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Anal Bioanal Chem (2007) 389:589–596

DOI 10.1007/s00216-007-1462-1

ORIGINAL PAPER

Migration of organic compounds from a multilayer


plastic–paper material intended for food packaging
Cristina Nerín & Esther Asensio

Received: 18 April 2007 / Revised: 12 June 2007 / Accepted: 21 June 2007 / Published online: 7 August 2007
# Springer-Verlag 2007

Abstract This paper deals with the study of the kinetic Introduction
migration of a series of organic compounds representative
of potential contaminants in packaging materials and used The use of paper and board (P&B) as food packaging
as surrogates (o-xylene, acetophenone, dodecane, naphtha- material is prevalent in the food industry. It is used as
lene, 2,3,4-trichloroanisole, benzophenone, isomeric mix of primary packaging in direct contact with dried foodstuffs,
diisopropylnaphthalene, diisobutyl phthalate and methyl as a layer in several multilayer structures, and as secondary
stearate). Migration to one side of a solid simulant, Tenax®, packaging. The recycled and multilayer material in contact
also referred to as MPPO (modified polyphenylene oxide), with the food must be analysed before it is used in order to
was investigated in this study. One spiked sample of investigate the potential migrants that could be transferred
multilayer material was used to optimise the extraction from the material to the food [1, 2]. A recently approved
procedures for the multilayer paper-based material and the proposal by the Council of Europe requires the control and
Tenax as well as to perform kinetic migration studies. Three analysis of a series of contaminants in recycled paper and
sequential extractions using ethanol were necessary for the board such as heavy metals, plasticisers, aromatic amines,
strips of the multilayer material but only one extraction was Michler’s ketone, polyaromatic hydrocarbons, benzophe-
necessary for the solid simulant to obtain >70% recovery of none, diisopropylnaphthalenes (DiPN’s), fluorescent whit-
the surrogates. These results enabled us to specify the ening agents (FWA), pentachlorophenol (PCP), and residual
extraction requirements of the multilayer sample and the solvents, among others [3].
solid simulant and as well as those of the migration tests at The parameters that should be applied in migration tests,
high temperature using Tenax as solid simulant. The matrix including the experimental conditions of temperature and
effect associated with the extraction of the contaminants time of contact between the material and the food, as well
from the multilayer sample is also discussed. as the food simulants to use, have been established for
plastic materials [4]. For paper and board, the liquid
Keywords Food packaging . Kinetic migration tests . simulants commonly used for plastics are not appropriate,
Multilayer . Tenax® . Surrogates . Paper . Polyethylene and several solid simulants have been proposed in order to
study the migration of compounds. As part of of the EU
Project CT 98-4318, Tenax has been used as solid food
simulant, and real food such as icing sugar [5], flour and
bakery products [6], pasta, milk powder [7–8] and dry soup
[9–10] has been placed in contact with several paper
samples in order to study migration [11–12].
However, multilayer materials behave differently. Mi-
C. Nerín (*) : E. Asensio gration tests in these cases depend on the layer in contact
Analytical Chemistry Department, University of Zaragoza,
CPS- Edif. Torres Quevedo. C/ María de Luna 3,
with the food, which can be either paper or plastic material.
Zaragoza 50018, Spain In this case, simulant selection can prove problematic, and
e-mail: cnerin@unizar.es it is often difficult to assess the contribution of each
590 Anal Bioanal Chem (2007) 389:589–596

