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A survey and health assessment of cosmetic products for children 5 Analysis results
The purpose of this project was to study whether cosmetic products for children contain problematic chemical substances but also to study whether the packaging contains problematic substances. Based on the survey and the provided database of the constituents of the cosmetic products for children, it was decided in consultancy with the Danish Environmental Protection Agency to focus on the 26 fragrances mandatory to declare and the allergenic preservative Kathon (it is a mixture of the two substances methylchloroisothiazolinone and methylisothiazolinone in the ratio 3:1). The reason for this is that a very large part of the mapped products has a declared content of perfume – in total 74% and one third of all the products has a declared content of one or more of the 26 fragrances mandatory to declare. Furthermore, Kathon was chosen as it is assessed to be allergenic (R43 – Might cause allergy via contact with the skin) according to the guiding list for self-classification of hazardous substances of the Danish Environmental Protection Agency (Environmental project 635, 2001). Kathon is not classified as allergenic according to the List of hazardous substances but at the beginning of the eighties when Kathon was introduced as a preservative in cosmetics it gave cause for an epidemic of allergy cases in Europe. Kathon is now applied in small quantities in cosmetics (0.0003 – 0.0015%) and gives nevertheless cause for many allergy cases (Denmark’s National Allergy Research Centre, 2006a). With regard to the packaging of the products focus has been on the content of heavy metals and phthalates. To identify packaging materials of PVC a quick and cheap analysis for the content of chlorine is carried out. A content of chlorine might be an indication of the packaging being made of PVC and thus possibly containing phthalates. Then the packaging materials of PVC have been selected for a quantitative analysis for the content of phthalates. In the table below the analysis programme of the project is presented. Analyses for constituents are made by the company Eurofins and analyses of the packaging are made by FORCE Technology, the Department of Chemical Analysis. Table 5.1: Analysis programme
5.1 Selection of products for analysis5.1.1 Analysis for the 26 fragrancesThe 17 products selected for an analysis for the 26 fragrances are stated in the table below. In the selection the emphasis has been on the more common product types, that means body shampoo/bath gel, shampoo and bobble bath but a few other product types have also been selected. The selected products for the analysis are primarily products which already had a declared content of perfume. However, one product is selected because it smelled of perfume but no content of perfume was declared. Furthermore, some products not having any separate declaration of the 26 fragrances are selected. The purpose of these analyses is to check whether the new regulation regarding separate declaration of these substances is introduced at the producers. Theoretically, there might still be legal products on the shelves in the shops without a separate declaration of the 26 fragrances as the regulation applies to all cosmetics being produced after 10 March 2005. In the project period we ourselves saw that the circumstance is so for some products as products which were initially bought for the survey had changed declaration when we bought the products again for the analyses. Now a content of the 26 fragrances was declared separately. Furthermore, the products are selected so they cover several producers and represent both retail trade products and products via the Internet; however, with a substantial majority of retail trade products. Table 5.2: Product selected for analysis for content of the 26 fragrances.
5.1.2 Analysis for KathonIn total, 15 products with a content of Kathon (a combination of methylchloroisothiazolinone and methylisothiazolinone) are found in the survey. Eight of these products were selected for a quantitative analysis for Kathon. These are stated in the table below. Two series of products contain Kathon – one series of five products and one series of two products. From these two series only one product from each series has been selected. The remaining six products for a Kathon analysis were selected randomly (out of the remaining eight possible products). The majority of the products with a contant of Kathon is non-stay-on products. One of the two stay-on products is selected for analysis (as the two stay-on products are from the same series). Due to a mistake products without a declared content of Kathon were also analyzed quantitatively for a content of Kathon. It proved that three products had a content of kathon despite the fact that it is not declared on the product. The results from these three products are also presented in the following. All in all, the following 11 products were analyzed for a content of Kathon. Table 5.3: Selected for analysis for content of Kathon
5.1.3 Analysis for heavy metals in the packagingThe 10 products selected for analysis of heavy metals in the packaging are stated in the table below. In the selection emphasis was on strongly colourful products as these products most probably contain the largest quantities of heavy metals. Furthermore, the emphasis is on the more common product types, i.e. body shampoo/bath gel, shampoo and bobble bath but the product types body lotion and hairstyling product are also selected due to strongly colourful packaging materials. Table 5.4: Selected for analysis for content of heavy metals in the packaging
