Food Bioprocess Technol (2014) 7:2136

DOI 10.1007/s11947-013-1106-8

REVIEW

Migration Phenomenon in Food Packaging. FoodPackage

Interactions, Mechanisms, Types of Migrants, Testing
and Relative LegislationA Review
Ioannis S. Arvanitoyannis & Konstantinos V. Kotsanopoulos

Received: 16 February 2013 / Accepted: 1 April 2013 / Published online: 18 April 2013
# Springer Science+Business Media New York 2013

Abstract The development of convenient and low-cost Abbreviations

packages, together with the increased consumer demands AC Acrylonitrile
for safer products, have resulted in the conduction of exten- AG Alcoholic grade
sive research and the publication of numerous studies relat- Al Aluminum
ed to the phenomenon of migration. The large number of BADGE Bisphenol A diglycidyl-ether
synthetic materials used for the manufacture of packages DEHP Ethylhexyl phthalate
makes the evaluation of the foodpackage interactions quite ESBO Epoxidised soybean oil
complicated. Different parameters such as the nature of the FS Food simulants
food of interest, the type of foodpackage contact, the time GC Gas chromatography
and temperature of contact, the packaging materials used, GC-MS Gas chromatographymass spectroscopy
the properties of the migrating substances, as well as the IR Spectroscopy
amount of potential migrants contained in the packaging LC Liquid chromatography
materials, can drastically affect the migration rate and ex- LC-MS Liquid chromatographymass
tent. Due to the extreme variety of foods used, several food spectroscopy
simulants have been suggested and applied for testing the LDPE Low-density polyethylene
migration phenomenon under various laboratory conditions. OM Overall migration
The use of many of those simulants is defined by national and PET Polyethylene teraphthalate
international legislation. This review article covers the main PO Polyolefin
migration phenomena, which are related to the most common- PS Polystyrene
ly used packaging materials. It is clearly demonstrated that the PVC Polyvinyl chloride
complexity of the migration phenomena requires more re- PVdC Polyvinylidene chloride
search to establish internationally accepted risk management SM Specific migration
procedures and standardised testing methods.

Keywords Migration . Food packaging . Migrants .

Foodpackage interactions . Food packaging legislation
I. S. Arvanitoyannis (*)
Department of Agriculture Ichthyology and Aquatic Environment,
Faculty of Agriculture, University of Thessaly, Fytokou Str,
Nea Ionia Magnesias, Volos 38446, Greece
e-mail: parmenion@uth.gr
K. V. Kotsanopoulos
Department of Food and Nutritional Sciences,
The University of Reading, Reading RG6 6AP, UK
Introduction
Nowadays, packaging is applied on a huge variety of prod-
ucts. The protection of goods during all stages of the supply
chain is mainly based on packaging (Brody et al. 2008).
According to Robertson (2006) without packaging, mate-
rials handling would be a messy, inefficient and costly
exercise and modern consumer marketing would be virtual-
ly important.
22
The food packaging section is developing continuously
to address specific needs and problems. This rapid advance
is attributed to recent advances in food packaging materials
used more extensively than the conventional packaging
materials line paper, glass and metals (Arvanitoyannis and
Stratakos 2011). Combinations of packaging materials such
as cardboard and low-density polyethylene (LDPE) are used
for developing active packaging technologies (Garca-
Garca et al. 2013) while advanced packaging conditions
such as modified atmosphere packaging can extend signif-
icantly the shelf life of perishable foods such as dairies
(Tsiraki and Savvaidis 2013). The most widely used plastic
materials are polyethylene, polyvinyl chloride (PVC),
polyvinylidene chloride (PVdC), polystyrene (PS), polyeth-
ylene terephthalate (PET), polyamide and regenerating resin
(Lord 2005).
It is commonly known that a high number of chemical
substances can be found in foodstuffs during the different
stages of the supply chain, including but not limited to food
additives, pesticides, environmentally derived contaminants,
mycotoxins, flavourings and micronutrients. There are also
occasions when packages and materials that come in direct
contact with foods can act as a source of chemicals and
elements. This phenomenon is termed migration (Poas
and Hogg 2007).
At this point it is important to mention that consumers
demand for safer products has enhanced the study of food
additives, which can be either intentionally or accidentally
found inside foods. Sources of these materials can be pack-
ages or processing equipment (Lau and Wong 2000).
Researchers continue to carry out studies on migration of
volatile compounds, additives and oligomers from packag-
ing plastic materials to foods. Furthermore, regulatory au-
thorities have introduced several laws to control these
contamination issues (Muncke 2009).
This review article aims at examining the most important
migration phenomena as well as the migrants connected
with the most commonly used food packaging materials. It
also presents some representative migration examples and
the relative legislation related to migration of substances
from packages into foods.
Interaction of Foods with Food Packaging Materials
The distribution of many food products could not be performed
without the use of packaging. The main purpose of food
packaging is to preserve and protect foods from physical,
chemical and microbiological hazards, which can affect their
safety and quality (Lee 2010). According to Lee et al. (2008)),
a physical interaction could be the transfer of chemical sub-
stances across the foodpackage interface to food, a chemical
one could be the result of the corrosive action of a food on a
Food Bioprocess Technol (2014) 7:2136
metal package, while the microbiological contamination of
foods due to contact with inappropriate packaging materials
could be an example of microbial interaction.
The interactions between food and packages include among
others the intrusion of micro- and macro-organisms, gases
and vapours, water and other compounds of low molecular
weight (Arvanitoyannis and Stratakos 2011). Migration can be
observed towards both directions: from packaging to food and
from food to packaging (Mousavi et al. 1998).
In the first case, molecularly diffused substances of low-
molecular weight (e.g. oligomers, polymers or additives) can
be transferred into foods (Helmroth et al. 2002), while, the
migration of chemical substances from food to package can
lead to both financial and nutritional problems because of the
loss of weight and constituents which can severely affect the
organoleptic characteristics of the food (Lee et al. 2008).
Migration
Migration Mechanism
The migration of substances from packages into foodstuffs
is characterised by high complexity. Diffusion is mainly
responsible for this type of migration, i.e. the macroscopic
movement of molecular structures from higher to lower
concentrations, while adsorption can be another way of
leading to this type of migration (Simoneau 2008).
Diffusion is the mass transfer due to random movement of
molecules from regions of high concentration to regions of
low concentration until equilibrium is reached (Miltz et al.
1997). The diffusion rate is expressed mathematically with the
following equation known as the second law of Fick:


