Analytical and Bioanalytical Chemistry

, Volume 403, Issue 10, pp 2869–2882 | Cite as

Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food simulants

  • Juliana S. Félix
  • Francesca Isella
  • Osvaldo Bosetti
  • Cristina NerínEmail author
Original Paper


Adhesives used in food packaging to glue different materials can provide several substances as potential migrants, and the identification of potential migrants and migration tests are required to assess safety in the use of adhesives. Solid-phase microextraction in headspace mode and gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) and ChemSpider and SciFinder databases were used as powerful tools to identify the potential migrants in the polyurethane (PU) adhesives and also in the individual plastic films (polyethylene terephthalate, polyamide, polypropylene, polyethylene, and polyethylene/ethyl vinyl alcohol). Migration tests were carried out by using Tenax® and isooctane as food simulants, and the migrants were analyzed by gas chromatography coupled to mass spectrometry. More than 63 volatile and semivolatile compounds considered as potential migrants were detected either in the adhesives or in the films. Migration tests showed two non-intentionally added substances (NIAS) coming from PU adhesives that migrated through the laminates into Tenax® and into isooctane. Identification of these NIAS was achieved through their mass spectra, and 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione were confirmed. Caprolactam migrated into isooctane, and its origin was the external plastic film in the multilayer, demonstrating real diffusion through the multilayer structure. Comparison of the migration values between the simulants and conditions will be shown and discussed.


Cross-section of multilayer packaging material (polyethylene terephthalate/adhesive /oriented polyamide/adhesive/cast polypropylene) viewed by optical microscopy


Food safety Multilayer food packaging Polyurethane adhesives Migration NIAS 



This work has been financed by the Project SAFEMTECH (IAPP-MARIE CURIE Actions 2011–2014, 7TH FP).


