Survey and release of chemical substances in "slimy" toys

4 Screening for possible harmful effects

4.1 Screening by “headspace”

For the screening of possible harmful substances the purchased products were analysed by headspace, i.e. evaporation from slimy toys (cf. section of methods). This means that the detected amounts of released substances (µg per g slimy toys) calculated from total VOC must be handled with some caution. The numerical values, however, give a certain impression of relative amounts (cf. analysis method description and total result in Enclosure C).

The preliminary qualitative screening was performed as a headspace analysis. The toys were placed in a plastic bag together with adsorbent at room temperature (approx. 20C) for 24 hours to collect all potential volatile compounds. The gas samples were analysed by capillary column gas-chromatography combined with mass spectrometer detection (GC-MS). The results show which organic compounds that evaporate from the slimy toys and their mutual relative proportion. A summary is shown in Table 3.2.

At the preliminary headspace analyses, all the substances, which might evaporate from the slimy toys (except for light aldehydes) are identified. 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), were found 61 identified single substances and various groups of substances consisting of various aliphatic and aromatic hydrocarbons, which are stated in groups characterised by the number of carbon-atoms, and finally 6 compounds, which could not be identified.

4.1.1 Screening for possible harmful effects on the basis of the headspace analyses

Based on the identified chemical compounds a screening for possible volatile 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 migration of the chemical substance is too high.

A number of volatile substances were detected, which might be considered to be problematic substances, and some, which may be of concern. These substances are shortly reviewed below as well as other classified substances. The substances are presented in alphabetical order (Table 4.1).

Table 4.1 Classification of substances detected in headspace analysis

Component CAS no. Classification  
Benzaldehyde 100-52-7 Xn;R22 Harmful. Harmful if swallowed
Butanal 123-72-8 F;R11 Highly flammable
Butanol 71-36-3 R10 Xn;R22 Xi;R37/38-41 R67 Flammable. Harmful. Harmful if swallowed. Irritant. Irritating to respiratory system and skin. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness
Butandiol + alcohol, e.g. ethanol, 2-propanol 110-63-4+    
Dimethyl-1,4-dioxane (C6
H12 O2) or similar
e.g. 10138-17-7    
2-Butanone 78-93-3 F;R11 Xi;R36 R66 R67 Highly flammable. Irritant. Irritating to eyes. Repeated exposure may cause skin dryness or cracking. Vapours may cause drowsiness and dizziness
2-Butoxyethanol 111-76-2 Xn;R20/21/22 Xi;R36/38 Harmful. Harmful by inhalation, in contact with skin and if swallowed. Irritant. Irritating to eyes and skin
n-Butylether 142-96-1 R10 Xi;R36/37/38 Flammable. Irritant. Irritating to eyes, respiratory system and skin
3-Carene 13466-78-9    
3-Carene 80-56-8    
Cyclohexanol 108-93-0 Xn;R20/22 Xi;R37/38 (conc.) Harmful. Harmful by inhalation and if swallowed. Irritant. Irritating to respiratory system and skin
Cyclohexanone 108-94-1 R10 Xn;R20 (conc.) Flammable. Harmful. Harmful by inhalation
2-Cyclohexen-1-one 930-68-7    
d-Limonene 5989-27-5 R10 Xi;R38 R43 N;R50/53 Flammable. Irritant. Irritating to skin. May cause sensitization by skin contact. Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment
Decanal 112-31-2    
2-Decanone 693-54-9    
Dichlormethan 75-09-2 Carc3;R40 Limited evidence of carcinogenic effects
1,1-Dimethoxypropane 4744-10-9    
N,N-Dimethylformamide 68-12-2 Rep2;R61 Xn;R20/21 Xi;R36 Reprotox. cat 2. May impair fertility. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to eyes
Dodecanal 112-54-9    
Ethanol 64-17-5 F;R11 Highly flammable
Ethylacetate 141-78-6 F;R11 Xi;R36 R66 R67 Highly flammable. Irritant. Irritating to eyes. Repeated exposure may cause skin dryness or cracking. Vapours may cause drowsiness and dizziness
Ethylbenzene 100-41-4 F;R11 Xn;R20 Highly flammable. Harmful. Harmful by inhalation
2-Ethylbutanal 97-96-1    
2-Ethyl-1-hexanol 104-76-7    
Eucalyptol (C10H18O) 470-82-6    
Heptanal 111-71-7    
Heptanol 53535-33-4    
2-Heptanone 110-43-0 R10 Xn;R20/22 Flammable. Harmful by inhalation and if swallowed
3-Heptanone 106-35-4 R10 Xn;R20 Xi;R36 Flammable. Harmful by inhalation. Irritant. Irritating to eyes
2-Heptenal 18829-55-5    
Hexanal 66-25-1    
2-Hexanone 591-78-6 R10 T;R48/23 Rep3;R62 R67 Flammable. Toxic: danger of serious damage to health by prolonged exposure through inhalation Possible risk of impaired fertility. Vapours may cause drowsiness and dizziness
1-Methoxy-2-propanol 107-98-2 R10 Flammable
3-Methylbutanal 590-86-3    
2-Methyl-1-propaneol 78-83-1 R10 Xi;R37/38-41 R67 Flammable. Irritant Irritating to respiratory system and skin. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness
Nonanal 124-19-6    
Nonanol 143-08-8    
Octane 111-65-9 F;R11 Xi;R38 Xn;R65 R67 N;R50/53 Highly flammable. Irritant. Irritating to skin. Harmful. Harmful: may cause lung damage if swallowed. Vapours may cause drowsiness and dizziness. Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment
Octanal 124-13-0    
2-Octanone 111-13-7    
2-Octen-1-ol 18409-17-1    
2-Pentanone 107-87-9    
2-Phenoxyethanol 122-99-6 Xn;R22 Xi;R36 Harmful. Harmful if swallowed. Irritant. Irritating to eyes
alpha-Pinene 80-56-8    
beta-Pinene 127-91-3    
1-Propanol 71-23-8 F;R11 Xi;R41 R67 Highly flammable. Irritant. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness
2-Propanol 67-63-0 F;R11 Xi;R36 R67 Highly flammable. Irritant. Irritating to eyes. Vapours may cause drowsiness and dizziness
1,2-Propanediol 4254-15-3    
2-Propenoic acid 2 methyl-methylester (methylmethacrylat) 80-62-6 F;R11 Xi;R37/38 R43 Highly flammable. Irritant Irritating to respiratory system and skin. May cause sensitization by skin contact
1-Propenylbenzene 873-66-5    
Styrene 100-42-5 R10 Xn;R20 Xi;R36/38 Flammable. Harmful. Harmful by inhalation. Irritant. Irritating to eyes and skin
Tetrahydrofuran 109-99-9 F;R11 R19 Xi;R36/37 Highly flammable. May form explosive peroxides. Irritant. Irritating to eyes and respiratory system
Toluene 108-88-3 F;R11 Xn;R20 (NB changed at ATP29): F; R11 Repr.Cat.3; R63 Xn; R48/20-65 Xi; R38 R67 Highly flammable. Harmful. Harmful by inhalation Added classification; Possible risk of harm to the unborn child Toxic: danger of serious damage to health by prolonged exposure through inhalation – Harmful: may cause lung damage if swallowed. Irritant. Irritating to skin. Vapours may cause drowsiness and dizziness
3,3,5-Trimethylcyclohexen
-1-one
78-59-1 Xn;R21/22 Xi;R36/37 Carc3;R40 Harmful. Harmful in contact with skin and if swallowed. Irritant. Irritating to eyes and respiratory system. Limited evidence of carcinogenic effects
Undecanal 112-44-7    
m-, p-Xylene 108-38-3/106-42-3 R10 Xn;R20/21 Xi;R38 Flammable. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to skin
o-Xylene 95-47-6 R10 Xn;R20/21 Xi;R38 Flammable. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to skin
Aliphatic hydrocarbons etc.      
C7H14 and C7H16 aliphatic hydrocarbons      
C8 + C9 aliphatic
hydrocarbons
     
