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Phenomena in Plastic
Phenomena in Plastic
Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma
a r t i c l e i n f o a b s t r a c t
Article history: In most cases, food packaging materials contain inks whose components can migrate to food by diffu-
Received 12 January 2016 sion through the material as well as by set-off phenomena. In this work, different mass spectrometry
Received in revised form 21 April 2016 approaches had been used in order to identify and conrm the presence of ink components in ethanol
Accepted 6 May 2016
(95%) and Tenax as food simulants. Three different sets of materials, manufactured with different print-
Available online 9 May 2016
ing technologies and with different structures, were analyzed. Sample analysis by ultra performance
liquid chromatography mass spectrometry (UPLCMS), using a quadrupole-time of ight (Q-TOF) as a
Keywords:
mass analyser proved to be an excellent tool for identication purposes while ion mobility mass spec-
High resolution-mass spectrometry
Ion mobility-mass spectrometry
trometry (IM-MS) shown to be very useful for the conrmation of the candidates proposed. The results
Desorption electrospray ionization showed the presence of different non-volatile ink components in migration such as colorants (Solvent Red
Inks 49), plasticizers (dimethyl sebacate, tributyl o-acetyl citrate) or surfactants (Schercodine M, triethylene
Migration glycol caprilate). An oxidation product of an ink additive (triphenyl phosphine oxide) was also detected. In
Food packaging addition, a surface analysis technique, desorption electrospray mass spectrometry (DESI-MS), was used
for analyzing the distribution of some ink components (tributyl o-acetyl citrate Schercodine L, phtha-
lates) in the material. The detection of some of these compounds in the back-printed side conrmed
the transference of this compound from the non-food to the food contact side. The results also showed
that concentration of ink migrants decreased when an aluminum or polypropylene layer covered the ink.
When aluminum was used, concentration of most of ink migrants decreased, and for 5 out of the 9 even
disappeared.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chroma.2016.05.032
0021-9673/ 2016 Elsevier B.V. All rights reserved.
M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133 125
Table 1
Composition of materials studied in sets FOS, FIS and RIS. Material 1 (base material), material 2 (base material + ink) and material 3 (base material + ink + layer).
OPP: oriented polypropylene; PET: polyethylene terephthalate; PT: printing technology; PU: polyurethane
antioxidants has also been studied by other authors [2124]. Some and retention time will be no longer useful. Since CCS values do not
migration models based on penetration and Ficks second law have depend on the chromatographic conditions or the column used,
been developed in order to predict ink migration from packaging it is possible to create CCS libraries using different experimental
materials [19]. However, in most cases migration of ink compo- conditions. The inclusion of CCS values can provide increased con-
nents did not occur by permeation of the components through the dence in compounds identication. Ion mobility technology has
material but from set-off phenomena. Set-off can be dened by the been previously used in different areas, such as the detection of
transference of ink components from the non-food contact side to trace substances [29], the determination of 2,4,6-trichloroanisole
the food contact side of the packaging material during storage in (2,4,6-TCA) in wine [30] or the identication of quality markers
rolls, and this phenomenon is enhanced due to the high pressure virgin olive oil [31]. In this work, the CCS values of the compounds
reached inside the rolls. Some authors have studied the develop- detected were measured and used for conrmation purposes.
