Radiation Physics and Chemistry 63 (2002) 841844

Migration and sensory changes of packaging materials caused

by ionising radiation
Frank Welle*, Alexandra Mauer, Roland Franz
Fraunhofer-Institute for Process Engineering and Packaging (IVV), Giggenhauser Str. 35, 85354 Freising, Germany

Abstract
Irradiation of packaging materialsFin most cases plasticsFgenerally lead to a formation of free radicals and ions,
with secondary eects such as cross-linking as well as oxidative chain scission. These eects result in a formation of
volatile radiolysis products which may induce o-odours in the polymers and may change the migration characteristics
of packaging materials. Irradiation aect also polymer additives which change the specic migration behaviour of
polymer additives and additive related decomposition products. Migration and sensory changes of pre-sterilised
packaging materials have consequences on the quality of packaged goods and consumers safety. Therefore, migration
and sensory properties of packaging materials have specic regulations. Within this paper the eects of the formation of
radiolysis products on overall migration, specic migration of food additives or radiolysis products as well as on
sensory changes are discussed in view of current European food law. r 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Packaging materials; Ionising radiation; Migration; O-odour

1. Introduction

2. Radiolysis products

Sterilisation of packaging materials with ionising

radiation is an alternative to other sterilisation methods
e.g. chemical or heat treatment. For this purpose, the
packaging materials are pre-sterilised in commercial
irradiation plants with ionising radiation from 60Cosources and electron accelerators, respectively. However,
specic regulations for irradiated goods by authorities,
low consumer acceptance and eects of ionising radiation on polymers and polymer additives lead in the past
to a low application level of irradiation for sterilisation
of packaging materials. In our point of view, rigorous
regulations and high requests by the authorities for
irradiated packaging materials going along with the lack
of information on migration data for irradiated packaging materials.

Irradiation of polymers generally lead to a formation

of free radicals and ions, with secondary eects such as
cross-linking as well as oxidative chain scission. Also
polymer additives are destroyed. In the last three
decades most publications dealing with formation of
radiolysis products (see, for example Allen et al., 1988;
Bourges et al., 1992a, b, 1993; Buchalla et al., 1999,
2000; Demertzis et al., 1999; Komolprasert et al., 2001).
Many of the radiolysis products are well known e.g. 1,3di-tert-butylbenzene and 2,4-di-tert-butyl-phenol. Both
are decompositions products of polymer additives like
Irgafos 168 which is typical for polyolens. Data on the
formation of radiolysis are very important for an
evaluation of the irradiation treatment of the polymer.
In view of consumers safety the migration of
specic compounds or the overall migration as a
sum parameter is the crucial parameter for an evaluation
of food packaging materials. It is therefore interesting
that the migration and sensory changes caused by

*Corresponding author. Tel.: +49-8161-491-724; fax: +498161-491-777.

E-mail address: fw@ivv.fhg.de (F. Welle).

0969-806X/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
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842

dependency of the applied dose are shown in Fig. 1.

As a result, the overall migration into non-polar food
simulants like iso-octane do not show signicant
changes up to doses of 45 kGy. Overall migration with
polar food simulants (95% ethanol) show similar results
(Welle et al., 2000). In all cases, the overall migration
was below or far below of the migration limit of
10 mg dm 2 given by EU regulations. The reason for
unchanged overall migration is not only an eect of the

formed radiolysis products are discussed only by a

few papers (Killoran, 1972; Marque et al., 1998; Welle
et al., 2000).

3. Overall migration
The inuence of ionising radiation (60Co) on the
overall migration of various packaging plastics in

iso-octane migration [mg dm-2]

10
9
8
7
6
5
4
3
44.5 kGy

17.6 kGy

1
0

unirradiated
LDPE 1 LDPE 2

PP 1

PP 2

PET

PA

60

Fig. 1. Amount of extractable substances from irradiated ( Co) packaging materials obtained with iso-octane (24 h, 401C, total
immersion)

Fig. 2. Headspace gas chromatograms of irradiated (e-beam) and non-irradiated polypropylene yoghurt cups.