C8H16 e.g. 1678-91-7    
C9H12 + C10H14 aromatic hydrocarbons      
C9H12 aromatic
hydrocarbons
     
C9H20 aliphatic
hydrocarbons
     
C10-C14 aliphatic hydrocarbons      
C10H16      
C10H16O e.g. 5948-04-9    
C11-C14 aliphatic hydrocarbons      
C11-C14 aliphatic hydrocarbons + decahydronaphthalenes+ methyl decahydro-
naphthalenes + dimethyl decahydronaphthalenes
     
C11-C14 aliphatic hydrocarbons      

4.1.2 Proposal for selected organic substances

Benzaldehyde

Benzaldehyde, CAS no. 100-52-7, is classified Xn;R22, (Harmful. Harmful if swallowed). The substance is detected in 1 product (G-01).

Butanal

Butanal, CAS no. 123-72-8 is classified F;R11, i.e. highly flammable. The substance is detected in 4 products (F-01, TO-01, TO-02 and G-01).

Butanol

Butanol, CAS no. 71-36-3 is classified R10 Xn;R22 Xi;R37/38-41 R67, i.e. flammable. Harmful if swallowed. Irritant. Irritating to respiratory system and skin - Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness.

The substance is detected in 4 products (F-01, TO-03, G-01 and TI-01). The classification is rather serious, but the headspace analysis implies that the exposure may be expected to be rather low.

2-Butanone

2-Butanone, CAS no. 78-93-3, is classified F;R11 Xi;R36 R66 R67 (Highly flammable. Irritant. Irritating to eyes. Repeated exposure may cause skin dryness or cracking. Vapours may cause drowsiness and dizziness. The substance is detected in 1 product (TI-01), in the exterior “slime” as well as in the containing liquid. As the consumer is expected to be exposed to the liquid at some time, a closer assessment is recommended.

2-Butoxyethanol

2-Butoxyethanol, CAS no. 111-76-2 is classified Xn;R20/21/22 Xi;R36/38, i.e. harmful. Harmful by inhalation, in contact with skin and if swallowed. Irritant. Irritating to eyes and skin.

2-Butoxyethanol is readily absorbed after inhalation or through oral or dermal contact (IPCS 1998, CICAD 10). 2-Butoxy-ethanol is a glycol ether commonly used as a solvent in coatings such as varnish and paint.

