| Front page | | Contents | | Previous | | Next |

Migration and health assessment of chemical substances in surface treated wooden toys

3 Analysis results

• 3.1 Analysis methods
  • 3.1.1 Inorganic substances
  • 3.1.2 Organic substances
• 3.2 Migration of inorganic substances
  • 3.2.1 Analysis results
• 3.3 Migration of organic substances
  • 3.3.1 Analysis results
• 3.4 Selection of chemical substances for evaluation

3.1 Analysis methods

A number of 15 products were selected for quantitative analysis of migration of heavy metals and organic chemical substances.

A representative area of the product was sampled for the analysis according to the standard prEN 71-10 (CEN standard EN 71-10: Safety of toys - Sample preparation and extraction). The sample was milled off the wooden toys surface to a depth of 3 mm and then further demolished/milled to uniformity.

The migration of heavy metals, inorganic and organic substances was measured according to the EN 71-3 standard where the simulant 0.07 M hydrochlorous acid (HCl) simulates artificial saliva or gastric acid.

The extraction was performed according to the standard EN 71-3, which prescribes 1 hour during agitation at 37±2°C and an additional 1 hour at standing at 37±2°C (CEN standard EN 71-3: Safety of toys – Migration of certain elements. EN71-3, 2003).

3.1.1 Inorganic substances

3.1.1.1 Test preparation

0.5 g sample – accurately weighed – in a polyethylene container was added 25 g 0.07 M hydrochloric acid and left under steady shaking at 37 ± 2 °C for 1 hour. Then the extraction container was left standing at 37 ± 2 °C for a further 1 hour after which the extract was filtered.

Blind samples were prepared correspondingly.

Double preparations were prepared.

3.1.1.2 Quantitative analysis

The extract was analysed for its content of antimony, arsenic, barium, cadmium, chromium, lead, mercury and selenium by inductively coupled plasma atomic emission spectrometry (ICP-AES) with quantitation against external standards in0. 07 M HCl.

3.1.2 Organic substances

3.1.2.1 Sample preparation

Approximately 2 g sample – accurately weighed – in a 100 ml glass beak was added 20 ml artificial saliva (saliva solution) and extracted at 37 ± 2 °C for 2 hours. The extract was filtered and then extracted using dichloromethane added deuterium labelled internal standards.

Blind samples were prepared correspondingly.

Double preparations were prepared.

3.1.2.2 Analysis

The dichloromethane extract was analysed for its content of organic components by capillary gaschromatography with mass spectrometric detection.

The quantitation against external standards of selected analytes and the internal standards.

3.2 Migration of inorganic substances

The migration of inorganic substances (heavy metals) are performed as described in the section on methods (cf. above).

3.2.1 Analysis results

The analysis results from the quantitative determinations for inorganic elements in the selected wooden toy products are presented in the table below.

Table 3 Measured migrated amount of inorganic substances in saliva extracts

-: below the detection level (DL)

Table 3 continued

-: below the detection level (DL)

Table 3 continued

-: below the detection level (DL)

Barium was the only metal detected in the analyses of the extracts. Barium was detected in 5 out of 15 analysed pieces of toy. The measured concentrations varied from 29 to 90 mg/kg sample of the products' surfaces.

A health evaluation of barium is performed in section 4.

3.3 Migration of organic substances

3.3.1 Analysis results

The analysis results from the quantitative determinations of identified organic substances extracted by saliva from the surface of the selected toy products are presented in the table below.

Table 4 Identified organic substances migrated from the surface of 15 toy products (μg/g)

Click here to see the table.

3.4 Selection of chemical substances for evaluation

From the detected substances and in co-operation with the Danish Environmental Protection Agency, were selected based on classification and detection a number of substances for further evaluation of a potential health risk to the consumers. The consumers are defined in this context as children 0 to 3 years of age.

