientific opinion on polybrominated diphenyl ethers (PBDEs) in food. EFSA J. 2011;9:2156.CrossRefGoogle Scholar
  4. 4.
    EFSA Panel on Contaminants in the Food Chain (CONTAM). Scientific opinion on hexabromocyclododecanes (HBCDDs) in food. EFSA J. 2011;9:2296.Google Scholar
  5. 5.
    Covaci A, Gerecke AC, Law RJ, Voorspoels S, Kohler M, Heeb NV, et al. Hexabromocyclododecanes (HBCDs) in the environment and humans: a review. Environ Sci Technol. 2006;40:3679–88.CrossRefGoogle Scholar
  6. 6.
    Law RJ, Allchin CR, de Boer J, Covaci A, Herzke D, Lepom P, et al. Levels and trends of brominated flame retardants in the European environment. Chemosphere. 2006;64:187–208.CrossRefGoogle Scholar
  7. 7.
    Lyche JL, Rosseland C, Berge G, Polder A. Human health risk associated with brominated flame-retardants (BFRs). Environ Int. 2015;74:170–80.CrossRefGoogle Scholar
  8. 8.
    Law RJ, Kohler M, Heeb NV, Gerecke AC, Schmid P, Voorspoels S, et al. Hexabromocyclododecane challenges scientists and regulators. Environ Sci Technol. 2005;39:281A–7A.CrossRefGoogle Scholar
  9. 9.
    Directive 2003/11/EC of the European Parliament and of the Council of 6 February 2003 amending for the 24th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (pentabromodiphenyl ether, octabromodiphenyl ether). Off J Eur Union. 2003; L42:45-46.Google Scholar
  10. 10.
    Judgment of the Court (Grand Chamber) of 1 April 2008 — European Parliament (C-14/06), Kingdom of Denmark (C-295/06) v Commission of the European Communit. (Joined Cases C-14/06 and C-295/06) 2008; C 116/04.Google Scholar
  11. 11.
    UNEP. Listing of decabromodiphenyl ether, Decis. SC-8/10. http://chm.pops.int/Convention/ConferenceofthePartiesCOP/COPDecisions/tabid/208/Default.aspx. Accessed 30 Jan 2019.
  12. 12.
    UNEP. Listing of tetrabromodiphenyl ether and pentabromodiphenyl ether, Decis. SC-4/18. http://chm.pops.int/Convention/ConferenceofthePartiesCOP/COPDecisions/tabid/208/Default.aspx. Accessed 04 Feb 2019.
  13. 13.
    UNEP. Listing of hexabromodiphenyl ether and heptabromodiphenyl ether, Decis. SC-4/14. http://chm.pops.int/Convention/ConferenceofthePartiesCOP/COPDecisions/tabid/208/Default.aspx. Accessed 04 Feb 2019.
  14. 14.
    European Commission Regulation (EU) No 1907/2006 of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency. Off. J. Eur. Union, L 396.Google Scholar
  15. 15.
    UNEP. Listing of hexabromocyclododecane, Decis. SC-6/13. http://chm.pops.int/Convention/ConferenceofthePartiesCOP/COPDecisions/tabid/208/Default.aspx. Accessed 04 Feb 2019.
  16. 16.
    Malliari E, Kalantzi O-I. Children’s exposure to brominated flame retardants in indoor environments - A review. Environ Int. 2017;108:146–69.CrossRefGoogle Scholar
  17. 17.
    Sahlström LMO, Sellström U, de Wit CA, Lignell S, Darnerud PO. Estimated intakes of brominated flame retardants via diet and dust compared to internal concentrations in a Swedish mother-toddler cohort. Int J Hyg Environ Health. 2015;218:422–32.CrossRefGoogle Scholar
  18. 18.
    Darnerud PO, Eriksen GS, Jóhannesson T, Larsen PB, Viluksela M. Polybrominated diphenyl ethers: occurrence, dietary exposure, and toxicology. Environ Health Perspect. 2001;109(Suppl 1):49–68.CrossRefGoogle Scholar
  19. 19.
    Cruz R, Cunha SC, Casal S. Brominated flame retardants and seafood safety: a review. Environ Int. 2015;77:116–31.CrossRefGoogle Scholar
  20. 20.
    Commission Reccomendation 2014/118/EU of 3 March 2014 on the monitoring of traces of brominated flame retardants in food. Off J Eur Union. 2014; L65:39-40.Google Scholar
  21. 21.
    Fulara I, Czaplicka M. Methods for determination of polybrominated diphenyl ethers in environmental samples--review. J Sep Sci. 2012;35:2075–87.CrossRefGoogle Scholar
  22. 22.
