Colorants in transferable picture tattoos for the skin

4 Results

All-in-all 42 products of picture tattoos (or products to which picture tattoos were attached) and similar products were purchased from the Danish retail outlets. Two of the products 4-0224 and 4-0225 were purchased twice (4-0287 and 4-0288 respectively) by different persons in the different part of the country. Often, the picture tattoos in each product were different figures composed of different colours. Therefore, 36 picture tattoos (22 products) were selected for the analysis, so that the most of the colorants used in the collected tattoo stickers were represented.

In a preliminary investigation, 6 different picture tattoos were extracted with various solvents (acetone, methanol, hexane, dichloromethane, acetonitrile, tetrhydrofuran, HPLC-solvent and water). Furthermore, both shaking and ultrasonic treatment was used to investigate the dissolution/release of the tattoo colorants into the solvent. The preliminary study revealed that ultrasonic treatment of the samples (picture tattoos sticking on a paper) in a solvent, followed by gently scraping off the remaining coloured material from the paper into the solvent, was the most suitable method for extracting the colorants from picture tattoos into the solvent. Most of the colorants (but not all) were soluble in HPLC-solvent and THF. But some colorants, especially Black and Blue, were not soluble in the solvents used. To perform a systematic investigation of colorants in all picture tattoo samples, the method described in 3.2 was chosen.

Both HPLC-solvent and THF extracts were analysed by HPLC. The colorants in the sample extracts were identified by matching the retention time and spectrum of each HPLC peak with the retention times and spectra of reference colorants analysed under the same conditions. The identification of colorants in some of the sample extracts is shown in Figures 2-5. As shown in Figures 2C and 5B, the spectrum of sample peak does not match 100% with the spectrum of reference colorant. However, this is not unusual when the concentration of the colorant is very low.

The colorants identified in the picture tattoos are described in Table 2. The unidentified colours in the sample extracts as well as the undissolved colours of the samples are also described in Table 2. The unidentified colorants may be those, which are not included in our library of colours or the concentration of these may be below the detection limit (0.5 ppm).

The colorant(s) in two out of the three Black picture tattoos could not be dissolved in the solvents used in the present study. The black colour in the third product (4-0460) was soluble in ACN:THF (1:1).However, the dissolved black colour from this sample could not be identified by the method used in the present investigation (no HPLC peak). Most of the remaining picture tattoos (31 out 33) were composed of colorant CI15850. Other colorants presents in the investigated picture tattoos were: CI 11920 in 2 out of 33 samples, CI 45220 in 10 out of 33 samples, CI 75300 and CI 74180 each in 4 out of 33 samples, CI 13015 and CI 45100 each in 3 out of 33 samples, and CI 14815 in 2 out of 33 samples. CI 15225, CI 16255 and CI 42170 were present only in one picture tattoo each.

The Blue colour CI 74180 was identified in four of the analysed tattoo stickers. However, the Blue colour in several of the samples could not be extracted. This may also be the reason that green (blue+yellow) and violet (blue+red) colours could not be identified in several of the investigated samples. Sample No. 4-0382 is declared to contain CI 19140 (yellow), CI 15985 (yellow) and CI 42090 (blue), but these colorants could not be identified in the subsamples investigated. It is possible that the content of these colorants in the investigated subsamples is below the detection limit (0.5 ppm) of these.

The contents (semi-quantitative determination) of the identified colorants in the investigated picture tattoos are described in Table 3. The content of the colorants is described as total content of these found in HPLC- solvent and THF extracts. In some samples, the content of certain colorants could not be determined because of the interference from other HPLC-peaks, very close to the HPLC-peak of the target colorant in the sample extract. Furthermore, in some samples the content of certain identified colorants could not be determined due to a very small HPLC-peak. In such cases, approximate content (<2 ppm) is given, calculated on the basis of detection limits of these colorants. The contents of the identified colorants in the investigated samples were: 6-4479 ppm CI 11920, <2 -2926 ppm CI 15850, <2-800 ppm CI 13015, <2-103 ppm CI 45220, <2-35 ppm CI 75300 and 217 ppm CI 15525. The contents of the remaining identified colorants in the tattoo stickers were <12 ppm.