ment of low-migration offset printing inks for reduce this effect Set-off phenomenon in food packaging materials had been pre-
[25]. Commission Regulation (EC) No 2023/2006 on good manufac- viously studied by other authors, in most of cases focusing on
turing practice (GMP) for materials and articles intended to come volatile migrants. For this purpose, techniques based on ambient
into contact with food established that the printed surfaces shall ionization had been used, such as direct analysis in real time cou-
not come into direct contact with food and that when printing inks pled to time-of-ight mass spectrometry (DART-QTOF-MS) [32,33]
are applied to the non-food contact side of a material, GMP should or optical approaches [34]. In this work, the analysis of set-off has
ensure that substances are not transferred into food by set-off or been focused on non-volatile ink migrants. Desorption electrospray
transfer through the substrate [26]. There are no specic Regula- mass spectrometry (DESI-MS), a new ambient ionization technique
tions at European level related to ink components allowed in inks has been tested in order to locate specic migrants coming from
for packaging materials. Nevertheless, there is a National printing set-off phenomena on the polymeric surface of packaging materi-
ink Regulation in Swiss, [27] concerning food packaging printing als. This technique had been previously used by other authors for
inks and a positive list of components recommended to formulate the determination of melamine in migration from plastic materi-
printing inks for food packaging compiled by the European printing als [35] or phthalates in toys [36]. The use of this technique was
ink association (EUPIA) that manufacturers are expected to comply based on the results previously obtained in the analysis performed
with [28]. As it has been described previously in the introduction, by UPLCMS (Q-TOF) of migration extracts, where migrants had
not only the intentionally added substances used in inks manufac- been identied.
turing must be controlled, but also the NIAS, that can be generated
by the processes described and also during the curing of inks. This 2. Materials and methods
work has been focused on two main objectives. First, the determi-
nation of non-volatile ink components capable to migrate to food 2.1. Reagents and solutions
from different multilayer materials, and second, the study of how
the structure of the material and the application of layers covering Puried water was obtained with a Milli-Q 185 Plus system
inks can reduce, or even eliminate, the set-off processes. Since the (Millipore, Bedford, MA, USA), and ethanol (HPLC quality) was pur-
work is focused on non-volatiles compounds, analyses were per- chased from Scharlau Chemie S.A (Sentmenat, Spain). Methanol
formed by UPLCMS, using Q-TOF as a mass analyser, that allows and water for UPLCMS analysis (ultra LCMS quality) were pur-
the structural elucidation of unknown compounds. TOF mass anal- chased from Baker (Deventer, The Netherlands). Citric acid triethyl
ysers allow higher sensitivity in full scan and very accurate mass ester (CAS 7793-0), Schercodine L (CAS 3179-80-4), tripropylene
measurements. A tandem Q-TOF allows accurate mass determina- glycol monobutyl ether (CAS 55934-93-5), tributyl o-acetyl citrate
tions of the precursor ion and also of the product ions and also (CAS 7790-7), Solvent red 49 (CAS 509-34-2), triphenyl phosphine
provides information about fragmentation patterns. This comprises oxide (CAS 791-28-6) and tributyl phosphate (CAS 126-73-8) were
excellent structural information and aids the correct identication purchased from Sigma Aldrich Qumica (Barcelona, Spain). Tenax
of unknown compounds [10]. was supplied by Supelco (Bellefonte, USA).
For the conrmation of the compounds identied, a novel tech-
nology was also used; IM-MS, a sensitive technique that has been
2.2. Packaging materials, inks and adhesives
recently developed and thatenables the determination of the col-
lision cross section (CCS) value of the ions detected. CCS values
Three different sets of materials were studied, its composition
are related to the key physicochemical properties of the ion, such
is described in Table 1. Each set was composed of a base mate-
as the ions size, shape and charge. Typically, retention time,
rial (material 1) and a base material with a printing ink (material
accurate mass and fragmentation ion information are the main
2). As base materials, two different polymers were used, oriented
parameters used for conrmation purposes. However, if different
polypropylene (OPP) and polyethylene terephthalate (PET). The
chromatographic methods are used, the retention times will vary
printing technologies used for the application of inks to the base
126 M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133
materials were exography and rotogravure. Depending on the set, 1.7 m particle size (2.1 100 mm) also from Waters (Milford, MA,
inks were applied on the non-food contact side (outer side) or on USA) was used. Injection volume was 10 L. Chromatography was
the food contact side (inner side) of the materials. Sets were codi- carried out at 0.4 mL min1 column ow and 40 C column temper-
ed depending on the printing technology used and side where the ature. The mobile phase was water with 0.1% formic acid (phase
ink was applied: set FOS (inks applied by exography in the outer A) and methanol with 0.1% formic acid (phase B). Chromatography
side), set FIS (inks applied by exography in the inner side) and set started at 98/2 phase A/phase B (1 min), changed to 0/100 in 6 min
RIS (inks applied by rotogravure in the inner side). The distribution and stays at 0/100 for an additional 2 min. The UPLC was connected
of inks through the surface of materials was not homogeneous. with an ESI probe to the mass spectrometer.