The substance is detected in several of the slimy toys (6 out of 14 (DK-02, DK-03. F-01, TO-03, G-01 and R-01). Although the relative amounts are low in the screening, except for the liquid part of R-01, the detection should be assessed.

n-Butylether

n-Butylether, CAS no. 142-96-1 is classified R10 Xi;R36/37/38, i.e. flammable. Irritant. Irritating to eyes, respiratory system and skin . The classification is concentration-dependent. The analyses from the screening indicate low exposures in the 2 products (TO-02 and TI-01), in which the substance was detected

3-Carene

3-Carene is identified by CAS no. 13466-78-9 (3,7,7-trimethyl-bicyclo 4,1,0-hept-3-ene) and CAS no. 80-56-8 (2,6,6-trimethyl-bicyclo 3,1,1 hept-2-ene). The substance is not classified, but 3-carene is a terpene. The terpenes are generally irritants to the mucous membranes. Turpentine from coniferous trees is skin sensitising. However, the sensitisation has not been confirmed for the individual terpenes with the exception of 3-carene, CAS no. 13466-78-9 (ASS 2000).

The substance is not classified in itself but can be evaluated on the basis of the group of vegetable terpenes, which are classified under vegetable turpentine with the classification Harmful; Xn, and R20/21/22 Harmful by inhalation, in contact with skin and if swallowed. The substance is also classified R65 Harmful: may cause lung damage if swallowed. The substance is an Irritant, Xi, with R 36/38, Irritating to eyes and skin and with R43, May cause sensitization by skin contact. The substance is Dangerous to the environment, N, with R51/53, Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. In addition, the substance is flammable.

The substance was detected in 7 products (DK-02, DK-03, F-01, TO-03, G-01, TI-01 and BR-01) at low concentrations.

Cyclohexanol

Cyclohexanol, CAS no. 108-93-0, is classified Xn;R20/22 Xi;R37/38, i.e. Harmful. Harmful by inhalation and if swallowed. Irritant: irritating to respiratory system and skin. The classification is concentration-dependent. The substance was detected in 1 product (F-01) at a low concentration.

Cyclohexanone

Cyclohexanone, CAS no. 108-94-1, is classified R10 Xn;R20, i.e. Harmful. Harmful by inhalation. The classification is concentration-dependent. Inhalation may be an actual route of exposure for users of slimy toys. The substance was detected at the screening in 9 out of 14 slimy toys, and with considerably higher concentrations in the analysed liquids (cf. e.g. product K-01).

d-Limonene

d-Limonene, CAS no. 5989-27-5, is classified R10 Xi;R38 R43 N;R50/53, i.e. Irritant: Irritating to skin. May cause sensitization by skin contact. Limonene has been included in the List of Undesirable Substances, due to a reasoned suspicion that it may cause allergy (Miljøstyrelsen 2004). The substance was detected in 4 products (DK-02, DK-03, TO-03 and G-01), but all at low concentrations.

Dichlormethane

Dichloromethane, CAS no. 75-09-2, is classified Carc3;R40, i.e. Limited evidence of carcinogenic effects. The classification is rather serious for a substance in toys. The substance was detected in the liquid in 1 product (TI-01). An assessment would be appropriate.

N,N-Dimethylformamide

N,N-Dimethyl formamide, CAS no. 68-12-2, is classified Rep2;R61 Xn;R20/21 Xi;R36, i.e. toxic to reproduction in category 2. May impair fertility. Harmful by inhalation and in contact with skin. Irritant: irritating to eyes. The classification is serious, and even though the substance was only detected in one product (TO-02), a further evaluation seems to be necessary.

Ethyl acetate

Ethyl acetate, CAS no. 141-78-6, is classified F;R11 Xi;R36 R66 R67, i.e. Highly flammable. Irritant: irritating to eyes. Repeated exposure may cause skin dryness or cracking. Vapours may cause drowsiness and dizziness. The substance was detected in one product (K-03) at low concentrations.

Ethylbenzene

Ethylbenzene, CAS no. 100-41-4, is classified F;R11 Xn;R20, i.e. Harmful. Harmful by inhalation. (The classification is concentration-dependent).

According to other sources ethylbenzene is irritating to skin, eyes and mucous membranes and may influence the central nervous system (Budavari 1996, IPCS 1996).

The substance was detected in all products from low to very high concentrations. It is recommended to make a further evaluation of the exposure.

Eucalyptol

Eucalyptol (C10 H18 O) with CAS no. 470-82-6 (1,3,3-Trimethyl-2-oxabicyclo 2.2.2 octane), is not classified.

However, the substance reminds of other terpenes or terpenoid substances and may consequently be irritating to skin or mucous membranes. The substance was only detected in one product (K-01) at low concentration.

2-Heptanone

2-Heptanone, CAS no. 110-43-0, is classified R10 Xn;R20/22, i.e. Highly flammable. Harmful by inhalation and if swallowed. The substance was detected in one product (TI-01) at low concentrations from the exterior ”slime”, but at somewhat higher concentrations in the interior liquid.

3-Heptanone

3-Heptanone, CAS no. 106-35-4, is classified R10 Xn;R20 Xi;R36, i.e. Flammable. Harmful by inhalation. Irritant: irritating to eyes. The substance was detected in one product (TI-01) at low concentration.