    Covaci A, Voorspoels S, Ramos L, Neels H, Blust R. Recent developments in the analysis of brominated flame retardants and brominated natural compounds. J Chromatogr A. 2007;1153:145–71.CrossRefGoogle Scholar
  23. 23.
    Król S, Zabiegała B, Namieśnik J. PBDEs in environmental samples: sampling and analysis. Talanta. 2012;93:1–17.CrossRefGoogle Scholar
  24. 24.
    Abdallah MA-E, Ibarra C, Neels H, Harrad S, Covaci A. Comparative evaluation of liquid chromatography-mass spectrometry versus gas chromatography-mass spectrometry for the determination of hexabromocyclododecanes and their degradation products in indoor dust. J Chromatogr A. 2008;1190:333–41.CrossRefGoogle Scholar
  25. 25.
    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
  26. 26.
    Poma G, Volta P, Roscioli C, Bettinetti R, Guzzella L. Concentrations and trophic interactions of novel brominated flame retardants, HBCD, and PBDEs in zooplankton and fish from Lake Maggiore (Northern Italy). Sci Total Environ. 2014;481:401–8.CrossRefGoogle Scholar
  27. 27.
    Poma G, Binelli A, Volta P, Roscioli C, Guzzella L. Evaluation of spatial distribution and accumulation of novel brominated flame retardants, HBCD and PBDEs in an Italian subalpine lake using zebra mussel (Dreissena polymorpha). Environ Sci Pollut Res. 2014;21:9655–64.CrossRefGoogle Scholar
  28. 28.
    Vetter W, Gallistl C, Schlienz A, Preston T, Müller J, von der Trenck KT. Brominated flame retardants (BFRs) in eggs from birds of prey from Southern Germany, 2014. Environ Pollut. 2017;231:569–77.CrossRefGoogle Scholar
  29. 29.
    Shi Z, Wang Y, Niu P, Wang J, Sun Z, Zhang S, et al. Concurrent extraction, clean-up, and analysis of polybrominated diphenyl ethers, hexabromocyclododecane isomers, and tetrabromobisphenol A in human milk and serum. J Sep Sci. 2013;36:3402–10.CrossRefGoogle Scholar
  30. 30.
    van Leeuwen SPJ, de Boer J. Brominated flame retardants in fish and shellfish - levels and contribution of fish consumption to dietary exposure of Dutch citizens to HBCD. Mol Nutr Food Res. 2008;52:194–203.CrossRefGoogle Scholar
  31. 31.
    Roosens L, Geeraerts C, Belpaire C, Van Pelt I, Neels H, Covaci A. Spatial variations in the levels and isomeric patterns of PBDEs and HBCDs in the European eel in Flanders. Environ Int. 2010;36:415–23.CrossRefGoogle Scholar
  32. 32.
    Shaw SD, Berger ML, Weijs L, Covaci A. Tissue-specific accumulation of polybrominated diphenyl ethers (PBDEs) including Deca-BDE and hexabromocyclododecanes (HBCDs) in harbor seals from the northwest Atlantic. Environ Int. 2012;44:1–6.CrossRefGoogle Scholar
  33. 33.
    Eulaers I, Jaspers VLB, Pinxten R, Covaci A, Eens M. Legacy and current-use brominated flame retardants in the Barn Owl. Sci Total Environ. 2014;472:454–62.CrossRefGoogle Scholar
  34. 34.
    Shi Z, Zhang L, Zhao Y, Sun Z, Zhou X, Li J, et al. Dietary exposure assessment of Chinese population to tetrabromobisphenol-A, hexabromocyclododecane and decabrominated diphenyl ether: Results of the 5th Chinese Total Diet Study. Environ Pollut. 2017;229:539–47.CrossRefGoogle Scholar
  35. 35.
    Wang J, Zhao X, Wang Y, Shi Z. Tetrabromobisphenol A, hexabromocyclododecane isomers and polybrominated diphenyl ethers in foodstuffs from Beijing, China: Contamination levels, dietary exposure and risk assessment. Sci Total Environ. 2019;666:812–20.CrossRefGoogle Scholar
  36. 36.
    Kalachova K, Cajka T, Sandy C, Hajslova J, Pulkrabova J. High throughput sample preparation in combination with gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS): a smart procedure for (ultra)trace analysis of brominated flame retardants in fish. Talanta. 2013;105:109–16.CrossRefGoogle Scholar
  37. 37.
