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Survey of liquid hand soaps, including health and environmental assessments

5 Chemical analyses

• 5.1 Selection of products for chemical analysis
• 5.2 Analytical methods
  • 5.2.1 Methyl eugenol and Methyldibromoglutaronitril
  • 5.2.2 Fragrance chemicals
• 5.3 Results
  • 5.3.1 Methyl eugenol
  • 5.3.2 Methyldibromoglutaronitril
  • 5.3.3 Fragrance chemicals
• 5.4 Summary of analytical results
  • 5.4.1 Methyl eugenol
  • 5.4.2 Methyldibromoglutaronitril
  • 5.4.3 Fragrance chemicals
• 5.5 Agreement between analytical results and list of ingredients/safety data sheets

5.1 Selection of products for chemical analysis

The main purpose of the survey of hand soaps is to investigate if the products contain fragrance chemicals and preservatives reported as contact allergens. The criteria for selection of products for chemical analysis were laid down in consultation with the Danish Environmental Protection Agency and comprise:

• Products containing perfume
• Products containing preservatives reported as contact allergens

From the initial screening of chemical ingredients in liquid hand soaps, 15 products were selected for chemical analysis. The programme included analysis of fragrance chemicals and the preservative Methyldibromoglutaronitril. When selecting the products the aim was to find products partly with a large distribution on the market and partly with a stated content of both well-known and unknown fragrance chemicals. As a result, the most neutrally smelling products were not selected for analysis.

The 15 products were analysed for the 26 fragrance chemicals listed on EU's list of fragrance chemicals reported as contact allergens (3). In addition, three products with scent of roses were analysed for Methyl eugenol. Methyl eugenol is a natural component of rose oil. Methyl eugenol has been found to be genotoxic and carcinogenic (4). According to the Danish "kosmetikbekendtgørelse", annex 2, the substance is prohibited in concentrations > 0.001% in rinse-off products and consequently relevant for further scrutiny. Moreover, three products were analysed for the preservative Methyldibromoglutaronitril (MG) as a result of the substance's contact allergen properties.

5.2 Analytical methods

5.2.1 Methyl eugenol and Methyldibromoglutaronitril

A part sample of the product is extracted with dichloromethane for one hour on shaking table and left to stand over night. A part sample of the extract is taken and analysed directly at combined gaschromatography and mass spectrometry (GC/MS). The content is calculated quantitatively. The analyses are performed as true double determinations.

Methyl eugenol:
Uncertainty is 10-15% RSD. The limit of detection is 10 mg/kg.

Methyldibromoglutaronitril:

Uncertainty is 20% RSD. The increased uncertainty is due to use of a technical product as reference standard. The limit of detection is 100 mg/kg.

5.2.2 Fragrance chemicals

A part sample of the product is taken and extracted with water and tert-butylmethylether by means of shaking, heating, and standing during a period of approximately 16 hours. A part sample of the extract is taken and analysed directly at combined gaschromatography and mass spectrometry (GC/MS). The analyses are performed as true double determinations. The limit of detection is 10 mg/kg and uncertainty is 10-15% RSD.

It is not possible to determine a limit of detection for Oak moss extract and Tree moss extract, as these are natural extracts with many components and not merely one single substance. An exact limit of detection cannot be calculated as the content of these natural extracts vary. Instead the limit is given as "Not determined".

5.3 Results

5.3.1 Methyl eugenol

Three products were analysed for methyl eugenol and the result of the analyses is given in table 1. Methyl eugenol was not detected in the products. The analyses have been performed in double thus 2 results (A and B) are given in the table. The unit is mg/kg and the limit of detection is 10 mg/kg.

Table 5.1 Results of the analysis for Methyl eugenol. The results are given in mg/kg.

<.: Means less than the stated limit of detection

# Product 3 is now marketed in a new formulationing

5.3.2 Methyldibromoglutaronitril

Three products were included in the analysis for Methyldibromoglutaronitril. The samples were analysed in double determinations (A and B). Content above the limit of detection could not be determined in the products. Unit is mg/kg and the limit of detection is 100 mg/kg.

Table 5.2 Result of the analysis for Methyldibromoglutaronitril. The results are given in mg/kg.

<.: Means less than the stated limit of detection

**Product is no longer on the market

5.3.3 Fragrance chemicals

A total of 26 substances were analysed in the 15 liquid soaps. The result of the analyses is given in table 3. Result A and B indicate double determinations.

The 26 fragrance chemicals were detected in 14 of the 15 products. The total content varies from 8 to 2600 mg/kg corresponding to a range from 0.0008 to 0.26 weight%.

Table 5.3 Result from the analysis for fragrance chemicals. Unit is mg/kg. Two results indicate double determinations.

LOD: Means limit of detection
-: Means not detected above the LOD
*: Not detectable. A limit of detection cannot be specified.
^: Product 6 is now marketed with a new formulation without any of the 26 specific fragrance
# Product 3 is now marketed in a new formulationing

Table 5.3 continued. Result from the analysis for fragrance chemicals. Unit is mg/kg. Two results indicate double determinations.

