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Mapping of perfume in toys and children's articles
6 Screening of products for ingredient substances
6.1 Selection of products for qualitative screening
Selection of products for qualitative screening with GC-MS was made on the basis of the following criteria.
The products were selected so that they in combination:
- Covered a wide spectrum of the declared fragrances.
- Covered the entire target group of children from 0 to 10 years.
- Were intended for as many different types of play activities as possible (writing/drawing, outdoor activity, soft toys, development and collector's items).
- Potentially exposed the child for both long and short periods of time.
- Resulted in different types of exposure (solid or floating product).
The selected products appear from table 6.1.
Only in the declarations for the selected products in the D08 product series (speed markers), sensitizing substances have been declared, also see section 5.3.1.
Table 6.1: Selected products for the screening analysis
Product
type number |
Product |
Scent |
Selected for screening
analyses |
D01 |
Soap bubbles |
Lemon & Lime, Chocolate chip,
Bubblegum, Banana Split,
Tropical punch, Strawberries &
Cream |
Lemon & Lime |
D02 |
Fragrant
rubber figures |
The Duke of Puke, Pizza Face
Pat, Oli Slick Rick, Dude Boy
Doug, Dandy Doo Dave,
Clammy Cliff, Zoo Boy Zach,
Elephant Drop Eric, Camel
Mouth Chris, Monkey Cage
Mike, Ra Boy Rob, Winnie the
Vulture, Ear Wax Max, Fartasarus
Frank, Billy Bob Booger, Toxic
Tyler, Spewy
Huey, Jurassic Josh,
Rotten Onion Ollie, Chill E.
Dawg Joey, Never Wash Nick,
Rankin' Ryan, Wart Hog Henry |
Dandy Doo Dave, Camel
Mouth Chris, Rankin'
Ryan |
D04 |
Writing paper |
Perfume |
Perfume |
D05 |
Mechanical
pencil |
Apple, grape, kiwi, banana,
orange, strawberry |
Kiwi |
D06 |
Eraser lipstick |
Apple, grape, kiwi, banana,
orange, strawberry |
Strawberry scent |
D07 |
Eraser pen |
Apple, grape, kiwi, banana,
orange, strawberry |
Apple scent |
D08 |
Speed markers |
Orange, lemon, strawberry,
blackberry, violet, rose,
chocolate, pine and 2 additional
unnamed scents |
Lemon, rose and
strawberry |
D09 |
Rabbit |
Chocolate |
Chocolate |
D10 |
Stacking rings |
Apple |
Apple |
D11 |
Activity box |
Apple |
Apple |
D12^ |
Soft cube |
Apple |
Apple |
D13 |
Cuttlefish |
Vanilla |
Vanilla |
D14^ |
Soft toy |
Vanilla |
Vanilla |
D15 |
Flower |
Vanilla |
Vanilla |
^ Is no longer on the Danish market
6.2 Screening methodology and results
Products were analyzed qualitatively for content of the 24 fragrances on the list of sensitizing substances prepared by SCCNFP (1999) and for any other volatile, organic compounds.
The analysis was a screening analysis limited to substances with masses between 45 and 300 g/mol.
The analysis was carried out as a head space analysis. The samples were packed separately in nitrogen atmosphere in Rilsan bags that were hermetically closed with a strip.
To minimize the risk of pollution of the air in the Rilsan bag, the bag containing the product was filled with nitrogen gas and was subsequently emptied again. This "scavenging" process was carried out three
times before the bag was filled with nitrogen for the last time and closed.
Erasers and pencil leads (the D05, D06 and D07 products) were taken out of their plastic cases, as the cases did not contain any fragrances. The speed markers (D08) were packed without caps in a Rilsan
bag. When handling the bags, the speed markers gave off some colour to the inner side of the bags. All price and cardboard tags and similar were removed from the textiles. Sewed on labels were not
removed.
After the rubber figures (D02) were put in the Rilsan bags, they were exposed to one single high pressure before the analyses were carried out. The figures were not exposed to any further pressures as the
analyses were repeated.
6.2.1 First screening
The preliminary screening tests were carried out without up-concentrating the air in the bags. The column temperature was maintained at 50 or 60º C during the entire analysis.
The result of these tests demonstrated a content of many different substances in all tested products. The substances included alkanes, alkenes, alcohols, estre, ketones, ethere and aromatic compounds,
meaning that all groups of volatile organic compounds were detected. An exception was the analyses of the mechanical pencil with kiwi scent (D05), which only showed traces of volatile, organic
compounds. None of the 26 selected sensitizing substances were identified in any of the tested products.
6.2.2 Second screening
The substances identified in the preliminary analyses were generally detected with low signals, which made it difficult to identify single components. To increase the security of the identifications and the
chance of identifying substances occurring in lower concentrations, the air in the bags was up-concentrated 10 times prior to the analysis. The air from the bags with rubber figures (D02) was not
up-concentrated, as the signals from these tests were apparent already at the first screening test.
To increase the chance of detecting the substances that only move slowly through the column, the analyses were made by heating the up-concentrated air gradually in the column from 60 to 160ºC. Again,
the results showed a content of many different substances in the tested products. A possible content of the sensitizing substance, D-limonen, could be demonstrated in the soap bubbles (D01) and in the
erasers with strawberry and apple scent (D06 and D07) respectively.
6.2.3 Third screening
The yellow and pink speed markers (D08) had a declared content of sensitizing substances (benzylalcohol, citral, geraniol and linalool). As these substances were not identified during the earlier mentioned
screening tests, the speed markers were tested once more.
In this test, the air was up-concentrated 250 times in the bags containing the product. However, it was not possible to detect any of the declared sensitizing substances. No further tests were made to identify
the substances searched for in the speed markers.
6.3 Selection of products for exposure tests and accredited analyses
Based on the results from the qualitative analysis, 10 products were selected for qualitative analysis and exposure test.
The following criteria were used at the selection:
- The screening analysis showed a possible content of at least one of the substances on the EU list of sensitizing substances or a content of harmful substances.
- The product had a declared content of sensitizing substances.
- The product gave off heavy odour/scent.
- The product is intended for babies.
- Use of the product causes risk of heavy exposure from for instance soft toys, soap bubbles and fragrant rubber figures.
- The screening analyses demonstrated a content of a large number of substances.
Furthermore, attempts were made to select products that represented a broad section of the market, aiming at the entire target group and covering the largest possible spectrum of play activities. Special
focus was, however, on the product for babies.
The soft cube (D12) and the soft toy (D14) were not analyzed in the screening tests. These products were selected for further analysis solely on the basis of them being intended for babies.
The mechanical pencil (D05) with kiwi scent was excluded due to its weak scent and missing identification of substances during the screening test.
The 10 selected products are listed in the below table.
Table 6.2: Selected products for laboratory experiments and accredited analyses
Product type number |
Product |
Selected for laboratory experiments and
accredited analyses |
D01 |
Soap bubbles |
Lemon & Lime |
D02 |
Rubber figures |
Camel Mouth Chris |
D04 |
Writing paper with scent |
Perfume |
D06 |
Eraser lipstick |
Strawberry scent |
D08 yellow |
Fragrant speed markers |
Lemon |
D08 red |
Fragrant speed markers |
Strawberry |
D09 |
Rabbit |
Chocolate |
D12^ |
Soft cube |
Apple |
D14^ |
Soft toy |
Vanilla |
D15 |
Flower |
Vanilla |
^ Is no longer on the Danish market
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Version 1.0 March 2006, © Danish Environmental Protection Agency
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