2 Screening of product ingredients

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

2.1 Applied analysis method for screening
- 2.1.1 Qualitative GC/MS-screening
- 2.1.2 NIR-spectrometry screening of shrink plastic
2.2 Results - chemical screening
2.3 Selection of substances for quantification

Based on information achieved about substances collected during the survey phase, chemical screenings have been carried out for organic and inorganic components, respectively.

Dependent on product group (marker pens, glitter glue, gel pens, acrylic paint and shrink plastic) an analysis program has been set up for screening for content of harmful substances, therefore, this substance group has been put in focus in the chemical screening.

Apart from the screening quantitative X-ray analyses have been carried out for identification of inorganic substances in acrylic paint, glitter glue, and shrink plastic. The results are described in chapter 3, Quantitative chemical analyses.

The shrink plastic products have been screened by NIR-spectrometry to determine whether they contain PVC which may contain phthalates.

Table 1.2, Table 1.3, Table 1.4, Table 1.5, and Table 1.6 give an overview of the screenings of all products.

2.1 Applied analysis method for screening

The chemical screening is based on GC/MS-analysis and NIR-spectrometry, respectively. The specific parameters for the applied methods are described below.

2.1.1 Qualitative GC/MS-screening

From the qualitative GC/MS-screening of the products a number of partial samples were taken, with the objective of obtaining a wide choice of the different colour variations in the various products.

Depending on product type 3 different extractions have been made.

Marker pens and gel pens

Half of one marker pen has been analysed corresponding to 0.1–1 g sample (excl. felt cartridge and depending on type), which was extracted with 10 ml dichloromethane with bromobenzene and o-terphenyl as internal standards.

Glitter glue

Approx. 2 g glitter glue has been weighed out and subsequently suspended in water and extracted with 3 ml pentane with toluene-d₈ og naphthalene-d₈ additives as internal standards.

Acrylic paints

Approx. 0.1 g was weighed off and subsequently extracted in a mix of 10 ml methanol and 15 ml dichloromethane added bromobenzene and o-terphenyl as internal standards.

The extracts were then analysed by GC/MS chromatography. The analysis parameters used for GC/MS-analysis are shown in Table 2.1.

Table 2.1 GC/MS analysis parameters

GC/MS-instrument	Agilent HP 5973 ALS
GC-parameters	Carrier gas: Helium, constant flow at 1.5 ml/min. Oven program.: 35 ºC for 1 min., 10 ºC/min. to 325 ºC, 325 ºC for 2 min. Column: CP-sil 5CB, 25 m x 0,25 mm id., 0.25 µm film thickness
MS-parameters	Autotune Scan mode: 35-550 m/z Solvent delay: 3 min

In connection with the screening the detected components were alone identified through a comparison with the NIST MS-library. AMDIS was used as deconvolution software.

2.1.2 NIR-spectrometry screening of shrink plastic

One sheet of the shrink plastic with a radius of 40 mm was analysed directly in the NIR- instrument. The spectra were compared visually with spectra of the reference substances.

Table 2.2 NIR analysis parameter

NIR-instrument	Technicon 500
Analysis area	1000-2500 nm
Interval	5 nm

2.2 Results – chemical screening

The substances identified by the screening are summarised in the following tables.

The results have been classified in product types and the detected substances are marked by an ”X”. All identified substances are provided with CAS-no.

In connection with the screening there has not been made an assessment of the amount of the identified substances.

Within the scope of this project it was not possible to analyse all the colour variations in the analysed products. In order to investigate the variations of substances in one product, all the colour variations in product no. 16 was included in the chemical screening.

2.2.1 GC/MS-screening results - marker pens

Table 2.3 GC/MS screening results of markers pens

Identification

CAS-no.

Sample no.