Click here to see figure 2.

Figure 2: Identification of colorants in the HPLC-solvent extract of sample no. 225-2. A: HPLC chromatogram, B: spectrum of 14,118 min chromatographic peak with the spectrum of CI 15850, C: spectrum of 33,122 min chromatographic peak with the spectrum ofCI 75300.

Click here to see figure 3.

Figure 3: Identification of colorants in THF extract of sample no. 226-2. A: HPLC chromatogram, B: spectrum of 14,169 min chromatographic peak with the spectrum of CI 15850, C: spectrum of 21,519 min chromatographic peak with the spectrum of CI 74180.

Click here to see figure 4.

Figure 4: Identification of colorants in the THF extract of sample no.229-2. A: HPLC chromatogram, B: spectrum of 14,841 min chromatographic peak with the spectrum of CI 45220.

Click here to see figure 5.

Figure 5: Identification of colorants n the THF extract of sample no. 250-2. A: HPLC chromatogram, B: spectrum of 24,535 min chromatographic peak with the spectrum of CI 11920.

Table 2: Identification of colorants in picture tattoos

Sample No. Tattoo sticker Extraction solvent Identified colorants Unidentified colorants on picture tattoos Comments
4-0223-1 Sitting eagle HPLC CI 15850    
4-0223-1 Sitting eagle THF CI 74180    
4-0223-2 Flying eagle HPLC CI 15850    
4-0223-2 Flying eagle THF CI 15850, CI 74180    
4-0224-1 Dynamite stick HPLC CI 15850    
4-0224-1 Dynamite stick THF CI 15850, CI 75300 Blue  
4-0224-2 Cat HPLC CI 15850, CI 14815    
4-0224-2 Cat THF CI 15850, CI 75300 Blue  
4-0225-1 Rabbit on roller-skate HPLC CI 15850    
4-0225-2 Rabbit on roller-skate THF CI 15850, CI 14815 Blue, Yellow  
4-0225-1 Rabbit on rostrum HPLC CI 15850    
4-0225-2 Rabbit on rostrum THF CI 15850, CI 75300 Blue  
4-0226-1 Barbie with Pink hand bag HPLC CI 15850    
4-0226-1 Barbie with Pink hand bag THF CI 15850, CI 74180    
4-0226-2 Barbie (Pink trousers+Blue T-shirt) HPLC CI 15850    
4-0226-2 Barbie (Pink trousers+Blue T-shirt) THF CI 15850, CI 74180    
4-0228-1 Woman with fire HPLC CI 45220, CI 45100    
4-0228-1 Woman with fire THF - Blue Undissolved Blue/Black
4-0228-2 Skull with horns HPLC CI 45220, CI 45100    
4-0228-2 Skull with horns THF CI 15850, CI 75300 Blue Undissolved Blue/Black
4-0229-1 Mummy HPLC CI 15850    
4-0229-1 Mummy THF CI 45220 Blue  
4-0229-2 Woman on chair with Sun HPLC CI 15850    
4-0229-2 Woman on chair with Sun THF CI 45220 Blue, Green  
4-0231-1 Blue flower HPLC CI 15850    
4-0231-1 Blue flower THF CI 15850 Blue  
4-0231-2 Red flower HPLC CI 15850    
4-0231-2 Bred flower THF CI 15850    
4-0232-1 Grasshopper HPLC CI 15850    
4-0232-1 Grasshopper THF CI 11920 Blue/Violet, Green  
4-0232-2 Larva HPLC CI 15850    
4-0232-2 Larva THF CI 45220, CI 11920 Blue  
4-0233 Vulcan (lava stone) HPLC CI 15850    
4-0233 Vulcan (lava stone) THF CI 15850, CI 11920    
4-0234 Dragon (dragon egg) HPLC CI 15850    
4-0234 Dragon (dragon egg) THF CI 15850, CI 11920 Green  
4-0235 Canon (Canon balls) HPLC CI 15850    
4-0235 Canon (Canon balls) THF CI 15850, CI 11920 Blue Undissolved Blue/Black
4-0250-1 Red/Orange Butterfly HPLC CI 15850    
4-0250-1 Red/Orange Butterfly THF CI 15850, CI 16255, CI 11920    
4-0250-2 Violet butterfly HPLC CI 15850    
4-0250-2 Violet butterfly THF CI 15850, CI 11920 Violet/Blue  
4-0250-3 Blue butterfly HPLC CI 15850    
4-0250-3 Blue butterfly THF CI 15850, CI 11920 Blue  
4-0251 “Wild” - - Black Undissolved Black
4-0294 Dragon HPLC CI 15850, CI11920    
4-0294 Dragon THF CI 15850 Blue, Violet, Green,  
4-0350 Flower branch HPLC CI 15850, CI15525, CI 11920, CI 42170    
4-0350 Flower branch THF CI 15850, CI 15525, CI 11920, CI 42170    
4-0351-1 Man with green mask HPLC CI 15850, CI 45220    
4-0351-1 Man with Green mask THF CI 15850 Green, Blue  
4-0351-2 Woman with Red dress HPLC CI 15850, CI 45220    
4-0351-2 Woman with Red dress THF CI 15850 Green, Violet  
4-0352-1 Indian with feather HPLC CI 15850, CI 45220    
4-0352-1 Indian with feather THF CI 15850 Blue  
4-0352-2 Heart with arrow and butterfly HPLC CI 15850, CI 45220    
4-0352-2 Heart with arrow and butterfly THF -   Many small (mixed) chromatographic peaks
4-0353 Snake (Black) - - Black Undissolved Black
4-0354-1 Snake (Green) HPLC CI 15850    
4-0354-1 Snake(Green) THF CI 15850 Green Undissolved Blue/Black
4-0354-2 Snake + rose HPLC CI 15850    
4-0354-2 Snake + rose THF CI 15850 Green Undissolved Blue/Black
4-0382-1 Yellow + Green birds HPLC CI 15850    
4-0382-1 Yellow + Green birds THF CI 15850, CI 11920, CI 13015 Green Undissolved Blue/Black
4-0382-2 Red + Blue birds HPLC CI 15850    
4-0382-2 Red + Blue birds THF CI 15850, CI 11920, CI 13015 Blue Undissolved Blue/Black
4-0459 Scorpion HPLC CI 45220, CI 45100    
4-0459 Scorpion THF CI 13065 Blue  
4-0460 Jing/jang (Black/Grey) ACN/THF - Balck/silver Dissolved in ACN:THF (1:1), no chromatographic peak

