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Mapping and health assessment of chemical substances in shoe care products 4 Analyses4.1 Analysis programme Based on the results of the mapping, a number of products have been selected in cooperation with the EPA for analysis for selected chemical substances. Emphasis has been placed on problematic dyes, PFOS compounds and any other ingredients that may be problematic to humans or the environment. A final analysis programme was prepared for qualitative and quantitative analyses of the selected products. 4.1 Analysis programmeBelow is a descriptioin of the analysis programme established based on the previous phases. 4.1.1 X-ray (screening for heavy metals)An x-ray screening is carried out to identify the elements, including any heavy metals. The heavy metals can occur in the form of impurities or as components of colour pigments. A sub-sample of products was investigated using x-ray technique for content of all metals. Analysis uncertainty: 10% RSD. The accuracy of x-ray analysis is poor as there are calibration difficulties, particularly in the case of complex matrices. The analysis should therefore be considered a screening analysis. Detection limit: 5-10 mg/kg. 4.1.2 PFOS-compoundsAn analysis has been carried out fo rPFOS-compounds as previous investigations have shown that these substances may occur in impregnation products. A sub-sample is extracted with methanol and the extract is then analysed directly though reversed phase-column liquid chromography using a mass spectrometric detector (HPLC-MS). Electro-spray ionisation in netagive mode is used for detection. Calibration with external standards analysed in series with the sample is used. The detection limit is 0.1 mg/kg and the analysis uncertainty is 15% RSD. The analysis includes the following components: perfluorobutane sulphonate, perfluorohexane sulphonat, perfluorooctane sulphonat, perfluorodecan sulphonat, perfluorooctane sulphonamid, N-ethyl perfluorooctane sulphonamid, perfluoroheptane acid and perfluorooctane acid. The analysis is carried out in double determination. 4.1.3 OctamethylcyclotetrasiloxaneOctamethylcyclotetrasiloxane is on the EPA list of unwanted subtsances as the substance is classified as toxic to reproduction (Rep3;R62 R53) and as the substance is evaluated as a PBT [15] and vPvB [16] substance. It is assumed that this substance may occur in products containing silicone. Dichlormethane is added to a sub-sample which is shaken for 2 hours and left at room temperature for 16 hours. A sub-sample of the extract is analysed directly through a combination of gaschromatography and mass spectrometry (GC/MS). The detection limit is 1 mg/kg and the analysis uncertainty is 10-15% RSD. 4.1.4 Organic solventsA sub-sample is extracted with DMF (dimethylformamid) with added internal standards. A sub-sample of the extract is removed and analysed directly using combined gaschromatography and mass spectrometry (GC/MS) by scanning across a larges mass area. All identifications of substances have been carried out from the mass spectre by comparison with mass spectres in a data library. The content is calculated opposite internal standards. The reporting limit is 10-100 mg/kg and the analysis uncertainty is 25-50% RSD. The reporting limit is above the detection limit as the reporting limit is the concentration which in this case is estimated to be interesting – here established at 10-100 mg/kg corresponding to 0.001 to 0.01%. Methodwise it is thus possible to go further down in concentration, but the efforts will not match the result. 4.1.5 C9-12 isoalkanesA sub-sample of the product with known weight is extracted using dichlormethan. A sub-sample is extracted and analysed directly through combined gas chromatography and mass spectrometry (GC/MS) by scanning across a larger mass area. The content is calcuated as isoalkan (C10). The reporting limit is 5000 mg/kg and the analysis uncertainty is 15-20% RSD. The reporting limit is above the detection limit as the reporting limit is the concentration which in this case is considered interesting – here established at 5000 mg/kg corresponding to 0.5%. Methodwise it is thus possible to go further down in concentration but the efforts will not match the result. 4.1.6 PreservativesBenzylbenzoat, benzylalcohol, cresoles, parabenes and ethylenoxide can be included in the GC/MS screening where calculations are carried out opposite external standards. The detection limit is estimated at 10 mg/kg and the analysis uncertainty at 15% RSD. During the analysis for chlormethyl- and methylisothiazolones (Kathon) a representative sub-sample is extracted and diluted in demineralised water. 