    Piersanti A, Tavoloni T, Bastari E, Lestingi C, Romanelli S, Rossi R, et al. A GC-EI-MS/MS Method for the determination of 15 polybrominated diphenyl ethers (PBDEs) in fish and shellfish tissues. Food Anal Methods. 2018;11:355–66.CrossRefGoogle Scholar
  38. 38.
    Piersanti A, Tavoloni T, Bastari E, Lestingi C, Romanelli S, Saluti G, et al. Polybrominated diphenyl ethers in mussels (Mytilus galloprovincialis) collected from Central Adriatic Sea. Mar Pollut Bull. 2015;101:417–21.CrossRefGoogle Scholar
  39. 39.
    Commission Regulation (EU) 2017/644 - of 5 April 2017 - laying down methods of sampling and analysis for the control of levels of dioxins, dioxin-like PCBs and non-dioxin-like PCBs in certain foodstuffs and repealing Regulation (EU) No 589/2014. Off J Eur Union. 2017; L92:9-34.Google Scholar
  40. 40.
    EURACHEM. The fitness for purpose of analytical methods a laboratory guide to method validation and related topics. 2014. https://www.eurachem.org/images/stories/Guides/pdf/MV_guide_2nd_ed_EN.pdf. Accessed 04 Feb 2019. 2014.
  41. 41.
    Domingo JL. Polybrominated diphenyl ethers in food and human dietary exposure: a review of the recent scientific literature. Food Chem Toxicol. 2012;50:238–49.CrossRefGoogle Scholar
  42. 42.
    Poma G, Malysheva SV, Goscinny S, Malarvannan G, Voorspoels S, Covaci A, et al. Occurrence of selected halogenated flame retardants in Belgian foodstuff. Chemosphere. 2018;194:256–65.CrossRefGoogle Scholar
  43. 43.
    Garcia Lopez M, Driffield M, Fernandes AR, Smith F, Tarbin J, Lloyd AS, et al. Occurrence of polybrominated diphenylethers, hexabromocyclododecanes, bromophenols and tetrabromobisphenols A and S in Irish foods. Chemosphere. 2018;197:709–15.CrossRefGoogle Scholar
  44. 44.
    Aznar-Alemany Ò, Trabalón L, Jacobs S, Barbosa VL, Tejedor MF, Granby K, et al. Occurrence of halogenated flame retardants in commercial seafood species available in European markets. Food Chem Toxicol Int J Publ Br Ind Biol Res Assoc. 2017;104:35–47.CrossRefGoogle Scholar
  45. 45.
    Chiesa LM, Labella GF, Panseri S, Pavlovic R, Bonacci S, Arioli F. Distribution of persistent organic pollutants (POPS) IN wild Bluefin tuna (Thunnus thynnus) from different FAO capture zones. Chemosphere. 2016;153:162–9.CrossRefGoogle Scholar
  46. 46.
    St-Gelais AT, Aeppli C, Burnell CA, Costa-Pierce BA. Non-dioxin like polychlorinated biphenyl indicator congeners in Northwest Atlantic spiny dogfish (Squalus acanthias). Mar Pollut Bull. 2017;120:414–21.CrossRefGoogle Scholar
  47. 47.
    Corsolini S, Guerranti C, Perra G, Focardi S. Polybrominated Diphenil Ethers, Perfluorinated Compounds and Chlorinated Pesticides in swordfish (Xiphias gladius) from the Mediterranean Sea. Environ Sci Technol. 2008;42:4344–9.CrossRefGoogle Scholar
  48. 48.
    Pardo O, Beser MI, Yusà V. Probabilistic risk assessment of the exposure to polybrominated diphenyl ethers via fish and seafood consumption in the Region of Valencia (Spain). Chemosphere. 2014;104:7–14.CrossRefGoogle Scholar
  49. 49.
    Trabalón L, Vilavert L, Domingo JL, Pocurull E, Borrull F, Nadal M. Human exposure to brominated flame retardants through the consumption of fish and shellfish in Tarragona County (Catalonia, Spain). Food Chem Toxicol Int J Publ Br Ind Biol Res Assoc. 2017;104:48–56.CrossRefGoogle Scholar
  50. 50.
    Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Off J Eur Union. 2013; L226:1-17.Google Scholar
  51. 51.
    Eljarrat E, Barceló D. How do measured PBDE and HCBD levels in river fish compare to the European Environmental Quality Standards? Environ Res. 2018;160:203–11.CrossRefGoogle Scholar

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© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Istituto Zooprofilattico Sperimentale dell’Umbria e delle MarcheAnconaItaly

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