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Liquid chromatography-mass spectrometry method for the determination of polyethylene terephthalate and polybutylene terephthalate cyclic oligomers in blood samples

Analytical and Bioanalytical Chemistry volume 414, pages 1503–1512 (2022)Cite this article

Abstract

Food contact materials (FCM) polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) used extensively in food packaging may contain cyclic oligomers which may migrate into food and thus cause toxic effects on human health. A simple, fast, and sensitive ultra-high-performance liquid chromatography method quadrupole time-of-flight mass spectrometer was developed for the analysis of 7 cyclic oligomers in post-mortem blood samples. The targeted analytes were separated on a Waters BEH C18 (150 × 2.1 mm, 1.7 µm) analytical column by gradient elution. Calibration curves were constructed based on standard solutions and blood samples and Student’s t-test was applied to evaluate the matrix effect. The LODs ranged from 1.7 to 16.7 μg mL−1, while the method accuracy was assessed by recovery experiments and resulting within the range 84.2–114.6%. Such an analytical method for the determination of PET and PBT cyclic oligomers in biological samples is reported for the first time. The developed methodology allows the determination of these oligomers in blood providing a useful analytical tool to assess the exposure and thus the potential hazard and health risks associated with these non-intentionally added substances (NIAS) from PET and PBT FCM through food consumption. The method was validated and successfully applied to the analysis of 34 post-mortem whole blood samples. Polyethylene terephthalate trimer was detected in four of them, for the first time in literature.

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References

  1. Lopes JA, Tsochatzis ED, Karasek L, Hoekstra EJ, Emons H. Analysis of PBT and PET cyclic oligomers in extracts of coffee capsules and food simulants by a HPLC-UV / FLD method. Food Chem. 2021;345:128739. https://doi.org/10.1016/j.foodchem.2020.128739.

    Article  CAS  Google Scholar 

  2. Tsochatzis ED, Lopes JA, Holland MV, Reniero F, Emons H, Guillou C. Isolation, characterization and structural elucidation of polybutylene terephthalate cyclic oligomers and purity assessment using a 1H qNMR method. Polymers (Basel). 2019;11:1–13. https://doi.org/10.3390/polym11030464.

    Article  CAS  Google Scholar 

  3. Piccinini P, Senaldi C, Lopes JFA (2013) Fibre labelling polytrimethylene terephthalate - PTT- DuPonthttps://doi.org/10.2788/34915

  4. Hoppe M, Fornari R, de Voogt P, Franz R. Migration of oligomers from PET: determination of diffusion coefficients and comparison of experimental versus modelled migration. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2017;34:1251–60. https://doi.org/10.1080/19440049.2017.1322222.

    Article  CAS  PubMed  Google Scholar 

  5. Tsochatzis E, Dehouck P, Lopes JA, Emteborg H, Robouch E, Hoekstra E. Determination of PBT cyclic oligomers in and migrated from food contact materials-FCM-19/01 Proficiency Testing Report. JRC Technical Reports. 2019; JRC118572, Ispra, European Commission.

  6. Ubeda S, Aznar M, Nerín C. Determination of oligomers in virgin and recycled polyethylene terephthalate (PET) samples by UPLC-MS-QTOF. Anal Bioanal Chem. 2018;410:2377–84. https://doi.org/10.1007/s00216-018-0902-4.

    Article  CAS  PubMed  Google Scholar 

  7. Muncke J, Backhaus T, Geueke B, Maffini MV, Martin OV, Myers JP, Soto AM, Trasande L, Trier X, Scheringer M. Scientific challenges in the risk assessment of food contact materials. Environ Health Perspect. 2017;125:1–9. https://doi.org/10.1289/EHP644.

    Article  Google Scholar 

  8. Brenz F, Linke S, Simat T. Linear and cyclic oligomers in polybutylene terephthalate for food contact materials. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2018;35:583–98. https://doi.org/10.1080/19440049.2017.1414958.

    Article  CAS  PubMed  Google Scholar 

  9. Kubicova M, Eckardt M, Simat TJ. Polybutylenterephthalat (PBT) im Lebensmittelkontakt: Migrationspotential von oligomeren Verbindungen. Lebensmittelchemie. 2019;73:1–2. https://doi.org/10.1002/lemi.201951018.

    Article  Google Scholar 

  10. Tsochatzis ED, Alberto Lopes J, Dehouck P, Robouch P, Hoekstra E. Proficiency test on the determination of polyethylene and polybutylene terephthalate cyclic oligomers in a food simulant. Food Packag Shelf Life. 2020;23:100441. https://doi.org/10.1016/j.fpsl.2019.100441.

