PACKAGING TECHNOLOGY AND SCIENCE

Packag. Technol. Sci. 2001; 14: 71±77

DOI:10.1002/pts.534

Migration of Alkylbenzenes from Packaging

into Food and Tenax1
By B. Aurela,* T. Ohra-aho and L. SoÈderhjelm
KCL Science and Consulting, PO Box 70, FIN-02151, Espoo, Finland.

Alkylbenzenes (alkyl chain C10±C13) are used as solvent components in certain

offset printing inks. Alkylbenzenes were identi®ed from 10 out of 15 samples of
offset-printed food packaging made of board. Printed hamburger collars intended
for hamburger restaurants had exceptionally high contents of alkylbenzenes (70±
500 mg/kg). Most of the collars had varnish on both the printed surface and the
non-printed food contact surface. Migration of alkylbenzenes from the hamburger
collar into a roll was 2 mg/kg. In another test, in which Tenax1 was used as
simulant, the effect of a varnish layer on the food contact surface was studied. It
was found that the varnish layer reduced migration by about 70%. Tests with
Tenax1 as a food simulant resulted in higher migration than in tests with rolls.
The European Commission has published a risk assessment report on alkylben-
zenes. The report concludes that there is no need for further testing or for risk
reduction measures beyond those which are currently applied. However, consumer
exposure was calculated without taking into account the possibility of oral
exposure to alkylbenzenes migrating from food packagings. The migration of
alkylbenzenes thus merits further study. Copyright O 2001 John Wiley & Sons,
Ltd.
Received 28 November 2000; Accepted 30 January 2001
KEY WORDS: alkylbenzenes; food packaging; migration; paper and board; printing inks;
Tenax1

INTRODUCTION through the packaging material and what are

Migration from paper and board packaging
materials has not been studied as extensively as
migration from plastic materials. However, it has
been demonstrated that migration from paper and
board packaging materials does occur.1±6 Most of
the migrants detected originated from the printing
inks or adhesives used in the manufacture of the
®nished packaging.
The risks of the contamination of food from
packaging materials by printing ink components
are associated with two phenomena: transfer
known as set-off phenomena. The latter means that
printing ink components are transferred to the
non-printed surface by direct contact with the
printed surface during manufacture, storage or use
of the material. It should be noted that these
phenomena usually involve substances other than
dyes and are therefore not visible. The use of
recycled materials, such as ®bres from recovered
paper, may also result in direct contact between
the ink components and food, or at least the route
through the material might be shorter. Castle has
published an extensive review of potential con-

* Correspondence to: B. Aurela, KCL Science and Consulting, PO Box 70, FIN-02151, Espoo, Finland.
Email: birgit.aurela@kcl.®
Contract/Grant Sponsor: National Technology Agency, Finland.

Copyright  2001 John Wiley & Sons, Ltd.