In the selection it was also emphasized that a part of the products had to be designed as a particular figure as these products might be used as toys (for instance in the bath) and especially small children (or small siblings) might be expected to put them into the mouth. Therefore, it is relevant to examine the quantity of heavy metals to be able to assess the impact in such situations. Furthermore, the products have been selected so they cover several producers and so they represent both the retail trade products and products via the Internet, however, with a substantial majority of retail trade products. 5.1.4 Analysis for chlorine and phthalates in the packagingThe 14 products selected for analysis of chlorine in the packaging are stated in the table below. In the selection emphasis was exclusively on products of soft plastic as these products are probably made of PVC and thus contain chlorine. Furthermore, the emphasis is on the most common product types, i.e. body shampoo/bath gel, shampoo and bobble bath. In the selection it is also emphasized that a part of the products was designed as a particular figure (more than half) as these products might be used as toys (for instance in the bath) and especially small children (or small siblings) might be expected to put them into the mouth. Therefore, it is relevant to examine for a possible content of PVC and later for a content of phthalates to be able to assess the impact in such situations. Furthermore, the products have been selected so they cover several producers and so they represent both the retail trade products and products via the Internet, however, with a substantial majority of retail trade products. Table 5.5: Selected for analysis for content of chlorine in the packaging
Based on the results of the survey (which showed that eight of the products had a packaging made of PVC) and of the results of the analyses for the content of chlorine in the packaging (see a description later) 10 products were selected for a quantitative determination of the content of phthalates in the products. The 10 products for analysis for a content of phthalates were selected so they mainly are products designed as a particular figure as these products might be used as toys (for instance in the bath) and especially small children (or small siblings) might be expected to put them into the mouth. Therefore, it is relevant to examine for a possible content of PVC to be able to assess the impact in such situations. Furthermore, the products have been selected so they cover several producers and so they represent both the retail trade products and products via the Internet, however, with a substantial majority of retail trade products. Table 5.6: Selected for analysis for content of phthalates in the packaging
5.2 Analyses for selected constituents5.2.1 Analysis methods5.2.1.1 FragrancesA partial sample of the product is extracted by water and tert-butylmethylether by means of suspending, heating, cooling and standing during about 16 hours. A partial sample of the extract is extracted and analyzed directly via combined gas chromatography and mass spectrometry (GC/MS). The analyses are conducted as real repeat determination. The detection limit is 1 mg/kg and the analysis error is 10-15% RSD. For Oak moss extract and Tree moss extract a detection limit cannot be set as they are natural extracts with many components and not exclusively one pure substance. As the content of these natural extracts varies an exact detection limit cannot be calculated. Instead the limit is state as “Not proven”. 5.2.1.2 Chlormethy- a methylisothiazolones (Kathon)A representative partial sample of about 2.5 g is extracted and diluted in demineralized water. It is filtered via a 0.45µm filter. The filtered solution is analyzed via liquid chromatography with UV detection (HPLC/DAD) with the following chromatographic conditions: Flow: 0.500 ml/min The analyses are conducted as real repeat determination. The analysis error is 10-15%. The detection limit is 2 mg/kg. Reference: Matissek, R; Zur Analytik mikrobiocider Isothiazolone, Fresenius Z Anal. Chem. (1985) 322: 465-469. 5.2.2 Analysis results5.2.2.1 Fragrances17 cosmetics samples were totally analyzed for 26 fragrances in repeat determination. The sum of the proven fragrances varied from 1 mg/kg to 7800 mg/kg corresponding to from 0.0001% (w/w) to 0.78 (w/w). The results are stated in the table in the unit mg/kg. As described in chapter 3 ”Legislation”, and according to Appendix 3 of the statutory order, the 26 fragrances mandatory to declare must be stated in the declaration of content, no matter their function in the products, when the concentration is higher than 0.001% (i.e. 10 mg/kg) in products which are not to be cleansed and 0.01% (i.e. 100 mg/kg) in products which are to be cleansed. This regulation with special statement of the 26 fragrances mandatory to declare became effective in 2005 and applies for all cosmetics being produced after 10 March 2005 (Stat. Ord. 422 §25, 2006). In theory, it is still possible to buy products in the shops which are produced before 10 March 2005 so that a non-declared content of one of the 26 fragrances mandatory to declare is legal. In connection with the survey we have seen that a number of products being bought for the survey did not have any separate declaration of the fragrances mandatory to declare but when buying for the analyses these fragrances were declared separately. In the tables below three columns for each analyzed product is presented. The first two columns state the results from the repeat determinations. The third column states with a “+” which of the 26 fragrances that is separately declared on the declaration of content of the products. A “+” in the sum row indicates whether there is a content of “perfume” according to the declaration of content – and correspondingly a “-“ in the sum row states that perfume is not a part of the product. At last, “Yes” or “No” states whether the declaration matches the analysis results. So a “No” means divergences in relation to the Cosmetics Statutory Order. Please note, with exception of two (ID no. 166 and 209), that all the analyzed products are not stay-on products; that means that only a content of perfume above 100 mg/kg must be declared according to the Cosmetics Statutory Order. Table 5.7: Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. Table 5.7 (cont’d): Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. Table 5.7 (cont’d): Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. Table 5.7 (cont’d): Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. Table 5.7 (cont’d): Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. Table 5.7 (cont’d): Results from the analysis for fragrances. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means detection limit In the row marked “Declaration matches the analysis results”: +: means that the fragrance is declared separately in the declaration of content on the product -: marked under ”Sum” means that there is no declared content of perfume in the product. The word “perfume” is not in the declaration of content. As it can be seen from the analysis results six of the 17 analyzed products have declaration of content which does not match the analysis results. With regard to these six products there are divergences in relation to the Cosmetics Statutory Order if the products are produced after 10 March 2005. For one of the products (ID no. 5) there is no declared content of perfume in the products – nor in the form of the word “perfume” but three of the fragrances mandatory to declare are identified in the product; however, each in a concentration so the substances have not to be declared separately. It shall also be mentioned that a part of the found concentrations of fragrances are very low. Here it may be the case that the fragrances are a part of the products as an impurity from the production and are not actively added. In such cases the substance is not seen as a constituent and therefore it is not to be declared. Table 5.8: Summary of the analysis results for fragrances
In a single product 18 of 26 fragrances mandatory to declare are declared but none of these 18 fragrances is identified when analyzing the product. The table below shows the fragrances occuring in the maximum concentration and above the 100 mg/kg requiring a separate declaration (for non-stay-on products). Table 5.9: Overview of fragrances measured in the maximum concentration in the analyzed products
5.2.2.2 Chlormethyl and methyliso-thiazolones (Kathon)Kathon is a mixture of methylisothiazolone and chlormethylthiazolone. In total 11 samples were analyzed and the results are stated in Table 2. Table 5.10: Results from the analysis for Chlormethyl and methylisothiazolones. The unit is mg/kg. The two results state the repeat determinations.
D.l.: means ”detection limit” According to the Cosmetics Statutory Order (Stat. Ord. 422 §25, 2006) the maximum allowed concentration of Kathon in cosmetic products is 0.0015% of a mixture in the ration 3:1 of methylchloroisothiazolinone and methylisothiazolinone. This corresponds to 15 mg/kg. Therefore, none of the 11 analyzed products exceeds the allowed value. However, it is worth noting that three of the analyzed products (ID 21, 82 and 170) have no declared content of Kathon despite an analyzed content of Kathon. Therefore, these products deviate from the Cosmetics Statutory Order. 5.3 Analyses of selected packaging materials5.3.1 Analysis methods5.3.1.1 Heavy metal determination by apply of X-ray analysis (XRF)The XRF analyses are prepared in a X-LAB 2000 instrument (Spectro). By apply of this technique all elements larger than or equal with no. 11, Natrium (Na), are analyzed. Minimum quantity which can be determined depends on matrix and element but for certain elements it is <10ppm. The sample which is to be analyzed is placed directly in the instrument. The analysis is a surface analysis, that means that the analysis is in a maximum depth of about 100µm dependent on the material. By use of the analysis the content of heavy metals is available and also an indication whether the sample contains chlorinated or brominated flame retardants. Detection limits and uncertainties are stated in Table 5.11. 5.3.1.2 Polymers (incl. PVC)Beilstein’s test is used to determine whether a polymer is PVC. Beilstein’s test is a quick quantitative method for determination of halogens as a little piece of the sample is burnt on a copper wire in a flame. Green colouring of the flame indicates a content of chlorine. Beilstein’s test is carried out as screening on all polymers. 5.3.1.3 PhthalatesProducts can be analyzed for the quantitative content of the different phthalates, for instance where a content of phthalates is identified via the FTIR analysis. The samples are extracted with dichlormethan and the extracts are analyzed with GC-MS. For the GC-MS analyses Varian Saturn 2000 ion-trap GC-MS system is used. Detection limits and uncertainties are stated in Table 5.11. Table 5.11: Detection limits and uncertainties for the stated analyses
5.3.2 Analysis results5.3.2.1 Content of chlorine in the packagingAs mentioned, 14 products have been analyzed for content of chlorine in the packaging. The results of Beilstein’s test are stated in the table below. A “+” states a content of chlorine in the packaging. A few products have been via both X-ray analysis (for metals) and Beilstein’s test. For these products the result of the chlorine content via the X-ray analysis is also stated (in %) in Table 5.12. The results confirm that all small body shampoo/bath gel or bobble bath products being produced in soft plastic and designed as a particular figure are most probably made of PVC as the packing materials contain chlorine. Products in this test which are tested negatively for content of chlorine are all of a different type, primarily produced in soft plastic. Table 5.12: Results of Beilstein’s test for chlorine in the packaging