@Cp =@t D @ 2 Cp =@x2 1
Cp (mg/g): the concentration of the migrant in the poly-
meric material
D (cm2/s): the coefficient of diffusion
t (s): the time into which the diffusion take place
x (cm): the distance between package and food (Silva et
al. 2007).
Adsorption is the controlled mass transfer due to the
contact of foods with another material resulting initially in
increased concentration of molecules on the interface of
food/packaging material. The number of molecules
absorbed on the surface at a particular temperature is given
by the Freundlich equation:
x=m Kp  1=n 2
x: mass of absorbed air
m (g): quantity of absorbed material under pressure P
K and n: constants (Arvanitoyannis and Stratakos 2011)
Food Bioprocess Technol (2014) 7:2136 23

Type of migration according to the number of migrants Factors That Affect Migration

Two terms of high significance that should not be Migration is affected by different factors that can have a
confused are the overall migration (OM) and the spe- direct influence over its extent and rate. The main of these
cific migration (SM). The OM is referred to the sum of factors are presented below:
all (frequently not known) mobile substances of pack-
The nature of the food
aging released per unit area of package under the influ-
Simulants were used in many investigations to gain
ence of specific predetermined conditions. On the other
an insight into the effect of food nature on migration.
hand, SM is only related to a specific, known substance
Most of these studies focus on interactions of foods with
(Robertson 2006).
packaging materials and their ability to dissolve the
substance to migrate. For example, foods with surplus
Type of Migration According to the Nature of the Food
of fat were reported to show high migration levels
(Triantafyllou et al. 2007).
Migration can be categorised in three different types depen-
The type of contact
dent on the food systems examined: non-migrating system,
There are a lot of studies indicating that the extent of
volatile system and leaching system.
migration is connected to the specific type of contact of
In non-migrating system, there is an insignificant
the food material with the package (direct and indirect
migration as regards high molecular weight polymeric
contact). Specifically, it is increasingly supported that
materials, a small number of inorganic substances or
migration extent is significantly increased when direct
pigments.
contact with food is applied (Anderson and Castle 2003).
In volatile system, although migration can be performed
The time of contact
without contact between the package and the food, it may be
Experimental data reveal that the concentration of the
affected by the contact. This type of migration is related to
migrating compound is directly proportional to the square
dry solid foodstuff with low direct contact potential with the
root of the contact time (Arvanitoyannis and Stratakos
packaging material. Under these conditions, the volatile
2011). Furthermore, there is evidence suggesting that the
substances migrate following three stages: diffusion or
log of time for equilibrium and the inverse of temperature
evaporation of migrant, desorption and adsorption onto
are linearly correlated (Poas et al. 2011).
product (Fig. 1).
The temperature of contact
In leaching system the contact between packaging and
The temperature factor seems to have a direct influ-
food is essential. The migration phenomenon is performed
ence on both rate and extent of migration. Increased
following three stages: diffusion of migrant, dissolution and
temperatures lead to higher migration rates and rapid
dispersion or diffusion into food. The system most usually
establishment of equilibrium (Triantafyllou et al. 2005).
related to this type of migration is the migration from plastic
The nature of the packaging material
packages to liquid foodstuffs or moist solid products, which
The characteristics of the package have a strong
come in direct contact with the packaging material (Lee et
effect on the level of migration. For example, it has
al. 2008).
been proved that the thickness significantly affects the
Type of Migration According to the Diffusion Coefficient

Diffusion is the principal factor that controls the rate of

migration and its evaluation can be proved quite challenging
since the food ingredients penetrating the package can en-
hance the rate of diffusion of packaging materials. The
migration can be categorised in three clearly distinguishable
categories. In the first category, the diffusion coefficient
approximates zero and as a result the migration potential is
minimal. In the second category, the diffusion coefficient is
a constant value and does not depend on time and compo-
sition of food contained into the package. Finally, in the
third category, the food contact can directly affect the mi-
gration phenomenon, implying that insignificant migration
takes place when there is no contact with food (Aurela Fig. 1 Migration over time of styrene from polystyrene into 8 %
2001). ethanol and cooking oil at 49 C (Murphy et al. 1992; Lehr et al. 1993)
24 Food Bioprocess Technol (2014) 7:2136

