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Pr
int
Migration of Substances from Plastic Food Contact Materials into Foods and
Food Simulants
Jan 5, 2005

By Dr P. Mercea, FABES GmbH Research Company (Mnchen - Germany)

Economic, Phenomenological, Consumer Protection & Regulatory Aspects
Migration Estimations for Compliance Purposes
Economic, Phenomenological, Consumer Protection & Regulatory Aspects
Economic Impact of Plastic Food Contact Materials

In European Union (EU) countries every year more than 10 million tons of plastics
are used for packaging, of which up to 50% are used in food packaging. Different
types of Polyethylenes (PE's) and Polypropylenes (PP's) make up to of the plastics
used as food contact materials. The rest is covered mainly by Polystyrenes (PS's),
Polyethylenetherephthalate (PET), plastified Polyvinylchloride (PVC's) and
Polyamides (PA's). The polymeric resins themselves are produced across the EU in
a quite limited number of large scale plants, involving only relatively few
workplaces. The conversion of these resins into different types of plastic food
contact materials involves the use of certain additives (antioxidants, stabilizers,
pigments, plastifiers, etc.) in the framework of specific manufacturing procedures.
This is done in the EU by a highly fragmented and specialised industry where
several hundred of thousands of workplaces are involved. Finally in the framework
of the food (packaging) industry the plastic materials are used to package/wrap
food products. This industry relies in the EU on many thousands of enterprises
(mainly small and medium ones) with other hundreds of thousands of workplaces.
Eventually the packaged foods, through the channels of distribution and
commerce, reach the end-consumer (now more than 350 millions in the EU). The
plastic materials and articles used nowadays to package food play a crucial role not
only in protecting the hygienic characteristics of foods but also to extend their
preservation time and adequate appearance.
Moreover, the visual appearance (shape, size and colour and layout of the prints) of
many plastic food packaging articles play an important role in the marketing
strategy of the food producing companies. From these few statements it is obvious
that plastic food contact materials play an important role in the economies of the
EU member states and in the everyday lives of their citizens.
Phenomenology of Migration from Plastic Food Contact Materials into Food.

From a phenomenological point of view it is well documented that, from the very
beginning an entity of food packed in a plastic material is not really inert. A series
of chemical and biologic phenomena take place into the food itself and there is an

interaction between the food and the packaging material, too. This later aspect is
the one in which we are interested here and it comprises:

the uptake of various food components by the packaging and respectively

the transfer of substances (additives, monomers, stabilizers, plastifiers,
printing-inks, etc.) from the plastic packaging into the food.

Both phenomena occur due to the existence of substance concentration gradients

between the plastic packaging material and food and due to the fact that the
boundary between these two entities exhibits a non-zero mass permeability in both
direction, i.e. substances can cross the boundary both from the food towards the
plastic and vice versa.
The uptake of food components by a plastic packaging is relevant for our
presentation because this process may lead to a considerable change of the initial
properties of the plastic material (for example by swelling). This increases usually
many times the rate of substance transfer from the plastic into the food and may
also accelerate the degradation of the plastic packaging.
The other process, the release/transfer of substances from the plastic packaging
into the food is commonly named "Migration" and it is a quite complex process.
The rate and dynamics of a migration process depend on a series of factors among
which the concentration of the substance (migrant) and its mobility (diffusion
coefficient) in the plastic matrix and the solubility of the migrant in the food play
an important role.
Both processes can be nowadays investigated experimentally with a high degree of
accuracy and thus information can be obtained about the parameters and conditions
which influence them as well as about the level of accumulation of migrants in a
certain packaged food. Moreover, it has been shown in recent years that most of
the migration processes taking place between plastic packaging and foods can be
estimated using theoretical models and adequate computer software.
Consumer Protection and Regulatory Aspects