Twelve different printing inks were used in the manufacture
of materials: white ink, four inks coded according to CMYK color 2.5. QTOF-MS detection and identication of non-volatile
system (cyan, magenta, yellow, black) and 7 inks coded according migrants
to its Pantone color (green 368, red 186, blue 287, yellow 109,
purple 2612, blue312, green 3435). The Pantone Color Matching A Xevo G2 QTOF mass spectrometer supplied by Waters (Mil-
System is largely a standardized color reproduction system. Even ford, MA, USA) was used for the identication of ink migrants.
though to know inks composition would have been very useful for Instrumental parameters were as follows: positive ionization, sen-
this study it was not possible due to condential reasons. sitivity mode, capillary at 2.5 kV, sampling cone at 30 V, extraction
In sets FIS and RIS a third material was also studied (material 3). cone at 4 V, source temperature at 120 C, desolvation tempera-
In this material, a layer of PP (FIS) or aluminum (RIS) was joint to the ture at 450 C, cone gas ow at 20 L h1 , desolvation gas ow at
food contact side of material 2 by the application of a polyurethane 650 L h1 . Acquisition was carried out in MSE mode, as this mode
adhesive covering the whole surface. allows both low and high collision energies (CE) in the collision cell
Packaging samples were provided by a converter company, so during the same run, and thus provides two kinds of mass spec-
it was possible to have the intermediate materials manufactured tra of the compounds. The low energy (CE at 4 V) spectra provide
during the process. Sets of materials were stored in rolls at room information about the precursor ion and high energy (CE ramp:
temperature by the converters. Afterwards, materials were deliv- from 15 to 30 V) spectra provide information about fragment ions.
ered in stacks to the laboratory. The company also provided the Analyses were also performed at 70 V cone voltage and in negative
inks and adhesives used for the manufacturing. Ink and adhesives mode (cone voltage 30 V) in order to detect compounds with dif-
were diluted 1/1000 with methanol and ltered through a 0.20 m ferent optimum ionization conditions. Data were recorded using
PET lters prior to the analysis. MassLynx v4.1 software.
For the identication of the compounds detected, the follow-
2.3. Migration tests ing methodology was used. First, the elemental composition of
the precursor ion was determined using the low energy spectrum.
Since the distribution of inks thorough materials was not For this purpose, the exact mass and the isotopic pattern of the
homogeneous, cut-off selection for migration experiments was precursor ion and the elemental compositions proposed by Mass-
performed focusing our attention on obtaining representative sam- lynx were compared. Those elemental compositions with a low
ples of all the inks used in the material. Two food simulants were mass error and a good isotopic t were selected. Afterwards, the
selected for this experiment, ethanol (95%) and Tenax [poly(2,6- elemental composition was linked to a chemical structure using
diphenyl-p-phenylene oxide)]. Ethanol (95%) was chosen on the different chemical database websites such as Chemspider [www.