Propylene glycol

57-55-6

N,N-Dimethylacetamide

127-19-5

3-Hexen-1-ol

544-12-7

Ethylbenzene and xylenes

100-41-4

1,3-Butanediol

107-88-0

1-Hydroxy-2-propanone

116-09-6

Cyclohexanone

108-94-1

1,2-Propanediol-2-acetate

6214-01-3

2-Butoxy-ethanol

111-76-2

Hexylene glycol

107-41-5

1,3-Dioxan

505-22-6

Diethylene glycol

111-46-6

Glycerine

56-81-5

o-Methylstyrene

611-15-4

2-Pyrrolidinone

616-45-5

N-Methyl-aniline

100-61-8

1,4-Dioxaspiro(4,5)decane

177-10-6

2-(2-(2-Methoxyethoxy)ethoxy)-ethanol acetate

3610-27-3

2-(2-Butoxyethoxy)-ethanol

112-34-5

Methenamine

100-97-0

1,2,3-Propantriol diacetate

102-62-5

Triethylene glycol

112-27-6

4,4-Dimethyl-2,5-dioxo-1-imidazolindinemethanol

16228-00-5

Tetramethylindoline

13034-76-9

1,2,3-Propantriol triacetate

102-76-1

5,5-Dimethyl-2,4-imidazolidinedione and similar compounds

77-71-4

1,3,3-Trimethyl-2-methylen indoline

118-12-7

3-Phenyl-2-propenoic acid methyl ester

103-36-6

3-Methoxy-4,7-dimethyl-1H-isoindole

100813-60-3

2,4,7,9-Tetramethyl-5-decyn-4,7-diol

126-86-3

1-Hexyl-3-butenyl acetate

2833-33-2

5-Hexyldihydro-2(3H)-Furanone

706-14-9

Tetraethylen glycol

112-60-7

3-Isopropyl-2,3-dimethyl-Indolin

18781-62-9

Carbamic acid, butyl-,3-iodo-2-propynyl ester

55406-53-6

4-(Diethylamino)-Benzaldehyde

120-21-8

2,2'-(Phenylimino)bis-ethanol

120-07-0

Pentaethylene glycol

4792-15-8

Trogers base

72151-03-2

Hexagol

2615-15-8

1,4-Benzen dicarboxyl acid bis(2-hydroxyethyl) ester

959-26-2

2-Butenedioic acid bis(2-ethylhexyl) ester

141-02-6

Cyclopentanecarboxylic acid octyl ester

100912-19-4

Heptaethylen glycol

5617-32-3

Oleic acid

112-80-1

bis-2(Ethylhexyl) hexanedioic acid ester

103-23-1

Diisooctyl phthalate

117-84-0

Octaethylen glycol

5117-19-1

Table 2.3 Results of GC/MS screening of marker pens

Identification

CAS-no.

Sample no.