The consumer protection problem with the migration process is that people
consuming foods packaged in plastic materials are inherently exposed to a series of
substances, originating not from the food itself but from the plastic, which may
become a health concern if they exceed certain limits. To prevent the occurrence of
situations in which the uptake of food components by the plastic packaging leading
to its swelling/degradation and thereof to a considerably increased migration of
substances from the plastic towards the food, the Good Manufacturing Practices
(GMP's) established at the level of the EU require nowadays that the industry
should avoid ab initio the occurrence of this situations. In other word this means
that if a plastic material swells or even degrades when it is in contact with a certain
food then this article is not suitable for manufacturing a packaging for the said
food.
Thus it remains that, from the point of view of interactions between plastic

packaging and food, the main aspect of concern for the consumer's health are the
substances which migrate from the plastic into the food. This problem was
recognised several decades ago not only by the consumer protection institutions of
the EU Member States (MS) but also by the Commission of the European
Community (EC). Since then laws and directives have been released at the level of
the MS and the EC with the aim to provide a framework of toxicological standards
and experimental procedures with which the impact of migration from plastic food
contact materials can be properly assessed and monitored. The aim of these
endeavours was and still is to provide a high level of consumer health protection to
the EU citizens. The central point of the EU legislative framework is that industry
must demonstrate that the plastic food packaging materials/articles released to the
market comply with the existing EU Directives.
To check the compliance of a plastic food contact material with the existing EU
regulations overall and specific migration tests shall be carried out using the food
simulants and the test conditions specified in the EU Directive 97/48/EC.
However, the experimental determination of a specific migration into a food
simulant is often a complex analytical task, which requires a considerable amount
of work-time and expertise and hence costs for the producer. In a certain number of
cases it is even impossible to obtain a reliable experimental migration data because
of technical/analytical problems, chemical degradation/volatilisation of the migrant
or non-availability of an appropriate analytical method. In addition, owing to an
increasing number of Specific Migration Limits (SML's) for additives in plastics,
the "Plastics Directive 90/128/EEC" was in danger of becoming impracticable in
terms of compliance testing for the enforcement laboratories and industries, due to
the large number of often sophisticated analytical methods needed for the
identification of these substances. There was no doubt that this Directive offered in
principle a high degree of protection of the consumer from chemical migrants
derived from plastic packaging materials. But there was no doubt that in practice
the regulations of this Directive were highly complex and expensive to enforce
only by experimental procedures. Faced with a plastic material - originating from
within the EU or from outside - an enforcement lab must apply a large number of
time-consuming and expensive analytical methods to determine the migration of
many chemicals that could in principle migrate into food.
Recognising this situations the European Commissions supported recently an
international group of experts, coordinated by the FABES
GmbH/Munich/Germany and CEFIC/FCA/Brussels/Belgium, to demonstrate that
the theoretical estimation of migration processes can be regarded as a valid and
reliable tool to calculate "reasonable worst-case" migration rates from the most
important food contact plastics into the EU official food simulants. These
simulants are normally used to mimic the contact with foodstuffs in experimental
migration testing. It was asked by the initiator of this project to show that the
calculated migration values can be used with a high degree of confidence to verify
compliance with the current legislation. The following considerations were the
foundation of this EU initiative.
In the last decades numerous scientific investigations have demonstrated that

migration of small organic molecules from a plastic (polymeric) material into a

liquid substance is a theoretically predictable physical process. To apply this
evidence to food contact materials and food simulants two important criteria must
be fulfilled;

the plastic food contact material which is designated for the market must be
manufactured according to GMP, and
the contact conditions (temperature, duration and interactions) between the
plastic material and food must be within the limits of what can be
considered normal, safe and practicable for the said packaging application.