  1. 1.
    Störmer A, Franz R (2009) Food Addit Contam 26:1581–1591CrossRefGoogle Scholar
  2. 2.
    Canellas E, Nerín C, Moore R, Silcock P (2010) Anal Chim Acta 666:62–69CrossRefGoogle Scholar
  3. 3.
    Aznar M, Vera P, Canellas E, Nerín C, Mercea P, Störmer A (2011) J Mater Chem 21:4368–4370CrossRefGoogle Scholar
  4. 4.
    Vera P, Aznar M, Mercea P, Nerin C (2011) J Mater Chem 21:420–431CrossRefGoogle Scholar
  5. 5.
    Aznar M, Canellas E, Nerín C (2009) J Chromatogr A 1216:5176–5181CrossRefGoogle Scholar
  6. 6.
    Nerin C, Canellas E, Aznar M, Silcock P (2009) Food Addit Contam 26:1592–1601CrossRefGoogle Scholar
  7. 7.
    Bradley EL, Castle L (2006) Chemical migration from adhesives used in food-contact materials and articles. FSA project A03044. London (UK): Food Standards Agency (FSA)Google Scholar
  8. 8.
    Bradley E, Castle L (2007) In: Barnes KA, Sinclair CR, Watson DH (eds) Chemical migration and food contact materials. Woodhead Publishing Limited, CambridgeGoogle Scholar
  9. 9.
    Sidwell J, Barber M, Cope R (2003) Investigation into the application of food-contact laminated materials: examination of migration potential and recommendations for safe use. Rapra Tecnhology, Shropshire, p 157Google Scholar
  10. 10.
    FDA (2011) US Food and Drug Administration. Code of Federal Regulations Title 21. Part 175 indirect food additives: adhesives and components of coatings. Subpart B-substances for use only as components of adhesives. Accessed 15 Nov 2011
  11. 11.
    FDA (2011) US Food and Drug Administration. Code of Federal Regulations Title 21. Part 177 indirect food additives: polymers. Subpart B-substances for use as basic components of single and repeated use Food Contact Surfaces. Sec. 177.1390 laminate structures for use at temperatures of 250 °F and above. Accessed 15 Nov 2011
  12. 12.
    EC (2004) Regulation (EC) no. 1935/2004 of the European Parliament and of the Council of 27 October 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 L338:4Google Scholar
  13. 13.
    EC (2011) Commission Regulation (EU) no. 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food. Off J Eur Union, L12:1-89Google Scholar
  14. 14.
    Real Decreto 847/2011, de 17 de junio, por el que se establece la lista positiva de sustancias permitidas para la fabricación de materiales poliméricos destinados a entrar en contacto con los alimentos. BOE, Sec. I., 164: 76316-76330Google Scholar
  15. 15.
    BfR (2010) Bundesinstitut für Risikobewertung Recommendation XXVIII. Cross-linked polyurethanes as adhesive layers for food packaging materials.;jsessionid=45419212FA368A10FCF046E4A0BCD050. Accessed 15 Nov 2011
  16. 16.
    Canellas E, Aznar M, Nerin C, Mercea P (2010) J Mater Chem 20:5100–5109CrossRefGoogle Scholar
  17. 17.
    Kolb B (1982) Chromatographia 15:587–594CrossRefGoogle Scholar
  18. 18.
    Ezquerro O, Pons B, Tena MT (2003) J Chromatogr A 999:155–164CrossRefGoogle Scholar
  19. 19.
    Ezquerro O, Pons B, Tena MT (2003) J Chromatogr A 985:247–257CrossRefGoogle Scholar
  20. 20.
    Licciardello F, Muratore G, Mercea P, Tosa V, Nerín C (2012) Packag Technol SciGoogle Scholar
  21. 21.
    Félix JS, Monteiro M, Manzoli JE, Padula M, Pezo D, Romero J, Nerin C (2008) Anal Bioanal Chem 391:847–857CrossRefGoogle Scholar
  22. 22.
    Viñas P, Campillo N, Martinez-Castillo N, Hernandez-Cordoba M (2009) Anal Bioanal Chem 397:115–125CrossRefGoogle Scholar
  23. 23.
    Ou Q-R, Whang C-W (2006) Anal Bioanal Chem 386:376–381CrossRefGoogle Scholar
  24. 24.
    ChemSpider (2009) Royal Society of Chemistry. Accessed 17 Oct 2011
  25. 25.
    SciFinder (2011) American Chemical Society. Accessed 17 Oct 2011
  26. 26.
    Nerín C, Asensio E (2007) Anal Bioanal Chem 389:589–597CrossRefGoogle Scholar
  27. 27.
    IdeaconsultLtd (2011) Toxtree-toxic hazard estimation by decision tree approach (Sofia, Bulgaria) Accessed 24 March 2011
  28. 28.
    Cramer GM, Ford RA, Hall RL (1978) J Cosmet Toxicol 16:255–276CrossRefGoogle Scholar
  29. 29.
    Barlow S (2005) Threshold of toxicological concern (TTC): a tool for assessing substances of unknown toxicity present at low levels in the diet. ILSI (International Life Sciences Institute). Accessed 01 Mar 2012
  30. 30.
    UNE-EN-14338 A (2004) Papel y cartón Para contacto alimentario. Condiciones para la determinación de la migración desde el papel y cartón utilizando óxido de polifenileno modificado (MPPO) como simulanteGoogle Scholar
  31. 31.
    Moon JH, Shul YG, Hong SY, Choi YS, Kim HT (2005) Int J Adhes Adhes 25:534–542CrossRefGoogle Scholar
  32. 32.
    Segura DM, Nurse AD, A. M, Phelps R, Segura A (2005) In: Cognard P (ed) Handbook of adhesives and sealants, v.1, 1st ed. Elsevier, KidlingtonGoogle Scholar
  33. 33.
    Wicks ZW Jr, Wicks DA, Rosthauser JW (2002) Prog Org Coat 44:161–183CrossRefGoogle Scholar
  34. 34.
    Nicolau A, Mariath RM, Martini EA, Martini DS, Samios D (2010) Mater Sci Eng C 30:951–962CrossRefGoogle Scholar
  35. 35.
    Espert A, de las Heras LA, Karlsson S (2005) Polym Degrad Stab 90:555–562CrossRefGoogle Scholar
  36. 36.
    Cruz JM, Silva AS, Garcia RS, Franz R, Losada PP (2008) J Food Eng 87:107–115CrossRefGoogle Scholar
  37. 37.
    Watanabe M, Nakata C, Wu W, Kawamoto K, Noma Y (2007) Chemosphere 68:2063–2072CrossRefGoogle Scholar
  38. 38.
    Pattono D, Battaglini LM, Barberio A, De Castelli L, Valiani A, Varisco G, Scatassa ML, Davit P, Pazzi M, Civera T (2009) Food Chem 115:285–289CrossRefGoogle Scholar
  39. 39.
    Thiebaut B, Lattuati-Derieux A, Hocevar M, Vilmont LB (2007) Polym Test 26:243–256CrossRefGoogle Scholar
  40. 40.
    Skjevrak I, Brede C, Steffensen I-L, Mikalsen A, Alexander J, Fjeldal P, Herikstad H (2005) Food Addit Contam 22:1012–1022CrossRefGoogle Scholar
  41. 41.
    Chattopadhyay DK, Webster DC (2009) Prog Polym Sci 34:1068–1133CrossRefGoogle Scholar
  42. 42.
    Dagostin VS, Golcalves DL, Pacheco CB, Almeida WB, Thome IP, Pich CT, Paula MMS, Silva L, Angioletto E, Fiori MA (2010) Mat Sci Eng C 30:705–708CrossRefGoogle Scholar
  43. 43.
    Félix JS, Monteiro M, Manzoli JE, Padula M (2010) J AOAC Int 93:1874–1881Google Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Juliana S. Félix
    • 1
  • Francesca Isella
    • 2
  • Osvaldo Bosetti
    • 2
  • Cristina Nerín
    • 1
    Email author
  1. 1.I3A, Department of Analytical ChemistryUniversity of Zaragoza (UNIZAR)ZaragozaSpain
  2. 2.Goglio SpA., Packaging DivisionR&D Chemical LaboratoryDaverioItaly

Personalised recommendations