Propylene glycol

57-55-6

2-Ethoxy ethanol

110-80-5

2-Butoxy-ethanol

111-76-2

Benzaldehyde

100-52-7

Diethylene glycol

111-46-6

Glycerine

56-81-5

1,1'-Oxydi-2-propanol

110-98-5

2-Ethyl-1-hexanol

104-76-7

Ditert.butoxy methane

2568-93-6

Acetophenone

98-86-2

1-Propanol, 3,3'-oxybis-

2396-61-4

Pyrrolidinone

616-45-5

1,2,3-Propantriol monoacetate

106-61-6

Chlorobenzaldehyde

89-98-5

2-Ethyl hexane acid

149-57-5

2-(2-Butoxyethoxy)-ethanol

112-34-5

p-Meth-1-en-8-ol

98-55-5

p-Anisidine

104-94-9

1,2,3-Propantriol diacetate

102-62-5

N-Methyl-p-anisidine

5961-59-1

Isobornyl acetate

125-12-2

Tetramethylindoline

13034-76-9

1,2,3-Propantriol triacetate

102-76-1

1,3,3-Trimethyl-2-methylene indoline

118-12-7

Triethanolamine

102-71-6

3-Methoxy-4,7-dimethyl-1H-isoindol

100813-60-3

Methylparabene

99-76-3

Tetraethylen glycol

112-60-7

N-Phenyl-2-pyridinamine

6631-37-4

4-(Diethylamino)-benzaldehyde

120-21-8

4-(2-Cyanoethyl)methylamino-benzaldehyde

94-21-3

Sorbitol

50-70-4

1,4-Benzenedicarboxylic acid bis(2-hydroxyethyl) ester

959-26-2

Table 2.4 Results of GC/MS-screening of sample no. 16

Identification	CAS-no.	Red	Green	Brown	Orange	Yellow	Light blue	Pink	Black
Propylene glycol (1,2-proanediol)	57-55-6	X		X	X	X	X	X	X
1-Butanol, 3-methyl-, acetate or isomer	123-92-2						X
3-Hexen-1-ol	544-12-7	X						X
Hexanal	66-25-1							X
1-Hexanol	111-27-3							X
1-Butanol, 3-methyl-, acetate or isomer	123-92-2						X
1,2-Propanediol, diacetate	623-84-7			X
D-Limonene	5989-27-5				X
Benzyl alcohol	100-51-6								X
Eucalyptol	470-82-6		X
2-Furanmethanol, 5-ethyenyltetrahydro-.alpha.,alpha.,5-trimethyl-,cis- (or isomer!)	5989-33-3					X
Benzene, methyl (1-methylethenyl)-	26444-18-8					X
1,3,7-Octatriene, 3,7-dimethyl or 3-carene	502-99-8				X
3-Caren	13466-78-9					X	X
Nonanal	124-19-6				X
Isopulegol	7786-67-6		X
Cyclohexanone, 5-methyl-2-(1-methylethyl)-	529-00-0		X
Acetic acid, phenylmethyl ester	140-11-4								X
L-menthol	2216-51-5		X
Menthol	89-78-1		X
Benzene, 1-methyl-4-(1-methylethenyl)	1195-32-0					X
Cyclohexanol, 5-methyl-2-(1-methylethyl)-, [1R-(1-alpha-,2.beta.,5.alpha.)]- or menthol or corresponding terpene	2216-51-5		X
Decanal	112-31-2				X
Pulegon	89-82-7		X
Beta-myrcene	123-35-3					X
2(3H)-Furanone, 5-butyldihydro-	104-50-7			X
2,6-Octadienal, 3,7-dimethyl-	5392-40-5				X	X
Isopulegolacetate	57576-09-7		X
Triacetin	102-76-1	X						X
Piperonal	120-57-0			X
cis-2,6-Dimethyl-2,6-octadien	2492-22-0					X
2-Propenoic acid, 3-phenyl-, methyl ester	103-26-4	X
Benzaldehyde, 3-hydroxy-4-methoxy-	621-59-0						X
Dodecanal	112-54-9				X
Caryophyllene	87-44-5		X
2(3H)-Furanone, 5-hexyldihydro-	706-14-9	X		X

2.2.2 GC/MS screening results – glitter glue

Table 2.5 GC/MS- screening results - glitter glue

Identification	CAS-no.	Sample No.
Identification	CAS-no.	53	33	28	13	14	15	23	26	29	38	50
Phenol	108-95-2								X
2-Ethyl-1-hexanol	104-76-7									X
2-Phenoxy ethanol	122-99-6	X	X	X						X
n-Alkanes (C21+)						X

2.2.3 GC/MS screening results - gel pens

Table 2.6 Results of GC/MS screening - gel pens

Identification	CAS-no.	Sample no.
Identification	CAS-no.	2	4	44
Diethylene glycol	111-46-6		X
Glycerine	56-81-5		X	X
Methylparabene	99-76-3		X
1H-Benzotriazole	95-14-7		X
BHT	128-37-0	X
3,3’-Dimethylbenzedine	119-93-7	X

2.2.4 GC/MS screening results - acrylic paints

Table 2.7 Results of GC/MS screening of acrylic paints

Identification	CAS-no.	Sample No.
Identification	CAS-no.	6	7	8	9	18	34	35	36	40
Propylene glycol	57-55-6						X
2-Butoxy-ethanol	111-76-2				X
Dipropylene glycol monomethyl ether	34590-94-8					X
Glycerine	56-81-5
1-(2-Methoxypropoxy)-2-propanol	13429-07-7					X
Benzoic acid, methyl ester	93-58-3				X
Chloroaniline	106-47-8	X
2,2,4-Trimethyl-1,3-pentandiol	144-19-4	X
2-(2-Butoxyethoxy)-ethanol	112-34-5	X	X	X
Propanoic acid, 2-methyl-, 2,2-dimethyl-1-(2-hydroxy-1-methylethyl)propyl ester	74367-33-2	X	X	X	X	X		X	X
Propanoic acid, 2-methyl-, 3-hydroxy-2,4,4-trimethylpentyl ester	74367-34-3	X	X	X	X	X	X	X	X
1-Dodecanol	112-53-8	X		X					X
Diethylene glycol dibenzoate	120-55-8				X
Bis(2-butoxyethyl) phthalate	117-83-9									X