If these criteria are fulfilled, in most cases, the migration of small organic
molecules from plastic food contact materials into foods and/or food simulants
obey Ficks laws of mass transport (diffusion), and therefore can be theoretically
predicted.
The said group of experts build up and validated a migration estimation model
which can be used, for a series of plastic food contact materials and migrants, for
regulatory purposes. The model comprises well known analytical algorithms
describing the migration from a plastic material in a limited amount of liquid food
simulant. To ensure a consumer safety margin "upper limit" values for the mobility
(diffusion coefficient) of migrants in the plastics were considered in the model and
"worst case" levels of solubility (partitioning coefficients) of migrants in the food
simulants were assumed.
The results obtained by the model were then validated, at a confidence level of
95%, by comparison with the available experimental evidence.
The final result of the work done by the said group of experts was that in 2002 the
European Commissions passed to their regulations the statement that in addition to
the experimental methods, the compliance of a plastic material might be
established by performing a theoretical migration estimation. Thus since 2002 the
corresponding EU Plastics Directive 2002/72/EC, Article 8, 4, states:
The verification of compliance with the specific migration limits provided for in 1
may be ensured by the determination of the quantity of a substance in the finished
material or article, provided that a relationship between that quantity and the
value of the specific migration of the substance has been established either by an
adequate experimentation or by the application of generally recognised diffusion
models based on scientific evidence. To demonstrate the non-compliance of a
material or article, confirmation of the estimated migration value by experimental
testing is obligatory.
The above paragraph is an important legislative step from several points of view.
First migration estimations will certainly contribute to reduce the need for time
consuming and expensive experimental control measurements.
Then, for the R&D establishments from industry and government involved in

developing new plastic food contact materials, migration estimations can be

used to obtain a quick and cheap first estimate of the migration behaviour from a
new type of polymer and/or for new type of migrant.
Finally for enforcement organisations migration estimations can be a very useful
additional tool to diversify and increase the efficiency of their experimental
control/testing procedures.

Migration Estimations for Compliance Purposes

Fundamentals of migration estimations in the EU regulations

For the lawmakers of the EU the prerequisite for legalising the use of migration
estimations from plastic contact materials for compliance purposes was to ensure
that the applied estimation model is scientifically recognised and valid for the
plastic-migrant system to be investigated theoretically. Taking into account the
wide spectrum of plastics used nowadays in food packaging and the large number
of substances which might migrate from these materials the fulfilment of these
requirements is a challenge.
Currently existing predictive theoretical models for migration estimation are
essentially based on the theory of mass diffusion in and through plastics (polymers)
and consideration of migrant partitioning effects at the plastic-food (simulant)
boundary. It is important to emphasize that a model for migration estimation for
compliance purposes may present some differences to a model developed for exact
scientific calculations.
The scope of the later model is to produce as exact as possible migration
estimations! To achieve this goal it is legitimate to develop complex mathematical
algorithms and rely on as many as necessary physical-chemical parameters which
describe the plastic-food system. However the use of such sophisticated models is
generally cumbersome and often limited to a rather restrained number of
applications.
The scope of a migration estimation model for compliance purposes is to produce,
in as many as possible cases from practice, reliable results with a sufficient safety
margin for regulatory purposes. It was shown and validated that this goal can be
achieved by using a relatively simple migration model based on some very general
requirements for the migration process. This model, known also as the "FABES
model", has proved to work very satisfactorily in terms of providing so-called
"Worst Case" migration scenarios for certain types of polymers and migrants
used in the food packaging industry.
General Conditions for Migration Estimations from Plastic Food Contact Materials

In order to consider a plastic packaging-food system for migration estimations the

following general requirements must be fulfilled.

1. In most cases of practical relevance a plastic food contact material or article, P,

can be regarded as a polymer film/sheet, of finite and constant thickness dP being
in contact with a food or food simulant, F ,of finite volume VF .
2. During the manufacturing process of P the migrant is distributed
homogeneously in P.
3. There is no boundary resistance for the transfer of the migrant between P and F.
4. The interaction between P and F is negligible and no swelling of P by uptake of
F occurs during the migration process.
5. The migrant is always homogeneously distributed in F , too. The sum total
amount of the migrant in P and F is constant during the whole migration process
Algorithms used in the EU Regulations for Migration Estimations from Plastic Food
Contact Materials

The differential equation - also known as Fick's 2nd diffusion equation - describing
a migration process corresponding to the general requirements 1 to 5 is :

(1)

where: c is the migrant concentration in the plastic contact material (P) at time t at
distance x and Dp is the constant diffusion coefficient of the migrant in P.
With requirements 1 to 5 and an appropriate set of initial and boundary conditions
Eq. (1) can be solved analytically and the amount of migrant, mF,t, released from P
into F until time t can be expressed as:

(2)

the partitioning coefficient KP/F is defined as:

and respectively qn are the roots of the equation:

(2*)