material in the multilayer structure. Several authors [13–15] appropriate concentrations were used for calibration and to
have studied the adsorption isotherms and the migrations of prepare the spiked sample.
several model compounds and contaminants from different Modified polyphenylene oxide (Tenax®, TA) was used
paper structures. However, no information about how the as the solid food simulant (80–100 mesh, Supelco, Madrid,
contaminants present in the paper layer migrate through a Spain).
multilayer structure has been presented. It is well known
that the migration depends on the diffusion coefficients of Apparatus
the migrants in the material and obviously also on the
different materials present and whether they are coated or A Hewlett-Packard HP 6890 gas chromatograph (HP,
laminated, since in this case the migrants have to cross Wilmington, DE, USA), coupled to a Hewlett-Packard HP
additional interfaces [8]. 5973 mass-selective (MS) detector with an SGL-5 GC
One of the critical points in the analysis of migrants is capillary column (60 m×0.25 mm i.d. and 0.25 μm film
the extraction of the paper samples. Most of the studies that thickness) was used. He C-50 (Carburos Metálicos,
have been published about the analysis of components in Barcelona, Spain) was used as carrier gas. The GC program
paper and board have employed solvent extraction with used was as follows: injector temperature 260 °C; oven:
ethanol [4] or toluene, in either a direct immersion or an initial temperature 60 °C for 3 min, and then 15 °C/min rate
accelerated solvent extraction procedure (ASE) [16]. In this to 170 °C and hold for 3 min, 10 °C/min to 270 °C and
case, the extraction of migrants from paper samples was hold for 8 min. Splitless injection mode was used with a
carried out with ethanol [2]. splitless time of 1 min. The analyses were carried out in
Through kinetic studies, the diffusion coefficients of the SIM mode. The following characteristic masses were
migrants and the influence of variables such as the multilayer selected (SIM mode): m/z 91 (o-xylene), m/z 105 (aceto-
composition, the sample thickness and the presence of phenone and benzophenone), m/z 57 (dodecane), m/z 128
different coating layers, have been obtained. The research (naphthalene), m/z 210 (2,3,4-trichloroanisole), m/z 197
work presented here corresponds to a study carried out as (diisopropylnaphthalene isomers), m/z 149 (diisobutyl
part of the EU project mentioned above [17]. A multilayer phthalate) and m/z 74 (methyl stearate). Only the most
sample containing a combination of polyethylene–alumin- abundant ion was selected for each compound. Figure 1
ium–polyethylene (PE/Al/PE) on one side of the paper and shows the chromatograms obtained in SCAN mode and
just polyethylene (PE) on the other was used for the study. SIM mode for calibration. Further studies validated these
A cocktail of several model migrant compounds considered ions for quantitative purposes [7].
to be common contaminants in paper samples [18] was
used. The selected complex multilayer sample was first Sample
immersed in the cocktail of compounds and then the
extraction and analytical features of this spiked multilayer The sample selected for the kinetic study was a multilayer
structure were optimised. We then performed a kinetic coated paper with the following properties: type = liquid
study on migration from the spiked multilayer structure to board triplex, pulp = bleached Kraft paper, 0% recycled
Tenax (used as food simulant). The results of the study are pulp, surface treatment = PE (35 μm)/Al (17 μm)/PE
shown and discussed. (26 μm) inside layer and PE (16 μm) outside layer,
grammage = 358 g/m2, thickness = 549 μm. Strips of size
7 cm×1 cm of this sample were totally immersed in an
Material and methods ethanol solution containing 250 μg/g of each of the nine
model compounds selected, all of them representative of
Reagents and solutions several common surrogates likely to be present in paper
samples. After two hours the strips were taken out and dried
The same criteria as those used by the FDA [19] and in at room temperature for about 30 min. They were then
previous EU projects [20] were applied here and the stored in 20 mL vials that were hermetically closed and
following contaminants were selected as surrogates: aceto- stored at 4 °C before use. Strips were analysed just before
phenone, benzophenone, diisobutyl phthalate (DiBP), iso- the migration study, following the procedure described
meric mix of DiPN, n-dodecane, methyl stearate, below.
naphthalene, 2,3,4-trichloroanisole and o-xylene. In this
way, different chemical families are represented, as well as Optimisation of the extraction procedure of the simulant
the likely contaminants from the misuse of paper and board,
which could not be eliminated with the recycling system. Before it was used, Tenax was cleaned with methanol (at
Standard solutions of these surrogates in ethanol at the 60 °C for 8 h) and then with hexane (at 40 °C for 8 h) in a
Anal Bioanal Chem (2007) 389:589–596 591