Table 2.7 Results of GC/MS-screening of acrylic paints

Identification	CAS-no.	Sample no.
Identification	CAS-no.	41	48	49	54	55	51	61	60	56
Dipropylene glycol monomethyl ether	34590-94-8							X	X
Glycerine	56-81-5			X
1-(2-Methoxypropoxy)-2-propanol	13429-07-7							X	X
Chloroaniline	106-47-8					X
Chloroisocyanato benzene	104-12-1					X
2-Phenoxy ethanol	122-99-6	X
2-Propenoic acid, 2-ethylhexyl ester	103-11-7							X	X
1-Propanol, 2,2'-oxybis-	108-61-2						X
1-Propanol, 3,3'-oxybis-	2396-61-4						X
Propanoic acid, 2-methyl-, 2,2-dimethyl-1-(2-hydroxy-1-methylethyl)propyl ester	74367-33-2							X	X
Propanoic acid, 2-methyl-, 3-hydroxy-2,4,4-trimethylpentyl ester	74367-34-3							X	X
Butanedioic acid, bis(2-methylpropyl) ester	925-06-4						X
Butanedioic acid, methyl-, bis(1-methylpropyl) ester	57983-31-0						X
Hexanedioic acid, bis(2-methylpropyl) ester	141-04-8						X
2-Naphthalenol, 1-[(4-methyl-2-nitrophenyl)azo]- (Toluidine Red)	2425-85-6				X

2.2.5 NIR-spectrometry analysis of shrink plastic

Table 2.8 Results of NIR-screening of shrink plastic

Identification	CAS-no.	Sample no.
Identification	CAS-no.	19	20	21	24	37
Polystyrene	9003-53-6	x	x	x	x	X

2.3 Selection of substances for quantification

A number of different substances were identified by the initial chemical screening. In consultation with the Danish EPA a selection was made of the product substances to be quantified.

The selection was made on basis of the information stated in Table 2.9 and on a prioritization model which is described below.

Table 2.9 Substances detected by GC/MS by screening of selected products

Name	CAS-no.	Classification	Presence No. of products	Selected ¹
2-Ethoxy ethanol	110-80-5	REP2;R60-61 R10 Xn;R20/21/22	1	X
N,N-Dimethylacetamide	127-19-5	REP2;R61 Xn;R20/21	1	X
1-Hydroxy-2-propanone	116-09-6	** Not in list maybe as propanone XI;R36 R66	1
Cyclohexanone	108-94-1	R10 Xn;R20	1	X
2-Butoxy-ethanol	111-76-2	Xn;R20/21/22 Xi;R36/38	7
Hexylene glycol	107-41-5	Xi;R36/38	1
1,3-Dioxane	505-22-6	* Xn;R22	1
Benzaldehyde	100-52-7	Xn;R22	14
Diethylene glycol	111-46-6	Xn;R22	1	X
Phenol	108-95-2	T;R23/24/25 C;R34 Xn;R48/ 20/21/22 MUT3;R68	1	X
O-Methylstyrene	611-15-4	Xn;R20 N;R51/53	1
Pyrrolidone	616-45-5	* Xn;R22	2
Acetophenone	98-86-2	Xn;R22 Xi;R36	1
N-Methyl-aniline	100-61-8	T;R23/24/25—R;33- - N;50/53	1	X
1,4-Dioxaspiro(4,5)decane	177-10-6	* N;R50/53	1	X
Chloroaniline	106-47-8	CARC2;R45 T;R23/24/25 R43 N;R50/53	2	X
Chloroisocyanato benzene	104-12-1	* Xn;R22 R43	1	X
2-(2-(2-Methoxyethoxy)ethoxy)-ethanol acetate	3610-27-3	* R52/53	3
Chlorobenzaldehyde	89-98-5	C;R34	1
2-Ethyl hexan acid	149-57-5	REP3;R63	1
2-(2-Butoxyethoxy)-ethanol	112-34-5	Xi;R36	5
2-Phenoxy ethanol	122-99-6	Xn;R22 Xi;R36	5	X
2-Propenoic acid, 2-ethylhexyl ester	103-11-7	Xi;R37/38 R43	2	X
p-Anisidine	104-94-9	Tx;R26/27/28 R33 N;R50	1
Methenamine	100-97-0	F;R11 R42/43	1
2-Phenoxy ethanol	122-99-6	Xn;R22 Xi;R36	5
4,4-Dimethyl-2,5-dioxo-1-imidazolindinemethanol	16228-00-5	* Xn;R22	2
N-Methyl-p-anisidine	5961-59-1	* Mut3;R40 Carc3;R40 R43	2
1,2,3-Propantriol triacetate	102-76-1	** Not in list (eye irritation hsdb)	5
3-Phenyl-2-propenoic acid methyl ester	103-36-6	** Not in list, ethyl cinnamate pheromone	1
Triethanolamine	102-71-6	* R43	2
3-Methoxy-4,7-dimethyl-1H-isoindol	100813-60-3	**Not in list maybe as 3131-52-0 R41	2	X
1-Dodecanol	112-53-8	*N;R51/53	3
Methylparabene	99-76-3	Not in list, parabene (least hazardous)	3
5-Hexyldihydro-2(3H)-Furanon	706-14-9	** Not in list (chemid:LD50 rat intravenous=56 mg/kg)	1
1H-Benzotriazol	95-14-7	*Xn;R22	1
Butylized hydroxytoluene (BHT)	128-37-0	*Xn;R22;R50/53	1
N-Phenyl-2-pyridinamin	6631-37-4	*R43	3
Hexanedioic acid, bis(2-methylpropyl) ester = Diisobutyladipate)	141-04-8	*N;R51/53	1
4-(Diethylamino)-benzaldehyde	120-21-8	*Xn;R22	1
4-(2-Cyanoethyl)methylamino-benzaldehyde	94-21-3	** Not in list benzaldehyde is marked R22	2
3,3’-Dimethylbenzedine	119-93-7	Carc2;R45 Xn;R22 N;R51/53	1
1,4-Benzenedicarboxylic acid bis(2-hydroxyethyl) ester = Bis(hydroxyethyl)terephthalate	959-26-2	** Phthalate	4	X
2-Butenedioic acid bis(2-ethylhexyl) ester	141-02-6	*R43	1
Bis(2-butoxyethyl) phthalate	117-83-9	* N;R50/53, ** phthalate	1
Bis-2(ethylhexyl) hexanedioic acid ester (Bis(2-ethylhexyl)adipat)	103-23-1	** Phthalate	1
Diisooctyl phthalate	117-84-0	** Phthalate	1
2-Naphthalenol, 1-[(4-methyl-2-nitrophenyl)azo]- (Toluidine Red)	2425-85-6	** Azo dye	1	X

