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Survey and health assessment of chemical substances in hobby products for children

3 Quantitative chemical analyses

In consultation with the Danish EPA we selected a number of the identified substances for quantification.

3.1 Applied method for the quantitative analyses

The quantitative analyses are based on GC/MS and X-ray analysis. The specific parameters for the applied method are described in the following:

3.1.1 Quantitative GC/MS analysis

3 different extractions have been made dependent on product type:

Marker pens and gel pens

Half of a marker pen equivalent to 0.1-1 g sample (excl. felt cartridge and depending on type), was extracted with 10 ml dichloromethane with bromobenzene and o-terphenyl as internal standards.

Glitter glue

1 g was weighed out, suspended in water and subsequently and extracted in 3 ml pentane with brombenzene and o-terphenyl as internal standards.

Acrylic paints

0.1 g weighed out and extracted in a mix of 10 ml methanol and 15 ml dichloromethane with brombenzene and o-terphenyl as internal standards.

The extracts were subsequently analysed by GC/MS.

Table 3.1 GC/MS analysis parameters

GC/MS-instrument Agilent HP 5973 ALS
GC-parameters Carrier gas: Helium, constant flow at 0.8 ml/min
Oven program.: 40 ºC in 0 min., 10 ºC/min. at 300 ºC, 300 ºC in 0 min.
Column: Zebron ZB-5ms w/Guardian, 30 m x 0,25 mm id., 0,25 µm film thickness
MS-parameters Autotune
Scan mode: 40-550 m/z
Solvent delay: 3.10 min

Calibration of the applied method is made from the detection limit to approx. 2-20 mg/g sample dependent on the individual parameter and the weighed-out sample. The detection limit appears from the following tables.

The uncertainty factor is calculated based on double determination and will appear from the following tables.

For the selected samples the extracts from the qualitative screening have been re-analysed. No weight and double determination have been recorded in connection with the qualitative determination, thus the uncertainty for these analyses cannot be determined.

3.1.2 X-ray measurement

The samples were cut in sizes to fit into the X-ray equipment.

The samples were analysed directly and the content of elements with atomic number higher than 10 were analysed against standards of pure elements or simple salts.

The degree of accuracy of the analysis method is ± 20 %.

Table 3.2 Parameters for X-ray analysis

X-ray equipment Wavelength dispersive X-ray equipment model Philips PW 2400 with UNIQUANT calculation program
Counting time 6-20 sec. per element
Power, tube 2400 W

3.1.3 Formaldehyde measurement

0.01-0.5 g sample was suspended in 5 ml water. The content of formaldehyde is derivated with PFBOA and analysed by SPME-GC/MS.

Table 3.3 GC/MS analysis parameters

GC/MS-instrument Thermo Electron DSQ
GC-parameters Carrier gas: Helium, constant pressure at 20 psi
Oven program.: 35 ºC for 5 min., 25º C/min. to 260 ºC held for 2 min.
Column: ZB-1MS, 20 m x 0,18 mm id., 0,18 µm film thickness
MS-parameters Autotune
Scan mode: 40-300 m/z
Solvent delay: 0,1 min
SPME-parameters SPME-fibre: 85µm Carboxen/PDMS

Calibration of the applied method has been made in the range of 0.05 -1500 mg/kg.

The detection limit for the applied analysis method is determined to 0.05 mg/kg and the uncertainty factors appear from Table 3.8.

3.1.4 Ingredients in marker pens

Table 3.4 Analysis results - marker pens mg/g (± standard deviation in mg/g)