Fig. 1 Chromatograms obtained Abundance


in SCAN mode and SIM mode TIC: PBR10-SCAN
700000
for calibration: 1, o-xylene;
2, acetophenone; 3, dodecane;
650000
TIC: PBR10-SIM
4, naphthalene; 5, 2,3, 600000
550000 7
4-trichloroanisole;
6, benzophenone; 7, 2, 500000 9
6-diisopropylnaphthalene; 450000 8
8, diisobutyl phthalate; 9, methyl 400000
stearate 350000 1 5
300000
250000
4 6
200000 3
150000
2
100000
50000
0
Time--> 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00

Soxhlet. To optimise the extraction procedure from the Experiment 1 The spiked paper strips were cut into small
solid simulant, 0.26 g of Tenax in an open 20-mL vial were pieces and placed into a 20-mL septum vial;
spiked with 50 μL of a standard solution of the cocktail of 2 mL of ethanol (1.58 g) were then added
surrogates used as model compounds (1000 μg of each as the extraction solvent and the vial was
surrogate/g ethanol). Then the open vials were placed in an sealed. The extraction of the surrogates into
oven at room temperature for 1 h to evaporate the ethanol. the ethanol was performed by gently shak-
Three different extraction procedures were studied as ing the vial for 30 min at room temperature.
follows; the experiments were carried out in triplicate. The ethanol extract was then analysed
directly by GC/MS [2] and the concentra-
Test 1 One extraction of spiked Tenax was performed tions of the contaminants were determined
with 3 mL of ethanol (2.37 g) and gentle shaking. from the respective calibration plots
The extract was directly analysed by GC/MS. The obtained with the external standard method.
extract of ethanol was under gravimetric control. Experiment 2 Two sequential extractions of the paper
Test 2 Two sequential extractions of spiked Tenax were strips were carried out. The first extraction
carried out. The first extraction used 5 mL of was done with 2 mL of ethanol and the
ethanol and the second extraction used another second extraction with another 2 mL of
8 mL of ethanol. The two sequential extracts ethanol. The two sequential extracts were
together were concentrated in a rotary evaporator concentrated together in a rotary evapora-
at 40 °C until a final weight of 1.58 g of extract tor at 40 °C until a final weight of 1.58 g of
was achieved. The final ethanol extract was extract was obtained. The final ethanol
directly analysed by GC/MS. extract was analysed directly by GC/MS.
Test 3 Three sequential extractions of spiked Tenax were Experiment 3 Three sequential extractions from the paper
applied. The volumes of extraction solvent used strips were carried out using volumes of
were 5 mL + 8 mL + 8 mL of ethanol. The three 2 mL + 2 mL + 2 mL. The three sequential
sequential extracts were concentrated together in a extracts were concentrated together in a
rotary evaporator at 40 °C until a final weight of rotary evaporator at 40 °C until a final
1.58 g of extract was obtained. The final ethanol weight of 1.58 g of extract was obtained.
extract, which was gravimetrically controlled, was The final ethanol extract was analysed
directly analysed by GC/MS. directly by GC/MS. All of the extracts were
gravimetrically controlled.
Optimisation of the extraction procedure for the paper As for the Tenax, three independent experiments were
carried out. The experiments were carried out in triplicate.
The optimisation of the extraction procedure for the All analyses of the spiked paper sample were performed at
surrogates trapped in the paper strips was performed as least 48 hours after preparing the spiked sample, so that the
follows. surrogates were linked to the matrix.
592 Anal Bioanal Chem (2007) 389:589–596

Table 1 Extraction recoveries for Tenax at room temperature, and the statistical significances of the differences obtained versus the number of
extractions