basis of previous experiments performed in the laboratory that chemspider.com] or Scinder [www.scinder.com]. The selection
showed a higher tendency of most of the non volatile compounds of candidates from the chemical database was made according
to migrate to it compare to other liquid simulants such as ethanol to the chemical criteria and background knowledge of the ana-
(10%) or acetic acid (3%). Tenax is a highly porous polymer and it lyst about polymers, inks and coatings. Finally, the selection of the
was selected in order to compare migration results with a solid sim- best candidate was carried out using the high energy spectrum of
ulant. Migration experiments with ethanol (95%) were performed the compounds detected. For this purpose, the MassFragment tool
in migration cells. In these cells, the food-contact side of the mate- from MassLynx was used. This tool allowed the comparison of high
rials studied (12.6 cm2 ) was in direct contact with 20 g of the liquid energy mass spectra of the unknown peaks and the candidate. For
simulant. Cells were placed in an oven at 40 C during 10 days. After- each fragment ion detected in the spectrum, MassFragment pro-
wards, ethanol (95%) was ltered through 0.20 m PET lters and vides a fragment structure and a score (S) with values between 1
analyzed by UPLC-QTOF-MS system. For migration experiments and 14, the lower the value, the more plausible is the structure
with Tenax 8.5 1 cm cut-outs of the materials studied were cov- proposed. When a candidate structure explained at least two main
ered with 0.34 g of Tenax, forming a uniform layer (4 g per dm2 fragment ions of the spectrum with scores values below 3, the can-
material surface according to UNE-EN 14338 19) [37]. This system didate was considered conrmed by MassFragment. A conrmation
was placed inside a Petri dish and kept in the oven at 40 C for by mass fragment only reects the possibility of having this com-
10 days. Afterwards the exposure, Tenax was extracted two consec- pound but a complete conrmation is only achieved when the pure
utive times with acetone (5 g and 3 g respectively) in an ultrasonic standard is injected and the candidate is conrmed by comparison
bath for 1 h, following the methodology designed by Vera et al. [3]. of the retention time and mass spectrum. In this case, the candi-
The recovered acetone was ltered through 0.20 m PET lters, date was named as conrmed by standard. Compounds of interest
concentrated under a stream of nitrogen up to 200 L and nally were codied using its retention time and exact mass, for example,
injected in the UPLC-QTOF-MS system. a compound with retention time 6.98 and exact mass 425.2151 was
Migration tests were performed in both simulants for all the codied as (6.98 425.2151).
materials studied. All the migration experiments were performed
in quadruplicate. 2.6. IM-QTOF-MS detection
2.4. UPLC separation A SYNAPT G2-Si HDMS supplied by Waters (Milford, MA, USA)
was used for the acquisition of collisional cross section (CCS) values.
Chromatography was carried out using an Acquity system sup- Instrumental parameters were as follows: positive ionization, sen-
plied by Waters (Milford, MA, USA). A UPLC BEH C18 column of sitivity mode, capillary at 3 kV, sampling cone at 30 V, extraction
M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133 127
Table 2
Migrants present in ethanol (95%) coming from inks in set FOS (ESI+ at 30 V cone voltage).Intensity of the peak in migration from material 2 (I M2), adduct detected, molecular
formula, candidates and conrmation by: mass error (mDa/ppm), MassFragment assignment (MF ), standard injection (Std), CCS value; Remarks and legislation. (Sets
and materials described in Table 1).
Migrants from ink I Adduct Molecular formula Candidates mDa/ppm MF Std CCS/error% Remarks and legislation
M2
4.93 299.11081 2 [MNa]+ C12H20O7 Citric acid triethyl 0.3/1.0 103.13/0.10% Common plastiziser in
ester packaging ink
CAS: 7793-0 EU/10/2011 [SML = 60 ppm
(G32)]
EUPIA1,2
5.63 285.2909 2 [MH]+ C17H36N2O Schercodine L 0.4/1.4 120.19/0.17% Emulsier, cationic surfactant
CAS: 3179-80-4
5.92 271.1885 1 [MNa]+ C13H28O4 Tripropyleneglycol 0.2/0.7 * 99.69/0.07% Packaging ink solvent
monobutyl ether EUPIAc ; SL(non evaluated)
CAS: 55934-93-5
5.96 299.1835 2 [MNa]+ C14H28O5 Triethylene glycol 0.0/0.0 116.48 Surfactant: emulsifying,
caprylate lubricating
CAS: 28397-10-6
6.09 313.3217 2 [MH]+ C19H4ON2O Schercodine M 0.4/1.3 129.75 Emulsier, Non-ionic
CAS: 45267-19-4 surfactants
6.39 343.29651 1 [MH]+ C19H38N2O3 Lauraimidopropyl 0.1/0.3 131.64 Surfactant
betaine EUPIAd , SL (non evaluated)
CAS: 4292-10-8
6.98 425.21511,2 2 [MNa]+ C20H34O8 TBoAC 1.1/2.6 137.45/0.38% Plastizicer
CAS: 7790-7 EU/10/2011 [SML = 60 ppm
(G32)];
EUPIAa,b ; SL (allowed without
SML)
cone at 4 V, source temperature at 120 C, desolvation tempera- place during this period. Since they had been manufactured dif-
ture at 450 C, cone gas ow at 10 L h1 , desolvation gas ow at ferently and they had different structures it was possible to study
800 L h1 . IMS wave velocity was 550 m s1 , IMS wave height was ink migration and ink set-off phenomena from different perspec-
40 V and IMS cell pressure was 3.5 mbar. Data were recorded using tives. It was also possible to evaluate the best way of reducing the
MassLynx v4.1 and processed using UNIFI v1.8 software. A com- presence of ink components in migration.