Hexanal

Hexanal, CAS no. 66-25-1, is not classified. However, in literature it is mentioned that hexanal is irritating to respiratory systems, eyes (Grant 1986) and skin. The irritation has been observed on skin and in eyes of laboratory animals (Larsen et al. 1999). The substance was detected in 9 products (DK-01, DK-02, DK-03, BR-01, TO-01, TO-02, G-01, K-03 and TI-01) at low concentrations.

2-Hexanone

2-Hexanone, CAS no. 591-78-6, is classified R10 T;R48/23 Rep3;R62 R67, i.e. Flammable. Toxic: danger of serious damage to health by prolonged exposure through inhalation. Possible risk of impaired fertility. Vapours may cause drowsiness and dizziness.

The substance was detected in one product (TI-01), in exterior layer as well as in interior liquid. The classification is so serious that a further evaluation seems necessary.

1-Methoxy-2-propanol

1-Methoxy-2-propanol, CAS no. 107-98-2 is classified R10. Flammable. The substance was detected in 2 products (TO-01 and TO-03) at low concentrations.

2-Methyl-1-propanol

2-Methyl-1-propanol, CAS no. 78-83-1, is classified R10 Xi;R37/38-41 R67, i.e. Flammable. Irritant: irritating to respiratory system and skin. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness.

The substance was detected in 2 products (TO-03 gel and lip-gloss) at low concentrations.

Octane

Octane, CAS no. 111-65-9, is classified F;R11 Xi;R38 Xn;R65 R67 N;R50/53, i.e. Highly flammable. Irritant: irritating to skin. Harmful. Harmful: may cause lung damage if swallowed. Vapours may cause drowsiness and dizziness. The substance was detected in one product (TO-02) at a low concentration.

2-Phenoxyethanol

2-Phenoxy ethanol, CAS no. 122-99-6, is classified Xn;R22 Xi;R36, i.e. Harmful. Harmful if swallowed. Irritant: irritating to eyes. The substance was detected in one product (TO-03) in a small amount.

alfa-Pinene

alpha-Pinene, CAS no. 80-56-8, is not classified under its own name, but if it is included under vegetable turpentine (Miljøministeriet 2002), the classification is R10 Xn;R20/21/22-65 Xi;R36/38 R43 N;R51/53, i.e. Flammable. Harmful. Harmful by inhalation, in contact with skin and if swallowed. Harmful: may cause lung damage if swallowed. Irritant. Irritating to eyes and skin. May cause sensitization by skin contact. Finally vegetable turpentine is toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment

The substance is moderately toxic by intake, but very toxic by inhalation (Lewis 1992) and a strong irritant to eyes, mucous membranes and skin (Budavari 1996, Lewis 1992). alpha-Pinene is known to be a contact-allergen (Thomsen 1990). The substance was detected in 9 products (DK-01, DK-02, DK-03, K-01, F-01, TO-03 (gel and lip-gloss), G-01 and TI-01) at low concentrations.

1-Propanol

1-Propanol, CAS no. 71-23-8, is classified F;R11 Xi;R41 R67, i.e. Highly flammable. Irritant. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness. The substance was detected in 2 products (TO-02 and TO-03) at low concentrations.

2-Propanol

2-Propanol, CAS no. 67-63-0, is classified F;R11 Xi;R36 R67, i.e. Highly flammable. Irritant: irritating to eyes. Vapours may cause drowsiness and dizziness. The substance was detected in one product (TO-03) at low concentration.

1,2-Propanediol

1,2-Propanediol, CAS no. 4254-15-3, is not classified, but it was detected in 2 products (TO-03 and BR-01), and in one of them (TO-03 gel) at high concentrations. It is therefore suggested to make a further evaluation of the substance.

2-Propenoic acid 2 methyl-methylester (methylmethacrylat)

2-Propenoic acid 2 methyl-methyl ester, (methylmethacrylate), CAS no. 80-62-6 is classified F;R11 Xi;R37/38 R43, i.e. Highly flammable. Irritant. Irritating to respiratory system and skin. May cause sensitization by skin contact.

The substance was detected in one product (TO-03 gel). Based on the classification it is suggested to examine the exposure more closely.

Styrene

Styrene, CAS no. 100-42-5, is classified R10 Xn;R20 Xi;R36/38, i.e. Flammable. Harmful. Harmful by inhalation. Irritant Irritating to eyes and skin. The classification is concentration-dependent. The health effects of concern are that styrene is considered to be neuro-toxic. Influence on the neurological development seems to be the most sensitive effect, which has been found.

The substance was detected in 2 products (TO-02 and TO-03) at low concentrations.

Tetrahydrofuran

Tetrahydrofuran, CAS no. 109-99-9, is classified F;R11 R19 Xi;R36/37, i.e. Highly flammable. May form explosive peroxides. Irritant. Irritating to eyes and respiratory organs.

The substance was detected in 2 products (K-03 and TI-01) at low concentrations.