Identification CAS-no. Product no. Detection limit
10
Purple		 10
Orange		 17
Red		 17
Light green
2-Ethoxy ethanol 110-80-5 - - - - 0,05-0,5
N,N-Dimethylacetamide 127-19-5 - - 0,22
(±0,01)		 0,40 0,01-0,1
Cyclohexanone 108-94-1 1,1
(±0,1)		 0,54 - - 0,01-0,1
2-Butoxy-ethanol 111-76-2 - - - - 0,01-0,1
Diethylene glycol 111-46-6 - - - - 0,1-1
Aniline* 62-53-3 - - - - 0,01-0,1
N-Methyl-aniline 100-61-8 - 0,44 - - 0,01-0,1
1,4-Dioxaspiro(4,5)decane 177-10-6 0,32
(±0,03)		 - - - 0,01-0,1
Pyrrolidinone 616-45-5 - - - - 0,01-0,1
p-Anisidine 104-94-9 - - - - 0,01-0,1
N-Methyl-p-anisidine 5961-59-1 - - - - 0,01-0,1
Triethanolamine 102-71-6 - - - - 3-30
3-Methoxy-4,7-dimethyl-1H-isoindol** 100813-60-3 0,16
(±0,01)		 0,27 - - 0,01-0,1
N-Phenyl-2-pyridinamine 6631-37-4 - - - - 0,01-0,1
4-(Diethylamino)-benzaldehyde 120-21-8 - - - - 0,01-0,1
4-(2-Cyanoethyl)methylamino-benzaldehyde*** 94-21-3 - - - - 0,3-3
bis(2-Ethylhexyl)-hexanedioic acid ester 103-23-1 0,32
(±0,02)		 0,35 - - 0,01-0,1

”-” Below the detection limit.

Table 3.4 Analysis results - marker pens mg/g (± standard deviation in mg/g)

Identification CAS-no. 45
Green		 45
White		 57
Orange		 57
Pink		 25
Pink		 25
Red		 Detection limit
2-Ethoxy ethanol 110-80-5 - - - - 19
(±3)		 7,4 0,05-0,5
N,N-Dimethylacetamide 127-19-5 - - - - - - 0,01-0,1
Cyclohexanone 108-94-1 - - - - - - 0,01-0,1
2-Butoxy-ethanol 111-76-2 - - - - - 0,11 0,01-0,1
Diethylene glycol 111-46-6 - - 16
(±2)		 >100 10
(±1)		 >100 0,1-1
Aniline* 62-53-3 0,22
(±0,05)		 - - - 0,11
(±0,02)		 - 0,01-0,1
N-Methyl-aniline 100-61-8 0,99
(±0,18)		 - 0,10
(±0,01)		 - - - 0,01-0,1
1,4-Dioxaspiro(4,5)decane 177-10-6 - - - - - - 0,01-0,1
Pyrrolidinone 616-45-5 - - - - 0,61
(±0,15)		 7,44 0,01-0,1
p-Anisidine 104-94-9 - - - 0,12 - - 0,01-0,1
N-Methyl-p-anisidine 5961-59-1 - - - 0,36 - - 0,01-0,1
Triethanolamine 102-71-6 - 13 - - - - 3-30
3-Methoxy-4,7-dimethyl-1H-isoindol** 100813-60-3 0,40
(±0,06)		 - - 0,24 - - 0,01-0,1
N-Phenyl-2-pyridinamine 6631-37-4 - - - 0,05 - - 0,01-0,1
4-(Diethylamino)-benzaldehyde 120-21-8 - - - 0,04 - - 0,01-0,1
4-(2-Cyanoethyl) methylamino-benzaldehyde*** 94-21-3 - - - 4,3 - - 0,3-3
bis(2-Ethylhexyl) hexanedioic acid ester 103-23-1 - - - - - - 0,01-0,1

”-” Below the detection limit
* The content of aniline is estimated against N-methyl-aniline.
** Content of 3-methoxy-4,7-dimethyl-1H-isoindol.
*** The compound is estimated against 4-(diethylamino)-benzaldehyde as the relevant standard could not be provided.

Table 3.5 Analysis results for sample no. 16, mg/g (± standard deviation in mg/g)

Identification CAS-no. 16 Red** 16
Brown		 16 Orange 16
Yellow		 16
Black		 Detection limit
D-Limonene 5989-27-5 - - 0,21
(±0,04)		 - - 0,01
Benzyl alcohol 100-51-6 - - - - 0,96
(±0,05)		 0,01
5-Butyldihydro-2(3H)-Furanone* 104-50-7 - 0,43
(±0,13)		 - - - 0,01
Citral (3,7-dimethyl-2,6-octadienal) 5392-40-5 (trans: 106-26-3, cis: 141-27-5) - - 0,30
(±0,06)		 0,70
(±0,05)		 - 0,01
5-Hexyldihydro-2(3H)-furanone 706-14-9 0,07 0,28
(±0,13)		 - - - 0,01

”-” Below the detection limit
* The compound is estimated against 5-hexyldihydro-2(3H)-Furanone, as the relevant standard could not be provided.
** The precise weight and the uncertainty factor is not known as it is extracted in connection with the qualitative screening. The result is calculated against an average weight of no. 16, brow.