taminants in recycled paper and board food
contact materials.7 Migration in to dry foods was
reported for phthalates, diisopropylnaphthalenes
(DIPN) and certain volatile compounds.
Migration of ink components from printed
paperboard into microwaved food was studied
by Johns et al.,8 who looked for the possible
migrant transfer routes. The photoinitiator benzo-
phenone was studied as an indicator migrant.
Migration to foods microwaved in a paperboard
packaging was up to 1 mg/kg. The authors
concluded that the mechanism of migration
depended on the design of the packaging, which
occurred through direct food contact, transient
contact with splashed food or by gas-phase
diffusion through an air gap. Migration mechan-
isms were studied further by Johns et al.9 using
model substances. It was shown that the migration
into foods heated in trays with cartonboard
splashguards was some 10 times higher when
there was direct contact between the food and the
lid than in situations where there was no direct
contact.
Residues of dialkylaminobenzophenone UV-
cure ink photoinitiators and their possible
migration into foods were investigated by Castle
et al.10 One of these dialkylaminobenzophenones,
Michler's ketone (4,4'-bis(dimethylamino) benzo-
phenone), is a suspected carcinogen. The concen-
trations of dialkylaminobenzophenones found in
paper and board packaging were low and migra-
tion into foods was not detectable. It was con-
cluded, therefore, that the concentrations of
Michler's ketone present in the packaging samples
analysed were unlikely to pose a risk to human
health.
The plasticizers present in the printing inks used
in ¯exible food packaging and their migration into
food have also been studied.11±13
In this study alkylbenzenes are de®ned as
benzene with a linear alkyl C10±13 chain (CAS No.
67774-74-7), also called linear alkylbenzenes
(LAB). LAB are used almost exclusively (>99%)
as intermediates in the production of linear
alkylbenzene sulphonates (LAS). LAS are used as
components in laundry detergents, some all-
purpose cleaners, some liquid dishwashing deter-
gents and industrial cleaners. LAB also ®nd minor
uses as solvents and binders in special applica-
tions, including the manufacture of printing inks,
paints, varnishes and cable oil. The amounts of
Copyright O 2001 John Wiley & Sons, Ltd.
È DERHJELM
B. AURELA, T. OHRA-AHO AND L. SO
LAB used are well below 1% of the total volume.
LAB were therefore neglected in the risk assess-
ment made by European Commission. The risk
assessment concluded that there is no need for
further testing or for risk reduction measures
beyond those that are currently applied.14 How-
ever, consumer exposure in the report was
calculated without taking into account the possi-
bility of oral exposure to alkylbenzenes migrating
from offset-printed food packaging into food. The
content of LAB mixtures in offset-printing inks is
generally 15±30%. Although LAB are good sol-
vents for binders because of their aromatic
character, they do not give rise to odour and taste
problems.
This paper reports studies of the migration of
alkylbenzenes from offset-printed hamburger col-
lars. The origin of the alkylbenzenes was studied
by investigating samples of board, varnished
board, printed and varnished board, and varnish
separately. Finally, in order to con®rm the results,
a sample of the relevant LAB mixture obtained
from the ink manufacturer was analysed.
EXPERIMENTAL
Samples and Materials
Board packaging materials for many kinds of
foodstuffs were received from manufacturers,
together with information about the materials
used in their production, including the brands,
printing methods and varnishes. All paper and
board samples were produced from virgin ®bre.
The hamburger collars studied were about 6 cm
wide. They are put around high hamburgers to
keep them together. The collars were made of
folding boxboard and were offset printed. Most of
the collars had a layer of varnish on both surfaces,
i.e. on the printed, non-food contact surface as well
the non-printed, food contact surface. The purpose
of the varnish layer on the food contact surface was
to act as a grease barrier. Without the varnish
layer, mayonnaise in the hamburgers penetrated
into the board collar, causing it to disintegrate.
The rolls consisted of bread made of wheat ¯our
and had a spongy structure. Tenax1 is the
registered trademark for modi®ed polyphenylene
oxide (MPPO). It is a porous polymer that
72 Packag. Technol. Sci. 2001; 14, 71±77
MIGRATION OF ALKYLBENZENES

Figure 1. Experimental set-up for migration test with
Tenax1. (A) Preparation of test: (1) lid, (2) aluminium foil,
(3) sample and (4) Tenax1. (B) Exposure to Tenax1.
ef®ciently traps volatiles. Tenax1 is recognized by
the Council of Europe (Committee of Experts on
Materials Coming into Contact with Food) for
testing paper and board as a dry, non-fatty food
simulant. It is also recognized by the European
Commission in the 2nd Amendment of Directive 82/
711/EEC for testing plastics as a substitute test
medium for fatty food. The Tenax1 used in the
migration tests was Tenax1 TA 60±80 mesh
(Chrompack).
METHODS
Alkylbenzenes in Packaging
The extraction method for alkylbenzenes was
similar to that used for phthalates reported ear-
lier.4 The packaging was cut into pieces and 5 g
amounts were used in the analysis. The internal
standards heneicosane (C21) and 2,6-di-tert-butyl-
4-methylphenol (BHT) were added to the pieces.
Extraction was performed in a conical ¯ask with
hexane for 30 min. Alkylbenzenes were deter-
mined from the hexane extract by GC±MS. The
alkylbenzenes were identi®ed using the speci®c
ions m/z 91 and 105. The total content of alkylben-
zenes was the sum of the 18 alkylbenzene homo-
logues.
As no model compounds or mixtures were
available at the beginning of the study, the
quanti®cation was based on docosane, assuming
that the response factor for alkylbenzenes was one.
Heneicosane was chosen as the basis for quanti®-
cation because it eluted shortly after the alkylben-
zenes. The alkylbenzene mixture used in the
printing ink was later obtained from the ink
manufacturer and it was con®rmed that the
compounds quanti®ed as alkylbenzenes were
indeed the same as in the ink.