migration rate; thinner packages are connected with
higher migration rates (Nerin et al. 2007), while the
amount of recycled ingredients presented no correlation
to migration (Poas et al. 2011).
The characteristics of the migrant
The characteristics of the migrant usually have a
significant impact on the migration route. Jickells et
al. (2005) demonstrated that highly volatile materials
present a higher rate and extent of migration. In addi-
tion, high molecular weight ingredients (>1,200) pres-
ent lesser migration levels in comparison to low
molecular weight materials. Triantafyllou et al. (2005)
proved that the microstructure of the substance that
migrates affects the migration level. Specifically,
should one approach the phenomenon molecularly,
it would be evident that complex molecular config-
urations (spherical oriented molecules, molecules
with side chains) are characterised by lower levels
of migration (Arvanitoyannis and Stratakos 2011).
The amount of the migrant contained in the packaging
material
Higher concentrations of a migrant in the packaging
material will inevitably lead to detection of higher levels
of the substance in food after a certain period of time
(Mariani et al. 1999).
characterised by low molecular weight, facilitating the
package-to-food migration (Pedersen et al. 2008).
Thermal Stabilisers
In addition to plasticisers, thermal stabilisers are often added
to plastic materials including PVC, PVdC and PS (Lau and
Wong 2000). Generally epoxidised seed and vegetable oils
(e.g. soybean oilESBO) are extensively applied to a wide
variety of food-contact plastic polymers, heat stabilisers,
lubricants and plasticisers (Food 2012). Their degree of
purity affects their toxicity, since the residual ethylene oxide
is a highly toxic (Lau and Wong 2000).
Slip Additives
Fatty acid amides are widely applied as food additives in a
wide range of plastics that can be used to form packages,
such as polyolefins, PS and PVC. Although the addition of
slip additives is directly performed to plastic formulations,
they tend to emerge and present surface blooming (Cooper
and Tice 1995). They are mainly used to form products with
certain characteristics, such as lubrication properties with
the aim to preventing films from sticking to each other or
present conglomeration and reduction of the static charge
(Arvanitoyannis and Bosnea 2004; Cooper and Tice 1995).

Light Stabilisers
Migration Compounds from Food Packaging Materials
Light stabilisers find many applications in improving the long-
Plastic Packaging term weathering properties of plastic polymers such as poly-
olefins. Polymeric hindered amines, (e.g. Tunuvin 622 and
Plasticisers Chimasorb 944) are widely applied in polyolefins as light