Of the 125 identified substances are 43 classified in the List of dangerous substances (Miljøministeriet 2002), further 16 substances could be self-classified according to the Advisory list for self-classification from the Danish EPA (Miljøstyrelsen 2001). Of the classified substances 2 were classified to be possible carcinogenic (Carc.cat.3), 1 substance to be possible mutagenic (Mut.cat.3), and 9 substances toxic to reproduction (Repr.cat.2-3).

Below is mentioned the substances that had the most rigorous classification and selected substances with a less rigorous classification. A possible reason for the selection of the substance for an actual health evaluation is presented.

Benzyl alcohol, CAS no. 100-51-6, is classified Xn;R20/22 i.e. Harmful by inhalation and if swallowed. The substance is detected in the extract from 3 products. Based on a low concentration and the classification the substance is not included.

Benzyl butylphthalate (BBP), CAS no. 85-68-7, is classified Repr.Cat.2;R61 Repr.Cat.3;R62, i.e. the substance is reproduction toxic (May cause harm to the unborn child, and Possible risk of impaired fertility). However, the substance is detected in the extract from 1 product only and at trace level. The substance is therefore not included for a further evaluation.

1-Butanol, CAS no. 71-36-3, is classified R10 Xn;R 22 Xi;R37/38-41 R67 (i.e. Flammable. Harmful if swallowed. Irritating to respiratory system and skin. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness). The substance was detected in extracts from 5 products and even if the substance is harmful and an irritant it is evaluated to be at such low concentrations that it is not selected for further evaluation.

2-Butoxyethanol, CAS no. 111-76-2, is classified Xn;R20/21/22 Xi;R36/38 (Harmful by inhalation, in contact with skin and if swallowed. Irritating to eyes and skin). The substance is harmful and an irritant. The substance was detected in extracts from 12 out of 15 tested products and in a few at very high concentrations. The substance is therefore selected for further evaluation.

2-(2-Butoxyethoxy)-ethanol (= butyldiglycol), CAS no. 112-34-5, is classified Xi; R36, i.e. Irritant (Irritating to eyes). The substance was detected in extracts from 5 out of 15 products and even if the concentrations were moderate a further evaluation is decided.

2-Butoxyethylacetate, CAS no. 112-07-2, is classified Xn;R20/21, i.e. Harmful (Harmful by inhalation and in contact with skin). The substance was detected in extracts from 3 products at low concentrations.

1-Butoxy-2-propanol, CAS no. 5131-66-8, is classified Xi;R36/38, i.e. Irritant (Irritating to eyes and skin). The substance was detected in extracts from 2 products.

Butylacetate, CAS no. 123-86-4, is classified R10 R66 R67, i.e. Flammable. Repeated exposure may cause skin dryness or cracking. Vapours may cause drowsiness and dizziness. The substance was detected in extracts from 6 products. The classification refers to effects from the pure substance and is therefore considered less relevant in this context.

Cyclohexanol, CAS no. 108-93-0, is classified Xn;R20/22 Xi;R37/38, i.e. both harmful and irritating (Harmful by inhalation and if swallowed. Irritating to respiratory system and skin). The substance was detected in the extract from 1 product at trace level.

Cyclohexanone, CAS no. 108-94-1, is classified R10 Xn;R20, i.e. Flammable and Harmful by inhalation. The substance was detected in extracts from 2 products at moderate levels. To evaluate the level the substance has been included for a further evaluation.

Dibutyl phthalate (DBP), CAS no. 84-74-2, is classified Repr.Cat.2;R61 Repr.Cat.3;R62 N;R50, i.e. May cause harm to the unborn child, Possible risk of impaired fertility and Very toxic to aquatic organisms. The substance is thus classified seriously for a substance that can be extracted from a toy. The substance was detected in extracts from 4 products but at very low concentrations.

Diethylhexylphthalate (DEHP), CAS no. 117-81-7, is classified Repr.Cat.2;R60-61, i.e. May impair fertility and May cause harm to the unborn child. The substance was detected in extracts from 1 product at trace level.