Toluene

Toluene, CAS no. 108-88-3, is classified F;R11 Xn;R20, i.e. Highly flammable. Harmful. Harmful by inhalation. However, it should be noted that the classification has been made more rigorous (ATP 29) as follows:

F; R11 Repr.Cat.3;R63 Xn; R48/20-65 Xi; R38 R67, i.e. Possible risk of harm to the unborn child. Toxic: danger of serious damage to health by prolonged exposure through inhalation. - Harmful: may cause lung damage if swallowed. Irritant. Irritating to skin. Vapours may cause drowsiness and dizziness.

The substance was detected in all products. In one product (K-01) toluene was found in quite large amounts, in the exterior part of the toy as well as in the liquid inside. Based on the widespread occurrence and the classification the exposure should be examined more closely.

3,3,5-Trimethylcyclohexen-1-one

3,5,5-Trimethyl-2-cyclohexen-1-one, CAS no. 78-59-1, is classified Xn;R21/22 Xi;R36/37 Carc3;R40, i.e. Harmful. Harmful in contact with skin and if swallowed. Irritant. Irritating to eyes and respiratory system. Carc3: Limited evidence of carcinogenic effects.

The substance was detected in 3 products (TO-03 (gel and lip-gloss) and TI-01) at low concentrations. Nevertheless, a further evaluation is recommended based on the classification.

Xylene

m-, p- and o-Xylene, with CAS no. 108-38-3 / 106-42-3 / 95-47-6, is classified R10 Xn;R20/21 Xi;R38, i.e. Flammable. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to skin. The classification is concentration-dependent.

The substances were detected in most of the products. In the screening analyses xylenes are hardly separable from ethylbenzene. Xylene was detected in a very high concentration (BR-01), and in another product ethylbenzene and xylene occur as the total mixture (100%). The exposure should be further evaluated.

Aliphatic hydrocarbons

The aliphatic hydrocarbons are presented one by one or in groups like e.g.:

C7H14 and C7H16 aliphatic hydrocarbons

C8 + C9 aliphatic hydrocarbons

C9H20 aliphatic hydrocarbons

C10-C14 aliphatic hydrocarbons

C11-C14 aliphatic hydrocarbons

C11-C14 aliphatic hydrocarbons + decahydronaphthalenes+ methyldecahydronaphthalenes + dimethyldecahydronaphthalenes

C11-C14 aliphatic hydrocarbons

The aliphatic hydrocarbons may be chained or branched.

The alkanes C9-19 (nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane) have been grouped in the measurements. Dermatitis, irritation, influences on the central nervous system and anaesthetic effects have been observed for many of the aliphatic hydrocarbons. The effects are increased by increased molecular weight.

The alkanes, C12-26-branched and chained, are adopted on the List of Dangerous Substances under CAS no.: 90622-53-0, EINECS no.: 292-454-3 (Miljøministeriet 2002) with the classification: Carc2;R45, i.e. May cause cancer.

Aromatic hydrocarbons

The aromatic hydrocarbons are presented one by one or in groups, like e.g.:

C8H16 E.g. 1678-91-7 (ethyl cyclohexane)

C9H12 + C10H14 aromatic hydrocarbons

C9H12 aromatic hydrocarbons

C10H16O e.g. 5948-04-9 (2-methyl-5-(1-methylethenyl)-cyclohexanone)

C11-C14 aromatic hydrocarbons + decahydronaphthalenes + methyldecahydronaphthalenes + dimethyldecahydronaphthalenes

A further evaluation will be complicated by the fact that they are grouped in the analysis.

Aldehydes – in general

Aldehydes are typically volatile organic compounds characterised by their irritating properties. Aldehydes irritate skin, eyes and the upper respiratory tract. The low molecular weight aldehydes, the halogenated aliphatic aldehydes, and the unsaturated aldehydes are particularly irritating. The mucous membranes of the nasal and oral passages and the upper respiratory tract are affected, producing a burning sensation, an increased ventilation rate, bronchial constriction, choking, and coughing. The eyes tear, and a burning sensation is noted on the skin of the face. During low exposures, the initial discomfort may abate after 5 to 10 minutes), if the exposure is ceased but the sensation will recur if exposure is resumed after the interruption (Clayton and Clayton 1981).

4.1.3 Proposal for selected inorganic substances

ICP screening showed trace occurrence of a number of substances. They are evaluated to be present in the form of inorganic compounds, which are included in the manufacturing of the product, fillers and pollutants in fillers or residues from dyes.

The majority of the substances are close to the limits of detection. The few that occur in larger amounts, are most frequently substances, which are less essential in this context, such as sodium, calcium and other salts. One single exception is boron, which has been quantitatively determined.

Boron

The assessment could be based on studies on boric acid, CAS no. 10043-35-3, which is proposed classified Repr.Cat.2;R60 - 61, i.e. May impair fertility and may cause harm to the unborn child.

Boron was detected in large amounts in 2 products (DK-01, TO-01), and a further evaluation is recommended.

Nickel

Nickel is classified: Carc3;R40 R43. Most nickel compounds are classified allergenic - R43, i.e. May cause sensitization by skin contact.

A number of nickel compounds are either known carcinogenic or are suspected carcinogenic such as e.g. nickel carbonate and nickel sulphate.

Skin contact with nickel is very essential, as most nickel compounds may cause allergenic reactions at sensitised persons.

Nickel was detected in the screening in 2 products (TO-01 and A-01), however in small amounts. Based on the allergenic properties of nickel a further evaluation is recommended.

