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MEAT

SCIENCE
Meat Science 77 (2007) 238–245
www.elsevier.com/locate/meatsci

Kinetic migration studies from packaging films into meat products


A. Sanches Silva a, J.M. Cruz a, R. Sendón Garcı´a a, R. Franz b, P. Paseiro Losada a,*

a
Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Pharmacy, University of Santiago de Compostela,
15782-Santiago de Compostela, Spain
b
Fraunhofer Institute for Process Engineering and Packaging IVV, Giggenhauser Street 35, 85354 Freising, Germany

Received 18 May 2006; received in revised form 5 December 2006; accepted 9 March 2007

Abstract

One of the main concerns regarding safety of food packaging is the possible migration of chemical substances (monomers and other
starting substances, additives, residues) from food contact materials into foods.
To evaluate the effect of the fat content and of the temperature of storage on the migration from plastics packaging films into meat
products as an important class of foodstuffs, the kinetic mass transport of a model migrant (diphenylbutadiene) from low density poly-
ethylene (LDPE) film in contact with different meat products was investigated. From the data, the diffusion coefficients were calculated
for the applied test conditions, by use of a mathematical model.
The results showed that migration increased with fat content and storage temperature. Analysis of migration data corresponding to
minced pork meat containing different amounts of fat, stored for 10 days at 25 C, revealed an excellent relationship between migration
level and fat content. This behaviour was also found for other types of meat products (chicken and pork neck).
A simplifying mathematical model was applied to derive effective diffusion coefficients in the polymer which, however, do take kinetic
effects in the meat also into account. In the case of pork meat contact, the effective diffusion coefficients derived from mathematical mod-
elling were ten times higher for storage at 25 C (1.88 · 109 cm2 s1) than for storage at 5 C (1.2 · 1010 cm2 s1).
 2007 Elsevier Ltd. All rights reserved.

Keywords: Food safety; Packaging; LDPE; Meat products; Migration; Mathematical modelling

1. Introduction ents to foodstuffs in quantities that could endanger human


health or bring about an unacceptable change in the compo-
Consumers are no longer only interested in sensory sition, or deterioration of the organoleptic characteristics
aspects of meat quality and nowadays tend to take a more (Regulation, 1935/2004). Plastic materials are specifically
holistic view of the concept of the ‘‘quality’’ of meat prod- regulated by EU Commission Directive, 2002/72/EC, which
ucts and food safety. Safety is now of paramount concern establishes a positive list that includes all monomers, other
in the food industry in general, and particularly in the meat starting substances and additives that can be used for man-
industry. One of the most important processes that occurs ufacturing FCM, as well as restrictions to migration levels
as result of packaging food is migration, defined as the of those chemicals into foodstuffs. The use of substances
mass transfer of substances from the packaging material not included in the list is forbidden. Therefore, the possible
to the foodstuff. transfer of constituents that could endanger human health is
The European Union (EU) regulations state that food known (Piringer, 1994).
contact materials (FCM) must not transfer their constitu- In order to guarantee food safety, the possibility of per-
forming migration tests under strictly controlled conditions
*
Corresponding author. Tel.: +34 981 598450; fax: +34 981 594912. is taken into account in the prevailing legislation. The
E-mail address: qnpaseir@usc.es (P. Paseiro Losada). results of these strict tests must demonstrate, on the basis

0309-1740/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.meatsci.2007.03.009
A. Sanches Silva et al. / Meat Science 77 (2007) 238–245 239