A plasticiser is defined as a substance which after incorpo-

ration into a material (usually a plastic or elastomer) can
make it more flexible and facilitate its processing. Most
plasticisers belong to the group of esters of phthalic acid
(phthalates) and adipic acid. The di-2-ethylhexyl phthalate,
the dioctyl phthalate and the di-2-ethylhexyl adipate are
systematically applied (Rahman and Brazel 2004).
Figure 2 diagrammatically represents the migration route
of di-n-octyl phthalate into Semolina powder and a solid-
food simulant. Many studies report that plasticisers can act as
migrants and can be transported from packages to foods (Biles
et al. 1997; Castle et al. 1988a; Castle et al. 1988b; Castle et al.
1988c; Castle et al. 1988d; Castle et al. 1988e; Castle et al.
1988f; Castle et al. 1990a; Castle et al. 1990b; Castle et al.
1993; Losada et al. 1997; Macias-Matos et al. 1990; Page and
Lacroix 1995; Startin et al. 1987). According to Pedersen et al.
Fig. 2 Migration over time of di-n-octyl phthalate into Semolina
(2008): phthalates are used in cap-sealing resins and sealing
powder packed in recycled paperboard (Grtner et al. 2009) and
gaskets of bottled food, PVC films and some plastic packag- Tenax in contact with paper spiked with the migrant (Poas et
ing. Phthalates used as plasticisers for polymers are al. 2011)
Food Bioprocess Technol (2014) 7:2136
stabilisers (Lee et al. 2008; Careri et al. 2002). An ultra-
performance liquid chromatography (UPLC) with ultraviolet
spectrophotometry detection system (UPLC-UV-visible) was
used by Noguerol-Cal et al. (2010) for the determination of
the light stabilisers Chimassorb 944 and Tinuvin 770. The
method provided quite reliable results offering a chance for
the development of an effective tool for verifying compliance
with legal limits.
Antioxidants
Exposing polymers to UV light and air can lead to signifi-
cant degradation of the materials due to oxidation reactions.
Antioxidants can be used to reduce the rate of oxidation and
enhance the stabilisation of the material of interest, through
degrading themselves. Tinuvin P, Tinuvin 326, Tinuvin 776
DF, Tinuvin 234, Chimasorb 81, Irganox 1076, Irganox
1330, Irganox 1010, Irganox168 and Irganox P-EPQ are
included among the most widely known chemical antioxi-
dant substances (Lau and Wong 2000). The most significant
natural antioxidants that are either contained or subsequent-
ly added to foods are substances such as: tocopherols and
tocotrienols (vitamin E) ascorbate (vitamin C), vitamin A
and carotenoids (-carotene, lycopene, lutein etc.), Se (and a
variety of other metals which are considered to play a key role
for the action of antioxidant enzymes), phytochemicals with
antioxidant activity, dietary and other supplements (CoQ10,
glutathione, lipoic acid etc.) and food antioxidants such as
butylated hydroxyanisole, butylated hydroxytoluene, propyl
gallate and tertiary butylhydroquinone (Papas 1999). Figure 3
presents the migration kinetics of Irganox 1076 from LDPE
into a food simulant and meat.
Solvents
During printing plastic packages, the inks are used in the
form of dissolutions or dispersions in solvents, which can
afterwards evaporated or removed by penetration, distilla-
tion and contact usually in specific types of ovens (Boon
2008). However, it is possible that a quantity of residual
solvent remains. The solvents most usually used are low
molecular weight, organic substances composed of hydro-
carbons, alcohols, glycol ethers, ketones and esters, which
may present migration into foods by directly contacting
them or through the free space in the interior of the package.
The quantity of solvents entering a food product is highly
dependent on portioning of the solvent between the package
materials and the food (Robertson 2006).
Monomers and Oligomers
Styrene Monomer Styrene is one of the most extensively
applied monomers in polymers used in contact with foods.
25
The main areas of application of its polymer, polystyrene
(PS), are in containers for yogurt, cream, cottage cheese,
ice-cream and fruit juice, meat trays, biscuit trays, egg
cartons, different food and drink cups and boxes for fresh
products (Tawfik and Huyghebaert 1998). Leibman (1975)
reports that styrene monomer can be degraded to styrene
oxide, which is characterised by severe mutagenic action,
while if further metabolised can lead to the production of
hippuric acid. The most commonly presented toxic effects
due to exposure to styrene are irritation of the skin, eyes and
respiratory tract and depression of the central nervous sys-
tem. According to Tang et al. (2000), the average detected
levels of styrene monomer in food packages range between
100 and 3,000 ppm. Figure 1 presents the migration over
time of styrene into ethanol and cooking oil while the
migrating styrene monomers are derived from the polysty-
rene packaging.
Isocyanate In the field of food packaging, isocyanates are
used for the production of polyurethane polymers and ad-
hesive substances. Furthermore, primary aromatic amines
are considered part of this group of chemicals, and their
detection in foods is attributed to a wide range of sources
such as rubber, epoxypolymers, azo-dyes and aromatic
polyurethane materials (Simoneau 2008). According to the
review article of Lau and Wong (2000), the consequences of
the use of isocyanates in human health have been extensive-
ly examined due to their commonly known toxicity. It is
demanded that any remained residues in the final package
must range below 1.0 mg kg1. Nowadays, a limited number
of 12 isocyanates are accepted for applications in food
packages.
Vinyl Chloride Monomer Under normal temperature and
pressure conditions, vinyl chloride is a colourless gas.
However, it is usually used as a liquid under pressure in steel
Fig. 3 Migration over time of Irganox 1076 from LDPE into Tenax
(at 23 C) (Reinas et al. 2012) and pork minced meat (at 25 C) (Beld
et al. 2012)
26
cylinders and is applied in PVC packages (Robertson 2006). It
is a highly toxic substance and maximum permitted levels in
food packaging have been established since the 1970s (Castle
et al. 1996). Vinyl chloride can leach from plastic PVC bottles
or food packages, but government authorities such as the Food
and Drug Administration (FDA) have established restrictions
as regards the quantities of vinyl chloride that can be found in
food packaging materials. Dietary exposure to vinyl chloride
from PVC packages used for food has been calculated for the
United Kingdom and the United States and it was found that
the daily exposure was <0.0004 g kg1 (for 1970s and early
1980s) (Agency for Toxic Substances and Disease Registry
ATSDR 2006).
Acrylonitrile Monomer Acrylonitrile (AC) is widely applied
for the production of plastics and synthetic rubber (Agency
for Toxic Substances and Disease Registry ATSDR 1999).
During the production of polymers, it can be applied as a
starting material for the formation of synthetic fibres, resins,
plastics, elastomers and rubbers (National Industrial
Chemicals Notification and Assessment Scheme NICNAS
2000). It is also contained in a wide variety of polymeric
materials, which are used in the food packaging industry. In
this case the terpolymer consists of approximately AC
monomer in combination with styrene and butadiene.
AC/butadiene/styrene resins can be used in contact with food
materials. The amounts of styrene, butadiene and AC in their
polymers can vary resulting in different particular character-
istics required for different products. AC monomer is quite
toxic and the correlation of the amount of AC monomer
residues in polymers is currently examined and evaluated with
the use of food simulants (FS) (Lickly et al. 1991).
Polyethylene Terephthalate Oligomer PET is widely applied
for the production of different types of bottles and trays used
in food packaging applications, including but not limited to
mineral water, carbonated beverages, juice, beer, milk, veg-
etables and other fresh foods. PET is a form of thermoplastic
polyester, which is produced through condensation poly-
merisation after performing an esterification reaction with
the use of monoethylene glycol and terephthalic acid or
dimethyl terephthalate (Kim and Lee 2012). Because of its
resistance to high temperatures, (up to 220 C), it can be
easily used for the production of dishes for microwave and
conventional thermal processing. However, analyses have
shown that PET contains small levels of low molecular
weight oligomers ranging from dimers to pentamers. The
main volatile substance found in PET is acetaldehyde,
which is of high significance due to its effects on odour
quality, especially in cola-type beverages. These cyclic