4.1.4 Conclusion headspace

Based on the above arguments the following substances are suggested for a further evaluation:

Organic substances:

2-Butanone

2-Butoxyethanol

Cyclohexanone

Dichlormethan

N,N-Dimethylformamide

Ethylbenzene

2-Hexanone

1,2-Propanediol

2-Propenoic acid 2 methyl-methylester (methylmethacrylat)

Toluene

3,3,5-Trimethylcyclohexen-1-one

Xylene

Inorganic substances

Boron

Nickel

Based on the detected substances the following slimy toys are suggested for quantitative analyses and further evaluation of the selected substances:

TI-01, green liquid-filled stick

Based on the detection of 2-butanone, dichloromethane, 2-hexanone and 3,3,5-trimethylcyclohexen-1-one.

R-01, green liquid-filled ball with spikes

Based on the detection of 2-butoxy-ethanol.

K-01, yellow, transparent ball with insect inside

Based on the detection of cyclohexanone and toluene.

TO-02, hard plastic container with green slime inside

Based on the detection of N,N-dimethyl formamide.

BR-01, pink transparent liquid-filled softball with insect inside

Based on the detection of ethylbenzene and xylene.

A-01, transparent liquid-filled disc with stars inside

Based on the detection of ethylbenzene and nickel.

TO-03, blue gel for hair, skin and lips

Based on the detection of 1,2-propanediol, 2-propenoic acid 2 methyl-methyl ester (methyl-methacrylate) and 3,3,5-trimethylcyclohexen-1-ol.

DK-01, multicoloured rubbery saurian

Based on the detection of boron.

TO-01, green slime with insects inside

Based on the detection of boron and nickel.

4.2 Screening of possible harmful effects based on the migration analyses

Migration analyses have been carried out in order to screen for possible harmful substances, which may be released from slimy toys when getting in contact with the consumer. The analyses have been made with artificial sweat in order to assess the release at skin contact (dermal contact) and with artificial saliva in order to assess the release when putting the toys in the mouth (oral contact). At the analysis 1-2 g weighed sample has been used, added 20 ml artificial saliva solution or artificial sweat solution and extracted for 4 hours in an incubator at 40C, cf. section of methods.

This means the detected amounts of released substances (µg per g slimy toys) are quantitative measurements over 4 hours, during which all potentially migrating compounds are collected (cf. analysis method description and total result in Enclosure D). A summary is presented in Table 4.2.

At the migration analyses of the 14 slimy toys (of which a few were analysed on exterior part and interior part, totally 17 analyses) were found 22 identified single substances and 3 groups of substances, e.g. aliphatic hydrocarbons or hydrocarbons with carbon chain lengths above C14, and finally a group of 6 compounds, which could not be identified, but they were all fatty acids.

4.2.1 Screening by migration

Based on the identified chemical compounds a screening for possible harmful substances among the migrated 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 substances from the slimy toys is too high.

Ten substances were detected, which might be considered problematic substances, and some, which may be of concern. These substances are shortly summarised below in Table 4.2 as well as the detected classified substances. The substances are presented in alphabetical order.

Table 4.2 Classification of substances detected in artificial sweat- and saliva extract analysis

Component CAS no. Classification  
Benzoic acid butylester 136-60-7 Xn;R22 N;R51/53 (Advisory list) Harmful. Harmful if swallowed
Benzoic acid phenylester 93-99-2 R43 N;R51/53 (Advisory list) May cause sensitization by skin contact
Benzoic acid propylester 2315-68-6    
Butylparabene 94-26-8    
Cyclohexanone 108-94-1 R10 Xn;R20 Flammable. Harmful. Harmful by inhalation
Diethylglycol dibenzoate or similar 120-55-8    
Ethanol-2-(butoxyethoxy)-acetate 112-15-2    
Ethylparabene 120-47-8    
Methyldihydrojasmonate 24851-98-7    
5-Methyl-2-(1-methylethyl-cyclohexanol) 23283-97-8    
Methylparabene 99-76-3    
Naphthalene 91-20-3 Xn;R22 N;R50/53 (changed in ATP29): Carc. Cat.3; R40 Xn; R22 N; R50-53 Harmful. Harmful if swallowed Limited evidence of carcinogenic effects
2-Phenoxyethanol 122-99-6 Xn;R22 Xi;R36 Harmful. Harmful if swallowed. Irritant. Irritating to eyes
2-Phenylmethylenoctanal (=hexylcinnamaldehyde) 101-86-0   Reasoned suspicion of allergenic fragrance (List of undesirable substances)
1,2-Propandion-1-phenyl-2-oxime 119-51-7 R43 (Advisory list) May cause sensitization by skin contact
N-Propylbenzamide + N-acetylbenzamide 10546-70-0, 1575-95-7    
Propylparabene 94-13-3    
Toluene 108-88-3 F;R11 Xn;R20 (NB changed in ATP29): F; R11 Repr.Cat.3; R63 Xn; R48/20-65 Xi; R38 R67 Highly flammable. Harmful. Harmful by inhalation. Added: Possible risk of harm to the unborn child. Toxic: danger of serious damage to health by prolonged exposure through inhalation – Harmful: may cause lung damage if swallowed. Irritant. Irritating to skin. Vapours may cause drowsiness and dizziness
o-, m-, p-Xylene 95-47-5, 108-38-3, 106-42-3 R10 Xn;R20/21 Xi;R38 Flammable. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to skin
Ethylbenzene 100-41-4 F;R11 Xn;R20 Highly flammable. Harmful. Harmful by inhalation
3,3,5-Trimethylcyclohexen-1-one 78-59-1 Xn;R21/22 Xi;R36/37 Carc3;R40 Harmful. Harmful in contact with skin and if swallowed. Irritant. Irritating to eyes and respiratory system. Limited evidence of carcinogenic effects
       