Diisobutyl phthalate, CAS no. 84-69-5, is not classified in the List of dangerous substances but is found in the Advisory list for self-classification with the classification N;R50/53, i.e. Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. The substance was detected in the extracts from 8 out of 15 products. All the measured concentrationswere low and the substance therefore not considered a candidate for further evaluation.

2,6-Dimethoxybenzoquinone, CAS no. 530-55-2, is not classified in the List of dangerous substances but is found in the Advisory list for self-classification with the classification Xn;R22 R43, i.e. Harmful if swallowed and May cause sensitization by skin contact. The substance was detected in extracts from 7 out of 15 products. Even if the concentrations are low the substance is selected for further evaluation.

3,5-Dimethoxy-4-hydroxycinnamaldehyde, CAS no. 87345-53-7, is not classified in the List of Dangerous substances but the substance was detected in 11 out of 15 products. The substance was detected at low concentrations. Because the substance probably has its origin from the wood used to make the toy it is not selected for a further evaluation.

3,6-Dimethyl-1,4-dioxan-2,5-dion, CAS no. 4511-42-6, is not classified in the List of dangerous substances but is found in the advisory list for self-classification with the classification Xn;R22, i.e. Harmful if swallowed. The molecular structure of the substance is identical to the following substance:

3,6-Dimethyl-2,5-dioxo-1,4-dioxane (EU: dilactide), CAS no. 95-96-5, which is also self-classified Xn;R22, Harmful if swallowed. The two substances appear to alternate in all products and a further evaluation is therefore performed.

N,N-Dimethylformamide, CAS no. 68-12-2, is classified Repr.Cat.2;R61 Xn;R20/21 Xi;R36, i.e. May cause harm to the unborn child. Harmful by inhalation and in contact with skin and Irritating to eyes. A serious classification but the substance was detected only in 1 product and at trace level.

2-Ethoxyethanol, CAS no. 110-80-5, is classified R10 Repr.Cat.2;R60-61 Xn;R20/21/22, i.e. Flammable, May impair fertility, May cause harm to the unborn child, Harmful by inhalation, in contact with skin and if swallowed. The substance was detected in extracts from 2 products but due to the classification it was selected for further evaluation.

2-(2-Ethoxyethoxy)-ethanol (= diethylene glycol ether), CAS no. 111-90-0, is not classified in the List of dangerous substances. The substance was detected in the extracts from 4 products at moderate to high concentrations. The substance is therefore selected for further evaluation.

2-Ethylhexanoic acid, CAS no. 149-57-5, is classified Repr.Cat.3;R63, i.e. Possible risk of harm to the unborn child. The substance was detected in extracts from 1 product at a very low concentration.

Formamide, CAS no. 75-12-7, is classified Repr.Cat.2;R61, i.e. May cause harm to the unborn child. The classification is serious and since the substance is detected in the extracts from 2 products at moderate concentrations it is selected for further evaluation.

Furfural, CAS no. 98-01-1, is classified Carc.Cat.3;R40 T;R23/25 Xn;R21 Xi;R36/37, i.e. Limited evidence of carcinogenic effects, Toxic by inhalation and if swallowed, Harmful in contact with skin, Irritating to eyes and respiratory system. The substance was detected in extracts from 4 products. Although the concentrations were low the substance was selected for further evaluation due to its classification.

Hexanoic acid, CAS no. 142-62-1, is not adopted on the List of dangerous substances. However it is noted that the substance was detected in 13 out of 15 products at concentrations from trace levels to high concentrations. Because the substance not immediate is considered to pose a health concern at the determined concentrations (1.8-120 μg/g) the substance is not selected for further evaluation.

4-Hydroxy-3,5-dimethoxy-benzaldehyde, CAS no. 134-96-3, is not classified in the List of dangerous substances but is found in the Advisory list for self-classification with the classification R43, i.e. May cause sensitization by skin contact. The substance was detected in extracts from 12 out of 15 products at low to moderate concentrations. Therefore, the substance is selected for further evaluation.

