Analytical and Bioanalytical Chemistry

, Volume 410, Issue 22, pp 5391–5403 | Cite as

Elucidation of non-intentionally added substances migrating from polyester-polyurethane lacquers using automated LC-HRMS data processing

  • Elsa Omer
  • Ronan CariouEmail author
  • Gérald Remaud
  • Yann Guitton
  • Hélène Germon
  • Paul Hill
  • Gaud Dervilly-Pinel
  • Bruno Le Bizec
Paper in Forefront
Part of the following topical collections:
  1. Food Safety Analysis


An untargeted strategy aiming at identifying non-intentionally added substances (NIAS) migrating from coatings was developed. This innovative approach was applied to two polyester-polyurethane lacquers, for which suppliers previously provided the identity of the monomers involved. Lacquers were extracted with acetonitrile and analyzed by liquid chromatography-high resolution mass spectrometry (LC-HRMS). Data, acquired in the full scan mode, were processed using an open-source R-environment (xcms and CAMERA packages) to list the detected features and deconvolute them in groups related to individual compounds. The most intense groups, accounting for more than 85% of cumulated feature intensities, were then investigated. A homemade database, populated with predicted polyester oligomer combinations from a relevant selection of diols and diacids, enabled highlighting the presence of 14 and 17 cyclic predicted polyester oligomers in the two lacquers, including three mutual combinations explained by common known monomers. Combination hypotheses were strengthened by chromatographic considerations and by the investigation of fragmentation patterns. Regarding unpredicted migrating substances, four monomers were hypothesised to explain several polyester or caprolactam oligomer series. Finally, considering both predicted and tentatively elucidated unpredicted oligomers, it was possible to assign hypotheses to features representing up to 82% and 90% of the cumulated intensities in the two lacquers, plus 9% and 3% (respectively) originating from the procedural blank.

Graphical abstract

Elucidation of non-intentionally added substances


Food contact material Non-intentionally added substance Oligomer Untargeted approach HRMS screening Chemical food safety 



The authors are grateful to the two lacquer suppliers, Metlac (Bosco Marengo, Italy) and Valspar Corporation (Chipping Norton, UK), for the information provided on formulations.

Compliance with ethical standards

Conflict of interest

The authors declare that there are no conflicts of interest.

Supplementary material

216_2018_968_MOESM1_ESM.pdf (1.2 mb)
ESM 1 (PDF 1270 kb)