of scientific evidence, that migration levels are equal to or (Castle, Honeybone, Irvine, Read, & Boenke, 2000; Spe-
higher than those achieved under real storage conditions, cific Migration EU project, 2000; Stoffers et al., 2004).
i.e., the tests represent a ‘‘worst case’’ scenario. Migration levels of DPBD from LDPE into different
Time-consuming, expensive analyses must be carried out types of meat products (chicken, pork neck and pork loin
to determine migration. In many cases, there are associated meat) were evaluated. Furthermore, in order to study the
analytical difficulties or analytical methods are not avail- effect of fat content on DPBD migration, different amounts
able (Begley et al., 2005). It is also difficult to analyse food of pork fat were added to pork loin to provide meat sam-
simulants (media that mimic the behaviour of foods) when ples with higher and more precisely defined fat contents.
the migrant is present at a low concentration (Feigenbaum Diffusion and partition coefficients were also calculated
et al., 2002). Nevertheless the most difficult matrices to according to a mathematical model based on Fick’s Second
analyse are foodstuffs, because of the diversity of potential Law, and the results are discussed in terms of the parame-
interferences (Quinto Fernández, Pérez Lamela, & Simal ters that may have the greatest effect on migration (fat con-
Gándara, 2003). tent and storage temperature).
Several studies have revealed that migration from a plas-
tic to a liquid substance is a theoretically predictable phys- 2. Materials and methods
ical process (Brandsch, Mercea, Tosa, & Piringer, 2002). In
the United States, the Food and Drug Administration 2.1. Polymeric film/Plastic
(FDA) uses the estimation of potential migration levels
as an additional tool in support of regulatory decisions The film used was a candidate certified reference mate-
(Begley, 1997b). Nowadays, migration estimation is also rial (CRM) for specific migration testing. It is an LDPE
accepted in the EU legislation (EU Commission Directive, film (thickness 444 lm; density 0.912 g/cm3) spiked with
2002/72/EC), and valid models based on scientific evidence 1,4-diphenyl-1,3-butadiene (DPBD) (CAS no. 538-81-8,
can be applied to test for compliance with existing regula- MW = 206.29) and was produced by Fraunhofer IVV
tions. This saves experimental testing, time and economic (Freising, Germany) according to a defined and recogni-
resources for both the food industry and the legislating sed protocol (Specific Migration EU project, 2000;
organizations, and should allow greater confidence in the O’Brien, Cooper, & Tice, 1997; Stoffers et al., 2004).
safety of foodstuffs. Nevertheless when the mathematical The initial concentration of the migrant in the polymer
predictions indicate non-compliance with the legislation, (Cp,0) was 121.4 mg kg1 ± 3.1% which corresponds to
the migration values must be confirmed by laboratory an area related maximum migration value of 491.6
testing. lg/dm2.
When the model predicts a certain level of migration
that is not consistent with the analytical evidence, this sug- 2.2. Sampling
gests that something is wrong. The additive may be react-
ing in the polymer or with the food/food simulant to Several types of meat were chosen for analysis: chicken
produce ‘‘new’’ compounds that are not being detected breast, pork neck meat and minced pork meat and mixed
(Begley, 1997a). Therefore, mathematical models are highly with different amounts of raw pork fat, to provide meat
valuable tools and are nowadays used in several research with 0%, 10%, 20%, 30% and 50% extra pork fat. All meats
fields. In the specific case of migration, they are used in were bought in a local supermarket and stored at two dif-
support of regulations for FCM. ferent temperatures: 5 C, (refrigeration temperature) and
Nevertheless, in some cases, mathematical models may 25 C (room temperature). A total of 10 samples were pre-
not predict migration into foods as well as they should pared for each kinetic curve for a given meat item and tem-
because of the scarce amount of information available perature. For each kinetic time point two samples were
regarding real food matrices (Brandsch et al., 2002; Euro- removed and analysed as described below.
pean Commission, 2003).
The aim of the present study was to generate reliable 2.3. Contact plastic/foods
migration data concerning meat products. The study was
carried out within the framework of the ‘‘FOODMIGRO- Samples were accurately weighed (approximately 10 g)
SURE’’ project (2002), the overall objective of which is to to fill a glass washer of 0.0989 dm2 diameter (the ratio food
provide a novel and economic mathematical model for esti- weight/contact plastic area was approximately 10 dm2/kg)
mation of migration from plastics food contact materials and 0.8 cm high, and were then placed in contact with
into foodstuffs and thereby consumer exposure to packag- the plastic containing the DPBD (one side only). Sodium
ing related chemicals. azide (0.1% (w/w)) was added to prevent microbial spoilage
Diphenylbutadiene (DPBD) which has previously been of the meat. Samples were then wrapped in aluminium foil
used as model migrant was selected also in this study as a and placed inside a transparent plastic bag.
test substance because of its stability, polarity, purity, The samples were vacuum packed to achieve an intimate
molecular weight and above all its availability in a certified contact between the meat and the test film, and were then
reference material and in other well defined LDPE films stored under the different conditions.
240 A. Sanches Silva et al. / Meat Science 77 (2007) 238–245

