No abstract

The main objective was to develop a technique to expose spots of invisible set-off of inks and lacquers on the food-contact surface of food-packaging materials. Set-off is the unintentional transfer of components of printing inks from the outer printed surface onto the food-contact surfaces. The target sensitivity was 20 microg cm(-2) and the technique should be capable of examining large areas of printed substrate for no more than 4% coverage by set-off. These requirements equate to an ability to detect a worst-case migration potential of less than 50 microg kg(-1). Other objectives were the industrial requirements that the equipment should be inexpensive, should be easy to use by existing personnel and should preferably be non-destructive with a clear criterion for pass or fail. The approaches investigated included chemical analysis of solvent extracts, Fourier-transform infrared spectroscopy and microbeam analytical techniques, but these were found to be cumbersome and had only limited success. The objectives were achieved using an optical approach to excite and observe luminescence from invisible set-off. In model experiments, resins were applied to different substrates (plastic, paper and cartonboard). For a given resin on a given material, the key to success was to maximize the discrimination between the luminescence from the resin and that from the substrate by selecting the optimal combination of exciting wavelength and viewing goggles with selective wavelength filters. The required level of detection (20 microg cm(-2)) was achieved or exceeded for all ten resins tested on three different plastics. It was also achieved for two different papers and in all but four cases of the resins on three different cartonboards. Quantitation was achieved by the use of a calibration palette prepared using different quantities of resin spotted onto the relevant blank packaging material.

A survey of retail samples was conducted in two phases with 50 general paper and board food contact materials and articles analysed in 1992, and 121 samples, specifically of printed cartonboard, analysed in 1995. Packaging samples were extracted with ethanol containing 0.4% triethylamine. The extracts were analysed using high performance liquid chromatography (HPLC) and the presence of 4,4'-bis (dimethylamino) benzophenone (Michler's ketone, MK) and 4,4'-bis (diethylamino)-benzophenone (DEAB) confirmed using gas chromatography coupled to mass spectroscopy (GC-MS). The limits of detection for MK and DEAB in packaging were 0.05 mg/kg and 0.1-0.2 mg/kg respectively. In the first phase, MK was detected in 24% of the 50 samples at concentrations of 0.06-3.9 mg/kg paper. DEAB was detected in 12% of samples (0.1-0.2 mg/kg). In the second phase, 26% of the 121 cartonboard samples contained detectable MK (0.1-1.6 mg/kg) and 4% contained DEAB (0.2-0.7 mg/kg). Residues of the monoamine 4-(dimethylamino)benzophenone (DMAB) were found in 10% of the 1992 samples (0.1-0.6 mg/ kg). DMAB was not surveyed in 1995. These levels are too low to indicate the use of these cure agents for printing the packages. Rather, the most likely origin is from the use of recycled fibres. For three samples where the highest concentration of MK was detected, the food was analysed by GC-MS after extraction and clean-up. There was no measurable migration of MK at a detection limit of 2 micrograms/kg food. It is concluded, therefore, that the concentrations of MK present in the packaging samples analysed are unlikely to pose a risk to human health.

Gas chromatography-Fourier transform infrared spectroscopy (GC/IR) was used to analyze a series of alkyl nitrites (butyl and pentyl) as well as some typical “street products” containing alkyl nitrites. The vapor phase IR spectra of the nitrites exhibited strong absorbances near 1665 and 1620 cm-1 (anti and syn R-O-N = O stretches) and 780 cm-1 (O-N stretch); yet enough variation exists to distinguish between them. Street samples, or purposely “aged” nitrites, showed mixtures of readily separated components consisting of alkyl nitrites and nitrous oxide.

The zone of inhibition method to test the release of biocides from paper and board food contact materials was evaluated. The method tests the paper by placing a small specimen directly onto culture plates of Bacillus subtilis and Aspergillus niger. The principle is that any extractable biocide will diffuse from the paper into the surrounding nutrient medium and so inhibit growth of the microorganism in the vicinity. The test was found to have insufficient sensitivity for assuring food safety, where detection limits for migration at or below the mg l(-1) (parts per million) level are needed. Also, the test does not mimic the actual or foreseeable conditions of use since most paper/board materials are not intended for direct contact with an aqueous medium for up to 3 days at 30°C (B. subtilis) or 25°C (A. niger), which are the incubation conditions used. The sensitivity of the test was increased approximately 100-fold by preparing a concentrated extract of the paper to be tested and applying this extract to the assay via a blank paper carrier. This was done using methanol as a good solvent for most biocides, as a proof of principle. Other solvents or food simulants could be used to mimic the conditions of use intended for the particular paper/board samples under examination, e.g. contact with dry, fatty, aqueous or acidic foods, hot or cold. Twenty-four plain (unconverted) paper and board samples and 100 food packaging samples were evaluated using the modified procedure. The results revealed that the method has been developed to the stage where background cytotoxic action of normal paper constituents gives a weak response. Unlike the original method, therefore, the modified method with its improved sensitivity and the facility to link with the intended food contact conditions may be considered a suitable bioassay screening test to complement chemical analysis of paper/board for composition and migration.