+ means that a content of chlorine is found by means of Beilstein’s test - means that no content of chlorine is found by means of Beilstein’s test 5.3.2.2 Content of heavy metals in the packagingAs mentioned, 10 products have been analyzed for content of heavy metals (metals) in the packaging. The results of the X-ray analysis are stated in the table below. Table 5.13: Results of X-ray analysis for heavy metals in the packaging Already during the study we knew that products no. 21, 27 and 32 were made of PVC (via plastic code). This is confirmed by the X-ray analysis. Generally, the results show values below 10 ppm whereas the values especially for nickel are somewhat higher (max. 32 ppm). Furthermore, two values for chromium are 15 ppm and a single value for tin is significantly higher than the other values – 360 ppm. A possible explanation might be use of organic tin compounds as heat stabilizer in PVC. According to Plastics Additive Handbook (Hanser Publications, 2001) sulphurous organic tin compounds are among the most efficient and most widespread heat stabilizer. In the European standard for safety for toys, EN 71-3, dealing with migration of special substances, limit values for migration of substances from toys materials are stated. These limit values are stated in the table below. For comparison the maximum analyzed values in the 10 cosmetic products for children are stated. The maximum measured values occur in all products with a special design of which some can be included in the Toys directive. Please note that these values are not migration values but on the contrary total values in the products. Table 5.14: Limit values for migration of substances from toy materials
Please note that the maximal analyzed values in the cosmetic products for children are total values and not migration values. From Table 5.14 can be seen that all the measured total values are substantially below the limit values for migration of the substances from toys (between 4 or 450 times below the limit values). Thus the measured total values are not a cause for concern in relation to the existing limit values for migration of substances from toy materials. For the same reason the planned migration analyses (according to EN 71-3) of the packaging materials are not conducted. 5.3.2.3 Content of phthalates in the packaging material10 products were selected for a quantitative analysis of phthalates in the packaging material where chlorine in the packaging material was proved or where statement on the packaging stated that it was made of PVC. Of the 10 product 3 are assessed to be toys (ID no. 21, 27 and 32) based on the indicative statement of the Danish Safety Technology Authority. The rest of the products are defined as child care articles. The results are stated in the table below. Table 5.15: Content of phthalates in 10 selected packaging materials
1: It is not an assured identification of DEHIP due to lacking reference substance. Here DEHIP is calculated as DEHP. But the found phthalate is most probably DEHIP or alternatively DnOP based on the spectras. DEHP: Bis(2-ethylhexyl)phthalate CAS no.: 117-81-7 DINP: Di-isononyl phthalate (isomeric mixture) CAS no.: 28553-12-0 DEHIP: Bis(2-ethylhexyl)iso phthalate DnOP: Di-n-octyl phthalate CAS no.: 117-84-0 According to the analyses, product no. 27 contains presumably acetyltributylcitrat (CAS no.: 77-90-7) as plasticizer but probably mixed with (CAS no. 77-94-1) and tributylaconitat (CAS no. 7568-58-3). Futhermore, several compounds in small quantities were found. Product no. 82 had no detectable content of extractable plasticizers. The analysis results confirm that the small bath products, designed as a particular figure and made in soft plastic, are made of PVC and have a high content of phthalates. For these figures the phthalate content is between 26 and 31% phthalates. Three large bath products designed as a standing cartoon figure and made in somewhat harder plastic were also analyzed for the content of phthalates. One of the figures was not softened by use of phthalates (content < 0.05%) while the two other figures had a phthalate content of 11 and 15% respectively. The identified types of phthalates are DEHP (Bis(2-ethylhexyl)phthalate) and DINP (Di-isononyl phthalate (isomeric mixture)). Furthermore, a content of something was found. From the spectra it seemed to be DEHIP[12] (Bis(2-ethylhexyl)iso phthalate). It might also be DnOP (di-n-octyl phthalate). This is not known for sure due to missing reference standard. As described in chapter 3.2.2 ”Ban on phthalates in toys for children”, from April 2007 DEHP, DINP and DnOP are banned in toys for children up to 14 years and in child care articles in a concentration above 0.1% - for DINP and DnOP only in products which children might put into the mouth. Some of the analyzed products are thus in discrepancy with the new phthalate legislation per 16 April 2007. However, on the date of purchase all the analyzed products were legal (spring 2006). Footnotes[9] Please note that this product is a stay-on product; that means the limit for separate declaration of the 26 fragrances is now 10 mg/kg. [10] Please note that this product is a stay-on product; that means the limit for separate declaration of the 26 fragrances is now 10 mg/kg. [11] Please note that the maximum measured concentration is only based on a few analysis results of products where the individual fragrance occurs. For the majority of the products it is unknown in which concentration the fragrances occur (only that it is above 100 mg/kg or 0.001%). [12] Please note that DEHIP (Bis(2-ethylhexyl)isophthalate) is not an ortho-phthalate but a meta-phthalate.
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