Skip to main content
Log in

Meeting the European Commission performance criteria for the use of triple quadrupole GC-MS/MS as a confirmatory method for PCDD/Fs and dl-PCBs in food and feed samples

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Until recently, European Union (EU) legislation required the use of high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC-HRMS) based on magnetic sector analyzers as a standard approach for confirmatory analysis of dioxins (PCDDs) and furans (PCDFs) in feed and food. However, recent technological advances in MS instruments enabled other alternative analytical techniques to meet the same analytical criteria as those requested for HRGC-HRMS. In this sense, triple quadrupoles (GC-MS/MS) can be a realistic alternative for the analysis of dioxins. In this work, the performance of GC-MS/MS technology was evaluated against the criteria demanded by the EU for confirmatory analysis of dioxins and PCBs in food and feed. Thus, the study comprises a number of parameters including chromatographic separation, limit of quantification, linearity, repeatability, and ion ratio precision. Analyses of solvent standards as well as sample extracts (inter-calibration extracts and certified reference materials) were also considered within the scope of this study. Additionally, direct comparisons of the results obtained by GC-MS/MS with those from GC-HRMS were made. The results of this work suggested that GC-MS/MS was highly sensitive and selective for confirmatory analysis of PCDD/Fs and related compounds in food and feed samples and meets all the criteria requested by the European Commission.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Safe SH. Endocrine disruptors and human health—an update. Organohalogen Compd. 1999;42:109112.

    Google Scholar 

  2. Düwel U, Nottrodt A, Ballschmiter K. Simultaneous sampling of PCDD/PCDF inside the combustion chamber and on four boiler levels of a waste incineration plant. Chemosphere. 1990;20:1839–46.

    Article  Google Scholar 

  3. Birat JP, Arion A, Faral M, Baronnet F, Marquaire PM, Rambaud P (2000) 58th Electric Furnace Conference and 17th Process Technology Conference Proceedings: November 12-15, 2000, Orlando, Florida. Warrendale, Iron & Steel Society

  4. Buekens A, Cornelis E, Huang H, Dewttinck T. Fingerprints of dioxin from thermal industrial processes. Chemosphere. 2000;40:1021–4.

    Article  CAS  Google Scholar 

  5. Fiedler H, Timms CW, Hutzinger O. Dioxins: sources of environmental load and human exposure. Toxicol Environ Chem. 1990;29:157–234.

    Article  CAS  Google Scholar 

  6. Travis CC, Hattemer-Frey HA. Human exposure to 2,3,7,8-TCDD. Chemosphere. 1987;16:2331–42.

    Article  CAS  Google Scholar 

  7. World Health Organization. Assessment of the health risk of dioxins: re-evaluation of the tolerable daily intake (TDI), WHO Consultation, Geneva, 25–29 May 1998. Geneva: WHO; 1998.

    Google Scholar 

  8. Liem D. Basic aspects of methods for the determination of dioxins and PCBs in foodstuffs and human tissues. Trends Anal Chem. 1999;18:429–39.

    Article  CAS  Google Scholar 

  9. Focant J-F, Pirard C, Thielen C, De Pauw E. Levels and profiles of PCDDs, PCDFs and PCBs in Belgian breast milk. Estimation of infant intake. Chemosphere. 2002;48:763–70.

    Article  CAS  Google Scholar 

  10. International Agency for Research on Cancer (IARC). IARC working group on the evaluation of carcinogenic risks to humans: polychlorinated dibenzo-para-dioxins and polychlorinated dibenzofurans. Lyon, France, 4-11 February 1997. IARC Monogr Eval Carcinog Risks Hum. 1997;69:1–631.

    Google Scholar 

  11. International Agency for Research on Cancer (IARC). Polychlorinated and polobrominate biphenyls. Monogr Eval Carcinog Risks Hum. 2015;107:1–503.