pound was conrmed by CCS when the difference between its CCS
value and the CCS of the standard was below 2%.
3.1. Identication of ink components in migration from
packaging materials by UPLC-QTOF-MS
2.7. DESI experiments
Non-volatile ink components were mainly detected in simu-
Desorption electrospray mass spectrometry was performed on lant ethanol (95%), only TBoAC was also detected in Tenax. All the
a Xevo G2 XS Q-ToF (Waters) that had been tted with a Prosolia 2D migrants detected at 70 V (ESI + ) had been previously detected at
DESI stage (Indianapolis, US). The DESI spray head geometries were 30 V (ESI + ) and no migrant coming from inks was detected in nega-
optimized for the sample type as were the gas pressure and sol- tive mode. These results let us establish that ESI+ at 30 V, is in most
vent ow which were set to 6 bar and 2 L respectively, the solvent cases, the ionization method that provides complete information
composition was 95% methanol 5% deionised water (Millipore). The about the migrants present in a solution. Tables 2, 3 and 4 show
electrospray voltage was set at 3.5 kV. the migrants coming from printing ink components in the three set
The sample surfaces to be analyzed were attached to clean of materials studied. The determination of ink migrants was per-
Superfrost glass slides using standard laboratory tape and the glass formed by the comparison of chromatograms from materials with
slide placed onto the DESI stage. During initial proling experi- and without printing inks in its composition. Due to the hetero-
ments, the MS scan time was set to 1 s, and the sample was moved geneous distribution of inks through materials surface, differences
automatically under the spray to ensure new regions were con- among migration replicates were observed.
stantly being sampled. For imaging experiments, the sample on the
glass slide was scanned with a at bed scanner, allowing regions of
3.1.1. Identication of ink components in migration from set FOS
interest to be dened within the Waters HDI 1.3.5 software. Once
This set of materials was composed by a PP lm (material 1) and
the experiment was dened, the system automatically scanned the
a PP with ink applied by exography on its non-food side (material
area, in this case at 50 m 50 m pixel size, and reconstructed the
2). In material 2, compounds present in migration could come from
data into an image which could be analyzed in the HDI software.
migration processes through the PP and also they could be due to
set-off phenomena. Table 2 shows the compounds related to inks
3. Results and discussion that were found in migration from set FOS, these compounds were
found in migration from material 2 [OPP/ink] but they were not
Sets of materials under study were stored in rolls at room tem- present in migration from material 1 [OPP]. Seven compounds were
perature by the converters and therefore, set-off phenomena took detected when a cone voltage of 30 V was used, three of them were
128 M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133
Table 3
Migrants present in ethanol (95%) coming from inks in set FIS (ESI+ at 30 V cone voltage). Intensity of the peak in migration from material 2 (I M2) and material 3 (I M3)[adduct
detected, molecular formula, candidates and conrmation by: mass error (mDa/ppm), MassFragment assignment (MF ), standard injection (Std), CCS value; Remarks
and legislation. (Sets and materials described in Table 1).