chemical substances have been detected at levels that range
between 0.06 and 1.0 % depending on the type of PET (Lau
and Wong 2000).
Food Bioprocess Technol (2014) 7:2136
Caprolactam Polyamides, widely known as nylons, are a
group of food packaging materials that can be used in
contact with foods during thermal processing. There are
indications that high amounts of nylon 6 oligomers and
caprolactam residues (monomer of nylon), present migra-
tion into boiling water. Although caprolactam does not have
acute toxic effects on oral administration, it can lead to a
minor protracted effect on thermo-regulation and undesir-
able bitter taste in foods (Bomfim et al. 2011). In addition, it
was proved that inhalation of high levels of -caprolactam
can lead to the occurrence of irritation symptoms and burn-
ing of eyes, nose, throat and skin, as well as headaches,
malaise, confusion and nervous irritation (Anonymous
2007). According to Ianneo (2009) neurological, gastroin-
testinal and cardiovascular effects as well as dermatological
and immunological changes were reported in workers that
were for long time exposed to caprolactam.
Epoxy Resins Epoxy resins of the bisphenol A type, such as
bisphenol A diglycidyl ethers (BADGE) are applied as
starting materials for cold-cured epoxy resins. Their toxic
effects are basically dependent on fractional concentration
of unreacted epoxy groups (Garca et al. 2006). Bisphenol A
is an endocrine disruptor that has been connected with
estrogenic action. It is used for the formation of epoxy resins
and polycarbonate plastics (Kang et al. 2006).
Contaminants
Other materials that can potentially migrate into foods in-
clude substances derived from the decomposition of addi-
tives or monomers. When direct contact with foods is
required, residues of chemical substances used during pro-
cessing of packaging materials can migrate and contaminate
foods. Moreover, the surrounding environment is also con-
sidered as a potential source of contamination (Lau and
Wong 2000).
Benzene and Other Volatiles Benzene and alkyl-benzene
could be generated from several types of food contact plas-
tics during high temperature applications. For example, it
has been reported that benzene might migrate into food from
contaminated PET, PVC and PS packaging. Benzene has
low molecular weight, so it can penetrate through the pack-
aging material to the food. Therefore, the determination of
the benzene level in plastic food packaging is necessary,
because it is a potentially carcinogenic compound
(Arvanitoyannis and Stratakos 2011; Anderson and Castle
2003).
Environmental Contaminants The surrounding environ-
ment can frequently act as a source of contamination.
Several environmental contaminants such as dust, odour-
Food Bioprocess Technol (2014) 7:2136
causing bacteria, insects and naphthalene can be transferred
into foods. The above contamination factors can contami-
nate foods if a damage to packaging occurs or in the case of
absorption of the contaminants by the packaging material
and subsequent migration to the food (Raloff 2000). For
example, the levels of naphthalene vapour in the air are
significantly enhanced in places exposed to paint and
naphthalene-based moth repellant. It was proved that envi-
ronments characterised by high levels of naphthalene can
lead to increased naphthalene concentration in milk drinks
packaged in low density PE bottles for a specific period of
time. Furthermore, the contamination of packaging mate-
rials and subsequently of food products can be enhanced
during their processing. Hydrogen peroxide is widely ap-
plied for sterilizing polypropylene and PE aseptic food
packages (Lau and Wong 2000).
Other Contaminants In addition to the compounds men-
tioned above, there are many different contaminants that
can possibly migrate and contaminate foods. For example,
dioxins could be found in PVC polymers as contaminants.
Moreover, diphenylthiourea (a thermal stabiliser), benzene
(Anonymous 1990; Griffith 1989), processing agents
(Satyanarayana and Das 1990) and other volatile compo-
nents can migrate into foods (Lawson et al. 1996;
Arvanitoyannis and Bosnea 2004). According to Careri et
al. (2002), diphenylthiourea and products formed through its
decomposition (e.g. isothiocyanatobenzene, aniline and
diphenylurea) were found in packaging materials as well
as packaged food.
Metal Packaging
Tin
Tin is currently found in low quantities in a variety of
canned foods and beverages, especially in foodstuffs pack-
aged in unlacquered or partially lacquered tinplate cans.
Although some case reports of acute gastrointestinal disor-
ders after consuming foods with a level of 100500 mg kg1
tin have been published (Benoy et al. 1971; Omori et al.
1973), these studies present several insufficiencies.
Controlled clinically performed experiments on acute ef-
fects of tin ingested after migration from packages indicate
that there is a threshold concentration for adverse effects
(AEs) of >730 mg kg1 (Boogaard et al. 2003). The tin layer
adheres significant protection against corrosion and in many
cases coating is not used since tin can act as an effective
oxygen scavenger. Nevertheless, the use of coating is usu-
ally applied since uncoated tin can lead to the occurrence of
numerous interactions between the metal surfaces (Oldring
and Nehring 2007).
27
Lead
Despite its toxicity, lead is often used in metal packages.
It was shown that lead is one of the most important
contaminants derived from packaging materials. The
highly toxic effects of lead, and specifically of organo-
lead species (such as neonate) can significantly affect the
central nervous system. It is often supported that infants
are much more susceptible to the toxic effects of lead in
comparison to adults, with a higher percentage of lead
being retained to bones and brain of infants. Subacute
ingestion of lead by children can lead to encephalopathy,
convulsions and mental retardation (Robertson 2006;
Skrzydlewska et al. 2003).
Aluminum
According to Elinder and Sjgren (1986), aluminum (Al)
is commonly used in food contact materials. Different
elements such as Mg, Fe, Si, Mn, Cu and Zn can be found
in Al alloys used in contact with foods (European
Committee or Standardisation CEN 2004a; European
Committee or Standardisation CEN 2004b). Al is detected
at low quantities in numerous plants and animals despite
the fact that it is the most abundant and widely distributed
metal, constituting 8.4 % of the Earths crust (Taylor
1964). However, it is important to mention that Al does
not constitute part of any known animal metabolism, in
contrast to a vast number of less widely distributed metals
involved in enzymes and other metabolic processes. High
intake and increased tissue amounts of this metal have
been connected to numerous disorders, such as dialysis
encephalopathy, osteodystrophy and microcytic anemia.
Apart from the unavoidable daily intake of Al via food,
exposure to Al can occur due to migration from cooking
utensils, storage containers and packages. Due to this fact,
pure Al is not used for the manufacturing of food-contact
packages and a certain amount of alloying elements, such
as Fe, Cu, Zn, Mn and Cr, may be added. However, all
these elements plus the Al can be found into foods if
corrosion occurs (Robertson 2006; Rodushkin and
Magnusson 2005).
Chromium
According to Kim et al. (2008), passivation is a Cr treatment
widely applied to make the tin layer in tinplate cans less
susceptible to oxidation damage and improve the enamel
adherence. Chromium is characterised by relative toxicity
and undesired organoleptic properties and according to
Skrzydlewska et al. (2003), its presence as Cr(VI) can have
severe effects on living organisms since it is known as both
carcinogenic and mutagenic.
28
Epoxy Resins Coatings
Epoxy resins are thermosetting resins which contain two or
more epoxide (oxirane) groups per molecule and can be
formed by condensing epichlorohydric and bisphenol A,
which leads to the formation of BADGE of different degrees
of condensation. The latter can be directly affected by the
reaction conditions and the mole ratio of the reactants.
Powder formulation of high MW epoxies are basically used
for coating internally the surfaces of two-piece DRD food
cans, while UV-treated coating mainly formed by low vis-
cosity aromatic, aliphatic and cycloaliphatic epoxy resins is
applied for coating the external part and ends of cans (Lord
2005). Among the advantages of epoxy resins are their
improved properties such as corrosion resistance, applica-
tion and limited environmental effects. Their toxicity level
has not been evaluated yet (MAMPA 2009).
Other Contaminants
Migration into foods can also include a variety of other