    Google Scholar 

  12. Safe SH. Comparative toxicology and mechanism of action of polychlorinated dibenzo-p-dioxins and dibenzofurans. Aim Rev Pharmacol Toxicol. 1986;26:371–99.

    Article  CAS  Google Scholar 

  13. Poland A, Glover E, Kende AS. Stereospecific, high affinity binding of 2,3,7,8-tetrachlorodibenzo-p-dioxin by hepatic cytosol. Evidence that the binding species is receptor for induction of aryl hydrocarbon hydroxylase. J Biol Chem. 1976;251:4936–46.

    CAS  Google Scholar 

  14. Brown NM, Manzolillo PA, Zhang JX, Wang J, Lamartiniere CA. Prenatal TCDD and predisposition to mammary cancer in the rat. Carcinogenesis. 1998;19:1623–9.

    Article  CAS  Google Scholar 

  15. Mimura J, Yamashita K, Nakamura K, Morita M, Takagi TN, Nakao K, et al. Loss of teratogenic response to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in mice lacking the Ah (dioxin) receptor. Genes Cells. 1997;2:645–54.

    Article  CAS  Google Scholar 

  16. Poland A, Knutson JC. 2,3,7,8-Tetrachlorodibenzo-p-dioxin and related halogenated aromatic hydrocarbons: examination of the mechanism of toxicity. Annu Rev Pharmacol Toxicol. 1982;22:517–54.

    Article  CAS  Google Scholar 

  17. Kimbrough RD, Jensen AA (1989) Halogened biphenyls, terphenyls, naphthalene, dibenzodioxins and related products, 2nd edn. Elsevier

  18. Exposure and human health reassessment of 2,3,7,8-tetrachlorodiobenzo-p-dioxin (TCDD) and related compounds (September 2000 Draft). Part I: estimating exposure to dioxin-like compounds. Volume 2: sources of dioxin-like compounds in the United States. EPA/600/P-00/001 Bb. U.S. Environmental Protection Agency, Washington, DC

  19. Rappe C, Nygren M, Lindstrom G, Buser HR, Blaser O, Wüthrich C. Polychlorinated dibenzofurans and dibenzo-p-dioxins and other chlorinated contaminants in cow milk from various locations in Switzerland. Environ Sci Technol. 1987;21:964–70.

    Article  CAS  Google Scholar 

  20. Liem AKD, Hoogerbrugge R, Kootstra PR, van der Velde EG, Jong APJM. Occurrence of dioxins in cow’s milk in the vicinity of municipal waste incinerators and a metal reclamation plant in the Netherlands. Chemosphere. 1991;23:1975–84.

    Article  Google Scholar 

  21. Malisch R. Increase of the PCDD/F-contamination of milk, butter and meat samples by use of contaminated citrus pulp. Chemosphere. 2000;40:1041–53.

    Article  CAS  Google Scholar 

  22. Llerena JJ, Abad E, Caixach J, Rivera J. A new episode of PCDDs/PCDFs in feed contamination in Europe: the choline chloride. Organohalogen Compd. 2001;51:283–6.

    CAS  Google Scholar 

  23. Hoogenboom R, Traag W. The German bakery waste incident. Organohalogen Compd. 2003;64:13–6.

    Google Scholar 

  24. Hoogenboom RL, Zeilmaker MJ, Kan KA, Mengelers MB, van Eijkeren J, Traag WA. Kaolinic clay derived dioxins in potato by-products. Organohalogen Compd. 2005;67:1470–3.

    Google Scholar 

  25. Hoogenboom R, Zeilmaker M, van Eijkeren J, Kan K, Mengelers M, Luykx D. Kaolinic clay derived dioxins in the feed chain from a sorting process for potatoes. Chemosphere. 2010;78:99–105.

    Article  CAS  Google Scholar 

  26. Tlustos C. The dioxin contamination incident in Ireland 2008. Organohalogen Compd. 2009;71:1155–9.

    Google Scholar 

  27. Borrello S, Brambilla G, Candela L, Diletti G, Gallo P, Iacovella N, et al. Management of the 2008 “buffalo milk crisis” in the Campania Region under the perspective of consumer protection. Organohalogen Compd. 2008;70:891–3.

