Kortlægning af kemiske stoffer i forbrugerprodukter, 67 – Kortlægning og afgivelse af kemiske stoffer i "slimet" legetøj

Kortlægning og afgivelse af kemiske stoffer i "slimet" legetøj

Summary and conclusions

As a part of the Danish Environmental Protection Agency's survey of chemical substances in a number of consumer products, knowledge of which substances are contained in "slimy" toys is requested. The aim of the project is to give a survey of the chemical substances that might be contained in rubbery and slimy toys. This knowledge can be used in connection with guidance of manufacturers and importers, and possible recommendations to the consumers to avoid certain substances in this kind of toys. Furthermore, the project will form the basis of evaluating unique batches of similar toys, when they get on the market.

Phase 1 concerns examination of the slimy toys market in Denmark. Furthermore, it has been examined which materials they consist of, or which materials are constituents, and to which degree they appeal to children and which age group.

It has not been possible to get information from the manufacturers regarding substances in their products. However, the detail trade has delivered data sheets as well as information as stated in Enclosure A. The examined products stated in Enclosure A do not give any cause for concern. The biggest importer of slimy toys in Denmark is K. E. Mathisen A/S (K. E. Leg).

In phase 2 the following qualitative analyses have been carried out:

screening analysis by means of FTIR in order to determine which materials the toys are made of and possible content of phthalates
qualitative screening analysis of elements by means of ICP and quantitative analysis of boric acid content
qualitative analysis of the substances released to the air by means of headspace analysis combined with GC-MS
qualitative analysis of the substances released to artificial saliva and sweat by means of GC-MS
quantitative analysis of phthalates

The FTIR analyses show two types of "slime", partly an aqueous type, hydro gels, and partly a type based on hydrocarbons with a small content of styrene.

The aqueous slime contains glycerol and acrylate and in some cases materials, which we have not been able to identify by FTIR. In a number of cases parabenes have been added. Generally, in the slime products made of hydrocarbons we cannot detect other components.

At the preliminary headspace analyses we have identified all the substances, which might degas from the slimy toys (except for light aldehydes). At the headspace analyses of the 14 slimy toys (of which a few were analysed on exterior part and interior liquid part, totally 20 analyses), we found 61 identified single substances and different groups of substances, aliphatic hydrocarbons and aromatic hydrocarbons identified by the number of C-atoms, and finally 6 compounds, which could not be identified.

At the migration analyses of the 14 slimy toys (of which a few were analysed on exterior part and interior part, totally 17 analyses) we found 22 identified single substances and various groups of substances consisting of various aliphatic and aromatic hydrocarbons, which are stated in groups characterised by a number of hydrocarbons, and finally a group of 6 compounds, which could not be identified, but they were all fatty acids.

The qualitative screening analyses by ICP show a considerable content of boron in 3 of the samples (DK-01, TO-01 and TO-02). Boron might have been added as preservative in the form of boric acid or sodium borate, as - at the same time - a content of sodium has been measured.

However, other sodium sources might have been added too, e.g. from sodium benzoate, which is also a preservative. The content of elements such as aluminium, calcium, potassium and zinc, which has been detected in most of the samples, presumably derives from fillers or auxiliary constituents used in the production of the products. Furthermore, the detection of traces from a few heavy metals in some of the samples is supposed to derive from contaminations from fillers and possibly from production equipment and production conditions.

Phase 3 deals with screening for possible harmful effects from substances, which are being released from slimy toys. A screening has been made of the substances, which have been identified by the headspace analyses. The screening is based on a literature survey in order to secure that the substances focused on at the quantitative analyses are the most relevant.

Based on the identified chemical compounds a screening for possible harmful substances has been made. The screening is based on the classifications in the List of Dangerous Substances and available information on effects that potentially may cause concern to the consumer, if the release of the chemical substance is too high.

Some substances were detected, which might be considered to be problematic substances, and some, which may be of concern.

The following substances are suggested for a closer examination:

Organic substances:

2-Butanone
2-Butoxy-ethanol
Cyclohexanone
Dichloromethane
Diethylglycol dibenzoate
N,N-Dimethylformamide
Ethylbenzene
2-Hexanone
2-Phenoxy-ethanol
1,2-Propanediol
2-Propenoic acid 2 methyl-methyl ester (methyl-methacrylate)
N-Propyl benzamide + N-acetyl benzamide
Toluene
3,3,5-Trimethylcyclohexen-1-one
Xylene

Inorganic substances

Boron
Nickel

Phase 4 deals with the quantitative analyses and preparation of exposure scenarios at the released substances. Because most problematic substances were detected by headspace at the screening, and because this screening is not immediately quantitative, it has been necessary to determine the amount and the release of these substances by means of calculations made on the basis of the screening analysis.

The problematic substances, which are migrated to artificial saliva and sweat, are determined quantitatively by GC-MS.

In addition, a quantitative ICP-MS analysis of nickel has been carried out.

For the health assessments, we have used parameters for small children in the scenarios, as the consumer in this case in particular is assumed to be children. It cannot be precluded that the pungent smell, which is observed from some products, may cause acute effects like eye-, nose- and throat irritations. At long term exposure there is a possibility that a few substances may cause contact allergy at particularly sensitive individuals.

The scientific committee for cosmetic products has identified 26 substances as recognized contact allergens (SCCNFP 1999). These substances have later been regulated in Directive 2003/15/EC (EC 2003). 2 out of these 26 substances were detected in the examination: D-Limonene was found in 3 products and hexylcinnam aldehyde in 1 product.

In addition, of other substances, which are potentially allergenic, we have detected 3-Carene, alpha-Pinene and Nickel. All 3 are terpenes. D-Limonene, 3-Carene (7 products) and alpha-Pinene (8 products) were only detected in the headspace analyses. It is a little uncertain whether the effect from contact allergens is the same at an exposure via the respiratory tract as at skin contact, but the are or can be rediscovered in aerosols, which may potentially also settle on skin surfaces.

Boron was detected in 3 products, at a maximum of 0.8% of the products. It is assessed that a health risk cannot be excluded at contact with the liquid in one of the products.

Nickel was detected in 2 products, at a maximum of 0.0003% of the toy. Consequently, it is assessed that the nickel content does not immediately constitute a problem, unless one is particularly sensitive (nickel allergy).

For the rest of the substances it applies that none neither occur as volatile substances nor migrated to sweat or saliva in such concentrations that absorptions should cause concern when letting children play with the products.

However, it should be noted that the consumer (child) may handle more than one slimy toy simultaneously or at intervals, thus increasing the exposure to one or more chemical substances correspondingly. Other sources of the same chemicals may also be present in the surroundings of the play activity. This may also contribute to the total exposure.