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Mapping of perfume in toys and children's articles

7 Laboratory test

• 7.1 Analytical methods and test
  • 7.1.1 Fragrance
  • 7.1.2 GC/MS screening (extractable organic compounds)
  • 7.1.3 Screening for content of solvents
  • 7.1.4 Specific migration
  • 7.1.5 Emission test
• 7.2 Results
  • 7.2.1 Classification of products
  • 7.2.2 Odorants
  • 7.2.3 GC/MS-Screening
  • 7.2.4 Solvents
  • 7.2.5 Migration
  • 7.2.6 Emission test

7.1 Analytical methods and test

The products have been analysed for content of sensitising fragrance substances, however, also a more general screening of chemicals in the 10 products has been carried out. The screening was performed prior to selection of products for migration test and emission test. Migration and emission test were selected performed on products aimed at children less than 3 years. Based on screening results rubber figure, Writing paper, and yellow scented ink (D02, D04, D08) were selected for emission test. The latter products are all products directed at children above 3 years. Among other things the GC/MS screening detected a high content of phthalates in erasers (D06). However, erasers were not further tested, as there are only regulations for content of these compounds in toys aimed at children under the age of 3 years.

7.1.1 Fragrance

The content of the sensitised fragrances was analysed in one sample. A partial sample was taken and extracted with water and tert-butylmethylether by means of suspension, cooling, and standing during a period of approximately 16 hours. A partial sample of the extract was taken and analysed directly through combined gaschromatography and mass spectrometry (GC/MS). The limit of detection is 1-10 mg/kg and uncertainty is 10-15% (relative standard deviation). If the product consists of more parts the analysis has been performed on the scented part of the product. The specific part is given in the results table.

7.1.2 GC/MS screening (extractable organic compounds)

The content of extractable organic compounds in the samples was analysed. A sample consisting of partial amounts of all components in the product was extracted with dichloromethane added internal standards. The selection of partial samples was determined from an assessment of the proportion of the materials in the product. A partial sample was taken and analysed directly at combined gas chromatography and mass spectrometry (GC/MS) by scanning over a larger mass area. The content of a large number of specific compounds was calculated semi quantitatively as C8 or C30 depending on retention time. The limit of reporting is 10-100 mg/kg depending on the single sample; the limit of reporting is usually higher than the limit of detection. The specific limit of reporting is given in the results section. A description of the parts included in the analysis is given in the results table.

7.1.3 Screening for content of solvents

A screening for content of solvents and quantification of these was performed in order to determine the content of solvents in a particular product (D02, rubber figure).

A partial sample is extracted with DMF (Dimethylformamide) added internal standards. A partial sample of the extract is taken and analysed directly at combined gas chromatography and mass spectrometry (GC/MS) by scanning over a larger mass area. All identifications of compounds are performed from retention time and the mass spectra by comparing with mass spectra in a data library. The content if calculated quantitatively. The limit of reporting is 50 mg/kg and uncertainty is 10-15%RSD.

7.1.4 Specific migration

At the test for specific migration the potential emission of compounds from the sample to sweat is tested. A sample of approximately 5 gram consisting of partial amounts of all components in the product under consideration of the proportion of the material in the product was added 100 ml artificial sweat and incubated at 40C for 24 hours. Artificial sweat was prepared from NaCl, ammonia, lactic acid, carbamide, and water according to DS/EN 1811. Following incubation the artificial sweat (simulant) was extracted with dichloromethane added internal standards. A partial sample of the extract was taken and analysed directly at combined gas chromatography and mass spectrometry (GC/MS) by scanning over a larger mass area. The content was calculated semi quantitatively as C8 or C30 depending on retention time. Generally the unit mg/dm² is used when reporting migration results. However, as the sample consisted of different part as e.g. filler where the area could not be specified, the unit is given as component per kg sample used for the migration test. The limit of reporting is 1 mg/kg.

The test is performed in triple with blank. A description of the parts included in the analysis is given in the results table.

7.1.5 Emission test

The emission test collects volatile compounds emitting from the sample to the air. Approximately 1 gram sample was placed in a 600 ml purifying bottle. A charcoal tube was fitted onto the lid with a Tenax-TA tube serial combined with a CS-tube for collection of volatile and semi volatile compounds at the exhaust. The air was absorbed through the test container with an air change of 2.9 times per hour.

The exposed CS- and Tenax-TA-tubes were desorbed at heating and analysed directly using GC/MS by scanning over a larger mass area. The content of the determined components were calculated by means of relative response factors (tables) or semi quantitatively as toluene (molar weight for toluene used for semi quantitative determination).