    Article  PubMed  PubMed Central  Google Scholar 

  11. Alberto Lopes J, Tsochatzis ED, Robouch P, Hoekstra E. Influence of pre-heating of food contact polypropylene cups on its physical structure and on the migration of additives. Food Packag Shelf Life. 2019;20:100305. https://doi.org/10.1016/j.fpsl.2019.100305.

    Article  PubMed  PubMed Central  Google Scholar 

  12. Dehouck P, Tsochatzis ED, Lopes JA, Cizek-Stroh A, Robouch P, Hoekstra EJ. Determination of the mass fractions of PBT and PET oligomers in food simulant D1-FCM-18-01 Proficiency Test Report. JRC Validated methods, Reference Methods and Measurements Report. 2018; JRC113664, Ispra, European Commission.

  13. Muncke J, Andersson AM, Backhaus T, Boucher JM, Carney Almroth B, Castillo Castillo A, Chevrier J, Demeneix BA, Emmanuel JA, Fini JB, Gee D, Geueke B, Groh K, Heindel JJ, Houlihan J, Kassotis CD, Kwiatkowski CF, Lefferts LY, Maffini MV, Martin OV, Myers JP, Nadal A, Nerin C, Pelch KE, Fernández SR, Sargis RM, Soto AM, Trasande L, Vandenberg LN, Wagner M, Wu C, Zoeller RT, Scheringer M. Impacts of food contact chemicals on human health: a consensus statement. Environ Heal A Glob Access Sci Source. 2020;19:1–12. https://doi.org/10.1186/s12940-020-0572-5.

    Article  Google Scholar 

  14. Cramer GM, Ford RA, Hall RL. Estimation of toxic hazard-a decision tree approach. Food Cosmet Toxicol. 1976;16:255–76. https://doi.org/10.1016/S0015-6264(76)80522-6.

    Article  Google Scholar 

  15. Tsochatzis ED, Alberto Lopes J, Kappenstein O, Tietz T, Hoekstra EJ. Quantification of PET cyclic and linear oligomers in teabags by a validated LC-MS method – in silico toxicity assessment and consumer’s exposure. Food Chem. 2020;317:126427. https://doi.org/10.1016/j.foodchem.2020.126427.

    Article  CAS  PubMed  Google Scholar 

  16. Ubeda S, Aznar M, Alfaro P, Nerín C. Migration of oligomers from a food contact biopolymer based on polylactic acid (PLA) and polyester. Anal Bioanal Chem. 2019;411:3521–32. https://doi.org/10.1007/s00216-019-01831-0.

    Article  CAS  PubMed  Google Scholar 

  17. Eckardt M, Schneider J, Simat TJ. In vitro intestinal digestibility of cyclic aromatic polyester oligomers from polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2019;36:1882–94. https://doi.org/10.1080/19440049.2019.1658903.

    Article  CAS  PubMed  Google Scholar 

  18. Begley TH, Dennison JL, Hollifield HC. Migration into food of polyethylene terephthalate (Pet) cyclic oligomers from pet microwave susceptor packaging. Food Addit Contam. 1990;7:797–803. https://doi.org/10.1080/02652039009373941.

    Article  CAS  PubMed  Google Scholar 

  19. Isella F, Canellas E, Bosetti O, Nerin C. Migration of non intentionally added substances from adhesives by UPLC-Q-TOF/MS and the role of EVOH to avoid migration in multilayer packaging materials. J Mass Spectrom. 2013;48:430–7. https://doi.org/10.1002/jms.3165.

    Article  CAS  PubMed  Google Scholar 

  20. Kim DJ, Lee KT. 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;31:490–9. https://doi.org/10.1016/j.polymertesting.2012.02.001.

    Article  CAS  Google Scholar 

  21. Lim BH, Kwon SH, Kang EC, Park H, Lee HW, Kim WG. Isolation and identification of cyclic oligomers of the poly(ethylene terephthalate)-poly(ethylene isophthalate) copolymer. J Polym Sci Part A Polym Chem. 2003;41:881–9. https://doi.org/10.1002/pola.10637.

    Article  CAS  Google Scholar 

  22. Tsochatzis ED, Alberto Lopes J, Gika H, Kastrup Dalsgaard T, Theodoridis G. Development and validation of an UHPLC-qTOF-MS method for the quantification of cyclic polyesters oligomers in pasta by applying a modified QuEChERS clean-up. Food Chem. 2021;347:129040. https://doi.org/10.1016/j.foodchem.2021.129040.

