Effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax® and modelling hereof
The aim of this study was to investigate the effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax®. Kinetic migration investigations were carried out with three relative humidities in the interval between 39% and >73%. All investigations were carried out at a constant temperature of 34°C. It was found that the migration of benzophenone after more than 30 days was 4.8 times higher at a relative humidity of 64%–71%, and 7.3 times higher at a relative humidity of >73%, compared with that at a relative humidity of 39%–49%. Diffusion and partition coefficients were derived from the results by using a software for modelling migration in multilayer materials. Both the diffusion coefficient and the partition coefficient, between paperboard and Tenax®, decrease with increasing relative humidity. The experimental results were correctly modelled only when the paperboard was regarded as a one-layer system as compared with a two-layer system: where the main part of the paperboard (B1) has a high diffusion rate and a thin part of the paperboard (B2) in contact with the foodstuff has a lower diffusion rate.
Toxicity testing and chemical analyses of recycled fibre-based paper for food contact
Food-contact materials, including paper, have to comply with a basic set of criteria concerning safety. This means that paper for food contact should not give rise to migration of components, which can endanger human health. The objectives of this pilot study were, first, to compare paper of different qualities as food-contact materials and to perform a preliminary evaluation of their suitability, from a safety point of view, and, second, to evaluate the use of different in vitro toxicity tests for screening of paper and board. Paper produced from three different categories of recycled fibres (B-D) and a raw material produced from virgin fibres (A) were obtained from industry, and extracts were examined by chemical analyses and diverse in vitro toxicity test systems. The products tested were either based on different raw materials or different treatments were applied. Paper category B was made from 40% virgin fibres, 40% unprinted cuttings from newspapers, and 20% de-inked newspapers and magazines. Paper categories C and D were based on newspapers and magazines. However, paper D was de-inked, whereas C was not. To identify constituents of the papers with a potential to migrate into foodstuff, samples of the paper products were extracted with either 99% ethanol or water. Potential migrants in the extracts were identified and semiquantified by GC-IR-MS or GC-HRMS. In parallel to the chemical analyses, a battery of four different in vitro toxicity tests with different endpoints were applied to the same extracts: (1) a cytotoxicity test using normal human skin fibroblasts. The test was based on measurements of the reduction of resazurin to resorufin by cellular redox processes and used as a screening test for acute or general toxicity; (2) a Salmonella/microsome assay (Ames test) as a screening test for mutagenic and potentially carcinogenic compounds; (3) a recombinant yeast cell bioassay as a screening test for compounds with oestrogenic activity; (4) an aryl hydrocarbon (Ah)-receptor assay (CALUX assay) as a screening test for compounds with dioxin-like activity. In addition, the papers were tested for microbial content and, in general, the microbiological load was quite low. The following microorganisms were counted and identified on both surface and homogenized pulp samples: the total number of aerobic bacteria, the number of aerobic and anaerobic spore formers, the number of Bacillus cereus/thuringiensis, and the number of yeast and moulds. The chemical analyses showed a significantly higher amount and different composition pattern of chemicals extracted with ethanol compared with water. Analyses of the ethanol extracts showed a distinctly smaller number and lower concentrations of chemicals in extracts prepared from sample A compared with extracts of samples B-D. The compounds identified in B-D were similar, but the amounts were lower in B compared with C and D. In accordance with the chemical analyses, the water extracts were less cytotoxic than the ethanol extracts. The extract prepared from virgin fibres was less cytotoxic than the extracts prepared from paper made from recycled fibres, and extracts prepared from C was the most cytotoxic. None of the extracts showed mutagenic activity. No conclusion about the oestrogenic activity could be made, because all extracts were cytotoxic to the test organism (yeast cells). Ethanol extracts of A and B showed a negligible positive response in the Ah-receptor assay at the highest nontoxic concentration, whereas C and D showed a more pronounced effect with C being the most potent. A comparable weak effect of water extracts of samples B-D was observed, too. However, the active compound(s) was not identified by chemical analyses.
Migration studies from paper and board food packaging materials. 1. Compositional analysis.
A survey of 32 paper and board materials intended for food contact has been undertaken. Sample composition was analysed to identify chemicals with a potential to migrate to foods. Representative materials covering a range of uses such as aqueous and fatty foods, and use at ambient and elevated temperatures, were obtained from industry. The samples were examined in their unfinished state, even where the final form would have included lamination to plastics, printing, or other treatments. A comprehensive and systematic analytical approach was applied which included determination of volatiles by headspace GC-MS, extraction using water, ethanol and chloroform with subsequent analysis by GC-MS and HPLC, and multi-element screening by ICP-MS. The solvent extracts were also weighed to determine the total amount of material available for migration. A large number of volatile substances were identified with alkyl and aryl aldehydes predominating in the majority of samples. Substances identified in solvent extracts included 2,6-di-tert-butyl-4-hydroxytoluene (BHT), di-tert-butylphenol, benzophenone, 4,4'-bis(dimethyl amino) benzophenone (Michler's ketone), triphenyl methane, bicyclohexylphenylphenanthrene carboxylic acid (and its methyl ester) and abietic acid. Levels of these substances were however generally below 1 mg/kg paper. Of the inorganic elements, arsenic and mercury were not detected above the limits of determination of 1.8 and 0.4 mg/kg respectively in any of the 10 samples examined. Cadmium was detected in teabag tissue and in unbleached Kraft paper at 0.3 mg/kg. Chromium was present in seven samples at 1.1-7.8 mg/kg, whilst lead was present in nine of the 10 samples at levels ranging from 0.3 to 5.9 mg/kg.