2.4. Chemicals and standard solutions water contents of the meat products under study (accord-
ing to the USDA database (SR17, 2001)) are shown in
All reagents were analytical grade. Ethanol, acetonitrile Table 1.
(ACN) and hexane were obtained from Merck (Darmstadt, Lean meat was selected because it is difficult to stan-
Germany). Ultrapure water was prepared using a Milli-Q dardize the fat content of fresh meat. Different amounts
filter system (Millipore, Bedford, MA, USA). Diphenylbut- of raw pork fat (0%, 10%, 20%, 30% and 50%) were added
adiene (DPBD) (purity 98%) was supplied by Aldrich. (Table 2) and samples were homogenised.
A primary stock solution of DPBD was prepared in eth-
anol (1.0 mg/ml). Intermediate standard solutions of 3.1.1. The effect of storage temperature
DPBD were prepared in ACN and hexane (0.1–10.0 For minced pork meat the expected observation was
lg/ml). Solutions were stored in a refrigerator. confirmed: the higher the storage temperature the higher
the migration levels (Fig. 1). For instance, for minced pork
2.5. Sample preparation meat with 50% plus of pork fat the migration after 10 days
of storage was approximately 90 lg/dm2 at 5 C and
Extraction of DPBD was performed as follows: 10 ± approximately 160 lg/dm2 at 25 C.
0.01 g of sample was homogenised with an ultra-turrax This was also true for pork neck but for chicken, there
homogenizer and extracted with 20 ml of hexane by shak- was no difference between migration achieved at 5 C and
ing for 20 min. The organic phase was separated by centri- 25 C (Fig. 2). This was probably because of the migration
fugation (1036g for 20 min). Extraction was repeated with in chicken (<15 lg/dm2) was closer to the minimum quan-
20 ml hexane and the supernatants were then pooled and tification level.
evaporated in a rotary evaporator. The fatty liquid residue
obtained was extracted with 2 · 20 ml ACN. Collected 3.1.2. The effect of fat content
phases were evaporated in the rotary evaporator and re- Comparison among minced pork meat, chicken and
dissolved with 10 ml of ACN (v/v). Finally, the solution pork neck showed the following order of migration levels
was filtered and a 50 ll aliquot injected into the HPLC. (after 10 days at 25 C): chicken < minced + 0% of added
pork fat < pork neck. At 25 C migration increased with
2.6. Chromatographic conditions increasing fat content. At 5 C, the migration was also
higher in pork neck meat, which has the highest fat content
The HPLC system (Hewlett-Packard, Waldbronn, Ger- of the meats studied.
many) was fitted with a HP1100 quaternary pump, a deg- Comparison among minced pork meat with different
assing device, an autosampler, a column thermostating amounts of added fat (Fig. 1) clearly showed that the
system and a diode array UV detector. migration increased with increasing fat content and that
An HP ChemStation chromatographic software was in most cases the increase was linear. Only at 25 C, for
used for data acquisition. Chromatographic separation higher fat contents (higher than 17% fat) the migration
was performed with a Kromasil 100 C18 column level did not appear to increase linearly in relation to fat
(15 cm · 0.4 cm I.D., 5 lm particle size) (Teknokroma, content.
Barcelona, Spain) at 30 C. There is little information available in the scientific lit-
A gradient elution method was used. Within the first erature as regards migration of DPBD from LDPE into
2 min the mobile phase was 65% ACN/35% water, after foodstuffs. Castle et al. (2000) evaluated migration in a
which the proportion of ACN was increased to 100% wide range of foodstuffs using a LDPE film of 149.7 lm
within 15 min. The total run time of each analysis was 30 thickness and contaminated with 12.58 mg of DPBD per
min to ensure that the column was cleaned between sam- kg (17.3lg/dm2) Migration levels for chicken portions
ples. The flow-rate was 1.0 ml/min (Sendón, Sanches-Silva, and pork steak were 1.5 and 1.4 lg/dm2 after 7 days stor-
& Paseiro, 2004). age at 4 C. Nevertheless, these results cannot be com-
pared with those of the present study because a different
3. Results and discussion film (higher thickness and migration potential) and stor-
age conditions were tested. Moreover, diffusion parame-
3.1. Migration levels ters, which could be compared with the present study,
cannot be calculated because migration kinetics were not
For comparison purposes in relation to the maximum studied.
possible migration it should be noted that the area related
migration potential of DPBD in the test film was 491.6 3.2. Mathematical models and determination of key
lg/dm2. parameters
The migration levels in different meat products (chicken,
pork neck and minced pork loin) were studied during sev- To assess migration of additives and contaminants from
eral days and were found to be strongly affected by fat con- food-packaging films, mathematical modelling based on
tent and storage temperature (Figs. 1 and 2). The fat and Fick’s second Law (Eq. (1)) was used. This differential
A. Sanches Silva et al. / Meat Science 77 (2007) 238–245 241