2-Methoxyethanol, CAS no. 109-86-4, is classified R10 Repr.Cat.2;R60-61 Xn;R20/21/22, i.e. Flammable, May impair fertility, May cause harm to the unborn child, Harmful by inhalation, in contact with skin and if swallowed. The substance was detected in extracts from 1 product.

1-Methyl-2-pyrrolidone, CAS no. 872-50-4, is classified Xi; R36/38, i.e. Irritant (Irritating to eyes and skin). The substance was detected in extracts from 5 products at moderate to high concentrations. Therefore, the substance is selected for further evaluation.

Phenol, CAS no. 108-95-2, is classified Muta.Cat.3;R68 T;R23/24/25 Xn;R48/20/21/22 C;R34, i.e. Possible risk of irreversible effects, Toxic by inhalation, in contact with skin and if swallowed, Harmful: danger of serious damage to health by prolonged exposure through inhalation, in contact with skin and if swallowed and Causes burns. The classification is very serious but the substance was only detected in extracts from 1 product and at trace level. Therefore the substance is not selected.

Phthalic acid anhydride, CAS no. 85-44-9, is classified Xn;R22 Xi;R37/38-41 R42/43, i.e. Harmful if swallowed, Irritating to respiratory system and skin, Risk of serious damage to eyes, May cause sensitization by inhalation and skin contact. The substance was detected in extracts from 4 products: at trace level in 3 and at low concentration in 1 product.

Toluene, CAS no. 108-88-3, is classified (29th ATP, Directive 2004/73/EC, EC 2004) F;R11 Repr.Cat.3;R63 Xn;R48/20-65 Xi;R38 R67, i.e. Highly flammable, Possible risk of harm to the unborn child, Harmful: danger of serious damage to health by prolonged exposure through inhalation, Harmful: may cause lung damage if swallowed, Irritating to skin and Vapours may cause drowsiness and dizziness. The substance was detected in extracts from 2 products but at low concentrations.

3,5,5-Trimethyl-2-cyclohexen-1-one (=isophorone), CAS no. 78-59-1, is classified Carc.Cat.3;R40 Xn;R21/22 Xi;R36/37, i.e. Limited evidence of carcinogenic effects, Harmful in contact with skin and if swallowed, Irritating to eyes and respiratory system. The substance was detected in extracts from 3 products at moderate concentrations. Due to the strict classification the substance has been included for further evaluation.

Vanillin, CAS no. 121-33-5, is not classified in the List of dangerous substances. The substance was detected in extracts from 12 out of 15 products and even if the concentrations were low the substance has been selected for further evaluation.

Xylene, CAS no. 95-47-6, is classified R10 Xn;R20/21 Xi;R38, i.e. Flammable, Harmful by inhalation and in contact with skin and Irritating to skin. The substance was detected in extracts from 2 products at trace level.

Summary of selected substances

For evaluation of individual substances the following substances have been selected in co-operation with the Danish Environmental Protection Agency.

Of organic substances:

2-Butoxyethanol

2-(2-Butoxyethoxy)ethanol

Cyclohexanone

2,6-Dimethoxybenzoquinone

3,6-Dimethyl-1,4-dioxan-2,5-dione

(3,6-Dimethyl-2,5-dioxo-1,4-dioxane)

2-Ethoxyethanol

(2-(2-Ethoxyethoxy)ethanol

Formamide

Furfural

4-Hydroxy-3,5-dimethoxy-benzaldehyde

N-Methyl-2-pyrrolidone

3,5,5-Trimethyl-2-cyclohexen-1-one (= Isophorone)

Vanillin

Of inorganic substances:

Barium

| Front page | | Contents | | Previous | | Next | | Top |

Version 1.0 July 2005, © Danish Environmental Protection Agency