Migrants from IM2 IM3 Adduct Molecular Candidates mDa MF Std CCS/error% Remarks and legislation
ink formula /ppm
5.40 443.23471 2 [MH]+ C28H30N2O3 Solvent Red 49 0.9/2.0 147.09/0.23 Colorant-FDA packaging ink
5.50 443.23471 CAS:509-34-2 EuPIAe ; SL (non evaluated)
6.01 385.3795 1 [MH]+ C23H48N2O2 Stearamidopropylamine 0.2/0.5 Antistatic agents/surfactants
oxide Cosmetic products Directive
CAS: 25066-20-0 76/768/EEC
6.04 279.0978 1 [MH]+ C18H15OP Triphenyl phosphine 3.9/15.0 97.94/0.10 Oxidation product of TPP
oxide-TPPO (EUPIA1 )
CAS: 791-28-6
6.19 379.1627 1 [MNa]+ 1.C20H24N2O4 1. Caprolactam 0.7/1.8 *
2. C21H20N6 derivate 1.6/4.2
2. Pyridine derivate
6.64 555.3190 1 = [2MNa]+ C12H27O4P Tributyl phosphate 0.2/0.4 116.6/0.10 FDA Indirect additive
CAS: 126-73-8 EUPIAa , SL (SML = 0.05 ppm),
6.65 396.4570 1 = [MH]+ C27H57N Trinonylamine 0.3/0.8 * Tertiary amine (catalyst)
CAS: 2044-22-6
6.98 425.21511,2 2 [MNa]+ C20H34O8 TBoAC 0.6/0.7 137.47/0.37 Plasticizer
CAS: 7790-7 EU/10/2011 [SML = 60 ppm
(G32)]; EUPIAa,b ; SL (allowed
without SML)
7.56 550.6298 2 [MH]+ C38H79N 1-Octadecanamine, 0.7/1.3 * Tertiary amine (catalyst)
N-ethyl-N-octadecyl
CAS: 30427-52-2
Table 4
Migrants present in ethanol (95%) coming from inks in set RIS (ESI+ at 30 V cone voltage). Intensity of the peak in migration from material 2 (I M2) and material 3 (I M3)
adduct detected, molecular formula, candidates and conrmation by: mass error (mDa/ppm), MassFragment assignment (MF ), retention time, (rt) and CCS value;
remarks and legislation. (Sets and materials described in Table 1).
Migrants from IM2 IM3 Adduct Molecular Candidates mDa/ppm MF Std CCS/error% Remarks and legislation
ink formula
5.11 415.20111 1 [MH]+ C26H26N2O3 Rhodamine 575 1 Dye (red)
5.35 415.20111 CAS 25152-49-2 .3/3.1
Fig. 1. Signal intensity of ink components in migration to ethanol (95%) from packaging materials studied (set FOS: 1a, set FIS: 1c, set RIS: 1e); and percentage of components
present in inks used for the manufacture of packaging materials (set FOS: 1b, set FIS: 1d, set RIS: 1f).
Fig. 2. DESI 2D images of the distribution of three ink components in the surface of material 2 from set FOS: Schercodine L (m/z 285.2909), TBoAC (m/z 425.2151) and a
phthalate (m/z of 149.0239).
also detected at 70 V. Among the compounds identied there were were also present in all migration samples, this was expected since
two plasticizers, citric acid triethyl ester and tributyl o-acetyl cit- all the material surface was printed with one of these inks. How-
rate (TBoAC), both of them were present in the positive list of EUPIA ever, other compounds such as Schercodine L (5.63 285.2909) that
that lists the compounds recommended to formulate printing inks was mainly present in green ink, was not present in all migration
for food packaging. Several surfactants and emulsiers were also samples, since its presence in migration depended on the cut-off of
found, such as Schercodine L, triethylene glycol caprilate, Scherco- the material selected for the migration test and on its contact with
dine M and lauraimidopropyl betaine, only the last one was present green ink during the material manufacture and storage. In addition,
in EUPIA list. Finally, a printing ink solvent, tripropyleneglycol something similar happened with Schercodine M (6.09 313.3217),
monobutyl ether, was found. Fig. 1a shows the intensity of the com- which was only present in ink green 368. Some of the compounds
pounds detected in migration samples from material 2 [OPP/ink] found in migration were not detected in these inks (4.93 299.1108,
and Fig. 1b shows the relative abundance (%) of each compound 5.92 271.1885, 5.96 299.1835, 6.39 343.29651). This could be due
detected in the ink global composition. Three inks were used for to the 1000 fold sample dilution carried out before the analysis of
the manufacturing of this material, coded as green 368 and red 186. ink samples because of the complexity its matrix.