    CAS  Google Scholar 

  28. Bernard A, Broeckaert F, De Poorter G, De Cock A, Hermans C, Saegerman C, et al. The Belgian PCB/dioxin incident: analysis of the food chain contamination and health risk evaluation. Environ Res. 2002;88:1–18.

    Article  CAS  Google Scholar 

  29. Dioxins and their effects on human health. Fact sheet No. 225 (2014) World Health Organization. http://www.who.int/mediacentre/factsheets/fs225/es/ Accessed 15 July 2014

  30. Commission Regulation, Commission Regulation (EC) (1999) No. 1198/1999. Mission report on a routine mission carried out in Brazil from 5 to 9 July 1999 concerning the organization of official inspections in the field of animal nutrition: dioxin contamination of citrus pulp pellets. DG(SANCO)/1198/1199-MR Final (08/10/99)

  31. Commission Regulation, Commission Regulation (EC). No. 589/2014 of 2 June 2014 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 252/2012. Off J Eur Union L. 2014;164:18–40.

    Google Scholar 

  32. Commission Regulation, Commission Regulation (EC). No. 709/2014 of 20 June 2014 amending as regards the determination of the levels of dioxins polychlorinated biphenyls. Off J Eur Union L. 2014;188:1–18.

    Google Scholar 

  33. Clement ER, Tosine HM. The gas chromatography/mass spectrometry determination of chlorodibenzo-P-dioxins and dibenzofurans. Mass Spectrom Rev. 1988;7:593–636.

    Article  CAS  Google Scholar 

  34. Taguchi VY, Reiner EJ, Wang DT, Meresz O, Hallas B. High-resolution mass spectrometric determination of polychlorinated dibenzo-p-dioxins and dibenzofurans using an alternative lockmass system. Anal Chem. 1988;60:1429–33.

    Article  CAS  Google Scholar 

  35. Abad E, Llerena J, Sauló J, Caixach J, Rivera J. Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain). Chemosphere. 2002;46:1435–41.

    Article  CAS  Google Scholar 

  36. Reiner EJ, Clement RE, Okey AB, Marvin CH. Advances in the analytical techniques for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like PCBs. Anal Bioanal Chem. 2006;386:791–806.

    Article  CAS  Google Scholar 

  37. Reiner EJ. Analysis of dioxins and related compounds. Mass Spectrom Rev. 2010;29:526–59.

    CAS  Google Scholar 

  38. Eljarrat E, Barceló D. Congener specific determination of dioxins and related compounds by gas chromatography coupled to LRMS, HRMS, MS/MS and TOFMS. J Mass Spectrom. 2002;37:1105–17.

    Article  CAS  Google Scholar 

  39. Focant J-F, Pirard C, Eppe G, De Pauw E. Recent advances in mass spectrometric measurement of dioxins. J Chromatogr A. 2005;1067:265–75.

    Article  CAS  Google Scholar 

  40. Eppe G, De Pauw E, Focant JF. High-resolution GC coupled to high-resolution MS in the analysis of dioxins and related substances, principles and applications. In: Niessen WMA, editor. The encyclopedia of mass spectrometry, volume 8. Oxford: Elsevier; 2006.

    Google Scholar 

  41. Hong JH, Miki Y, Honda K, Toita H. Development of the automated cleanup system for the analysis of PCDDs, PCDFs and DL-PCBs. Chemosphere. 2012;88:1287–91.