Compounds % Recovery (Tenax) ANOVA

Test 1 Test 2 Test 3 p F

o-Xylene 45.98±2.88 11.27±2.19 6.62±0.09 0.976421 0.023956


Acetophenone 94.71±8.25 75.60±1.80 65.28±2.32 0.790054 0.245157
Dodecane 93.59±7.42 69.48±3.34 50.08±1.60 0.978227 0.022095
Naphthalene 78.05±6.22 68.09±3.86 54.88±2.30 0.948596 0.053239
Trichloroanisole 48.20±7.04 41.51±2.22 39.06±2.05 0.448808 0.918331
Benzophenone 86.68±3.90 88.51±4.06 90.07±2.52 0.310177 1.431846
Diisopropyl naphthalene 73.26±4.07 63.16±3.00 61.48±1.69 0.488921 0.808099
Dibutyl phthalate 88.63±9.12 108.95±6.65 103.99±2.11 0.719882 0.347348
Methyl stearate 86.60±8.84 87.85±8.80 81.54±3.49 0.671345 0.426147

Kinetic migration studies ethanol [4], as these solvents are polar enough to extract the
most relevant contaminants, such as benzophenone, phthal-
Migration studies were carried out with the spiked strips of the ates, chloroanisols and DiPNs. For this reason, ethanol was
P&B sample (7 cm×1 cm). Each paper strip was placed in a selected as the extraction solvent in which all of the
20 mL vial and the PE layer was completely covered with compounds under study could be solubilized.
0.26 g of Tenax [4]. The vial was then hermetically closed As the spiking solution was also ethanol-based too, the
and placed in horizontal position in the oven at 25 °C and spiked samples were stored at room temperature for a
50 °C for the following periods [21]: period of at least 48 h before being analysed. This ensured
that the contaminants would be trapped in the matrix in a
a) 25 °C for 6 h, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 days
similar way to that the natural process.
b) 50 °C for 15 min, 30 min, 1, 2, 4, 6, 8, 23, 31 and 48 h.
Following the procedure described in the “Experimental”
These values were selected in order to assess the kinetic section, the recoveries obtained using different extraction
performance of the samples, as previously described [22], tests were measured. Table 1 shows the recovery results
assuming that equilibrium was reached in each case at each obtained for the extraction of Tenax. As can be seen, the
temperature. recoveries did not improve significantlyupon applying
sequential extraction. In fact, the opposite was observed
for the most volatile compounds, because sequential steps
Results and discussion also involve increases in both evaporation and the time
needed to remove the higher volume of solvent, which
Analysis of the Tenax and the paper sample results in a higher risk of volatilisation. Thus, it was
decided that it would be best to apply only one extraction
The first variable of choice in an extraction procedure is the step to Tenax.
solvent. Contaminants in paper samples that are intended Table 2 shows the values obtained during the process of
for contact with food are usually extracted with methanol or optimising the extraction of spiked samples, as calculated

Table 2 Results obtained when optimising the extraction of the spiked multilayer sample

Compounds Unspiked sample Factor = (Ci,exp/C3,exp)×100 Number of extractions ANOVA

C0,exp (μg/dm2) 1 extraction 2 extractions p F

Acetophenone - 52.33±0.79 71.15±3.90 0.00067237 193.942478


Dodecane - 78.67±5.59 85.75±0.81 0.00076154 178.370997
Naphthalene - 61.84±1.55 78.69±1.74 0.00013455 569.762695
Trichloroanisole - 63.69±2.61 90.25±11.55 0.10587558 5.20235462
Benzophenone - 50.40±2.76 72.03±7.09 0.03626363 12.1912711
DiPN - 64.42±4.49 94.61±21.92 0.2172924 2.65012879
DBP 1.37 39.81±2.45 64.59±12.32 0.01061134 29.5630774
Methyl stearate - 45.78±0.71 72.33±3.23 0.00040819 271.095909
Anal Bioanal Chem (2007) 389:589–596 593