  1. 1.
    European Chemical Agency. MSC unanimously agrees that Bisphenol A is an endocrine disruptor. ECHA/PR/17/12. [Internet]. 2017 [cited 2017 Jun 21]. Available from:
  2. 2.
    Commission Implementing Regulation (EU) No 321/2011 of 1 April 2011 amending Regulation (EU) No 10/2011 as regards the restriction of use of Bisphenol A in plastic infant feeding bottles. Off J Eur Union. 2011;L 87/1.Google Scholar
  3. 3.
    LOI no 2010-729 du 30 juin 2010 tendant à suspendre la commercialisation de biberons produits à base de bisphénol A. J Off la République Française. 2010.Google Scholar
  4. 4.
    LOI no 2012-1442 du 24 décembre 2012 visant à la suspension de la fabrication, de l’importation, de l’exportation et de la mise sur le marché de tout conditionnement à vocation alimentaire contenant du bisphénol A. J Off la République Française. 2012.Google Scholar
  5. 5.
    European Commission. Regulation (EC) No 1935/2004 on materials and articles intended to come into contact with food and repealing Directives 80/590/EEC and 89/109/EEC. Off J Eur Union. 2004;L338/4.Google Scholar
  6. 6.
    Council of Europe Framework Resolution ResAP (2004) 1 on coatings intended to come into contact with foodstuffs. 2009.Google Scholar
  7. 7.
    European Commission. Regulation (EU) No 10/2011 on plastic materials and articles intended to come into contact with food. Off J Eur Union. 2011;L 12/1.Google Scholar
  8. 8.
    Wicks ZW. Blocked isocyanates. Prog Org Coatings. 1975;3(1):73–99.CrossRefGoogle Scholar
  9. 9.
    Nerin C, Alfaro P, Aznar M, Domeño C. The challenge of identifying non-intentionally added substances from food packaging materials: A review. Anal Chim Acta. 2013;775:14–24.CrossRefPubMedGoogle Scholar
  10. 10.
    ILSI Europe. Guidance on best practices on the risk assessment of non intentionally added substances (NIAS) in food contact materials and articles. [cited 2017 Apr 27]; Available from:
  11. 11.
    Hoppe M, de Voogt P, Franz R. Identification and quantification of oligomers as potential migrants in plastics food contact materials with a focus in polycondensates - A review. Trends Food Sci Technol. 2016;50:118–30.CrossRefGoogle Scholar
  12. 12.
    European Food Safety Authority. Food contact materials: Note for guidance for petitioners presenting an application for the safety assessment of a substance to be used in food contact materials prior to its authorisation. EFSA J. 2008;7:1–125.Google Scholar
  13. 13.
    Besnoin J-M, Choi KY. Identification and characterization of reaction byproducts in the polymerization of polyethylene terephthalate. J Macromol Sci Part C Polym Rev. 1989 Feb;29(1):55–81.CrossRefGoogle Scholar
  14. 14.
    Milon H. Identification of poly(ethylene terephthalate) cyclic oligomers by liquid chromatography-mass spectrometry. J Chromatogr. 1991;554(1–2):305–9.CrossRefGoogle Scholar
  15. 15.
    Barnes KA, Damant AP, Startin JR, Castle L. Qualitative liquid chromatographic-atmospheric-pressure chemical-ionisation mass spectrometric analysis of polyethylene terephthalate oligomers. J Chromatogr A. 1995;712(1):191–9.CrossRefGoogle Scholar
  16. 16.
    Bryant JJL, Semlyen JA. Cyclic polyesters: 6. Preparation and characterization of two series of cyclic oligomers from solution ring-chain reactions of poly(ethylene terephthalate). Polymer. 1997;38(10):2475–82.CrossRefGoogle Scholar
  17. 17.
    Harrison AG, Taylor MJ, Scrivens JH, Yates H. Analysis of cyclic oligomers of poly(ethylene terephthalate) by liquid chromatography/mass spectrometry. Polymer. 1997;38(10):2549–55.CrossRefGoogle Scholar
  18. 18.
    Lim B, Kwon S, Kang E, Park H, Lee H, Kim W. Isolation and identification of cyclic oligomers of the poly(ethylene terephthalate)-poly(ethylene isophthalate) copolymer. J Polym Sci Part A Polym Chem. 2003;41(7):881–9.CrossRefGoogle Scholar
  19. 19.
    Nasser ALM, Lopes LMX, Eberlin MN, Monteiro M. Identification of oligomers in polyethyleneterephthalate bottles for mineral water and fruit juice: Development and validation of a high-performance liquid chromatographic method for the determination of first series cyclic trimer. J Chromatogr A. 2005;1097(1):130–7.CrossRefPubMedGoogle Scholar
  20. 20.
    Kim D-J, Lee K-T. Determination of monomers and oligomers in polyethylene terephthalate trays and bottles for food use by using high performance liquid chromatography-electrospray ionization-mass spectrometry. Polym Test. 2012;31(3):490–9.CrossRefGoogle Scholar
  21. 21.
    Bignardi C, Cavazza A, Corradini C, Salvadeo P. Targeted and untargeted data-dependent experiments for characterization of polycarbonate food-contact plastics by ultra high performance chromatography coupled to quadrupole orbitrap tandem mass spectrometry. J Chromatogr A. 2014;1372:133–44.CrossRefGoogle Scholar