substances, which are detected in metal packages. Off-
flavour in two-piece cans is due to the lubricant used for
their manufacture. Fatty acids and esters are highly
oxidisable and can lead to contamination of canned bever-
ages such as beer, by producing stale, rancid, woody or
cardboard-like flavours. A potent flavour component of
mineral oil that was shown to be naphthenic has also been
detected. The elimination of these problems is based on the
use of several cleaning agents and washings designed to
remove fatty acids, esters and mineral oil (Robertson 2006).
Paper Packaging
Dioxins
Dioxin is a general term describing a vast number of
polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans, which are used for manufacturing paper
food packages. The majority of studies indicate that
dioxins are characterised by high toxicity and the most
toxic isomer is the 2,3,7,8-tetrachlorodibenzo-p-dioxin
(Ackermann et al. 2006).
Benzophenone
Benzophenone is mainly used as a photoinitiator for inks
and varnishes/lacquers treated with UV radiation. Further to
the above uses, benzophenone can be perfectly used as a
wetting agent for pigments or for enhancing the flow rate of
inks. Five to 10 % photoinitiator is usually included into
these inks (Anderson and Castle 2003). UV is widely used
for treating printing cardboard inks since that rapid
Food Bioprocess Technol (2014) 7:2136
treatment enables online cutting and folding, resulting in
fast production of finished packaging. Since only a limited
amount of the initiator is used up during treatment, benzo-
phenone is not totally removed from the printing material
and migration can occur through the open structure of
cartonboard. Moreover, its presence is also possible when
the cartonboard is manufactured from recycled fibres recov-
ered from printed materials. Apart from benzophenone, 4-
methoxybenzophenone can also be used. Studies on the
toxic effects of this product indicate that it can act as
carcinogen, while it is related to estrogenic effects and
highly toxic effects on genes (Muncke 2009).
Nitrosamines
Nitrosamines are genotoxic carcinogenic substances com-
monly found in foods and other media, and their formation
can be endogenously occur in the human body (Tricker and
Preussmann 1991). Robertson (2006) claimed that N-
nitrosamines have been found in numerous foods and bev-
erages. Potential sources of origin include a variety of food
contact materials, such as papers and waxed containers. In
these packaging materials, N-nitrosomorpholine and
morpholine can be found as contaminating factors and can
be transferred into foods that come into direct contact with
packaging for certain periods of time. Ingested amines can
lead to the formation of nitrosamines inside the human body
by interacting with salivary or ingested nitrite.
Chlorophenols and Chloroanisoles
Tainting and production of off-flavours in food products
contaminated with chlorophenols and chloroanisoles have
been recorded (Jeln 2006). These substances migrate into
foods from packages. Chlorophenols have been industrially
applied for the production of fungicides, biocides and her-
bicide intermediates (Brown et al. 2011).
Glass Packaging
From a chemical point of view, glass is very resistant to
attacks from water, aqueous solutions and organic sub-
stances. Both water and acidic components have minimal
effects on silica, despite the fact that they can attack some
other components of the glass. Standardisation of several
tests which examine the migration of substances from glass
to different media through autoclaving the glass container
with a variety of test liquids, have demonstrated that silica
and alkali are the basic components leached from the glass.
These components are unlikely to significantly affect the
organoleptic characteristics of foods. Contamination by
leaching of lead and cadmium is minimal since these two
metals are very rarely used in glass food containers (Poas
Food Bioprocess Technol (2014) 7:2136
and Hogg 2007). It was shown that although the production
processes have been highly improved and the recycling rates
enhanced, elemental migration from commonly used glass
materials is still very low (GTS 2003).
Migration Testing
Determination methods of migrating compounds from pack-
aging materials to foods greatly depend on the extraction
capability of the under study compound. This property can
be quantitatively determined by exposing the packaging
material in contact with food for specific time and temper-
ature and determination of migrating compound to food
(Arvanitoyannis and Stratakos 2011). However, the deter-
mination of migration under real conditions is quite difficult.
It is because of this reason that in most cases simulation of
migration conditions takes place. For example, for a food of
lengthy preservation the migration studies are carried out for
lesser time at higher temperature. Furthermore, standard
compounds known as food simulants are used (instead of
foods) for facilitating the investigations (Stoffers 2005).
Food Simulants
Due to the extremely complex chemical and physical struc-
ture of foods, migration tests are usually performed using
FSs. The latter are either liquid or solid substances that have
a simple and known composition making tests easier and
better interpreted. A variety of different FSs have been
used from time to time and some of them are now
official simulants indicated by mandatory regulations
(Lee et al. 2008).
According to EU Directive 85/572 and Grob (2008), the
above-mentioned FS are classified based on the assumption
that they have similar properties to those of one or more
categories of foods. Although the FS are distinguished in
several categories (see the following paragraphs) there are
foods which are mixtures of fatty and aqueous foods.
Water
The use of water is common for aqueous foods with a
pH higher than 4.5. This group of foods includes non-
alcoholic beverages or alcoholic beverages of an alco-
holic strength lower than 5 % vol. such us water, ciders
fruit or vegetable juices of normal strength or concen-
trated, musts, fruit nectars, lemonades and mineral wa-
ters, syrups, bitters, infusions, coffee, tea, liquid
chocolate, beers, pastry, cakes and other bakers fresh
wares, moist, honey, molasses and sugar syrups, fruits
after processing, vegetables as purees, fish, crustaceans,
molluscs, meat, processed meat foods, cheeses, ice
creams, eggs and many products in aquatic medium.
29
Acetic Acid
A 3 % concentration of acetic acid solution in water
is commonly used for acidic aqueous foods (pH below
4.5) such as vinegar and non-alcoholic beverages or
alcoholic beverages of an alcoholic strength lower than
5 % vol. such us yoghurt, buttermilk and similar foods
with or without fruit and fruit products.
Ethanol
Ten percent aqueous ethanol is commonly applied
for the production of alcoholic products. The concen-
tration of the solution is adapted to the alcoholic grade
(AG) of the food provided the AG exceeds 10 %v/v. As
an example the aqueous ethanol can be used to simulate
alcoholic beverages of an alcoholic strength equal to or
higher than 5 % vol (winers, spirits, liqueurs etc.).
Oil
Olive oil and other oils, such us sunflower oil
and synthetic mixtures of triglycerides are common-
ly used for the production of fatty foods. Animal-
and vegetable-derived fats and oils, many kids of
sauces (mayonnaise, mustard), milk, processed meat
products and products in oily medium are grouped
in this category.
The most recent EU regulation 10/2011 for pack-
aging materials made of plastic refers to three cat-
egories of FS, except for water and addition of
different concentrations of ethanolic solution.
Acetic acid (3 %v/v)
Ethanol (10, 20 and 50 %v/v)
Vegetable oil
Specific Migration Testing
After the food simulant is chosen based on the under inves-
tigation food, a specimen of the under study material (i.e.
polymer, metal etc.) comes in contact with the food simulant
under specific conditions (temperature, time). The time
temperature conditions established by legislation for the
conduction of migration testing are presented in Table 1.
The most frequently applied method for analytically evalu-
ating migration is the gravimetric test. Specifically, the
simulant is either evaporated (in the case of volatile
simulants) or removed (oils) and the residual substance, or
the sample material after the contact, is weighted to calcu-
late by difference the percentage of migration of solid ma-
terials (Grob 2008). The equation below can be used for the
estimation of the total migration.
OM W1  W2 3
Where W1: weight of sample before the contact
W2: weight of sample after the contact (Arvanitoyannis
and Stratakos 2011).
30 Food Bioprocess Technol (2014) 7:2136