Compounds present in both inks, such as TBoAC (6.98 425.2151)
130 M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133
Fig. 3. Mass spectrum intensity corresponding to the accurate masses m/z 285.2909 (Schercodine L), m/z 425.2151 (TBoAC) and m/z of 149.0239 (phthalate) in the non-printed
side of material 1 and in the back-printed and front-printed side of material 2 from set FOS.
M. Aznar et al. / J. Chromatogr. A 1453 (2016) 124133 131
3.1.2. Identication of ink components in migration from set FIS The same patterns observed for set FOS were also observed in set
This set of materials was composed of a PET lm (material 1), a FIS: compounds present in all inks, such as TBoAC (6.98 425.2151)
[PET/ink] lm with ink applied by exography on its food contact were also present in all migration samples, while other compounds
side (material 2), and a [PET/ink/adhesive/aluminum] lm where an such as Solvent Red 49 (5.40 443.2347) that was mainly present in
aluminum layer had been joined by an adhesive covering the whole purple 2612 and magenta, presented very different intensities in
surface (material 3). Since aluminum is in the food-contact side of migration depending on the cut-off of the material selected.
material 3, no transference of ink components to food simulants In migration from this set, also some of the migrants were
due to its permeation trough the material was expected. There- not detected in the inks (6.04 279.0978, 6.65 396.4570 and
fore, the presence of ink components in food simulants was due 7.56 550.6298).
to a set-off phenomena during storage. Table 3 shows the com-
pounds related to inks that were found in migration from material 3.1.3. Identication of ink components in migration from set RIS
2 [PET/ink] but that were not present in migration from mate- In these set of samples, a rotogravure was used for the applica-
rial 1 [PET]. Eight compounds were detected. The colorant Solvent tion of inks. This set was composed of an oriented polypropylene
Red 49 (5.40 443.2347 and 5.50 443.2347) was detected, which is lm [OPP] (material 1), an [OPP/ink] lm with an ink applied
dened as a printing ink for food packaging by the FDA and also by rotogravure in the food contact side (material 2) and an
present in the EUPIA list and Swiss legislation as a pigment or [OPP/ink/adhesive/OPP] (material 3) where an OPP lm was joined
dye. This compound had the highest intensity of all compounds by an adhesive coating to the food contact side. Table 4 and 1 show
detected in one of the replicates of migration from material 2 the results obtained. Nine compounds were detected in migration
(Fig. 1c). This colorant, present predominantly in ink purple 2612 from material 2 that were not present in migration from material 1,
and magenta inks (Fig. 1d), was only found in some migration and therefore they came from inks. Solvent Red 49 (5.63 285.2906)
replicates, as its presence in migration depended on the cut-off was again one of the peaks with the highest intensity. Another peak
selected. Compounds with the next highest intensities were TBoAC with high intensity in at least one replicate was 6.84 295.1889, a
(6.98 425.2151), previously detected also in set FOS, and a tertiary possible azelate, these compounds are common plasticizers in inks.