Table 1. Alkylbenzenes in unused offset printed packaging samples

Material Food Suppl. Alkylbenzenes

1 Boxboard Cereals A ±
2 Boxboard Cereals A X
3 Boxboard Rice A X
4 Boxboard Chocolate B X
5 Boxboard Chocolate B ±
6 Boxboard Chocolate B X
7 Boxboard Chocolate D X
8 Boxboard Chocolate D X
9 Boxboard Hamburger D ±
10 Solid board Ice cream F X
11 Boxboard Hamburger G 670 mg/kg
12 Boxboard Hamburger G X
13 Boxboard Apple pie G X
14 Corrugated board Fatty H ±
15 Corrugated board Liquorice H ±
Suppl. = supplier of the packaging.
X = identi®ed, but not quanti®ed.
± = not identi®ed.

Copyright O 2001 John Wiley & Sons, Ltd. 73 Packag. Technol. Sci. 2001; 14, 71±77

Table 2. Alkylbenzenes in the hamburger
collar samples (QM)
Sample mg/kg mg/dm2
A (lightly printed) 70 0.2
B (lightly printed)
C wide (heavily printed)
130
460
0.3
1.0
C narrow (heavily printed) 500 1.2
Migration Tests with Tenax
The samples were exposed to the simulant using
single-side contact (see Figure 1). The migration
tests were similar to those reported for phthalates.4
As large a sample as practically possible was used.
The amount of Tenax1 was 4 g dm2, as described
in the draft CEN method for overall migration at
high temperatures.15 The tests were performed in
triplicate and a method blank (migration test
without sample) was prepared alongside the
samples.
Exposure temperature and time are based on the
2nd Amendment of Directive 82/711. Consequently,
the test conditions for hamburger collars were
30 min at 70°C. After exposure, the Tenax1 was
extracted with ethyl acetate using an ultrasonic
bath, and the extract was analysed using GC±MS.
Migration Tests with Rolls
Four hamburger rolls were used to test one kind of
collar. Three rolls with collars were triplicates and
the fourth roll was a blank sample without collar.
The collar was put tightly around the roll and this
was then wrapped in aluminium foil. The test
conditions were the same as for Tenax1 (30 min,
Table 3. Migration of alkylbenzenes (LAB) from hamburger collars into rolls and Tenax1
Migration of LAB into rolls
(ratio of roll/collar = 24 g/dm2)
LAB in collar (QM) Found in roll
460 mg/kg 2 mg/kg
Copyright O 2001 John Wiley & Sons, Ltd.
È DERHJELM
B. AURELA, T. OHRA-AHO AND L. SO
70°C). After exposure, the rolls were cut into small
pieces and extracted with hexane twice using an
ultrasonic bath. The alkylbenzene contents of the
rolls were determined as for board.
RESULTS AND DISCUSSION
Alkylbenzenes in Packagings
Alkylbenzenes were identi®ed in 10 out of 15
offset-printed packaging samples (see Table 1).
Most samples contained only traces of alkylben-
zenes, but one hamburger collar had an exception-
ally high content of alkylbenzenes. More samples
of this type of collar were analysed, and the collars
were also found to have high contents of alkyl-
benzenes. The results of these additional samples
are presented in Table 2. All of these collars had
varnish on both sides, i.e. also on the food contact
surface.
Migration of Alkylbenzenes
The collar sample `C wide' was used for migration
tests with rolls and Tenax1. Table 3 presents the
migration results. The relative standard deviation
of three replicates was 14% in both tests. The total
alkylbenzene content varied from collar to collar,
depending on the amount of printing ink used
(Table 2). However, the relative contents of
individual alkylbenzene compounds were similar
in different collar samples. The alkylbenzenes also
migrated similarly into Tenax1 and rolls. Conse-
quently, the pattern of the alkylbenzene pro®le in
the chromatograms was identical. Figure 2 pre-
sents the chromatograms of a collar and a roll after
a migration test.
As mentioned earlier, the migration test with the
Migration of LAB into Tenax1
(ratio of Tenax/collar = 4 g/dm2)
% of QM Found in Tenax % of QM
4 52 mg/kg 15
74 Packag. Technol. Sci. 2001; 14, 71±77
MIGRATION OF ALKYLBENZENES

Figure 2. Chromatograms of a hexane extract (A) of a collar and (B) of a roll after the migration test. Alkylbenzenes are marked
by * and TMPDiB is 2,2,4-trimethyl-1,3-pentanediol di-isobutyrate. BHT and C21 are internal standards.

roll was done by putting the collar around the roll
to simulate the actual use in hamburger restau-
rants. The contact conditions were 1 kg/42 dm2, as
the rolls were very spongy. This differed signi®-
cantly from the EU conventional ratio of 1 kg/6
dm2. The ratio of Tenax1 to collar was 1 kg/250
dm2 (equivalent to 4 g/dm2), because it is not
practical to use more Tenax1 than this in a test.
These tests showed that migration into Tenax1
clearly exceeded the migration into rolls. It is
important to know this when standardized
methods for paper and board migration tests are
developed in Europe.
Alkylbenzenes were also identi®ed in packaging
samples intended for chocolate (Table 1). Accord-
ing to the 2nd Amendment of Directive 82/711, these
packagings should be tested for 10 days at 40°C,
which is recognized to be more severe than 30 min
at 70°C. Although the alkylbenzene contents in
these packagings were less than in the collars,
signi®cant migration might be observed. How-
ever, this was not studied.