Table 1 Timetemperature conditions established by legislation for compound from packaging material to food. This method
the conduction of Migration testing (Adapted from Council Directive
is mainly applied by using chromatographic techniques and
82/711/EEC)
plasmatography analysis such as spectroscopy (IR), gas
Real contact conditions Migration testing conditions chromatography (GC), gas chromatographymass spectros-
copy (GC-MS), liquid chromatography and liquid chroma-
t5 min Depend on the materials examined. The
worst foreseeable conditions of contact
tographymass spectroscopy (LC-MS) (Garca et al. 2006).
must be considered Furthermore, in some cases, solid-phase extraction, liquid-
5 min<t1/2 h 0.5 h phase extraction (Dopico-Garca et al. 2005), supercritical
T5 C 5 C fluid extraction and head space sorptive extraction can be
5 C<T20 C 20 C applied in combination with IR, GC, GC-MS, LC and LC-
20 C<T40 C 40 C MS (Lee et al. 2008).
40 C<T70 C 70 C
70 C<T100 C 100 C
100 C<T121 C Depend on the simulant, in accordance Legislation
with Directive 82/711/EEC
1/2 h<t1 h 1h Initially, the commission established a general framework
T5 C 5 C directive for determining the key requirements that should
5 C<T20 C 20 C be met for all materials and articles, as well as prerequisites
20 C<T40 C 40 C and processes that should be taken into account when drafting
40 C<T70 C 70 C certain directives, such as directives related to specific groups
70 C<T100 C 100 C of materials (e.g. plastics, ceramics etc.) or specific substances
100 C<T121 C Depend on the simulant, in accordance (e.g. vinyl chloride). The framework Directive 76/893/EEC of
with Directive 82/711/EEC 26 November 1976 (since superseded by 89/109/EEC of 21
1 h<t2 h 2h December 1988) set up two general principles. The one is the
T5 C 5 C principle of the inertness of the material and the purity of
5 C<T20 C 20 C the food, and the second is the positive labelling.
20 C<T40 C 40 C
40 C<T70 C 70 C The principle of the inertness of the material and the
70 C<T100 C 100 C purity of the food which states that no components of
100 C<T121 C Depend on the simulant, in accordance
the materials and articles that constitute risk for the
with Directive 82/711/EEC health of the consumers or can lead to unacceptable
2 h<t24 h 24 h at 5 C change in the composition of the foodstuffs or deterio-
T5 24 h at 5 C rate their organoleptic properties should migrate into
C5 C<T40 C Conditions adjusted by national regulations foods. The latter is not only referred to packaging, but
T>40 C also to all articles whose surface is not used in contact
t>24 h with foods during producing, storing, transporting or
T5 C 10 days at 5 C
consuming foods.
5 C<T40 C 10 days at 40 C
The positive labelling indication required for mate-
T>40 C Conditions adjusted by national regulations rials and articles intended to be used in contact with
food products must be accompanied with the indication
for food or a certain symbol, as referred in Directive
80/590/EEC. During retailing, EU members have the
The management of migration presents the same prob- right not to insist on marking where articles are due to
lems and is a matter of the same principles like those applied their nature unavoidably intended to come into contact
in accordance with ISO 9001:2008 for the continuous im- with foodstuffs.
provement of food products. Figure 4 diagrammatically pre-
sents the basic interactions between all factors involved in After defining the basic guidelines, the Commission
the commercial development of foods. moved towards the study of three of the basic packaging
material groups that should be examined at Community
Specific Migration Testing level: cellulose film, ceramics and plastics.
Directive 82/711/EC takes into account the time and
Determination of specific migration is carried out by mea- temperature parameters that can be used for simulating real
suring every time the migration of a specific chemical product use conditions. Migration under the above
Food Bioprocess Technol (2014) 7:2136 31