Aliphatic hydrocarbon >C14      
Hydrocarbons >C14      
Fatty acids      

4.2.2 Proposal for selected organic substances

At the migration analysis, using artificial saliva and sweat, the same substances - more or less - were detected, and frequently in approximately the same concentrations.

Benzoic acid butylester

Benzoic acid butylester, CAS no. 136-60-7, is not classified in the List of Dangerous Substances, however it is self classified Xn;R22 N;R51/53 (Advisory list, Miljøstyrelsen 2001), i.e. Harmful. Harmful if swallowed. The substance was detected in 2 products; one of them, however, only in small amounts.

Benzoic acid phenylester

Benzoic acid phenylester, CAS no. 93-99-2, is not classified in the List of Dangerous Substances, however it is self classified R43 N;R51/53 (Advisory list), i.e. May cause sensitization by skin contact. Like the above-mentioned, the substance was detected in 2 products.

Benzoic acid propylester

Benzoic acid propylester, CAS no. 2315-68-6, is not classified but follows the two above-mentioned benzoic acid esters. The substance was detected in 3 products.

Parabenes

Four parabenes were detected:

Methylparabene, CAS no. 99-76-3

Ethylparabene, CAS no. 120-47-8

Propylparabene, CAS no. 94-13-3

Butylparabene, CAS no. 94-26-8

Parabenes is the name of a group of chemical substances, which are frequently used as preservatives in cosmetics, food and medicaments to prevent bacterial- and fungal growth in the products. It is often noted that the substances are endocrine disrupters. Parabenes are very slightly allergenic, and they rarely cause allergy. Parabene allergy is particularly observed at persons, which have had severely chronic eczema and/or venous leg ulcer, where the skin is frail making it easier for the allergenic substances to penetrate the skin.

The substances were detected in 3 products at low concentrations. Apparently the concentrations are below levels, which might cause problems.

Cyclohexanone

Cyclohexanone, CAS no. 108-94-1, is classified R10 Xn;R20, i.e. Flammable. Harmful. Harmful by inhalation. The substance was detected in 4 products, but only one of them (TO-01) in large amounts.

Diethylglycol dibenzoate

Diethylglycol dibenzoate or the like, CAS no. e.g. 120-55-8, is not classified. However, the substance occurs in considerable amounts, for which reason an evaluation would be appropriate.

Naphthalene

Naphthalene, CAS no. 91-20-3, is classified Xn;R22 N;R50/53, and the classification is further updated in ATP29 with Carc. Cat.3;R40, i.e. Limited evidence of carcinogenic effects. However, the substance was only detected in one product in trace concentrations.

2-Phenoxy ethanol

2-Phenoxy ethanol, CAS no. 122-99-6 is classified Xn;R22 Xi;R36, i.e. Harmful. Harmful if swallowed. Irritant. Irritating to eyes. The substance was detected in 4 products and in large amounts in one of them (TO-03, gel). A further evaluation is suggested.

2-Phenyl-methyleneoctanal

2-Phenyl-methyleneoctanal (=Hexylcinnamaldehyde), CAS no. 101-86-0, is not classified in the List of Dangerous Substances. However, there is a reasoned suspicion that the substance is an allergenic fragrant according to the List of Undesirable Substances. The substance was detected in one product (TO-03, gel) at a low concentration.

1,2-Propandione-1-phenyl-2-oxime

1,2-Propandione-1-phenyl-2-oxime, CAS no. 119-51-7 is not classified in the List of Dangerous Substances, but it is self-classified R43 (Advisory list), i.e. May cause sensitization by skin contact. The substance was detected in 2 products at low concentrations.

Benzamide

N-Propyl benzamide + N-acetyl benzamide, CAS no. 10546-70-0 and 1575-95-7, are not classified in the List of Dangerous Substances. The substance was detected in 2 products and in an average amount in one of them (TO-01). A further evaluation is suggested.

Toluene

Toluene, CAS no. 108-88-3, is classified F;R11 Xn;R20, i.e. Highly flammable. Harmful. Harmful by inhalation. As mentioned under ”headspace” the classification is more rigorous in ATP 29 with:

Repr.Cat.3;R63 Xn;R48/20-65 Xi;R38 R67, i.e. Possible risk of harm to the unborn child. Toxic: danger of serious damage to health by prolonged exposure through inhalation – Harmful: may cause lung damage if swallowed. Irritant. Irritating to skin. Vapours may cause drowsiness and dizziness.

The substance was detected in 11 products. Although the concentrations are very low, an evaluation is suggested.