3.1.5 Ingredients in acrylic paint

Table 3.6 Analysis results for acrylic paint, mg/g (± standard deviation in mg/g)

Identification CAS-no. Product no. Detection limit
54
Red		 55
Ligth green		 61
Cubber
Chloroaniline 106-47-8 - 0.37
(±0.08)		 - 0.1
2-Propenoic acid, 2-ethylhexyl ester 103-11-7 - - 0.35
(±0.08)		 0.1
Propanoic acid, 2-methyl-, 2,2-dimethyl-1-(2-hydroxy-1-methylethyl)propyl ester* 74367-33-2 - - 1.44
(±0.97)		 0.1
Propanoic acid, 2-methyl-, 3-hydroxy-2,4,4-trimethylpentyl ester* 74367-34-3 - - 1.79
(±0.03)		 0.1
2-Naphthalenol, 1-[(4-methyl-2-nitrophenyl)azo]- (Toluidine Red) 2425-85-6 104
(±11)		 - - 20

”-” Below the detection limit.
* The compound is estimated against 2-ethyhexyl-2-propenoic acid ester, as the relevant standard could not be provided.

Table 3.7 Elements in acrylic paint, mg/g

Identification CAS-no. 8
Black		 18
Pink		 34
Yellow		 35
Ultramarin		 36
Rose madder		 41 Detection limit
Chrome   - - - - - 0,034 0,01
Nickel   - - - - - - 0,01
Copper   - - - - - - 0,01
Zinc   - - 0,039 0,021 - - 0,01
Silver   - - - - - - 0,01
Tin   - 0,015 - - - 0,035 0,01
Barium   - - - - 0,10 - 0,01
Lead   0,021 - - - - - 0,01

”-” Below the detection limit.

Table 3.7 Elements in acrylic paint, mg/g

Identification CAS-no. 49
Silver		 51
Dark brown		 54
Red-302		 55
Ultra marin blue		 60
Silver		 61
Metallic cubber		 Detection limit
Chrome   - 0,047 - - - - 0,01
Nickel   - - - - - 0,043 0,01
Copper   - 0,059 - - - - 0,01
Zinc   - - - 0,017 - - 0,01
Silver   - - - - 0,025 - 0,01
Tin   0,075 0,013 - - 0,022 - 0,01
Barium   - - 160 0,61 5,0 5,1 0,01
Lead   - - 0,024 - - - 0,01

”-” Below the detection limit.

3.1.6 Content in glitter glue

Table 3.8 Formaldehyde in glitter glue

Product no. Formaldehyde
[mg/kg]		 Uncertainty factor
[%-RDS]
13 pink 0,43 2,1
15 red 59 9,6
23 green 0,06 18
26 purple 46 0,21
28 green 0,94 36
29 light blue 13 7,1
33 gold 63 0,80
38 0,59 17
50 purple 110 13
53 gold 9,5 11

Table 3.9 Analysis results - glitter glue, mg/g (± standard deviation in mg/g)

Identification CAS-no. Sample no. Detection limit
26
Silver		 29
Pink
Phenol 108-95-2 0.054
(±0,003)		 - 0.02
2-Phenoxy ethanol 122-99-6 - 0.24
(±0.01)		 0.02

”-” Below the detection limit

Table 3.10 Elements in glitter glue, mg/g

Identification CAS-no. Sample no. Detection limit
14
Red		 26
Gold		 28
Dark purple		 33
Green		 38 50
Orange
Chrome   0.17 0.066 - - - - 0.01
Copper   - - 0.12 0.015 - - 0.01
Zinc   - - - - 0.017 0.22 0.01
Tin   1.1 0.017 - - - - 0.01
Antimony   - - 0.22 - - - 0.01

”-” Below the detection limit

3.1.7 Elements in shrink plastic

Table 3.11 Elements in shrink plastic, mg/g

Identification CAS-no. Sample no. Detection limit
19 20 21 24 37
Aluminium   0.16 - - - 0.62 0.02
Silicium   0.096 - - - 0.21 0.02
Calcium   1.7 - - - 0.19 0.01
Titanium   11 - - - 17 0.01
Zinc   0.13 0.084 0.079 0.079 0.20 0.01

”-” Below the detection limit

The X-ray analysis revealed no other elements.