1: Substances for quantification have been chosen based on their hazardous effect, expected concentration and presence in products as described below
*: Self-classification, see text
**: Additional information, see text

Table 2.9 shows only substances classified according to the List of Dangerous Substances (Miljøministeriet, 2005), the Advisory List for Self-classification.

The substances are shown according to their retention time on a volatile scale. Thus substances at the top of the list are easily emitted to air and therefore also present a higher risk of absorption via the respiratory system.

The classification of the substances marked “*” is taken from the advisory list for self-classification (Vejledende liste, Miljøstyrelsen 2001).

Substances marked “**” have been found relevant for analysis as they belong to a substance group which contains undesirable hazardous components (.e.g. phthalates).

Apart from the substances selected for quantification, there is probably formaldehyde content in the glitter glue and pheromones in the aroma pens in product No.16, these substances will be subjected to a quantitative analysis.

Prioritization has been based on an assessment of health hazard * concentration, where the substance concentration level is estimated from the peaks in the gas chromatography in the qualitative analysis.

By assessing the relative health hazard, the substances marked T, Tx and CMR or allergens are weighted more than substances marked Xn, Xi.

In the selection we have tried to have the substances represented relative to how often they appear in the products.

Based upon the selection of substances hazardous to the environment and health we have picked 12 products which represent the most important of the substances and most likely have the highest concentrations.

Products selected for substance quantification

Marker pens

No. 10 in orange and purple
No. 16 in red, brown, orange, yellow and black
No. 17 in red and pink
No. 25 in red and pink
No. 45 in green and white
No. 57 in orange and pink
The price ranges between 0.49-3.63 DKK apart from product No. 45, which is more expensive.

Gel pens

No. 4 in metallic yellow and pastel pink
The cheapest product.

Acrylic paint

No. 54 in red-302
No. 55 in green and ultramarine blue
No. 61 in metallic cubber
The selected colours cover the price spread.

Glitter glue

No. 26 in gold, purple, green and silver
No. 29 in orange/yellow, pink, light blue and gold
The products are at medium price level.

Shrink plastic

No products have been selected as they did not contain PVC, which may contain phthalates.