Table 3: Colorants contents (semi-kvantitativt) in picture tattoos

Sample No.   Colorant content in ppm
Colorant CI 15850 CI 11920 CI 45220 CI 75300 CI 74180 CI 13015 CI 45100 CI 14815 CI 15525 CI 16255 CI 42170
4-0223-1   580       5            
4-0223-2   556       6            
4-0224-1   76     <2              
4-0224-2   74     <2       <2      
4-0225-1   47             <2      
4-0225-2   72     14              
4-0226-1   161       7            
4-0226-2   314       5            
4-0228-1   -   27       52        
4-0228-2   4   29 35     55        
4-0229-1   982   4                
4-0229-2   561   <1                
4-0231-1   54                    
4-0231-2   230                    
4-0232-1   25 19                  
4-0232-2   69 20 <1                
4-0233   276 4479                  
4-0234   82 2907                  
4-0235   114 6                  
4-0250-1   633 81               5  
4-0250-2   815 99                  
4-0250-3   594 125                  
4-0251   -                    
4-0294   1496 *                  
4-0350   36 *             217   <2
3-0351-1   <3   <1                
3-0351-2   868   11                
3-0352-1   48   96                
3-0352-2   58   103                
3-0353                        
3-0354-1   58                    
3-0354-2   332                    
3-0382-1   8 888       <2       12  
3-0382-2   2391 150       800          
3-0459   -   4     3 6        
4-0460   -                    

 



Version 1.0 August 2005, © Danish Environmental Protection Agency