Xylene

o-, m-, p-Xylene, CAS no. 95-47-5, 108-38-3, 106-42-3, is classified R10 Xn;R20/21 Xi;R38 (concentration- dependent), i.e. Flammable. Harmful. Harmful by inhalation and in contact with skin. Irritant. Irritating to skin. The substance was detected together with ethylbenzene in 3 products at low concentrations. An evaluation is suggested.

Ethylbenzene

Ethylbenzene, CAS no. 100-41-4, is classified F;R11 Xn;R20, i.e. Highly flammable. Harmful. Harmful by inhalation. The substance was detected together with xylene in 3 products at low concentrations. An evaluation is suggested.

3,3,5-Trimethylcyclohexen-1-one

3,3,5-Trimethylcyclohexen-1-one, CAS no. 78-59-1, is classified Xn;R21/22 Xi;R36/37 Carc3;R40, i.e. Harmful. Harmful in contact with skin and if swallowed. Irritant. Irritating to eyes and respiratory system. Limited evidence of carcinogenic effects. The substance was detected in 4 products at low concentrations. Due to the severe classification an evaluation is suggested.

4.2.3 Conclusion based on the migration analyses

On the basis of the above arguments the following substances are suggested for a further evaluation (previously mentioned substances under “headspace” are written in italics).

Cyclohexanone

Diethylglycol dibenzoate

2-Phenoxyethanol

N-Propylbenzamide + N-acetylbenzamide

Ethylbenzene

Toluene

3,3,5-Trimethylcyclohexen-1-ne

Xylene

Based on the detected substances the following slimy toys are suggested for quantitative analyses and a further evaluation of the selected substances:

TO-01, green slime with insects inside

Based on the detection of cyclohexanone, diethylglycol dibenzoate, N-propylbenzamide + N-acetylbenzamide.

TO-02, hard plastic container with green slime inside

Based on the detection of cyclohexanone, diethylglycol dibenzoate, N-propylbenzamide + N-acetylbenzamide.

TO-03, gel

Based on the detection of 2-phenoxyethanol.

TO-03, lip-gloss

Based on the detection of 3,3,5-trimethylcyclohexen-1-one.

K-01, yellow, transparent ball with insect inside

Based on the detection of toluene.

DK-01, multicoloured rubbery saurian

Based on the detection of toluene.

BR-01, pink transparent liquid-filled softball with insect inside

Based on the detection of ethylbenzene and xylene.

4.3 Conclusion on screening of possible harmful effects

On the basis of the above arguments the following substances are suggested for a further evaluation:

Organic substances

2-Butanone

2-Butoxyethanol

Cyclohexanone

Dichloromethane

Diethylglycol dibenzoate

N,N-Dimethyl formamide

Ethylbenzene

2-Hexanone

2-Phenoxyethanol

1,2-Propanediol

2-Propenoic acid 2-methyl-methyl ester (methylmethacrylate)

N-Propyl benzamide + N-acetyl benzamide

Toluene

3,3,5-Trimethylcyclohexen-1-one

Xylene

Inorganic substances

Boron

Nickel

On the basis of the detected substances the following slimy toys are suggested for a further evaluation:

TI-01, green liquid-filled stick

Based on the detection of 2-butanone, dichloromethane, 2-hexanone and 3,3,5-trimethylcyclohexen-1-one.

R-01, green liquid-filled ball with spikes

Based on the detection of 2-butoxyethanol.

K-01, yellow, transparent ball with insect inside

Based on the detection of cyclohexanone and toluene.

TO-02, hard plastic container with green slime inside

Based on the detection of N,N-dimethyl formamide, cyclohexanone, diethylglycol dibenzoate and N-propyl benzamide + N-acetyl benzamide.

BR-01, pink transparent liquid-filled softball with insect inside

Based on the detection of ethylbenzene and xylene.

A-01, transparent liquid-filled disc with stars inside

Based on the detection of ethylbenzene, xylene and nickel.

TO-03, blue gel for hair, skin and lips

Based on the detection of 1,2-propanediol, 2-propenoic acid 2-methyl-methyl ester (methylmethacrylate), 3,3,5-trimethylcyclohexen-1-one and 2-phenoxyethanol.

DK-01, multicoloured rubbery saurian

Based on the detection of toluene and boron.

TO-01, green slime with insects inside

Based on the detection of cyclohexanone, diethylglycol dibenzoate and N-propyl benzamide + N-acetyl benzamide, boron and nickel.

4.4 Selection of substances for quantitative determination

Based on above arguments and according to agreement with the Danish Environmental Protection Agency the following substances are selected for quantitative determination and preparation of exposure scenarios.

alpha-Pinene

2-Butanone

2-Butoxyethanol

3-Carene

Cyclohexanone

Diethylglycol dibenzoate

d-Limonene

Ethylbenzene

2-Hexanone

2-Phenoxyethanol

2-Phenylmethylene octanal

1,2-Propanediol

2-Propenoic acid 2-methyl-methyl ester (methyl-methacrylate)

N-Propyl benzamide + N-acetyl benzamide

Styrene

Toluene

Xylene

Boron (has been determined quantitatively and results are stated in section 3.5)

Nickel

 



Version 1.0 March 2006, © Danish Environmental Protection Agency