amine, 1-octadecanamine, N-ethyl-N-octadecyl (7.56 550.6298). Components found with medium intensity include two plasticizers
Tertiary amines can be used as catalysts for UV curing processes and one emulsier: dimethyl sebacate (6.11 253.1420) and TBoAC,
in coatings. Another tertiary amine was found at lower intensity, both present in EUPIA list and Directive EU/10/2011, and Scherco-
trinonylamine (6.65 396.4570). Although no application examples dine L. All of them had been previously detected in the exography
were found for this compound, another trialkylamine, tridodecy- sets. Four more compounds were detected but at low intensity:
lamine, was used as an antistatic agent for cosmetic purposes. In the dye Rhodamine 575, a cyclic polyester (5.37 251.1261) coming
addition, dialkylamines are listed by EUPIA. from the condensation of adipic acid and hexane diol and two com-
Other compounds were identied at lower intensities such as pounds with similar spectra that were only detected in one of the
tributyl phosphate (6.64 555.3190), an additive listed by EUPIA replicates, 8.26 615.1400 and 8.45 689.1600. The rst one was an
or TPPO (6.04 279.0978), an oxidation product of TPP, an additive imidazole derivate and the second one an isoquinoline derivative,
regulated by EUPIA. The mass error for TPPO was above 10 ppm, both families are commonly used in dyes. These compounds were
which is outside the acceptance criteria for this type of analysis. found mostly in green 3435 and also in magenta inks. Most of the
This would, typically, lead us to reject the candidate. However, compounds found in migration were mainly present in magenta
higher than expected mass errors can be caused by the presence ink, except for 5.37 251.1261 and 5.63 285.2906 that were mostly
of other compounds chromatographically coeluting with our can- in yellow and white. When an OPP layer was joined to the food
didate. This analysis was carried out using IM-MS, which means contact side of material 2, the concentration of most of the com-
that chromatographically coeluting compounds can be separated pounds decreased (material 3), and this was due to the effect of
according to their size, shape and conformation in the IM drift OPP. However, some compounds remained at a similar concentra-
tube, and CCS can be measured for every species. CCS is a unique tion or even increased in some replicates, such as 6.11 253.1420 or
physico-chemical property of each ion that can be used as an 6.84 295.1883. This fact could be attributed to both a set-off process
additional identication point to differentiate species in complex and to the presence of these compounds in the adhesive coating. In
mixtures. In this case, the TPPO measured CCS value had a very migration from this set, only one migrant was not detected in inks,
low error compared to the expected CCS value (0.1% error), which 6.11 253.1420.
enabled us to conrm its identity. For compound 6.19 379.1627,
two possible candidates were found, a caprolactam derivative and 3.2. Determination of set-off by DESI-MS
a pyridine derivative, corresponding to the formulas C20H24N2O4
and C21H20N6, respectively. Some caprolactams such as vinyl DESI experiments allowed the acquisition of 2D images of the
caprolactams have been used as ink diluents and some pyridine distribution of ink components in the material surface. This exper-
derivatives have been related to yellow inks. This compound was iment was performed after having identied the main non-volatile
present principally in yellow ink (Fig. 1d) and for this reason the ink components in migration, in this way it was possible to perform
pyridine derivative was considered to be the most probable one. a target DESI-MS analysis. The distribution of two differentiating
The sodium adduct of this compound was formed during its ion- compounds was studied along the surface of material 2 from set FOS
ization, since the high stability of sodium adducts makes difcult [PP/ink] (Fig. 2) On one side, the 2D image TBoAC (m/z 425.2151), a
its fragmentation, it was not possible its conrmation by MassFrag- component present in both inks applied in this material (green 368
ment. and red 186), showed a clear distribution all over the surface, except
When an aluminum layer was placed between inks and food for the white zones where no ink had been applied. On the other
simulant, [PET/ink/adhesive/aluminum] (material 3), concentra- side, the 2D image of Schercodine L (m/z 285.2909), a component
tion of ink migrants mostly decreased and even disappeared only found in one ink, green 368, was only bright in the surface zone
(Table 3) (Fig. 1c). However, some of them such as tributyl phos- where green ink has been applied. This procedure was also used to
phate (6.64 555.3190) and trinonylamine (6.65 396.4570) were check the presence of a fragment ion related to phthalates with a
still present in migration at a similar concentration, probably due typical mass m/z of 149.0239, since phthalates are common addi-
to a set-off effect. tives in PP polymers. Its 2D image showed that they were present all
over the surface, even when no inks had been applied. In Fig. 3, the
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