2 drops of concentrated saltsyre is added to the solution which is then filtered through a 0.45µm filter. The filtrerede solution is analysed by liquid chromatography with UV detection (HPLC/DAD). The detection limit is estimated to be 10-100 mg/kg. The analysis uncertainty is 10-15%. 4.1.7 Azo-dyesThe samples are extracted with an aquous buffer solution and reduced with dithionit whereby the amin part is split off from the azo-dye. The reaction products area extracted with t-butylmethylether and the extractions are then analysed using high pressure liquid chromatography with Diode-Array Detection (HPLC/DAD). The detection limit is 30 mg/kg and the analysis uncertainty is 15% RSD. The analysis includes the following aromatic amines: 2,4-diaminoanisol, 2,4-toluylendiamin, o-toluidin, 4,4-oxydianilin, benzidin, p-chloranilin, p-cresidin, 4,4'-methylendianilin, 2-naphthylamin, 4,4-thiodianilin, 3,3-dimethoxybenzidin, 4-chlor-o-toluidin, 2,4,5-trimethylanilin, 3,3-dimethylbenzidin (= o-Tolidin), 3,3-dimethyl-4,4-diaminodiphenyl methan, 4-aminodiphenyl, 3,3-dichlorbenzidin and 4,4-methylen-bis(2-chlor-anilin). 4.1.8 ChlorparaffinesA sub-sample of the product with known weight is extracted with n-heptane. A sub-sample is extracted and analysed directly by combined gas chromatography and electron capture detection (GC/ECD). The content is calculated quantatively. The detection limit is 50 mg/kg and the analysis uncertainty is 15-20% RSD. 4.1.9 GC/MS – screening for extractable organic substancesA sub-sample is extracted with dichlormethane with added internal standards. A sub-sample of the extract is extracted and analysed directly by combined gas chromatography and mass spectrometry (GC/MS) by scanning across a mass area. All identification of subtances have been carried out from retention time and mass spectre by comparison with mass spectres in a data library. The content is calculated semi-quantatively. The reporting limit is 10 mg/kg. The reporting limit is above the detection limit as the reporting limit is the concentration which in this case is considered interesting – here established at 10 mg/kg corresponding to 0.001%. Methodwise is is thus possible to go down further in concentration but the efforts will not match the result. As it is a screening examination, no analysis uncertainty is stated. 4.2 Analysis results4.2.1 X-rayThree products were analysed for elements using x-ray technique and the results are stated in table 10. The result is stated as intervals as the analysis is a screening. The intervals are stated as:
The elements not mentioned in the table have not been found in the analysis. Single determinations have been carried out. The unit is mg/kg and the detection limit is 10-20 mg/kg. As it is a screening alaysis, no analysis uncertainty is stated. Table 10 Results of analysis for elements. The results are stated in intervals in the unit mg/kg.
-: means not found above the detection limit 4.2.2 PFOS-compoundsFour products were analysed in double determination for eight specific PFOS-compounds. Components could only be determined in one product where two PFOS-compounds were detected. The results from the double determination are stated in table 2. The unit is mg/kg and the detection limit is 0.1 mg/kg. Tabel 11 Results of analysis for PFOS-compounds. The results are stated in mg/kg.
-: means not found above the detection limit 4.2.3 OctamethylcyclotetrasiloxanAn analysis for Octamethylcyclotetrasiloxan was carried out for eight shoe care products. The analysis was carried out in double determination and the results are stated in table 12. The unit is mg/kg and the detection limit is 0.5 mg/kg. Table 12 Results of analysis for Octamethylcyclotetrasiloxan. The results are stated in mg/kg.
-: means not found above the detection limit * CAS-no: 556-67-2 4.2.4 SolventsThe screening for solvents should components in all 6 analysed products. In three of the products, mineral turpentine was found in concentrations of 72, 88 and 85%, respectively. In one impregnation product (ID301), 93% isopropanol was found and in a cleaning product (ID296), 30% ethanol was found. In the final sample, only small amounts of methylethylketon (0.02 %) and xylen (0.004 %) were found and they were probably impurities in the product. The analysis has only been carried out in single determination as stated in table 13. The unit is mg/kg and the detection limit is 10 mg/kg. Table 13 Results of analysis for solvents. The results are stated in mg/kg.