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843

Table 1
Results of the sensory examinations (odour) of irradiated packaging materials in comparison to the unirradiated reference sample
Polymer

Irradiation dose (kGy)

Value

Description of odour

LDPE

Unirradiated
7.2
17.6
44.5
Unirradiated
17.6
44.5
56.9

2
23
34
4
1
12
1
2

Waxy polyolene odour, slightly pungent

Plastic odour, burnt, pungent
Pungent, waxy, distinct plastic odour
Strong plastic odour, pungent, waxy, slightly sour
Slight plastic odour
Slight plastic odour
Sweet plastic odour
Plastic odour

PET

irradiation itself. It is mainly based on the overall

migration testing procedure which loose volatile substances during sample preparation. Therefore, the
migration of volatile radiolysis products into the foodstu could not be excluded. A gas chromatographic
screening of the polymers using the headspace technique
conrm this thesis. A representative example is shown in
Fig. 2 which shows that volatile radiolysis products
are formed during irradiation (e-beam) in polypropylene
yoghurt cups. We have found similar results for
other polymers like polystyrene, low density polyethylene, high density polyethylene, poly(ethylene terephthalate), etc.)

4. Specic migration
The specic migration of additives, e.g. of Irgafos 168,
decreases with increasing radiation dose due to degradation of additives. In a conclusion, due to the reduced
specic migration of additives irradiation could be
benecial with regard to food safety (Marque et al.,
1998). But this conclusion is only one part of the
migration behaviour of irradiated polymers. The concentration of additive related degradation products e.g.
1,3-di-tert-butylbenzene or 2,4-di-tert-butylphenol increase during irradiation. However, the specic migration of these radiolysis products formed under practical
irradiation conditions (o10 kGy) is below 0.1 mg dm 2
under usual contact conditions (10 d, 401C, food
simulants 10% and 95% ethanol, respectively) (Welle
et al., 2000).

5. Sensory examinations
Volatile substances formed during irradiation aected
the sensory properties of the investigated packaging
materials. A typical o-odour occurred after irradiation
with increasing irradiation dose. The results of sensory
examinations of low density polyethylene and PET are
summarised in Table 1.

6. Conclusions
A inherent problem of irradiated polymers is the
formation of volatile radiation products, which aect
the sensory properties of the packaging materials.
Using the test procedure for overall migration given
by EU regulations these volatile substances could not
be detected. Therefore, the overall migration is unchanged with increasing dose. Due to the unspecic
fragmentation pattern in the mass spectrometer a clear
identication of volatile substances is often impossible.
However, the detected volatile radiolysis products
are in concentration ranges of other polymer impurities.
Similar to radiation products these technical impurities
are in most cases also unidentied. In view of European
food law such unavoidable technical impurities are
tolerated as long as the consumers safety is ensured
and sensory properties of the packed food are not
aected. From this point of view migration of unidentied substances into the foodstu is not only a
problem of irradiation and in consequence specic
regulations for irradiated packaging materials are not
necessary. But an Europe-wide accepted standard for
the evaluation of unidentied impurities in packaging
materials is needed. In the United States radiolysis
products as well as other polymer impurities are
examined as indirect food additives which are
suspected to the threshold-of-regulation concept. This
concept allows the migration of unidentied substances
from the packaging material into the foodstu as long as
the daily concentration of 0.5 ppb per substance is not
exceeded. A similar concept should be very useful for
evaluation of the inuences of irradiation on food
packaging materials in the EU.
A general evaluation of the inuence of irradiation on
packaging materials and additives is very dicult due to
the strong dependency on polymer material, additive
mix, additive concentration and irradiation dose. However, an evaluation of the food law compliance of the
packaging material intended for irradiation should be
done under consideration of the applied radiation dose
and in comparison to the unirradiated polymer. In
addition to the overall migration a suitable method for

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F. Welle et al. / Radiation Physics and Chemistry 63 (2002) 841844

detection of volatile substances should be involved, for

example headspace GC.

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