by applying the following equation: acceptable recoveries. Consequently, the new concentra-
tions of the surrogates in the multilayer sample were
Ci; exp
 100 ¼ % recovery ð1Þ obtained after three sequential extractions.
C3; exp
Here Ci, exp is the concentration of each compound in Kinetic migration studies
each extraction step (one or two sequential extractions). C3,
exp is the concentration found after the three sequential Once the surrogates released by the multilayer samples
extractions. Table 2 also shows the ratio of the concentra- were identified, we investigated their migration to Tenax,
tion value obtained for each extraction over the maximum which had been selected as the solid food simulant in line
concentration after the three extractions. with the proposal from the Council of Europe [4]. The final
To obtain the recovery values, it is important to account migration values and results from kinetic studies performed
for the initial concentration of each compound in the paper at different temperature values and for different contact
sample at room temperature before the kinetic studies are times between the samples and the Tenax were all recorded.
performed, as some compounds were originally present in For the migration study, the 16-μm layer of PE, called the
the paper sample. However, the concentrations of some of outer plastic layer, was placed in contact with Tenax. In this
the compounds in the raw sample were very low, and the way, the influence of the PE coating on the migration of the
interactions of the surrogates with both the paper matrix surrogates could be studied. Figure 2 shows the chromato-
and the coating layers were also different to the interactions grams obtained in the kinetic migration experiments carried
of the compounds in the raw sample. For this reason, it was out at 25 °C and 50 °C for 48 h.
difficult to calculate the real recovery values. One useful After each migration test, the solid simulant was
approach is to consider that the three sequential extractions analysed according to the experimental procedure described
with ethanol will provide 100% extraction, in which case a above. The amount of migration was calculated as the ratio
comparison with the values obtained after one and two between the concentration of each compound in the Tenax
extractions yields the extraction profile. (CTenax) and the initial concentration in the spiked sample
When a significance test, such as a one-factor ANOVA, (Cinitial, paper), as expressed in the following equation:
is applied to the extraction data shown in Table 2,
significant differences in the amounts extracted during each  
C Tenax μg dm2
extraction step are observed for the different compounds. % Migration ¼    100 ð2Þ
Acetophenone, dodecane, naphthalene, benzophenone, C initial;paper μg dm2
dibutyl phthalate and methyl stearate provided high
extraction efficiency after three sequential extractions from Here, all of the concentrations are expressed in μg of
the multilayer material, while o-xylene (which was not compound per dm2 of paper sample. In this way, the
detected), trichloroanisole and the DiPNs did not present migrated mass is assumed to be that contained in the solid
significant differences because of their high relative simulant.
standard deviation values. Therefore, three sequential Figure 3a,b shows how the migration evolves over time
extraction of the paper sample is required to obtain at 25 °C for all of the model compounds after correcting for

Fig. 2 Chromatograms obtained Abundance


in the kinetic migration experi-
ments carried out at 25 °C and 95000 7
50 °C for 48 h. 1, o-Xylene; 2, TIC: Sample25C-48h
acetophenone; 3, dodecane; 4,
85000
naphthalene; 5, 2,3,4-trichloroa- 75000 TIC: Sample50C-48h
nisole; 6, benzophenone; 7, 2,6-
diisopropylnaphthalene; 8, dii- 65000
sobutyl phthalate; 9, methyl 55000
stearate
45000
35000
8
25000 3 4 6
9
15000 1 5
5000 2
0
Time--> 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00
594 Anal Bioanal Chem (2007) 389:589–596

a Migration behaviour of surrogates at 25 C with Tenax as b Migration behaviour of surrogates at 25 C with Tenax as
simulant 100 simulant
100
90