-: means not found above the detection limit 4.2.5 C9-12 IsoalkanesThree of the products were analysed for isoalkanes (C9-12). In one of the products, isoalkanes were found in a concentration of 26-27 %. In the remaining two samples, isoalkanes were not found above the reporting limit of 5000 mg/kg (0.5%). Table 14 Results of analysis for C9-C12 isoalkanes. The results are stated in mg/kg.
-: means not found above the reporting limit The product which contains isoalkanes also contains mineral turpentine. The content of isoalkanes is assumed to be a sub amount of the amount of mineral turpentine. Mineral turpentine typically contains up to 48% alkanes. Product 256 contains 72% mineral turpentine and a content of 26.5% isoalkanes in the product would correspond to the mineral turpentine containing approximately 37% isoalkanes which is not unrealistic. In addition, it seems unlikely that the manufacturer would choose to use different types of hydrocarbon destillates as solvent in the product. 4.2.6 PreservativesFive products were analysed for a selection of preservatives: ID-no. 27, 40, 124, 296 and 304 The analysis included the following preservatives: Methylparaben, ethylparaben, propylparaben, butylparaben, benzylbenzoat, o-cresol, m+p-cresol and benzyl alcohol. The detection limit for the parabens and benzylbenzoat is 20 mg/kg except for product no. 124 where the detection limit for propylparaben was raised to 60 mg/kg due to interference. The detection limit for the cresols and benzyl alcohol is 50 mg/kg. None of the preservatives were found above the detection limit in the products tested. The content of chlormethyl and methyl isothiazolones was tested in 4 products: ID-no. 27, 40, 123, 124, 296 and 304 No content of chlormethyl and methyl isothiazolones was found above the dtection limit of 50 mg/kg in the products tested. 4.2.7 Azo-dyesAn analysis for aromatic amines from azo-dyes was performed in 5 products: ID-no. 40, 123, 124, 168 and 256 No aromatic amines above the detection limit of 100 mg/kg were found in the products tested. The detection limit was raised to 100 mg/kg due to interference from the highly concentrated dyes in the products. The following amines were included in the analysis: 2,4-Diaminoanisol, 2,4-toluylendiamin, o-toluidin, 4,4-oxydianilin, benzidin, p-chloranilin, p-cresidin, 4,4'-methylendianilin, 2-naphthylamin, 4,4-thiodianilin, 3,3-dimethoxybenzidin, 4-chlor-o-toluidin, 2,4,5-trimethylanilin, 3,3-dimethylbenzidin (= o-tolidin), 3,3-dimethyl-4,4-diaminodiphenyl methan, 4-aminodiphenyl, 3,3-dichlorbenzidin and 4,4-methylen-bis(2-chlor-anilin). 4.2.8 Chlorparaffins2 products were analysed for chlorparaffins: No. 256 and 266 No chlorparaffins were found above the detection limit of 50 mg/kg in the products tested. 4.2.9 GC/MS-screeningTable 15 Results of GC/MS-screening. The results are stated in mg/kg.