LOD: Means limit of detection
-: Means not detected above the LOD
*: Not detectable. A limit of detection cannot be specified.

Table 5.3 continued. Result from the analysis for fragrance chemicals. Unit is mg/kg. Two results indicate double determinations.

LOD: Means limit of detection
-: Means not detected above the LOD
*: Not detectable. A limit of detection cannot be specified.
**: Product is no longer on the market

Table 5.3 continued. Result from the analysis for fragrance chemicals. Unit is mg/kg. Two results indicate double pdeterminations.

LOD: Means limit of detection
-: Means not detected above the LOD
*: Not detectable. A limit of detection cannot be specified.

5.4 Summary of analytical results

5.4.1 Methyl eugenol

Methyl eugenol is not on the list of the 26 fragrance chemicals reported as contact allergens. However, the substance has been included in the analysis in the light of its carcinogenic effects and its natural occurrence in rose oil. The three products that were analysed for Methyl eugenol had a scent of roses but did not contain detectable concentrations of Methyl eugenol.

5.4.2 Methyldibromoglutaronitril

Methyldibromoglutaronitril was stated on the list of ingredients of three products, however, the substance was not detected in the products at the detection limit of 100 mg/kg (0.01%). Consequently, the concentration in the products is estimated at being less than 0.01%. In the literature concentrations of 0.0075 – 0.06% are mentioned for the substance (5). Maximum tolerated concentration in cosmetics is 0.1% in rinse-off products (1).

5.4.3 Fragrance chemicals

In one of the products (no. 16) none of the fragrance chemicals could be detected and in another product (no. 1) only one of the fragrance chemicals was detected. Between 3 and 12 of the tested fragrance chemicals were found in the remaining 13 products. The following 7 fragrance chemicals were not found in any of the analysed products: Anisyl alcohol, Amylcinnamyl alcohol, Benzylcinnamate, Cinnamal, Methyl heptin carbonate, Oakmoss, and Treemoss. Occurrence of the remaining 19 fragrance chemicals in the products is shown in table 5.4.

Table 5.4 Occurrence of fragrance chemicals in the 15 analysed products.

As appears from table 5.4 some of the most commonly used fragrance chemicals in the analysed hand soaps are Linalool, Geraniol, Citronellol, Hexylcinnamaldehyde, Lilial, Benzyl alcohol, Benzyl salicylate and Eugenol. These are the substances found in the largest concentrations in the products. The highest content of a single fragrance chemical is 2400 mg/kg for D-limonen. The total content of the 26 fragrance chemicals in the tested products is between 1 mg/kg and up to 2600 mg/kg.

Table 5.5 is a summary of the analytical results showing occurrence in number of products, minimum and maximum measured values, and the maximum value as a percentage by weight in the products.

Table 5.5 Summary of analytical results.

5.5 Agreement between analytical results and list of ingredients/safety data sheets

As mentioned above, the 26 allergen fragrance chemicals must be stated on the product label of hand soaps (rinse-off products) if the concentration of a single substance is above 0.01%, equal to 100 mg/kg, for products marketed after 11 March 2005. The products, which were selected for chemical analysis, did not state content of allergen fragrance chemicals on the label with the exception of product nos. 45 and 50. This may be because the products had been in store for a long time prior to being sold. However, the chemical analysis showed that one or more of the 26 fragrance chemicals were identified in 9 of the 15 analysed products in concentrations > 0.01% (>100 mg/kg). Table 5.7 lists fragrance chemicals identified in the products in concentrations > 0.01%.

Table 5.6 Fragrance chemicals, which are identified in the products by chemical analysis (content > 0.01%), must be stated on the product label.

* Stated on the product label
(P): Products for occupational use
^: Produkt 6 is now sold inforhandles nu i variant uden de 26 parfumestoffer
^^: Produkt 7 is now labelled with the content of allergen fragnance.
**: Produkt is no longer on the market

As can be seen from the above product nos. 5, 6, 7, 8, 15 and 21 contain allergen fragrance chemicals in concentrations above > 0.01%, which are not stated on the list of ingredients. The formulation of product 6 has been changed after the analysis were carried out so that the product no longer contains any of the 26 allergen fragrances. Produkt 7 is now labelled according to the regulation with content of Hexylcinnamaldehyde, D-limonen and the product does not contain Linalool in concentration above 0,01% according to the information the Danish EPA has received. Product 21 and 8 is no longer on the market. Only a safety data sheet is available for product no. 34, and consequently the list of ingredients on the product label could not be verified. In order to label the products correctly it is a prerequisite to have information from the raw material suppliers on the content and concentration of the fragrance chemicals reported as contact allergens in the perfumery raw materials.

Although Methyldibromoglutaronitril was stated on the product label of three products (no. 8, 15, and 21), the content of the substance could not be detected in concentrations > 100 mg/kg in the products. This may be due to the fact that the substance is used in lower concentrations in the products.

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Version 1.0 June 2006, © Danish Environmental Protection Agency