Copyright O 2001 John Wiley & Sons, Ltd. 75 Packag. Technol. Sci. 2001; 14, 71±77

Effect of Varnish Layer
Although the speci®c migration route of the
alkylbenzenes could not be explained by these
tests, it was possible to study the effect of the
varnish layer as a barrier for migration by
comparing the collars with and without a varnish
layer on the food contact surface. Two collars (No.
11 in Table 1 and `C wide' in Table 2), having
roughly the same alkylbenzene content, were
tested using Tenax1. It was found that the varnish
layer reduced the migration by about 70%. The
same phenomenon was seen using the rolls. It is
thus clear that the varnish layer on the food contact
surface substantially reduces migration.
Transfer Route
The migration of alkylbenzenes occurs either from
the printed surface through the board collar or
from the invisible set-off on the food contact
surface. Set-off might have taken place during
the manufacture of the collars, because printed
and varnished boards are stored in piles for a
while before being stamped.
A printed and varnished collar was split in order
to determine the LAB content in the printed and
non-printed parts separately. The board collar was
split quite easily by hand. The LAB content in the
unprinted part was signi®cant, although it was
only half of that in the printed part. This suggests
that set-off had occurred. However, it is unclear
whether the varnish layer reduces migration by
hindering transfer through the board, or by
reducing set-off, which results in less migration.
Risk Assessment
In the risk assessment report published by the
European Commission, the MOS oral (margins of
safety) is calculated for consumers using a NOAEL
(no observed adverse effect level) value 50 mg/
kg/day, derived from reproductive toxicity. The
consumer exposure used in the report comes from
the LAB traces present in detergents. The oral
exposure is estimated to be 0.00019 mg/kg/day
due to deposits on dishes. The oral exposure based
on the migration results from this study (2 mg/kg)
is 0.03 mg/day/kg bw. The calculation is based on
the widely used assumption that a 60 kg person
Copyright O 2001 John Wiley & Sons, Ltd.
È DERHJELM
B. AURELA, T. OHRA-AHO AND L. SO
consumes daily 1 kg of food packed in the speci®c
material. However, the MOS oral is still 1656,
which is very acceptable.
Other Components from Printing Ink
In addition to the LAB mixture, another ingredient
of both printing ink and varnish was found to
migrate into both rolls and Tenax. This ingredient
was TMPDiB (2,2,4-trimethyl-1,3-pentanediol di-
isobutyrate, CAS 6846-50-0), which is used as a
plasticizer or solvent component. Its concentration
in the collar samples varied (35±190 mg/kg). The
concentration of TMPDiB in rolls was 1 mg/kg
after the migration test, and the migration percen-
tage of TMPDiB was 6%, i.e. the same magnitude
as for LAB.
After the completion of this work, it appeared
that at least one printing ink manufacturer will
replace alkylbenzenes by some other components.
This demonstrates that the ink industry has
reacted in a fast, positive and responsible manner.
CONCLUSIONS
Components of the inks used for printing board
may migrate into food, even though there is no
direct contact between the printed surface and the
foodstuff. Alkylbenzenes from offset printing inks
migrated from printed hamburger collars into rolls
in migration tests performed at 70°C for 30 min. It
might be worthwhile to investigate the migration
of alkylbenzenes at 40°C for 10 days, as these
conditions are more severe, and should be applied
for articles that are stored at room temperature for
more than 24 h.
The route of alkylbenzene transfer remains
unclear. Such routes need to be known if the
migration of unwanted substances is to be re-
duced. Application of a varnish layer is a good
example of how minor changes in the manufacture
of a packaging material can have a signi®cant
effect. It is obvious that a lot of testing and research
is needed to ensure the safety of packagings.
ACKNOWLEDGEMENTS
We would like to thank Hannu Laine of Sicpa for
valuable cooperation. This work has been partially
76 Packag. Technol. Sci. 2001; 14, 71±77
MIGRATION OF ALKYLBENZENES
®nanced by the National Technology Agency, Finland,
which is gratefully acknowledged.
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