a 140
D = 1.20x10
-10 2
cm /s
__ + 0% fat
120 RMSE = 1.85%
KP/F = 720.9

100 --- + 10% fat


DPBD (µg / dm2)

RMSE = 2.88%
KP/F = 128.7
80
--- + 20% fat
RMSE = 0.79%
60
KP/F = 94.9

40 ___x + 30% fat


RMSE = 1.89%
KP/F = 54.6
20
_._ + 50% fat
RMSE = 0.94%
0 KP/F = 34.7
0 5 10 15 20
Time (days)

b 200
-09 2
D = 1.88x10 cm /s
180
_ + 0% fat
160 RMSE = 1.81%
KP/F = 419.1
140
---
DPBD (µg / dm2)

+ 10% fat
120 RMSE = 3.93%
KP/F = 75.1
100
--- + 20% fat
80 RMSE = 3.15%
KP/F = 50.1
60
___x + 30% fat
40 RMSE = 1.91%
KP/F = 37.5
20
_._ + 50% fat
0 RMSE = 5.34%
0 2 4 6 8 10 12 K P/F = 35.3

Time (days)

Fig. 1. Migration of DPBD in pork minced meat at 5 C (a) and at 25 C (b).

equation describes migration of an additive or contaminant with


from an amorphous polymeric packaging film:
1 VF
oC p o2 C p a¼
¼D 2 ð1Þ K P=F VP
ot ox
where, Cp (mg/kg) is the concentration of the migrant in where mF,t is the mass of migrant from P into F after time
the packaging film at time t (s) and position x and D is t (lg); A, the area of P in contact with F (cm2); CP,0, the
the diffusion coefficient (cm2/s). initial concentration of migrant in P (mg/kg); qP, the den-
Eq. (1) can be resolved to express the amount of migrant sity of P (g/cm3); t the migration time (s); dp, the thickness
released from the polymer (P) into food (F) at time t and of P (cm); VP, the volume of P (cm3); VF, the volume of
expressed as (Brandsch et al., 2002; Crank, 1975; Piringer, F (cm3); qn the positive roots of the equation tan qn =
1994): a Æ qn; DP, the diffusion coefficient of migrant in
  P (cm2/s); KP/F, the partition coefficient of the migrant be-
mF;t a tween P and F.
¼ cP;0 qP d P
A 1þa To allow working with this model also in the investi-
" !#
X 1
2að1 þ aÞ q2n gated polymer–meat contact cases instead of DP, an effec-
 1 exp Dp t 2 ð2Þ tive (for the whole polymer–meat system) diffusion
n¼1
1 þ a þ a2 q2n dP
coefficient D is introduced. In the following DP will be
242 A. Sanches Silva et al. / Meat Science 77 (2007) 238–245