% migration Ctenax/Cinitial,paper*100
90
% migration Ctenax/Cinitial,paper*100

80
80
70
70
60
60
50
50
40
40
30
30
20 20

10 10

0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time (hours) Time (hours)

o-xylene acetophenone dodecane naphthalene trichloroanisole benzophenone 2,6-DiPN Dibutyl phthalate methyl stearate
Fig. 3 Migration of (a) volatile and (b) nonvolatile surrogates into Tenax (the solid simulant) at 25 °C

the extraction recoveries of both the Tenax and the paper layers are probably different, after approximately 150 h the
sample. The low recoveries obtained could be attributed to concentrations of the volatile compounds released increase
the presence of the polyethylene layer, which efficiently again. This behaviour can be attributed to the contribution of
traps alkanes. the 26 g/m2 PE layer behind the paper. A concentration
Since all these tests were carried out in closed vials, gradient from this PE layer to the Tenax is established, which
equilibrium will be reached between the two solid phases, largely explains the migration. The profiles in Fig. 3a indicate
which includes the surrogates in the Tenax, the paper that the surrogates move through the different layers at
sample, and the vapour phase. slightly different rates, which confirms the different diffusion
As can be seen, at 25 °C the migration behaviour is coefficients in different materials measured by several authors,
nonlinear and the profile obtained is a consequence of the who established that the migration occurs more rapidly in the
different diffusion coefficients of these surrogates in the PE than in paper [23].
different layers. In fact, the surrogates are released from However, for the nonvolatile compounds such as
the external layer until the equilibrium is reached, which occurs benzophenone, 2,6-DiPN, DBP and methyl stearate, the
after about 75 h for volatile compounds. However, as the amount of compound that has migrated gradually increases
diffusion coefficients of the surrogates through the different over time and finally reaches equilibrium. In this case, the

Fig. 4 Migration of surrogates


into Tenax (solid simulant) at
Migration behaviour of surrogates at 50°C with Tenax as
50 °C simulant
100
90
% migration (Ctenax/Cinitial*100)

80
70
60
50
40
30
20
10
0
0 10 20 30 40 50
Time (hours)
acetophenone dodecane naphthalene trichloroanisole
2,6-DiPN dibutyl phthalate methyl stearate
Anal Bioanal Chem (2007) 389:589–596 595

final values are considerably lower that those obtained for when it is heated to 50 °C. Under these conditions, the
volatile compounds, even at room temperature. capacity of Tenax for thermal desorption during a sampling
Figure 4 shows the migration behaviour over time at 50 °C step or a migration study is negligible, and the results
for all model contaminants. obtained for migration into it are valid.
The migration behaviour at 50 °C was found to be The multilayer structure of the sample has a strong
somewhat different to that at 25 °C; continuously increas- influence on how the migration evolves over time and with
ing time profiles were obtained for both the volatile and the temperature. Based on the composition of the multilayer
nonvolatile compounds (although a plateau was observed sample, the kinetic behaviour of some compounds can be
after 30 h of contact time). This behaviour suggests that the predicted. The migration of 2,3,4-trichloroanisole, 2,6-
diffusion coefficients of these surrogates in both paper and DiPN, DiBP and methyl stearate did not reach 100%,
PE increase with temperature, and so equilibrium is reached which means that multilayer structures are safer than paper
more quickly in the multilayer structure (PE-paper) at 50 °C monolayers if they are likely to be contaminated with these
than at 25 °C. Consequently, the amount of surrogate that compounds [22].
has migrated increases with time, as expected. The presence of a PE layer in the structure strongly
When the extraction process is applied to the paper influences the migration behaviour, trapping alkanes such
sample before the migration test, all of the analytes are as dodecane nonreversibly.
distributed equally among the different layers of the
multilayer structure. The extraction process probably
removes the compounds from the closest layers to the Acknowledgements EU Project CT98-4318 and Project CAL01-
084 from the Instituto Nacional de Investigación Agroalimentaria
surface (Cinitial, paper). However, when the sample is heated,
(INIA, Spain) financed this work.
the diffusion coefficients of the compounds increase and so
they migrate to the paper/PE interface and become
concentrated on the PE surface, from where they are
trapped in the Tenax (CTenax). This process requires both
time and increased temperature, and only happens with the
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