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Published by: georgiana on May 30, 2009
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E. T. Contis et al. (Editors)Food Flavors: Formation, Analysis and Packaging Influences© 1998 Elsevier Science B.V. All rights reserved 719
Studies cm the develapment of a qmcd^ test for piedictiiis thesorption properties of refillable polycarbonate bottles
P,G. Demertzis^ and R. Franz^^Laboratory of Food Chemistry, Department of Chemistry, University ofloannina, GR-45110 loannina, Greece^Fraunhofer - Institute for Food Technology and Packaging, Giggenhauserstr.
35,
D-85354 Freising, Germany
Abstract
Quick tests are recently proposed in the literature as alternatives to the largescale contamination studies performed to assess the quality and safety-in-useof recycled and reused plastic beverage bottles (Demertzis et al. PackagingTechnology and Science, in press; Nielsen et al. Food Additives andContaminants, in press). The work reported here has measured theinteraction of small plastic specimens (strips) in place of bottles with selectedmixtures of surrogate contaminants to model the great number of chemicalsthat could in principal contaminate returned bottles because of consumer misuse.Results showed that significant amounts of chemicals can be sorbed intothe plastic material if mis-used to establish a re-migration potential in thebottle material after refilling. Results were also compared with tests usingactual polycarbonate bottles.
1.
INTRODUCTION
Polycarbonates offer a unique combination of properties not encounteredwith any other thermoplastics. The main features are excellent mechanicalproperties which remain constant over an unusually broad temperaturerange, low absorption of liquids, resistance to weather, chemical resistance,total inertness to food components and transparency. These properties haveallowed them, in spite of their high cost, to penetrate several packagingapplications such as plates for ovenable dinners and refillable bottles for water,soft drinks and milk
[1-3].
Recently, in certain European countries, a system for washing andrefilling polyethylene terephthalate (PET) and polycarbonate (PC) bottles usedfor soft drinks and other food packaging applications has been introduced.Although the result of this approach is a reduction in the production of newplastic bottles, serious contamination problems might arise if safeguards arenot provided. If, for instance, these bottles are used for storage of anyhousehold chemicals, such as detergents, photographic liquids, pesticides etc.,before being returned to the loop, they might become contaminated bysubstances
 
720
which, unless removed during the washing process, could damage the qualityand/or the safety of the product filled subsequently.Many studies, some of them highly time-consuming, have been made fordetermining the transfer of pollutants into foods
[4-121.
The potential publichealth risks in connection with the use of PET refillable bottles as aconsequence of possible mis-use have also been reviewed and summarisedrecently [13]. From the results of all mis-use studies carried out so far andfrom probability considerations, it is generally concluded that returnable PETbottles can be safely reused, provided that specific food manufacturingprocedures and inspection systems are required to eliminate abused bottles.Although this approach can be recommended because it is thorough and teststhe actual re-use system in practice, it does have the disadvantage that manyhundreds of bottles must be contaminated, large quantities of toxic substancesare used, and these are by necessity introduced into a commercial washingand bottling plant which must be set-aside for the trials and subsequently willneed decontamination until the process is judged acceptable.In order to test refillable bottles for inertness it is, therefore, desirable toestablish a practical, cost efficient and relatively quick standard test procedurethat could also be carried out in the surveillance laboratories. To this end, aquick inertness test procedure for multi-use PET bottles has been recentlyproposed, based on the sorption behavior of surrogate contaminants into bottlewall strips [14-15].The principle of the intended work was to measure the uptake of four setsof model contaminants onto PC bottle strips and the subsequent remigration ofthese chemicals in food simulants and to test if the sorption into PC stripsexposed to contaminants by immersion is comparable to sorption into wholebottles exposed single-sided by filling. This correlation would allow for anestimation, from the measured sorption values for the strips, of theremigration of these chemicals from a bottle contaminated under the sameconditions as the strips.
2.
EXPERIMENTAL
2.1.
Materials
Returnable PC bottles were supplied by Continental PET Europe, France.The four sets of model contaminants used are listed in table 1. All chemicalswere of analytical grade (i.e. purity > 99%).
2.2.
Methods
2.2.1.
Preparation of contamination liquids from sets A-D.- Set A : Mixture of equal weight parts of each of the contaminants (withoutdilution).- Set B : After mixing equal weight parts of the contaminants a 8 % dilution ofthe mixture with PEG-400 was made.- Set C : After mixing equal weight parts of the contaminants a 6 % dilution ofthe mixture with PEG-400 was made.
 
721- Set D : The mixture of equal weight parts of the contaminants was 12 %diluted with PEG-400.Table 1Model contaminants (mol. weight) appliedSet Aalcohol-typecompoundsEthylene glycol(62)Phenol(94)n-Hexanol(102)SetBester/ketone-typecompoundsEthyl acetate(88)Cyclohexanone(100)iso-Amyl acetate(130)2-Phenylethanol Benzophenone(122) (182)Menthol(156)1,2-Decanediol(174)Linalyl acetate(196)Methyl stearate(299)SetChydrocarbon-typecompoundsToluene(92)n-Heptane(100)p-Xylene(106)Limonene(136)Phenyl cyclohexane(218)Phenyl decane(218)SetDchlorinated(strongly interactive)compoundsChlorobenzene(112)1,14-Trichloroethane(133)2.2.2. Contamination of bottle wall strips and whole bottles.A number of strips having dimensions of approx. 1.1 x 6.0 cm were cutfrom the middle part of the PC bottle walls. Strips were placed each in 20 mlscrew-cup glass vials containing enough volume (10 ml) of contaminationliquid to contact the whole strip area. The vials were then stored horizontally at40 oC for 14 days.The whole PC bottles were filled with glass beads of 4 mm diameter and thecontamination liquid was added, so that it just exceeded the bead's level. Thebottles were then closed with plastic caps and placed at 40 ^C for 14 days.
2.2.3.
Work up and washing of bottles and strips.After the contamination phase, the bottles were emptied and rinsed 4-5times with tap water and one time with ethanol. They were then washed byfilling with 80 ^C hot 1.5 % NaOH solution and keeping this temperature for 10min. After washing, the bottles were emptied and rinsed again several timesuntil pH was neutral.Contaminated strips were removed from the vials and briefly immersedthree times in ethanol (for approx. 5 seconds each time) to removecontaminants from the surface. They were then wiped clean using soft wipepaper to remove excess ethanol from the surface. Strips cleaned in this waywere either going directly into the sorpt ion/re-migration determination orfurther washed with 1.5% NaOH (as the bottles) and then going into the re-migration process.

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