Toward the characterisation of non-intentionally added substances migrating from polyester-polyurethane lacquers by comprehensive gas chromatography-mass spectrometry technologies.

Polyester-polyurethane lacquer, used to cover the inner surface of metallic food contact materials, may transfer non-intentionally added substances (NIAS) to the food. The identification of such a diversity of compounds, considered as migrating substances, requires taking advantage of complementary analytical platforms. Therefore, four types of gas chromatography-mass spectrometry (GCMS) couplings were investigated and compared for their abilities to identify migrating substances after acetonitrile extraction of two commercialised lacquers. In parallel, various ionisation sources, i.e. electron ionisation (EI) (70 eV and soft energies) and atmospheric-pressure chemical ionisation (APCI) as well as various mass analysers, i.e. quadrupole, time-of-flight (low and high resolution) and Orbitrap, were tested. Comparison of mass spectra with a commercial library for EI ionisation source led to the identification of two NIAS compounds, isophorone diisocyanate and 4,4'-diphenylmethane diisocyanate. Additionally, many cyclic oligoesters (four monomer units) were unambiguously identified according to supplier's declaration on starting materials used, primarily based on the molecular ion observed by APCI mode and characteristic fragment ions. High resolution mass analysers also enhanced confidence level in such NIAS identification. One- and two-dimensional GC were also investigated for separation assessment. Although GC × GC did not reveal additional NIAS, its use provided a valuable mapping of oligomers according to monomers composition. These results were compared to our previously published LC-MS study, carried out on the same lacquer samples. This study shows that LC and GC, along with their related ionisation techniques and their own selectivity, are complementary approaches, revealing different classes of compounds covering a wide range of volatility and polarity.

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

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.