  22. 22.
    Brenz F, Linke S, Simat T. Linear and cyclic oligomers in polybutylene terephthalate for food contact materials. Food Addit Contam Part A. 2017.Google Scholar
  23. 23.
    Bignardi C, Cavazza A, Laganà C, Salvadeo P, Corradini C. Release of non-intentionally added substances (NIAS) from food contact polycarbonate: Effect of ageing. Food Control. 2017;71:329–35.CrossRefGoogle Scholar
  24. 24.
    Canellas E, Vera P, Nerín C. UPLC-ESI-Q-TOF-MS(E) and GC-MS identification and quantification of non-intentionally added substances coming from biodegradable food packaging. Anal Bioanal Chem. 2015;407(22):6781–90.CrossRefPubMedGoogle Scholar
  25. 25.
    Biedermann M, Grob K. Food contamination from epoxy resins and organosols used as can coatings: Analysis by gradient NPLC. Food Addit Contam. 1998 Jul 10;15(5):609–18.CrossRefPubMedGoogle Scholar
  26. 26.
    Bradley EL, Driffield M, Harmer N, Oldring PKT, Castle L. Identification of Potential Migrants in Epoxy Phenolic Can Coatings. Int J Polym Anal Charact. 2008;13(3):200–23.CrossRefGoogle Scholar
  27. 27.
    Vaclavikova M, Paseiro-Cerrato R, Vaclavik L, Noonan GO, DeVries J, Begley TH. Target and non-target analysis of migrants from PVC-coated cans using UHPLC-Q-Orbitrap MS: evaluation of long-term migration testing. Food Addit Contam Part A. 2016;11:1–12.CrossRefGoogle Scholar
  28. 28.
    Schaefer A, Ohm VA, Simat TJ. Migration from can coatings: Part 2. Identification and quantification of migrating cyclic oligoesters below 1000 Da. Food Addit Contam. 2004;21(4):377–89.CrossRefPubMedGoogle Scholar
  29. 29.
    Bradley E, Driffield M, Guthrie J, Harmer N, Thomas Oldring PK, Castle L. Analytical approaches to identify potential migrants in polyester–polyurethane can coatings. Food Addit Contam Part A. 2009;26(12):1602–10.CrossRefGoogle Scholar
  30. 30.
    Paseiro-Cerrato R, MacMahon S, Ridge CD, Noonan GO, Begley TH. Identification of unknown compounds from polyester cans coatings that may potentially migrate into food or food simulants. J Chromatogr A. 2016;1444:106–13.CrossRefPubMedGoogle Scholar
  31. 31.
    Martínez-Bueno MJ, Hernando MD, Uclés S, Rajski L, Cimmino S, Fernández-Alba AR. Identification of non-intentionally added substances in food packaging nano films by gas and liquid chromatography coupled to orbitrap mass spectrometry. Talanta. 2017 Sep;172:68–77.CrossRefPubMedGoogle Scholar
  32. 32.
    Tautenhahn R, Böttcher C, Neumann S. Highly sensitive feature detection for high resolution LC/MS. BMC Bioinformatics. 2008;9:504.CrossRefPubMedPubMedCentralGoogle Scholar
  33. 33.
    Cariou R, Omer E, Léon A, Dervilly-Pinel G, Le Bizec B. Screening halogenated environmental contaminants in biota based on isotopic pattern and mass defect provided by high resolution mass spectrometry profiling. Anal Chim Acta. 2016;936:130–8.CrossRefPubMedGoogle Scholar
  34. 34.
    Smith CA, Want EJ, O’Maille G, Abagyan R, Siuzdak G, Smith CA, et al. XCMS: processing mass spectrometry data for metabolite profiling using Nonlinear Peak Alignment,Matching,and Identification. Anal Chem. 2006;78(3):779–87.CrossRefPubMedGoogle Scholar
  35. 35.
    Kuhl C, Tautenhahn R, Böttcher C, Larson TR, Neumann S. CAMERA: An Integrated Strategy for Compound Spectra Extraction and Annotation of Liquid Chromatography/Mass Spectrometry Data Sets. Anal Chem. 2012;84(1):283–9.CrossRefPubMedGoogle Scholar
  36. 36.
    Sumner LW, Amberg A, Barrett D, Beale MH, Beger R, Daykin CA, et al. Proposed minimum reporting standards for chemical analysis. Metabolomics. 2007;3(3):211–21.CrossRefPubMedPubMedCentralGoogle Scholar
  37. 37.
    Jenke D, Poss M, Sadain S, Story J, Smith W, Reiber D. Identification of caprolactam oligomers and related compounds in aqueous extracts of nylon-6. J Appl Polym Sci. Inc. 2005;95(5):1262–74.CrossRefGoogle Scholar
  38. 38.
    Úbeda S, Aznar M, Vera P, Nerín C, Henríquez L, Taborda L, et al. Overall and specific migration from multilayer high barrier food contact materials – kinetic study of cyclic polyester oligomers migration. Food Addit Contam Part A. 2017;12:1–11.Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Elsa Omer
    • 1
    • 2
    • 3
  • Ronan Cariou
    • 1
    Email author
  • Gérald Remaud
    • 2
  • Yann Guitton
    • 1
  • Hélène Germon
    • 3
  • Paul Hill
    • 3
  • Gaud Dervilly-Pinel
    • 1
  • Bruno Le Bizec
    • 1
  1. 1.LABERCA, Oniris, INRA, Université Bretagne-LoireNantesFrance
  2. 2.CEISAM, Université de Nantes, UMR CNRS 6230NantesFrance
  3. 3.ARDAGH MP WEST France SASCrosmièresFrance

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