    Article  CAS  Google Scholar 

  42. USEPA Method 1613 (1994) Revision B. Tetra- through octa-chlorinated dioxins and furans by isotope dilution HRGC/HRMS. U.S. Environmental Protection Agency Office of Water Engineering and Analysis Division, Washington, DC

  43. USEPA Method 1668 (1999) Revision A. Chlorinated biphenyl congeners in water, soil, sediment, biosolids and tissue by HRGC/HRMS. U.S. Environmental Protection Agency Office of Water Engineering and Analysis Division, Washington, DC

  44. Santos FJ, Galceran MT. Modern developments in gas chromatography-mass spectrometry-based environmental analysis. J Chromatogr A. 2003;1000:125–51.

    Article  CAS  Google Scholar 

  45. Reiner EJ, Schellenberg DH, Taguchi VY, Mercer RS, Townsend JA, Thompson TS, et al. Application of tandem quadrupole mass spectrometry for the ultra-trace determination of polychlorinated dibenzo-p-dioxins and dibenzofurans. Chemosphere. 1990;20:1385–92.

    Article  CAS  Google Scholar 

  46. Hoh E, Dodder NG, Lehotay SJ, Pangallo KC, Reddy CM, Maruya KA. Nontargeted comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry method and software for inventorying persistent and bioaccumulative contaminants in marine environments. Environ Sci Technol. 2012;46:8001–8.

    Article  CAS  Google Scholar 

  47. Peterson AC, McAlister GC, Quarmby ST, Griep-Raming J, Coon JJ. Development and characterization of a GC-enabled QLT-Orbitrap for high-resolution and high-mass accuracy GC/MS. Anal Chem. 2010;15:8618–28.

    Article  Google Scholar 

  48. Hubert Po-on T. Recent development in analysis of persistent organic pollutants under the Stockholm Convention. Trends Anal Chem. 2013;45:48–66.

    Article  Google Scholar 

  49. Malavia J, Santos FJ, Galceran MT. Gas chromatography-ion trap tandem mass spectrometry versus GC-high-resolution mass spectrometry for the determination of non-ortho-polychlorinated biphenyls in fish. J Chromatogr A. 2004;1056:171–8.

    Article  CAS  Google Scholar 

  50. Malavia J, Abalos M, Santos FJ, Abad E, Rivera J, Galceran MT. Ion-trap tandem mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in food. J Agric Food Chem. 2007;55:10531–9.

    Article  CAS  Google Scholar 

  51. Malavia J, Santos FJ, Galceran MT. Comparison of gas chromatography-ion-trap tandem mass spectrometry systems for the determination of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like biphenyls. J Chromatogr A. 2008;1186:302–11.

    Article  CAS  Google Scholar 

  52. Tondeur V, Niederhut WN, Campana JE, Missler SR. A hybrid HRGC/MS/MS method for the characterization of tetrachlorinated-p-dioxins in environmental samples. Biomed Environ Mass Spectrom. 1987;14:449–56.

    Article  CAS  Google Scholar 

  53. Fraisse D, Gonnard, Becchi M. High resolution chromatography/tandem mass spectrometry. Analysis of polychlorinated dibenzo-p-dioxins and furans. Rapid Commun Mass Spectrom. 1989;3:79–84.

    Article  CAS  Google Scholar 

  54. Kotz A, Malisch R, Wahl K, Bitomsky N, Adamovic K, Gerteisen I, et al. GC-MS/MS determination of PCDD/Fs and PCBs in feed and food-comparison with GC-HRMS. Organohalogen Compd. 2011;73:688–91.

    Google Scholar 

  55. L’Homme B, Scholl G, Eppe G, Focant J-F. Validation of a gas chromatography-triple quadrupole mass spectrometry method for confirmatory analysis of dioxins and dioxin-like polychlorobiphenyls in feed following new EU Regulation 709/2014. J Chromatogr A. 2015;1376:149–58.

    Article  Google Scholar 

  56. Garrido Frenich A, González-Rodriguez MJ, Arrebola FJ. Potentiality of gas chromatography-triple quadrupole mass spectrometry in vanguard and rearguard methods of pesticide residues in vegetables. Anal Chem. 2005;15:4640–8.

