When plastics are collected for recycling, possibly contaminated articles might be recycled into food packaging, and thus the contaminants might subsequently migrate into the food. Multilayer functional barriers may be used to delay and to reduce such migration. The contribution of the work reported here is to establish reference values (at 40 degrees C) of diffusion coefficients and of activation energies to predict the functional barrier efficiency of a broad range of polymers (polyolefins, polystyrene, polyamide, PVC, PET, PVDC, [ethylene vinyl alcohol copolymer], polyacrylonitrile and [ethylene vinyl acetate copolymer]). Diffusion coefficients (D) and activation energies (Ea) were measured and were compiled together with literature data. This allowed identification of new trends for the log D=f(molecular weight) relationships. The slopes were a function of the barrier efficiency of the polymer and temperature. The apparent activation energy of diffusion displayed two domains of variation with molecular weight (M). For low M (gases), there was little variation of Ea. Focusing on larger molecules, high barrier polymers displayed a larger dependence of Ea with M. The apparent activation energy decreased with T. These results suggest a discontinuity between rubbery and glassy polymers.

Different types of packaging (glass bottle, PVC, and PET) were compared for the preservation of aroma quality of a strawberry syrup during shelf life. Esters, alcohols, and aldehydes were analyzed by solid-phase micro-extraction (SPME) and solvent extraction. During storage, hydrolysis of esters in acids and alcohols led to a modification of the aroma profile which can be explained by the replacement of "fruity" and "fresh" notes by "dairy note" in the syrup. Aroma compounds that are responsible for fruity notes, such as methyl cinnamate, methyl anthranilate, and methyl dihydrojasmonate, were strongly reduced after 90 days. This could be explained by a selective interaction of these compounds with the polymer matrix (PET or PVC). After 330 days, a later and important decrease of the "fruity notes" occurred in both PETs; so PVC2 and the glass bottle were found to be able to maintain a balanced aroma for long-term storage.

Functional barriers are multilayer structures deemed to prevent migration of some chemicals released by food-contact materials into food. In the area of plastics packaging, different migration behaviours of mono- and multilayer structures are assessed in terms of lag time and of their influence of the solubility of the migrants in food simulants. Whereas barriers to oxygen or to aromas must prevent the diffusion of these compounds under conditions of use, a functional barrier must also be efficient under processing conditions, to prevent diffusion of substances when the polymer layers are in contact at high (processing) temperatures. Diffusion in melted polymers at high temperatures is much slower for glassy polymers, than in polymers that are rubbery at ambient temperature. To evaluate the behaviour of functional barriers under conditions of use, a set of reference diffusion coefficients in the 40-60 degrees C range were determined for 14 polymers. Conditions for accelerated migration tests are proposed based on worst-case activation energy in the 40-60 degrees C range. For simulation of migration, numerical models are available. The rules derived from the models can be used both by industry (to optimize a material in terms of migration) or by risk assessors. Differences in migration behaviour between mono- and multilayer materials are discussed.

Plastic packaging materials are often associated to aroma losses and to a decrease of the organoleptic quality of foods. This work defines situations where, on the contrary, plastics play a regulating role on the concentration of reactive aroma compounds in foods. These systems can be described by a two step mechanism; first, aroma is sorbed in the polymer, while the fraction in solution degrades quickly; in a second step, as the concentration is close to zero in the solution, the polymer liberates progressively the sorbed aroma back to the food. A simple numerical model is proposed, describing competitive processes of aroma degradation in solution and sorption by a polymer in contact with a homogeneous aqueous food. The classical limonene/low density polyethylene (LDPE) system is studied experimentally for the validation of the model: in an acidic medium, limonene both degrades quickly and is sorbed quickly, with a large solubility in LDPE. To define which aroma packaging systems could also display this interesting behavior, all types of possible interactions, using thermodynamic and kinetic parameters describing most practical situations, are simulated. For that purpose, 35 values of reference diffusion coefficients and 35 partition coefficients of usual aroma compounds between polymers and water have been measured and combined with the few available data from literature. The situations where polymers regulate the aroma concentration in food correspond to large partition coefficients (above 10), large diffusion coefficients (>10(-9) cm2 x s(-1)), and large degradation constants.

Recycling of used bottles into new bottles is associated with possible migration of pollutants arising from the previous life of the packages. To reduce or delay such migration, the recycled resin is depolluted or a functional barrier layer made of virgin plastics is used. Testing migration from such recycled bottles relies on the use of model pollutants (surrogates). In order to enable modelling of migration kinetics, each step of the use of surrogates is carefully investigated here in the case of PET. First, criteria underlying the selection of surrogates are carefully examined; together with volatility, polarity and diffusion behaviour, it is shown here that their solubility in the food simulant and their chemical stability strongly influence migration results. For aqueous test media, 2,4-pentanedione and phenol should be used as surrogates. Second, a procedure is developed to impregnate surrogates at very large concentrations (several thousands of mg/kg PET) which are necessary to monitor migration kinetics. This procedure, which uses dichloromethane as solvent, allows a quick and reproducible impregnation, not sensitive to temperatures between 11-23°C, factors which favour its use at a plant scale. Third, flakes impregnated with this procedure are processed into bottles, and their physicochemical properties are compared to those of commercial bottles. Last, monolayer and tri-layer polluted bottles (model pollutants in inner layer) are tested for migration for more than 1.5 years. With multilayers, the migration lag time of the fastest surrogates is 6 months with 3% acetic acid and 3 months with ethanol as the simulant, due to plasticization of PET by ethanol. The sequence of migration of surrogates is different with monolayer and multilayer bottles, which shows that partition effects (solubility) play an essential role, especially with monolayer materials.