20.0

18.0

16.0
5ºC
D = 1.30x10-12 cm 2/s
14.0 RMSE = 0.300%
DPBD (µg / dm2)

KP/F = 163.8
12.0

10.0 25ºC
D = 2.86x10-12 cm 2/s
RMSE = 0.896%
8.0
KP/F = 383.5

6.0

4.0

2.0

0.0
0 5 10 15 20 25
Time (days)

80.0

70.0

60.0 5ºC
D = 6.41x10-12 cm 2/s
DPBD (µg / dm2)

RMSE = 0.227%
50.0 KP/F = 316.2

40.0 25ºC
D = 5.41x10-11 cm 2/s
RMSE = 0.719%
30.0
KP/F = 78.4

20.0

10.0

0.0
0 5 10 15 20 25
Time (days)

Fig. 2. Migration of DPBD in chicken (a) and in pork neck (b).

replaced where appropriate by this effective D value. In this are. Nevertheless, because of the considerable amount of
way a simplified but pragmatic mathematical model can be work involved in the calculation, and in order to make the
applied. estimation feasible, 12 roots (1 6 n 6 12) were calculated
In order to predict theoretical migration, the first step was for 0.01 6 a 6 1000.
to calculate the positive roots of equation tan qn =  a qn. In the present study, when migration levels were lower
The greater the number of roots, the more reliable the results than 35 lg/dm2, Eq. (2) did not provide a good fit because
it requires a very large number of roots, and therefore Eq.
(3) was used (Crank, 1975; Han, Selke, Downes, & Harte,
Table 1
Fat and water contents of the meat products studied, according to the
2003).
" #
USDA database X 1
M F;t 2að1 þ aÞ Dq2n t
Foodstuff Fat Water ¼1 exp ð3Þ
content (%) content (%)
M F;1 n¼1
1 þ a þ a2 q2n L2p
Pork meat (fresh, loin, sirloin (chops or 4.22 73.55
roasts), boneless, separable lean only, raw) Table 2
Pork fat (Pork, fresh, separable fat, raw) 47.64 41.89 Total fat content of tested pork minced meat products used to study
Pork neck (fresh, loin, sirloin (chops or 6.31 71.93 migration
roasts), boneless, separable lean and fat, Pork minced meat
raw)
Added pork fat (%) 0 10 20 30 50
Chicken (broilers or fryers, breast, meat only, 1.24 74.76
raw) Total fat content (%) 4.2 8.6 12.9 17.2 25.9
A. Sanches Silva et al. / Meat Science 77 (2007) 238–245 243

With MF,t, the migrant amount in food at time t; MF,1, the material, on the basis of specific migration limits for testing
migrant amount in food at equilibrium; a, the mass ratio of compliance.
migrant in food to that in packaging film at equilibrium; D, SML  V F  qP
the diffusion coefficient of the system packaging + food MIC ¼      
a
P
1
2að1þaÞ q2n
and Lp, the thickness of packaging film. A  qP d P 1þa
 1  1þaþa2 q2 exp Dp t d 2
n P
Eq. (3) can be simplified in order to obtain the follow n¼1

equation: ð6Þ
M F;t where all the parameters apply as for Eq. (2) and
¼ ð1 þ aÞ½1  ex erfcðx0:5 Þ ð4Þ
M F;1 SML = specific migration limit, (mg/kg) and MIC = max-
imum initial concentration of migrant in P, (mg/kg).
With x ¼ aDt
2 L2
p Eq. (6) is therefore a useful tool for calculating MIC for
Experimental data were fitted to the proposed model any migrant with a SML, using the a and Dp values calcu-
(Eqs. (2) or (3)) using commercial software (Solver of lated by Eq. (2).
Microsoft Excel 2003), by non-linear regression. From
the series of experimental data on migration level 3.2.1. The effect of storage temperature on the diffusion
(lg/dm2) versus time, the model parameters a and D were coefficient
calculated for each sample and storage temperature. D val- The values of the effective diffusion coefficients increased
ues for pork minced meat, pork neck and chicken at 5 and with storage temperature; for minced pork meat,
25 C are shown in Figs. 1 and 2. For minced pork meat D5 C = 1.2 · 1010 cm2/s and D25 C = 1.88 · 109 cm2/s
mixed with different amounts of raw pork fat an average and for pork neck, D5 C = 6.41 · 1012 cm2/s and
of D values at 5 and 25 C was used. D25 C = 5.41 · 1011 cm2/s, i.e., D at 25 C was approxi-
In order to measure the fit between experimental and mately ten times higher than D at 5 C.
estimated data, the % root of the mean-square error (% For chicken there was only a slight difference between the
RMSE) was calculated as (Helmroth, Dekker, & Han- diffusion coefficients for the two storage temperatures
kemeier, 2002): (D5 C = 1.3 · 1012 cm2/s and D25 C = 2.86 · 1012 cm2/s).

vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
1 u X N
RMSEð%Þ ¼ t1 ððM F;t Þexperimental;i  ðM F;tÞ Þð predicted;iÞ  100
2
ð5Þ
C p;0 N i¼1

with N, the number of experimental points per migration 3.2.2. The effect of fat content
curve and i, the number of observations. In Section 3.1.2 we have already observed that migra-
A good correlation was found between experimentally tion increased with fat content and that the increase was
obtained migration values and those estimated by Eq. (2) linear. To evaluate the importance of this factor on the dif-
or (3) (RMSE lower than 5%, except for pork minced meat
with 50% added pork fat at 25 C). RMSE % data are given 0.05
in Figs. 1 and 2 legend.
0.045
The partition coefficient (KP/F) was calculated from the
(at 5ºC) y = 0.0018x - 0.004
a value and polymer and food volumes. The VP for all 0.04
(at 25ºC) R2 = 0.9829
assays was 0.439 cm3 and the VF was 7.912 cm3. The 0.035
KP/F values calculated for all foodstuffs studied are shown
in Figs. 1 and 2. 0.03

The parameters that determine the migration process are 1


0.025
KP/F
Dp, respectively D, and KP/F, where KP/F corresponds to
0.02
the relative solubility of the migrant at equilibrium between y = 0.0013x - 0.004
R2 = 0.9904
the plastic and the foodstuff (Begley et al., 2005). 0.015
According to Gandek et al. the dependence of the KP/F 0.01
on temperature appears to be much lower than the depen-
dence of Dp on temperature (Chung, Papadakis, & Yam, 0.005

2002). However, the temperature dependency of KP/F was 0


great enough to be included in the model in the present 0 5 10 15 20 25 30
Total fat content (%)
study.
Eq. (2) can be rearranged for estimating the maximum Fig. 3. Correlation between fat content and 1
K P=F
values for pork minced
initial concentration (MIC) of migrant in the food contact meat at 5 and 25 C.
244 A. Sanches Silva et al. / Meat Science 77 (2007) 238–245

fusion process, the fat content of pork minced meat (with Resources, Key Action 1 on Food, Nutrition and Health.
different amounts of added fat) was plotted against a values The conclusions are the sole responsibility of the authors
(Fig. 3). The correlation was extremely high (r2 = 0.990 at and do not represent the opinion of the European Commis-
5 C and r2 = 0.983 at 25 C) considering that food matri- sion. Authors are grateful to the ‘‘Ramón y Cajal’’ Pro-
ces are heterogeneous and complex, that during the analyt- gram financed by the Ministry of Education of Spain.
ical procedure there are many factors to be taken into The authors are grateful to Ms. Patricia Carro Blanco
account and that duplicates are completely independent and Mr. Gonzalo Hermelo Vidal for their excellent techni-
assays. At 5 C the relationship was linear for the whole cal assistance.
range of fat contents assayed (4–26%), but at 25 C the
relationship was not linear for fat contents higher than
17%. For fat contents higher than 17% it appears that References
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account the specific migration limit for each migrant. This supported by European Commission (re. QLK1-CT2002-2390) http://
is of special importance for the meat industry for cost-effi- www.foodmigrosure.com.
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