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Survey and health risk assessment of products for treatment of sports injuries and pains
2 Screening of substances
Based on the selection criteria described in paragraph 1.5.2 screening analyses were made of the content of organic substances in the selected products with the main purpose of detecting and identifying substances with negative health effects.
2.1 Chemical screening analysis
As the tested products had rather different base formulations, see Table 1.5, it has been chosen to use a headspace-based analysis method.
The applied sampling method based on sampling on ATD-tubes measures organic compounds from the volatile, organic solvents (ethanol, acetone, etc.) to the semi-volatile compounds (parabenes, phthalates etc.).
The examination of the product declarations did not discover any substances which are not covered by the applied measuring method. Therefore, it was not considered necessary to have the products analysed for contents of inorganic substances.
2.1.1 Method of GC/MS headspace-analysis
A weighed out sample amount was put in a 100 ml glass jar.
A glass tube with adsorbent (tenax TA) was placed next to the sample and the Tenax filters were passively exposed for different time periods (10 and 15 minutes resp.).
Subsequently, the Tenax filters were analysed by thermal desorption combined with gas chromatography - mass spectrometry. (ATD/GC-MS in scan mode). The following parameters were applied.
Table 2.1 Analysis parameters
GC/MS-Instrument |
Perkin Elmer Turbomass and ATD 400 |
MS-parameters |
Scan mode 29-500 m/z, solvent delay: 0,1 min. |
GC-parameters |
Furnace prog: 35° C for 3 min., 10° C/min. to 260° C hold for 5 min.
Carrier gas: Helium
Column:, CP Sil 8CB Low bleed MS 30 m x 0,25 mm, film: 0.5 ∝m |
ATD-parameters |
ATD-pipes: Tenax TA
Desorption temp: 290° C |
Detected substances are solely identified by using the NIST-library of mass spectres.
In connection with the qualitative screening no quantitative assessment of the contents of the identified organic compounds was carried out.
2.1.2 Substances
Table 2.2 shows the total screening result of the 12 tested products. Detected substances are marked with "X".
Table 2.2 Screening results - 12 products
Substance name |
CAS no. |
Product no. |
1 |
2 |
3 |
4 |
5 |
8 |
12 |
13 |
15 |
C |
E |
H |
1,2-Propandiol |
57-55-6 |
|
|
|
|
|
|
|
x |
|
|
|
|
2-Methyl-1,3-dioxane |
626-68-6 |
|
|
|
|
|
|
|
x |
|
|
|
|
2-Methyl-2-propanol |
75-65-0 |
|
|
|
|
|
|
|
|
|
x |
|
|
2-Phenoxy-ethanol |
122-99-6 |
|
|
|
|
|
|
|
x |
|
|
|
|
2-Propanol |
67-63-0 |
|
|
|
|
|
x |
x |
|
x |
|
|
|
3-Carene |
13466-78-9 |
|
x |
|
|
|
|
|
|
|
|
|
|
Acetaldehyde |
75-07-0 |
|
|
|
|
|
|
|
x |
|
|
|
|
Acetone |
67-64-1 |
|
|
|
|
|
|
|
x |
|
|
|
|
Benzaldehyde |
100-52-7 |
|
x |
|
|
|
|
|
|
|
|
|
|
Benzyl acetate |
140-11-4 |
|
|
|
|
|
|
|
x |
|
|
|
|
Borneol acetate |
76-49-3 |
|
|
|
|
x |
|
|
|
|
|
|
|
Camphene |
79-92-5 |
x |
x |
|
x |
|
x |
|
|
x |
|
x |
x |
Caryophyllen |
87-44-5 |
|
|
|
x |
|
|
|
|
|
|
|
|
Camphor |
76-22-2 |
|
x |
x |
x |
x |
|
x |
|
|
x |
|
|
Cinnamaldehyde |
104-55-2 |
|
x |
|
x |
|
|
|
|
|
|
|
|
Dimethyl sulphone |
67-71-0 |
|
|
|
|
|
|
|
x |
|
|
|
|
Ethanol |
64-17-5 |
|
|
|
|
x |
|
|
x |
|
x |