    Article  CAS  PubMed  Google Scholar 

  23. Ubeda S, Aznar M, Rosenmai AK, Vinggaard AM, Nerín C. Migration studies and toxicity evaluation of cyclic polyesters oligomers from food packaging adhesives. Food Chem. 2020;311:125918. https://doi.org/10.1016/j.foodchem.2019.125918.

    Article  CAS  PubMed  Google Scholar 

  24. Úbeda S, Aznar M, Vera P, Nerín C, Henríquez L, Taborda L, Restrepo C. Overall and specific migration from multilayer high barrier food contact materials–kinetic study of cyclic polyester oligomers migration. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2017;34:1784–94. https://doi.org/10.1080/19440049.2017.1346390.

    Article  CAS  PubMed  Google Scholar 

  25. Úbeda S, Aznar M, Alfaro P, Nerín C. Migration of oligomersfrom a food contact biopolymer based on polylactic acid (PLA) and polyester. Anal Bioanal Chem. 2019;411:3521–32. https://doi.org/10.1007/s00216-019-01831-0.

    Article  CAS  PubMed  Google Scholar 

  26. Diamantidou D, Begou O, Theodoridis G, Gika H, Tsochatzis E, Kalogiannis S, Kataiftsi N, Soufleros E, Zotou A. Development and validation of an ultra high performance liquid chromatography-tandem mass spectrometry method for the determination of phthalate esters in Greek grape marc spirits. J Chromatogr A. 2019;1603:165–78. https://doi.org/10.1016/j.chroma.2019.06.034.

    Article  CAS  PubMed  Google Scholar 

  27. Likas DT, Tsiropoulos NG, Miliadis GE. Rapid gas chromatographic method for the determination of famoxadone, trifloxystrobin and fenhexamid residues in tomato, grape and wine samples. J Chromatogr A. 2007;1150:208–14. https://doi.org/10.1016/j.chroma.2006.08.041.

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

The authors would like to thank Dr. João Alberto Lopes (JRC-Geel) for his support.

Funding

This research is carried out/funded in the context of the project “Method development for the determination of cyclic oligomers from food contact materials and exposure assessment.” (MIS 5048286) under the call for proposals “Supporting researchers with emphasis on new researchers” (EDULLL 103). The project is co-financed by Greece and the European Union (European Social Fund-ESF) by the Operational Programme Human Resources Development, Education and Lifelong Learning 2014–2020.

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Author notes

  1. Emmanouil Tsochatzis

    Present address: European Food Safety Authority-EFSA, Via Carlo Magno 1A, Parma, 43126, Italy

Authors and Affiliations

  1. Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, 54124, Thessaloniki, Greece

    Dimitra Diamantidou & Georgios Theodoridis

  2. Biomic_AUTh, Center for Interdisciplinary Research and Innovation (CIRI-AUTH), Balkan Center, B1.4, 10th km Thessaloniki-Thermi Rd, P.O. Box 8318, 57001, Thessaloniki, Greece

    Dimitra Diamantidou, Georgios Theodoridis, Nikolaos Raikos, Helen Gika & Stavros Kalogiannis

  3. Laboratory of Toxicology, Forensic Service of Thessaloniki, 56334, Thessaloniki, Greece

    Orthodoxia Mastrogianni

  4. Department of Food Science, iFOOD, Centre for Innovative Food Research, Aarhus University, Agro Food Park 48, 8200, Aarhus, Denmark

    Emmanouil Tsochatzis

  5. Laboratory of Forensic Medicine and Toxicology, School of Medicine, Aristotle University of Thessaloniki, 54124, Thessaloniki, Greece

    Nikolaos Raikos & Helen Gika

  6. Laboratory of Chemical Biology, Department of Nutritional, Sciences and Dietetics, International Hellenic University, 57400, Thessaloniki, Greece

    Stavros Kalogiannis

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Correspondence to Stavros Kalogiannis.

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The collection and analysis of post-mortem blood samples used in this study were approved by Forensic Service of Thessaloniki.

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Diamantidou, D., Mastrogianni, O., Tsochatzis, E. et al. Liquid chromatography-mass spectrometry method for the determination of polyethylene terephthalate and polybutylene terephthalate cyclic oligomers in blood samples. Anal Bioanal Chem 414, 1503–1512 (2022). https://doi.org/10.1007/s00216-021-03741-6

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  • DOI: https://doi.org/10.1007/s00216-021-03741-6

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