In Eqs. (2) and (2*)

m F,t, - mass of migrant from P into F after time t, (mg)
A - area of P in contact with F , (dm2)
cP,O - initial concentration of migrant in P, (mg/kg)
3
P - density of P, (g/cm )
3
F - density of F, (g/cm )
Dp - diffusion coefficient of migrant in P, (cm2/s)
t - migration time, (s)
dP - thickness of P, (cm)
VP - volume of P, (cm3)
VF - volume of F, (cm3)
cP, - equilibrium concentration of migrant in P, (mg/kg)
cF, - equilibrium concentration of migrant in F, (mg/kg)
KP/F - the partition coefficient of the migrant between P and F
qn - the non-zero, positive roots of equation (2*)
Eq. (2) can be rearranged to give Eq. (3) which can be used to estimate the
Maximum Initial Concentration of migrant (MIC) in the food contact material
or article

(3)

where: all parameters apply as for Eq. (2), except

SML - Specific Migration Limit, (mg/kg)
MIC - Maximum Initial Concentration of migrant in P, (mg/kg).

Migration Estimations for Compliance/Regulatory Purposes

In order to perform a Migration Estimation (ME) and/or a Maximum Initial

Concentration (MIC) calculation all parameters listed above for Eqs. (2) and (3)
must be known. This requirement should not discourage any user who intends to
make such an estimations, in fact the problem is quite simple!
A series of the required parameters are given by the physical properties of the

plastic contact material P and respectively of the contacted food simulant F:

the thickness, dP , (in cm) of the sample P can be either measured by the
user with an appropriate precision instrument or is given in the P product
data sheet,
the density, P , (in g/cm3 ) of P, can be either measured by the user with an
appropriate technique or is given in the P product data sheet.

Note! If none of these two possibilities is practicable, the user may take, in a first
approximation, for any P, P = 1.00 g/cm3. This may lead to slight overestimations
of the migration (less than 10%) for polymers like polyolefines and
underestimations (with up to 40%) for dense polymers like polyesters,

in the framework of the EU Directive 97/48/EC the density, F, ( in g/cm3)

of all four food simulants, F's, is considered to be 1.00 g/cm3 , regardless of
the temperature, - the area, A, (in dm2) of P is either 6 dm2 (for EU standard
packaging as given in EU Directive 48/97/EC) or can be calculated
knowing the geometric form and dimensions of P,
the volume, VP , (in cm3) of P is given by its thickness, dP, times the area A,
while
the volume, VF, of the food simulant F which comes into contact with P is
either 1,000 cm3 (for EU standard packaging as given in EU Directive
97/48/EC) or can be calculated/measured directly from the experimental
migration set-up.

Two other parameters must be also known, namely the total migration time, (in
seconds) and respectively the initial concentration of migrant in P, cP,O , (in
mg/kg ). While t is in fact either a contact time as given in the EU Directive
97/48/EC or the real contact time between a packaging and food the knowledge of
the second parameter, cP,O , is often a challenge for the applicant. Despite this, in
order to perform a migration estimation, cP,O must be known either from a data
sheet of P or determined experimentally by an appropriated method.
The remaining two parameters needed for a migration estimation are the diffusion
coefficient of the migrant in P, dP , (in cm2/s) and the partition coefficient of the
migrant between the plastic and the food simulant KP/F . Both play a crucial role in
determining the level of migration. The problem with these two coefficients is that
usually their exact value is not known a priori but must be determined either by an
experimental or theoretical method. But the aim of theoretical migration
estimations was to make compliance testing simpler and less expensive not to
replace experimental migration tests with sophisticated measurements of diffusion
and partitioning coefficients. Therefore for compliance purposes it is recommended
to develop a model which allows the theoretical estimation of these coefficients in
such a way as to ensure that the obtained values lead to "Worst Case" scenarios
with respect to migration. This is of primary interest from a regulatory stand point.
This requirement is addressed by the predictive migration model developed for the
EU Commission from Bruxelles, known also as the"FABES model". The main
assumptions of this model are:

1. It is generally recognised from practice that, for cases where the migrant is
soluble a food simulant or food, the partitioning coefficient of the migrant between
P and F can be taken as KP/F= 1.
For all other cases, that means where the migrant is not soluble in the food
simulants or food , one can take KP/F = 1,000. Using these KP/F 's for migration
estimations leads to"Worst Case" values.
2. The actual diffusion coefficient dP of a migrant in the P matrix is replaced with a
polymer specific "Upper Limit" diffusion coefficient, dP *. Using such a dP * for
migration estimations leads to "Worst Case" values. From phenomenologic
derivations and a statistical evaluation of experimental diffusion and migration data
dP * can be estimated by Eq. (4):

(4)

where:

(5)

and where:
Mr - relative molecular mass of migrant,
T - temperature, (K)
A'p - a polymer specific athermal parameter
t - a polymer specific temperature parameter (K).
Eqs. (4) and (5) are known as the "FABES formula" and they rely on four
specific parameters which must be known in order to perform a migration
estimation.
The relative molecular mass of the migrant, Mr , and respectively the absolute
temperature, T, are not linked to a specific plastic (polymer) and can be known
from the chemical directories and respectively are given by the contact conditions
during the migration process.
AP , is primarily linked to the properties of the polymer and describes its basic
behaviour or a "conductance"towards the diffusion of migrants. AP depends not
only on the nature of the polymer but also on the temperature at which the
migration takes place.
As a general rule AP decreases with the increasing stiffness of the polymer matrix.
Consequently for polymers such as Polyethylenes (PE's) AP is larger than for stiff
chain polymers such as Polyesters (PET's) and Polystyrenes (PS's). Therefore for
the same migrant the dP * values and migration levels will be higher in PE's than

in PET's and/or PS's.

In the framework of the "FABES model" a statistical approach was used to
determine, for a series of polymers the actual value of AP . It must be emphasized
that at present this approach is not available for all plastics used in food packaging.
But the AP 's computed yet and included in the EU legislation cover a large part of
the plastics used nowadays as food contact materials. They are:
Polyolefines
Low Density Polyethylene and Linear Low Density Polyethylene (LDPE and
LLDPE),
High Density Polyethylene (HDPE) and
Polypropylenes (PP-random, PP-homo and PP-rubber).
Polystyrenes
General Purpose Polystyrene (PS) and High Impact Polystyrene (HIPS).
Polyesters
Polyethylene Therephthalate (PET) and Polyethylene Naphthalate (PEN) and
Polyamides
Polyamide (6,6) (PA 6,6).
Using product knowledge about these polymers one can define for each of them
the temperature range for the applicability of migration estimations, as established
by the general requirements given above.
Moreover, the actual values of AP and t to be used for the dP * estimation in these
polymers, Eq. (5), have been determined by using a data bases consisting of more
that thousand well defined diffusion and migration experiments reported in the
literature over the last four decades.
Both above information are summarized in the "Practical Guide for Users of the
EU-Directive" issued by the EU Commission SANCO-DGIII/LR.

Migration Estimations for Compliance/Regulatory Purposes

Assuming that all aspects presented so far are understood and all information
(parameters) needed to perform a migration estimation are known an interested
person is in the position to perform a migration estimation and/or maximum initial
concentration and learn so if in a certain application the plastic material complies
or not with the existing EU-regulation. For this Equations (2) to (5) must be used
and the result given by solving eventually Eq. (2) compared with the specific
migration limit of the considered migrant. This can be done in principle by any
interested person having computational skills and hardware which are nowadays
required in any R&D facility or enforcement institution. However this approach to
make migration estimations leads to so called "individual computational schemes",

which are most likely not validated by an independent panel, and thus may produce
calculation errors that are hard to identify. This is not really in the aim of a
compliance testing procedure and moreover it is not user-friendly.
Recognising these aspects of migration estimation for compliance purposes the
FABES company from Mnchen/Germany pioneered several years ago the
development of the"MIGRATEST" family of user-friendly software for the
estimation of migration according to the EU criteria. This software not only
includes all equations and specific parameters mentioned above but also includes
data banks with information about polymers and migrants agreed by the EU
legislation for migration estimation procedures. An on-line version of this
software, called MIGRAPASS, is now available at
www.specialchem4polymers.com.