3.2 Comments on the results of the quantitative analyses

By a comparison of the findings of the quantitative analysis and the findings of the chemical screening it has been observed that the different colour variations in the same product often contain different components.

Within the scope of this project it has not been possible to analyse all colour variations of the selected products. Therefore, it is possible that one or more of the products may contain components with a larger content of the identified substances than recorded in the quantitative analyses, or may contain not identified hazardous substances, because the colour variation was not taken out for analysis.

These variations are also assumed to be the reason why more of the components, revealed by the qualitative screenings, were not detected in the same product in connection with the quantitative analyses, as these were carried out on different colours variations. In addition, deconvolution software was used in the qualitative analysis, making it possible to detect contents in small amounts, which could not subsequently be quantified.

Sample no. 4 was selected for the quantitative analysis. In the colour variation selected for the analysis it was not possible to detect any of the substances, which were identified in connection with the screening.

3.3 Legislation and standards

Liquids in marker pens, glue, and acrylic paint are thus covered by the requirements in Statutory Order No. 329 on classification, packaging, labelling, sale, and storage of chemical substances and products, 2002 cf. § 1 and § 2.

The Danish Safety Technology Authority has classified the hobby products to be covered by the regulations stipulated in the Statutory Order No. 1116 on toys.

The order stipulates that toys may not be marketed if they constitute a hazard to the safety or the health of the consumers. Appendix 2 of the order includes the limit values for heavy metals and states that toys may not contain dangerous substances or preparations as defined in directive 67/548/EØF and directive 88/379/EØF in amounts which may be hazardous to children.

As mentioned in the Statutory Order, Appendix 3, there are a number of standards regarding safety regulations for toys (DS/EN 71-1 to DS/EN 71-7). Three new standards have been completed for organic chemical substances (DS/EN 71-9, EN 71-10 and EN 71-11), but these standards are not harmonised.

This standard lay down requirements to accessible liquids in toys under item 4.2, saying that the liquids may not be classified as toxic, harmful, corrosive, irritant or sensitizing according to directive 1999/45/EC. Beyond this, there may not be any substances classified as carcinogenic, mutagenic or reprotoxic classified as category 1 and 2.

Table 1 standard EN 71-9 specifies limits for coloured liquids, as the requirements to colorants (table 2b) and primary aromatic amines (table 2C) shall be observed. Table 2c specifically mentions 4-chloraniline, o-anisidine and aniline, which were all found in the products. Under A11 it is stated that these substances may not be detected in toys according to (DS/EN 71-11).

It should be mentioned that the detected concentration of substances is in the range of 100-400 ppm, which is far beyond the detection limits stipulated in the standard.

The conclusion is that primary aromatic amines have been detected in marker pens and acrylic paint in concentrations beyond the requirements to the detection limits in (DS/EN 71-9 and DS/EN 71-11). Marker pens and acrylic paint with primary amines do not comply with the standards for content organic substances.

3.4 Prioritization of substances in hobby products

Based on the health screening described in chapter 2.2 and the quantitative analysis we have in consultation with the Danish EPA selected a number of substances for extended health assessment.

The substances are:

  • Aniline
  • P-chloroaniline
  • N-methylaniline
  • C.I. Pigment Red 3
  • N,N-Dimethylacetamide
  • Bis (2-ethylhexyl)adipate
  • p-anisidine
  • 2-ethoxy ethanol
  • Citral
  • 2-ethylhexyl acrylate

The health effects of formaldehyde have also been assessed.

Substances used for assessment of environmental effect:

  • Aniline
  • Chloraniline

These substances are extremely toxic for aquatic organisms and –chloraniline alone is difficultly degradable, and the substances are therefore suitable for assessment of a worst case effect.

 

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Version 1.0 May 2008, © Danish Environmental Protection Agency