Summary and conclusion

Analysis of chemical substances in balloons

For this study 20 different packs of balloons have been purchased at different retailers. The balloons normally come in different colours and the various brands differ in size and geometry.

During the purchasing phase we went to a number of supermarkets and the general impression was that the Danish balloon market is limited to a few wholesalers, supplying the same products to different supermarkets and therefore our purchases were confined to only three supermarkets. Other types of shops have also been included in our analysis but still the general impression is that only a few wholesalers/manufacturers are dominating the Danish balloon market.

As balloons are dangerous toys for children less than 8 years labelling regulations are laid down in the Toys Act 88/378/EEC. According to the standard in the Toys Act, EN 71-1, the balloons shall to in order comply with the CE-standard be provided with warning labels saying that children under 8 years should be supervised and that defective balloons or parts hereof shall be discarded. A further requirement is that the balloons made of natural latex shall be marked ”contain natural rubber latex”.

The labelling of the purchased balloons differs a lot. Most of them are however CE labelled and most of the packaging had warning labels about use by children under 8 years. Further, the packaging often advised caution with children less than 3 years. In some cases the warnings were not in Danish and some of the balloons had inadequate labelling.

The majority of the balloons are made of natural latex, but more of them had no informative label about this.

Twelve of the purchased balloons have been screened by thin layer chromatography (TLC) in order to determine the accelerator types used by vulcanisation.

On basis of these screenings and the amount of extracted substance four balloons were selected for analysis for nitrosamines and nitrosatable substances according to DS/EN 12868, ”Child Care Articles: Methods for determination of the release of N-nitrosamines and N-nitrosatable substances from bottle teats and soothers of elastomers or rubber”. Likewise, analyses have been made on release of volatile substances from balloons at 80 °C. Further, three balloons were selected for test of bioavailable heavy metals according to EN 71-3 ”Safety of Toys - Migration of certain elements.

The result was that there was no measurable release of heavy metal, but all the balloons gave off nitrosamines in concentrations higher than allowed for soothers and bottle teats. Surprisingly, the release of nitrosatable substances was generally in very high concentrations. In two cases the contents was so high that the standardised method could not completely convert those of the amines, which were highest in concentration, within the reaction time for conversion to nitrosamines. It is therefore assessed that this method provides too low results for nitrosatable substances at high amine concentrations. Not unexpectedly, the most frequent nitrosatable amine is dibutylamine, which is often present as accelerator in vulcanised latex products in the form of the zinc salt of dibutyldithiocarbamic acid. Second comes the zinc salt of dimethyldithiocarbamate, which is often applied in combination with the zinc salt of dibutyldithiocarbamatic acid.

Germany has laid down limit values for release of nitrosamines and nitrosatable substances from balloons.

The analysed balloons all complied with the limit value of 0.2 mg/kg for migration of nitrosamines according to DS/EN 12868, but only one of the four analysed balloons complied with the requirement to nitrosatable substances of 2 mg/kg. This balloon type bore the TÜV quality mark.

At 150 °C a headspace GC/MS analysis was made of the volatile substances formed by decomposition of rubber chemicals. A wide range of different degradation products are formed from the chemical substances in the balloons. This analysis has been used to confirm the results from the TLC screening.

The analysis established evaporation of several hazardous organic substances from a balloon purchased in a discount store. The other three balloon types showed no degassing of these chemical substances.

A headspace analysis at 80 °C of the balloons demonstrated liberation of carbon disulfide from the four analysed balloons. The balloon from the discount store also liberated dibutylamine and BHT (antioxidant).