Fig. 4 The basic interactions

between all factors involved in
the commercial development
and continuous quality
improvement of foods (Adapted
from Hoyle 2008)

simulations should be maintained below specific limits iden-
tified in the positive list. Directive 85/572/EC includes all
simulants that can be applied for migration simulations as
well as a table of correlations between food categories and
their food-simulating liquids.
Directive 90/128/EC established the OM limit at the
level of 10 mg/dm2 of food-contact surface area of material
or article. Assuming that a common package would have a
food-contact surface area: volume ratio of 6 dm2/L, the limit
for OM should not exceed 10 mg/dm2 for a contact area of
 32

Table 2 EEC Directives related to migration of packaging material to foods

EEC Subject Material

Directives

76/893/EEC Relating to plastics materials and articles intended to come into contact with foodstuffs. Plastic materials
78/142/EEC Approximation of the laws of Member States relating to materials and articles contain vinyl chloride monomer and are intended to come into Plastics
contact with foodstuffs.
80/590/EEC Determining the symbol that may accompany materials and articles intended to come into contact with foodstuffs. All materials
80/766/EEC Community method of analysis for the official control of the vinyl chloride monomer level in materials and articles which are intended to come Plastics
into contact with foodstuffs.
81/432/EEC Community method of analysis for official control of vinyl chloride released by materials and articles into foodstuffs. Plastics
82/711/EEC Basic rules necessary for testing migration of the constituents of plastics materials and articles intended to come into contact with foodstuffs. Plastics
84/500/EC Approximation of the laws of Member States relating to ceramic articles intended to come into contact with foodstuffs. Ceramics
85/572/EEC List of simulants to be used for migration of constituents of plastic materials and articles intended to come into contact with foodstuffs. Plastics
89/109/EEC Approximation of the laws of the Member States related to materials and articles intended to come into contact with foodstuffs. All materials
90/128/EEC Relating to plastic materials and articles intended to come into contact with foodstuffs. Plastics
92/39/EEC Amending Directive 90/128/EEC relating to plastics materials and articles intended to come into contact with foodstuffs. Plastics
93/8/EEC Amending Council Directive 82/711/EEC laying down the basic rules necessary for testing migration of constituents of plastics materials and articles Plastics
intended to come into contact with foodstuffs.
93/9/EEC Amending Directive 90/128/EEC relating to plastics materials and articles intended to come into contact with foodstuffs. Plastics
93/10/EEC Relating to materials and articles made of regenerated cellulose film intended to come into contact with foodstuffs. Regenerated cellulose
93/11/EEC Concerning the release of the N-nitrosamines and N-nitrosatable substance from elastomer or rubber teats and soothers. Elastomers
95/3/EEC Amending Directive 90/128/EEC relating to plastics materials and articles intended to come into contact with foodstuffs. Plastics
96/11/EEC Amending Directive 90/128/EEC relating to plastic materials and articles intended to come into contact with foodstuffs. Plastics
97/48/EEC Amending for the second time Council Directive 82/711/EEC laying down the basic rules necessary for testing migration of the constituents Plastics
of plastics materials and articles intended to come into contact with foodstuffs.
2002/72/ Relating to plastic materials and articles intended to come into contact with foodstuffs. Plastics
EEC
1935/2004 Regulation on materials and articles intended to come into contact with food and repealing Directive 80/590/EEC and 89/109/EEC. All materials
1895/2005 Regulation on the restriction of use of certain epoxy derivatives in materials and articles intended to come into contact with food. All materials
2023/2006 Regulation on good manufacturing practice for materials and articles intended to come into contact with food. All materials
2007/42/ Relating to materials and articles made of regenerated cellulose film intended to come into contact with foodstuffs. Regenerated cellulose
EC
282/2008 Regulation on recycled plastic materials and articles intended to come into contact with foods and amending Regulation (EC) No. 2023/2006. Recycled plastic
450/2009 Regulation on active and intelligent materials intended to come into contact with food. Active and intelligent
materials
10/2011 Regulation on plastic materials and articles intended to come into contact with food. Plastics
Food Bioprocess Technol (2014) 7:2136
Food Bioprocess Technol (2014) 7:2136
60 mg/L. Moreover, the directive includes two lists of
chemical materials (1,340 in total of which 540 are mono-
mers and 800 additives), which are used for preparing
plastics for food packages.
EU regulation 1935/2004 defines the general rules in
relation to food packages, transportation and storage of
foodstuffs. All directives related to migration phenomena
and materials in contact with foods from 1976 up to 2011
are summarised in Table 2.
Although the simulants as testing tools for examining the
migration phenomenon are of high importance, their rele-
vancy should be defined more accurately. The conditions
referred into legislation can only be applicable if the deter-
mination in food is not possible; adjustment of simulation to
migration into food is the first priority, overruling the con-
ditions referred into legislation in case of conflict (Grob
2008). Predictive mathematical modelling has been recently
suggested as a potential alternative to traditional simulation
tests. The mathematical interpretation of the diffusion
phenomena can lead to the development of effective
and low-cost migration-predicting tools. Nevertheless,
the reliability of this method has not been finalised yet
(Helmroth et al. 2002.
Conclusions
The migration phenomenon is of high importance nowadays
especially due to the continuously increasing requirements
of consumers for safer products, and the establishment of
international regulations to meet these requirements.
Migration in both directions (from packaging to food and
conversely) can affect both the organoleptic characteristics
(quality) and the safety of products. This complex process
can be affected by several factors such as the nature of the
food, the packaging material, time and temperature condi-
tions etc. Migration can be affected by the characteristics of
both the package and the contained food, while the charac-
teristics and the nature of the migrant itself can significantly
affect the migration route.
The food simulants are extensively used for examining
the migration phenomenon, mainly due to the high variety
of food products that need to be examined. A variety of food
simulants have been applied for testing the migration phe-
nomenon. The international legislation defines specific
simulants that can be used under certain time-temperature
conditions for the conduction of migration testing.
The extreme variety of potential migrants indicates the
need for establishment of not only internationally recognised
testing tools, but also appropriate risk management proce-
dures (better identification of potential consumers and estab-
lishment of maximum permitted limits, assessment of safety
for all potential migrants etc.).
33
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