The products were stored in original packaging until initiation of emission test preparations.

The limit for achievable reliable quantitative results is set to 10 g/m³ air. This limit was raised to 20 g/m³ for one sample as the uncertainty was assessed too high due to noise peaks on the GC-chromatogram.

7.2 Results

7.2.1 Classification of products

As all products were toys aimed at emitting scent, the location of the odorant in the product was tested. In several cases the toys were equipped with odorant balls, however, there were also cases of drenched gauze and textile. All results tables are added a column with information as to the analysed part the product.

7.2.2 Odorants

The ten tested products were all analysed for 26 odorants. Three products did not contain a content of any of the 26 odorants. The total content of all 26 odorants is given in table 7.1 and varies from 32 to 5,500 mg/kg.

The two largest contents were found in amounts from 2,500 to 5,500 mg/kg corresponding to 0.25-0.55 weight percentage, while the highest content of one single odorant in a product was 4,000 mg/kg corresponding to 0.4 weight percentage.

Table 7.1: Results from the analysis for odorants. The unit is mg/kg.

LOD: Means limit of detection
-: Means not determined above the limit of detection

Tabel 7.1 Continued. Results from the analysis for odorants. The unit is mg/kg.

LOD: Means limit of detection
-: Means not determined above the limit of detection
^ No longer available on the Danish market

7.2.3 GC/MS-Screening

The screening for extractable organic compounds detected odorants that are already given in table 7.1 for some of the products. These are thus omitted from table 7.2.

The content is calculated semi quantitatively in which case the results must be considered guiding. Unit is mg/kg. The limit of reporting for the single product is given in the table.

Following there has been quantitative determination of the content of tris(2-chloroethyl)phosphate in product D12. This is also seen in the table.

Table 7.2: Results from GC/MS-screening. Unit is mg/kg.

-: Means not determined above the limit of detection
*: sum of isomer compounds

Table 7.2 - Continued. Results from GC/MS-screening. Unit is mg/kg.

-: Means not determined above the limit of detection
*: sum of isomer compounds
**: Quantitative determination
^ No longer available on the Danish market

7.2.4 Solvents

There were further analyses for solvent content in the product D02. Quantitative analysis is solely performed in double determination as given in table 7.3. Gauze from 2 products have been applied – one for each double determination, which most likely cause the relatively large difference in some of the components. Unit is mg/kg and the limit of detection is 10-50 mg/kg.

Table 7.3. Quantitative analysis of solvents in product D02. Unit is mg/kg.

7.2.5 Migration

Four products were selected for migration test based on the identified substances in the screening, penetration, and the fact that they were aimed at children under 3 years. Migration test with artificial sweat as simulant was performed as the products are considered used for e.g. soft toys and in close skin contact during use. The test was performed in triple determination and the results in table 7.4 are averages of the three determinations.

The content is calculated semi-quantitatively, thus the results must be considered guiding. Unit is mg of the component in the simulant per kg product used for the migration test.

Accordingly a quantitative determination of the compound tris(2-chlorethyl)phosphate was performed. The substance was detected in the analysis of artificial sweat. The below mentioned table provides the quantitative value for content of tris(2-chloroethyl)phosphate in the simulant from the migration test performed on the three part components: Textile, fill, and plastic part of the product D12. The unit is calculated as mg of the compound per kg of the product used for the migration test. The average value for content of tris(2-chlorethyl)phosphate in product D12 is calculated to 5,900 mg/kg.

Table 7.4: Results from GC/MS-screening of the simulant from the migration test. Unit is mg/kg.

-: Means not determined above the limit of detection
*: Quantitative determination performed on the three parts of the product
^ No longer available on the Danish market

7.2.6 Emission test

Seven products were selected based on the screening analyses and consumption pattern for emission tests. The tests were performed by collection on solid adsorbents and analyses at GC/MS screening. The result of the screening is given in table 7.5.

The content is calculated as toluene (semi-quantitative) for the components marked with *. The other components are calculated quantitatively. The unit of µg per m³ air. The limit for achievement of reliable results is set to 10 µg/m³ air with the exception of sample D02, where this limit was raised to 20 µg/m³ due to "noise"-peaks on the GC chromatogramme.

Table 7.5: Results from emission test. The unit is g/m³.

-: Means not determined above the limit of detection
*: Means calculated as toluene

-: Means not determined above the limit of detection
*: Means calculated as toluene
^ No longer available on the Danish market

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Version 1.0 March 2006, © Danish Environmental Protection Agency