-: means not found above the detection limit The GC-MS screening showed that product ID266 contains 70% of an aliphatic hydrocarbon destillate and 25% wax which means that the product composition is similar to the one stated for the remaining shoe polishes. In addition, the preservative BHT was found in a concentration of 0.12 %. According to the analysis, product ID266 contains solvents 88% mineral turpentine, and according to the GC/MS-screening it contains 70% aliphatic hydrocarbons (C9-11) which indicates that the product contains a mineral turpentine with an aromatic content of approximately 20%. This is a typical aromatic content for this type of mineral turpentine. However, the aromatic content could not be determined exactly based on the available analysis results. Product ID301 contained very small amounts of perfluoride compounds (less than 0.002%) and furthermore a very small amount of pentamethylheptane (0.0022%) which should be considered as impurities in the product. 4.3 Summary of analysis resultsNone of the preservatives analysed for were found. However, the GC-MS screening showed BHT in one of the samples in a concentration of 0.12%. No azo-dyes were found in concentrations above the respective detection limits in any of the samples analysed. The safety data sheet for product number 123 states a content of 0.15 to 0.25% 5-chloro-2-methyl-4-Isothiazolin-3-on but it is possible that the product has been reformulated and therefore no longer contains the substance. Very small amounts of 2 PFOS compounds (1.1 and 0.36 mg/kg, respectively) were found in 1 of the 4 analysed samples of impregnation products. The amounts of PFOS compounds found are likely impurities in a flourcarbonpolymer added due to the water and dirt repellant properties. In addition, very small amounts (from 0.79 to 3.4 mg/kg) octamethylcyclotetrasiloxan were found in 5 of the 8 analysed products. 3 of the 5 products are known to contain silicone. It is assumed that octamethylcyclotetra-siloxan is found as impurity in the silicone oil added to the product due to is imprenating and tending properties. The x-ray screening of 3 products found no metals, including heavy metals, in 2 of those products in concentrations above 1000 mg/kg (corresponding to 0.1%) and for most of the substances, the content was below the detection limit (either 10 or 20 mg/kg). In the third sample, a content of silicium and titan of between 10,000 and 100,000 mg/kg was found corresponding to between 1 and 10%. These elements likely come from silicium dioxide (SiO2) and titan dioxide (TiO2) used as filler and colour pigment, respectively. In addition, the sample contained Na, Al, S, Cl, Mn and Ba in concentrations between 1,000 and 10,000 mg/kg corresponding to 0.1-1%. These elements are assumed to come from colour pigments as the product in question is a coloured shoe polish. The content of chlorine may, however, come from other compounds such as chlorparaffins or chlorinated solvents. Many of the products contain organic solvents used to dissolve dirt on the footwear or to dissolve the tending oils and waxes in the product. The screening of 6 products for solvents found mineral turpentine in three of the products (all shoe polishes) in concentrations of 72, 88 and 85%, respectively. In one impregnation product (ID301), 93 % isopropanol was found and in a cleaning product (ID296), 30% ethanol was found. In the final sample, only small amounts of methylethylketon (0.02 %) and xylen (0.004 %) was found which are probably impurities in the product. Of the 3 samples selected for specific analysis for the solvent C9-C12 isoalkanes, 265,000 mg/kg corresponding to 26.5% was found in one of the samples. The results of the analyses are compared in table 16 below as the analyses carried out for each product are marked and the found content of substances of = 0.1% are stated. Table 16 Found content of substances in concentrations of 0.1% or above
- : < 0.1% Based on the analysis results it can be concluded that no substantial amounts of either PFOS or octamethyltetrasiloxan have been found. PFOS compounds have only been found in one of the four products analysed and only in a combined amoutn of 1.5 mg/kg corresponding to 0.00015%. Very small concentrations of octamethylcyclotetrasiloxan were found in 5 of the 8 products analysed and the highest concentration was 3.4 mg/kg corresponding to 0.00034%. The very low concentrations of these substances indicate that they are found as impurities from fluorcarbonpolymers and silicone, respectively. In addition, no preservatives or azo-dyes were found in any of the samples analysed. However, the analyses confirm that a number of shoe polishes contain solvents as large amounts of mineral turpentine (72, 88 and 85%) was found in 3 products along with 93% propanol and 30% ethanol respectively in 2 products . In addition, 26.5% C9-C12 isoalkanes was found in 1 of 3 products analysed for this specific solvent. According to the supplier's information, product ID266 contained 10-25% turpentine oil. This could not be confirmed through an analysis for organic solvents which showed a content of 88% mineral turpentine. Another analysis method identified 70% aliphatic kulbrinter in the same product. This may indicate that the product contains a mineral turpentine with an aromatic content of approximately 20% which is typical for certain aromatic turpentines. As the analyses showed a relatively high content of chlorine and hydrocarbons in ID256, this product and product ID266, which is a similar product, were further analysed for content of chlorparaffins. However, this analysis disproved the suspicion of content of chlorparaffins. Fodnoter [15] Persistent, bio-accumulating and toxic [16] Very persistent and very bio-accumulating substances [17] Mainly C9-11, with a possible minimal content of C12.
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