|
|
Ethyl acetate |
147-78-6 |
|
|
|
|
x |
|
|
|
|
x |
|
|
Eucalyptol |
470-82-6 |
|
x |
|
|
|
|
|
x |
|
x |
|
|
Eugenol |
97-53-0 |
|
x |
|
|
|
|
|
|
|
|
|
|
Geranyl benzoate |
94-48-4 |
|
|
|
|
|
|
|
x |
|
|
|
|
d-Limonene |
5989-27-5 |
|
|
x |
x |
|
x |
|
|
x |
x |
x |
x |
Menthol |
1490-04-6 |
|
x |
x |
x |
|
|
x |
x |
|
x |
|
|
Methyl salicylate |
119-36-8 |
x |
|
|
|
|
x |
|
|
x |
|
x |
x |
b-Myrcene |
123-35-3 |
|
x |
x |
|
|
x |
|
x |
x |
|
x |
x |
b-Phellandrene |
555-10-2 |
x |
|
|
|
|
|
|
|
|
|
|
|
α-Pinene |
80-56-8 |
x |
x |
x |
x |
x |
x |
|
x |
x |
|
x |
x |
β-Pinene |
127-91-3 |
|
x |
x |
x |
x |
x |
|
x |
x |
|
x |
x |
p-Cresol methyl ether |
104-93-8 |
|
|
|
|
|
|
|
x |
|
|
|
|
2.2 Health Risk screening
The preliminary screening revealed a number of substances and substance groups, e.g. aliphatic hydrocarbons. The substances which were identified with an unambiguous name were subjected to a screening based on
- Chemical structure
- Physical/chemical properties
- Classification etc.
Table 2.3 shows selected physical/chemical data of these substances.
The physical/chemical data of the selected substances have been found through searchings in ChemID and HSDB under TOXNET.
Table 2.3 Physical/chemical data of substances revealed by the screening
Name |
CAS no. |
Melting point
°C |
Boiling point
°C |
Vapour pressure
mmHg |
Water solubility
mg/l |
Log KOW |
1,2-Propandiol |
57-55-6 |
-60 |
187.6 |
0.129 |
∝ |
-0.92 |
2-Methyl-1,3-dioxane |
626-68-6 |
|
|
|
- |
|
2-Methyl-2-propanol |
75-65-0 |
25.4 |
82.4 |
40.7 |
∝ |
0.35 |
2-Propanol |
67-63-0 |
-89.5 |
82.3 |
45.4 |
∝ |
0.05 |
3-Carene |
13466-78-9 |
<25 |
170 |
3.72 |
- |
4.38 |
Cinnamaldehyde |
104-55-2 |
-7.5 |
246 |
0.0289 |
1420 |
1.90 |
Acetaldehyde |
75-07-0 |
-123 |
20.1 |
902 |
∝ |
-0.34 |
Acetone |
67-64-1 |
-94.8 |
56 |
232 |
∝ |
-0.24 |
α-Pinene |
80-56-8 |
-62.5 |
156 |
4.75 |
2.5 |
4.83 |
Benzaldehyde |
100-52-7 |
-26 |
179 |
0.127 |
6570 |
1.48 |
Benzyl acetate |
140-11-4 |
-51.3 |
213 |
0.177 |
3100 |
1.96 |
Borneol acetate |
76-49-3 |
29 |
221 |
0.228 |
|
3.86 |
b-Phellandrene |
555-10-2 |
- |
171.5 |
1.59 |
|
4.7 |
β-Pinene |
127-91-3 |
-64.5 |
166 |
2.93 |
- |
4.16 |
b-Myrcene |
123-35-3 |
<-10 |
167 |
2.01 |
5.6 |
4.17 |
Camphene |
79-92-5 |
51.2 |
160 |
2.51 |
4.2 |
4.22 |
Eucalyptol |
470-82-6 |
1.5 |
176.4 |
1.9 |
3500 |
2.74 |
Caryophyllen |
87-44-5 |
<25 |
- |
- |
- |
6.3 |
Camphor |
76-22-2 |
180 |
204 |
0.072 |
1600 |
2.38 |
Dimethyl sulphone |
67-71-0 |
109 |
238 |
5.15 |
∝ |
-1.41 |
D-limonene |
5989-27-5 |
-74.3 |
176 |
1.98 |
13.8 |
4.57 |
Ethanol |
64-17-5 |
-114 |
78.2 |
59.3 |
∝ |
-0.31 |
Ethanol, 2-phenoxy |
122-99-6 |
14 |
245 |
0.007 |
26700 |
1.16 |
Ethyl acetate |
141-78-6 |
-83.6 |
77.1 |
93.2 |
80000 |
0.73 |
Eugenol |
97-53-0 |
-7.5 |
253.2 |
0.0226 |
2460 |
2.27 |
Menthol |
1490-04-6 |
43 |
212 |
0.0637 |
456 |
3.4 |
Methyl salicylate |
119-36-8 |
-8.0 |
222.9 |
0.034 |
700 |
2.55 |
p-Cresol methyl ether |
104-93-8 |
-32.0 |
175.5 |
1.14 |
- |
2.66 |
∝: Miscible with water
2.2.1.1 State of matter
From Table 2.3 it appears that the majority of the substances are liquid at room temperature. Camphene, Camphor, Menthol and Dimethylsulphone, however, have high melting points and are solid at room temperature.
