Beruflich Dokumente
Kultur Dokumente
(Editors)
Food Flavors: Formation, Analysis and Packaging Influences
© 1998 Elsevier Science B.V. All rights reserved 759
Abstract
Migration of dioctyladipate (DOA) and acetyltributylcitrate (ATBC)
plasticizers from plasticized polyvinyl chloride (PVC) and polyvinylidene chloride
(PVDC/PVC) (Saran) films into ground meat of varying fat content (3%, 12%, 30%
and 55%) has been studied. Meat samples were wrapped in PVC or Saran film
and cooked for 0.5, 1, 1.5, 2, 2.5, 3, 4 min in a microwave oven on full power
(~700W). The plasticizer migrating into meat was determined using an indirect
GC method after saponification of the ester-type plasticizer (DOA or ATBC) and
subsequent collection of the alcohol component of the ester, namely, 2-ethyl-l-
hexanol and 1-butanol, respectively. Migration was dependent on heating time,
meat fat content and initial concentration of plasticizer in the film. The
migration of plasticizer into meat did not reach equilibrium after heating for 4
min even in high fat content (55%) meat samples. Migration values of DOA and
ATBC into 55% fat content meat samples after heating for 4 min was 846.0
mg/kg (14.7mg/dm2) and 95.1 mg/kg (2.5 mg/dm^) respectively.
1. INTRODUCTION
A variety of foods have been developed and modified over the past few years for
the microwave market. Many of these food products are cooked with the
packaging material (container or wrapping film) in the microwave oven. Such
microwavable materials include plastics, paperboard and composites [4-8].
However, during cooking due to a significant increase in temperature, a variety
of plastics additives contained in most packaging materials, i.e. plasticizers,
antioxidants, stabilizers, residual monomers etc. may migrate from the
packaging material into the food. This may result in the deterioration of food
quality i.e. off-flavor and/or safety problems [9-12].
The migration of low molecular weight compounds from a polymeric material
into a food-contacting phase is dependent on: the nature and thickness of the
packaging material, the nature of the food in contact, initial concentration of the
additive in the polymer, compatibility of the additive/polymer system,
temperature, time of contact etc. [13-15]
Polyvinylchloride (PVC) and polyvinyhdene chloride (PVCD)/PVC (Saran),
films have found wide applications in the packaging of a large variety of
foodstuffs. Also for covering foods during cooking in the microwave oven in order
to prevent the drying out of the food surface and when baking dishes, reheating
precooked meals and covering frozen dishes during reheating from the freezer.
The most commonly used plasticizer for PVC is dioctyladipate (DOA) added at
levels up to 40% (w/w), and for Saran it is acetyltributylcitrate (ATBC) added at
levels up to 5% (w/w).
There are several published studies dealing with the migration of plasticizers
into different foods and/or food simulants during microwave heating [9, 11, 12,
15, 16-19]. All of them report equilibrium migration values.
The present work involves a kinetic study of the migration of DOA and ATBC
plasticizers from food grade PVC and PVDC/PVC (Saran) films respectively, into
ground meat of varying fat content.
2.1. Materials
The PVC film used was MX-B LM, 15|im in thickness, containing 28.3% DOA
(w/w) supplied by Borden, Chemical Division, N.Andover, Mass., USA. The Saran
film used was 12|im in thickness containing 4.9% ATBC (w/w) supplied by Dow,
Indianapolis, Ind., USA. Analytical grade DOA was purchased from Fluka
(Buchs, Switzerland). Analytical grade ATBC was purchased from Unitex,
Greensboro, N.C., USA. Analytical grade 2-ethyl-l-hexanol was purchased from
Merck, Darmstadt, Germany. Analytical grade 1-butanol was purchased from
Mallinckrodt, St. Louis, Mo., USA. Beef meat and fat were purchased locally.
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ABS 60/80 Mesh. The temperatures used were: column, 165°C; injection port,
220°C; detector, 220°C.
The alcohol component of ATBC, namely, 1-butanol, was determined under the
following conditions: The GC unit was the same as that described above, the
column was of stainless steel (Im long, 3.17mm o.d.) packed with 10% Carbowax
20 M on Supelcoport 80/100 Mesh. The temperatures used were: column, 65°C;
injection port, 200°C; detector, 220°C.