    Article  Google Scholar 

  57. García-Bermejo A, Ábalos M, Sauló J, Abad E, González MJ, Gómara B. Triple quadrupole tandem mass spectrometry: a real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls. Anal Chim Acta. 2015;889:156–65.

    Article  Google Scholar 

  58. Bolaños PP, Garrido-Frenich A, Vidal JL. Application of gas chromatography-triple quadrupole mass spectrometry in the quantification-confirmation of pesticides and polychlorinated biphenyls in eggs at trace levels. J Chromatogr A. 2007;1167:9–17.

    Article  Google Scholar 

  59. Onwudili J, Hajizadeh Y, Zainal S, Upton J, Williams PT. Application of low-temperature CP-Sil 88 column for the isomeric analysis of toxic 2378-substituted PCDD/Fs in incinerator flyash and sewage sludge using a triple quadrupole GC–MS/MS. Talanta. 2011;87:143–51.

    Article  CAS  Google Scholar 

  60. van Bavel B, Geng D, Cherta L, Nácher-Mestre J, Portolés T, Ábalos M, et al. Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins. Anal Chem. 2015;87:9047–53.

    Article  Google Scholar 

  61. Organtini K, Haimovici L, Jobst KJ, Reiner E, Ladak A, Stevens D, et al. Comparison of atmospheric pressure ionization gas chromatography-triple quadrupole mass spectrometry to traditional high-resolution mass spectrometry for the identification and quantification of halogenated dioxins and furans. Anal Chem. 2015;87:7902–8.

    Article  CAS  Google Scholar 

  62. Kotz A, Malisch R, Focant J, Eppe G, Cederberg TL, Rantakokko P, et al. Analytical criteria for use of MS/MS for determination of dioxins and dioxin-like PCBs in feed and food. Organohalogen Compd. 2012;74:156–9.

    Google Scholar 

  63. Wu JJ, Zhang B, Dong S-J, Zheng M-H. Determination of ultratrace polychlorinated dibenzo-p-dioxins and dibenzofurans by gas chromatography-triple quadrupole mass spectrometry. Chinese J Anal Chem. 2011;39:1297–301.

    Article  CAS  Google Scholar 

  64. Hayward V. Determination of polychlorinated dibenzo-p-dioxin and dibenzofuran background in milk and cheese by quadrupole ion storage collision-induced dissociation MS/MS. Chemosphere. 1997;34:929–39.

    Article  CAS  Google Scholar 

  65. Reference Materials. European Commission (EC) (1996) The certification of the contents (mass fractions) of five polychlorodibenzo-p-dioxins (D48, D54, D66, D67, D70) and six poly-chlorodibenzofurans (F83, F94, F114, F118, F121, F130) in milk powder CRM 607. Reference Materials. European Commission, BCR Information Series. Reference Materials. Report EUR 16999 EN

  66. Commission Regulation, Commission Regulation (EC) (2006) No. 1883/2006 of 19 December 2006 laying down methods of sampling and analysis for the official control of levels of dioxins and dioxin-like PCBs in certain foodstuffs. Off J Eur Union L 364/32-364/43

Download references

Acknowledgments

The authors want to thank M.G. Martrat, M. Adrados, J. Parera, and O. Palacios for their participation and contribution to the project. In addition, the authors would like to thank Brock Chittim of Wellington Laboratories for providing analytical standards. D.P. gratefully acknowledges COLCIENCIAS for her doctoral fellowship.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Esteban Abad.

Ethics declarations

Conflict of interest

The authors declare that they have no conflicts of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 69 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ábalos, M., Cojocariu, C.I., Silcock, P. et al. Meeting the European Commission performance criteria for the use of triple quadrupole GC-MS/MS as a confirmatory method for PCDD/Fs and dl-PCBs in food and feed samples. Anal Bioanal Chem 408, 3511–3525 (2016). https://doi.org/10.1007/s00216-016-9428-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-016-9428-9

Keywords

Navigation