Most substances have boiling points above 150 °C. The six substances: 2-methyl-2-propanol, 2-propanol, acetaldehyde, acetone ethanol and ethyl acetate have boiling points below 100 °C and vapour pressures above 40 mm Hg (highest for the low-boiling substances).
Several substances have very low vapour pressures and do not evaporate. This is the case for 1,2-propandiol, Benzaldehyde, benzyl acetate, borneol acetate, camphor and methyl salicylate, all having a vapour pressure below 1 mm Hg.
2.2.1.2 Fat/water-ratio
As to solubility, the lower alcohols and ketones/aldehydes have high water solubility, which is also the case for the sulphur compound dimethyl sulphone.
Most of the compounds containing an oxygen atom will have solubility between 0.1 and 10 g/litre.
Among the selected substances, 8 have water solubilities below 25 mg/litre.
The octanol/water partition coefficient is expressed by the value log KOW. With a negative log KOW the substance will primarily be at the aqueous phase and when the value is positive in the fat phase. It is assumed that substances with log KOW below 4 will be 100 % absorbed through the skin, while substances with higher values are absorbed only by 10 % (TGD, 2003).
Five of the selected substances have a negative log KOW and are therefore primarily water-soluble. This is seen via a very high water solubility of these substances.
3-carene, α-Pinene, b-Phellandrene, β-Pinene, b-mycene, camphene and d-limonene have a log KOW above 4. Common to these substances is the sum formula C10H16 and their cyclic structure.
2.2.2 Classification etc. for selected substances
Information has been retrieved about the classification and limit values of the selected substances and further whether they are listed in "List of Cosmetic Ingredients" (INCI, 2005).
Information about classification has been procured from "List of Hazardous Substances (liste, 2005) and from the Danish EPA's Advisory List for Self-classification (Advisory List 2001). Data from the list is marked by ”*”.
Information about limit values has been taken from Threshold limit
values for substances and materials (C.0.1, 2005) from the Danish Working Environment Service.
Abbreviations:
L: Threshold value
H: Skin penetration
K: Carcinogenic
Searchings for all substances have been made in the INCI database. Table 2.4 gives information about the substances in the list and their functions and limitations.
Table 2.4 Classification for substances revealed by screening
Nr. |
Name |
CAS no. |
Classification |
GV mg/m³ |
INCI, function |
Cosmetics Regulations and other |
1 |
1,2-Propanediol |
57-55-6 |
|
|
Solvent |
|
2 |
2-Methyl-1,3-dioxane |
626-68-6 |
|
|
|
No info |
3 |
2-Methyl-2-propanol |
75-65-0 |
F;R11
Xn; R20 |
150 LH |
Fragrance |
|
4 |
2-Propanol |
67-63-0 |
F;R11
Xi;R36 R67 |
490 |
Fragrance
Antifoaming
Solvent |
|
5 |
3-Carene |
13466-78-9 |
N;R51/53 * |
|
Fragrance |
|
6 |
Cinnamaldehyde |
104-55-2 |
R43 *
N;R50 * |
|
Denaturants |
EU List of contact allergens.