^ 1000
(DO
> 800
< 600 i
o
Q 400 4-
o
'^o 200 -L
Time (min)
Figure 1. Migration of DOA from PVC film into ground meat of fat
content a) (A) 3%, b) (•) 12%, c) (•) 30% and d) (•)55% during
microwave heating on full power.
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DOA was not detected in unwrapped (control) meat samples. The migration
amount of DOA into ground meat of fat content 3%, 12%, 30% and 55% after
heating for 4 min was 195.2 mg/kg (5.42 mg/dm^), 565.1 mg/kg (15.70 mg/dm^),
771.8 mg/kg (21.44 mg/dm2) and 846.0 mg/kg (23.50 mg/dm2) respectively.
Bishop and Dye [9] reported an average migration value of 21.2mg DOA/20 mL
vegetable oil (1060 mg/1) after 10 min of cooking in the microwave oven. No
further details were given on the dimensions and thickness of the film used,
power setting of the oven, or the plasticizer content of the film used. Our DOA
migration value into meat of 55% fat content after heating for 4 min is
comparable to the above mentioned value (1060 mg/1), given the differences in
nature of the food product (fat content), time of heating, area of contact between
the foodstuff and PVC film, temperature etc.
Startin et al [19] studied the migration of DOA into a variety of food products
during microwave cooking and reported values of 435 mg/kg for peanut biscuits,
351 mg/kg for pork spare ribs, 191 mg/kg for cakes and 3 mg/kg for carrots. The
film contained 17.2% DOA while its thickness, contact area between film and
food and the cooking time were not specified. It is clear that as the fat content of
the food increases the migration amount of the plasticizer will also increase. Our
migration values are generally higher than the above, a fact which can be
attributed to differences in experimental conditions, area of the film used,
percentage of the plasticizer in PVC film, fat content etc.
Harrison [12] reported DOA migration values ranging from 146 to 435 mg/kg
for fatty foods such as chicken (152 mg/kg), pork (351 mg/kg), trout (146 mg/kg)
and peanut biscuits (435 mg/kg). No further details were given in this work so it
is difficult to attempt comparison of these values to ours.
Finally, Castle et al [16] studied the migration of DOA into foods during the
"reheating" process in a microwave oven and reported values ranging from 27
mg/kg for pizza to 2.6 mg/kg for potatoes. The film used contained 10% DOA
along with polymeric plasticizer. It is obvious that the migration amounts under
the above mentioned experimental conditions are much lower than our migration
values.
ground meat of fat content 12%, 30% and 55% after heating for 4 min was 40.2
mg/kg (1.06mg/dm2), 72.4 mg/kg (1.91 mg/dm2) and 95.1mg/kg (2.50 mg/dm2)
respectively.
Time (min)
Health and Reilly [18] reported that the migration of ATBC into poultry
products during microwave cooking was time dependent, reaching equilibrium
after 8 min of cooking (0.834 mg butanol/g). This value is much higher than our
value 0.05 mg/g for meat of fat content 55% heated for 4 min at full power. This
can be attributed to differences in time of heating and fat content of the
foodstuffs used in the two studies. Health and Reilly also showed that an
increased fat content of the food resulted in increased migration of the
plasticizer.
Castle et al [17] studied the migration of ATBC into various foods and reported
values ranging from 79.8 mg/kg for peanut biscuits to 0.9 ^glhg for Brussels
sprouts. The migration value of 79.8 mg/kg for peanut biscuits coirelates well
with our value of approximately 95.1 mg/kg obtained for meat of fat content 55%
after 4 min of microwave heating at full power.
Finally, Castle et al [16] reported a migration value for ATBC of 79.9 mg/kg for
high fat biscuits and 35.0 mg/kg for pizza under reheating conditions in a
microwave oven. Both these values are of the same order of magnitude as our
values, given the differences in experimental conditions between the two studies.
What should be stressed is that under present experimental conditions the
DOA migration is higher than the upper limit for global migration (60 mg/kg or
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10 mg/dm^) set by the E.U. even for meat samples of low fat content. The ATBC
migration is higher than the upper limit for global migration only for meat
samples of high fat content. The present results indicate that PVC film should
not be used in direct contact with foodstuffs in the microwave oven while Saran
film may be used with appropriate caution in the microwave oven avoiding direct
contact of high fat foodstuffs with the film.
Further study on migration of the two plasticizers (DOA, ATBC) from cling
films (PVC, Saran) into solid foodstuffs (pizza, sausage etc.) is in progress.
4. REFERENCES