III/23, 76, when concentrations exceed 0.001 % in products which are not cleaned off, 0.01 % in products to be cleaned off. |
7 |
Acetaldehyde |
75-07-0 |
F+; R12
Carc3; R40
Xi; R36/37 |
25 LK |
Additives |
CMR substances not permitted in cosmetics |
8 |
Acetone |
67-64-1 |
F; R11
Xi; R36 R66 R67 |
600 |
Denaturants/ solvent |
|
9 |
α-Pinene |
80-56-8 |
N;R50/53 * |
|
Fragrance |
|
10 |
Benzaldehyde |
100-52-7 |
Xn; R22 |
|
Solvent |
|
11 |
Benzyl acetate |
140-11-4 |
- |
61 |
Additive |
|
12 |
Borneol acetate |
76-49-3 |
- |
|
Not in the INCI list |
|
13 |
β-Phellandrene |
555-10-2 |
Xn;R22 N;R51/53 * |
|
Fragrance |
|
14 |
β-Pinene |
127-91-3 |
N;R50/53 * |
|
Fragrance |
|
15 |
β-Myrcene |
123-35-3 |
- |
|
Fragrance |
|
16 |
Camphene |
79-92-5 |
N;R50/53 * |
|
Fragrance |
|
17 |
Eucalyptol |
470-82-6 |
- |
|
Fragrance |
|
18 |
Caryophyllen |
87-44-5 |
- |
|
Fragrance |
|
19 |
Camphor |
76-22-2 |
- |
12 |
Fragrance |
|
20 |
Dimethyl sulphone |
67-71-0 |
- |
|
Solvent |
|
21 |
d-Limonene |
5989-27-5 |
R10
Xi; R38 R43
N; R50-53 |
|
D VI/1,29
Max 1 % fragrance |
EU's list of contact allergens
III/27,88.
To be declared when the concentration exceed 0.001 % in products which are not cleaned off, and 0.01 % in products to be cleaned off. |
22 |
Ethanol |
64-17-5 |
F; R11 |
1900 |
Solvent |
|
23 |
Ethanol, 2-phenoxy |
122-99-6 |
Xn; R22
Xi; R36 |
|
Fragrance Preservative |
38, VI/1,29
Max 1 % |
24 |
Ethyl acetate |
141-78-6 |
F; R11
Xi; R36, R66, R67 |
540 |
Solvent |
|
25 |
Eugenol |
97-53-0 |
Xn; R22 Mut3;R40
R43 * |
|
Fragrance |
EU List of contact allergens.
III/23, 76, when concentrations exceed 0.001 % in products which are not cleaned off, 0.01 % in products to be cleaned off. |
26 |
Menthol |
1490-04-6 |
- |
|
Fragrance |
|
27 |
Methyl salicylate |
119-36-8 |
- |
|
Denaturant |
|
28 |
p-Cresol methyl ether |
104-93-8 |
- |
|
Fragrance |
|
As can be seen a good deal of the substances are classified - 8 substances are on the List of Hazardous substances and 7 on the Advisory List. The remaining substances are not listed.
Preliminarily it is estimated that 1,2-propandiol (no. 1) is not covered by the labelling requirements. The other 11 substances may not be self-classified due to lack of information.
The substances 3-carene (no. 5), α-Pinene (no. 9), β-Pinene (no. 14) and camphene (no. 16) are entered on the Advisory List for classification with (N, R50/53) Environmental Hazard, however, no classification for health hazard.
Of the classified substances, two substances are suspected of causing chronic damages - Acetaldehyde (no. 7), suspected of being carcinogenic (Carc3, R40) and Eugenol (no. 25), suspected of changing the genes (Mut3, R40).
Three substances are classified as contact allergens (R43) and are on the EU List of Major contact allergens. (nos. 6, 21, 25).
The vast majority of the detected substances are odorants. According to data INCI, there are 17 odorants and 7 are solvents. Of the selected substances there is only one preservative and two of the substances are not included in the INCI list.
Four of the detected substances are mentioned in the Statutory Order for Cosmetic Products. The preservative 2-phenoxy ethanol is permitted in concentrations up to max. 1 %. Cinnamale, d-Limonene and Eugenol are to be declared when the concentration exceeds 0.001 % in products which are not cleaned off, and 0.01 % in products which are cleaned off.
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Version 1.0 Decmeber 2006, © Danish Environmental Protection Agency
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