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Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue.

Schreiver I, Hutzler C, Laux P, Berlien HP, Luch A - Sci Rep (2015)

Bottom Line: Applying dynamic headspace-gas chromatography with mass spectrometric detection (DHS-GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension.Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue.According to the literature such regular tattoos hold up to 9 mg pigment/cm(2) skin.

View Article: PubMed Central - PubMed

Affiliation: German Federal Institute for Risk Assessment (BfR), Department of Chemical and Product Safety, Max-Dohrn-Strasse 8-10, 10589 Berlin, Germany.

ABSTRACT
Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace-gas chromatography with mass spectrometric detection (DHS-GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm(2) skin.

No MeSH data available.


Related in: MedlinePlus

Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon laser irradiation.(a)–(c) left: Levels of BDCN, BCN and HCN depending on the number of applied ruby laser pulses (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (a)–(c) middle: BDCN, BCN and HCN levels as function of the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (a)–(c) right: Only slightly increased fragment concentrations were found upon Nd:YAG laser irradiation when compared to ruby laser irradiation (3 laser pulses at 1 mg/ml pigment; control = no laser beam). (d) left: Fraction (in %) of pigment destroyed depending on the number of ruby laser pulses applied (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (d) right: Fraction (in %) of pigment destroyed depending on the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (e) UV/VIS cuvette after 3 laser pulses (left) compared to an untreated sample (right) containing 0.2 mg/ml of pigment B15:3 each. The laser-treated sample is carbonized at the outer cuvette surface but appears more intensely blue colored (see text for further details). All values are displayed as mean ± SD (n = 3).
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f3: Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon laser irradiation.(a)–(c) left: Levels of BDCN, BCN and HCN depending on the number of applied ruby laser pulses (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (a)–(c) middle: BDCN, BCN and HCN levels as function of the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (a)–(c) right: Only slightly increased fragment concentrations were found upon Nd:YAG laser irradiation when compared to ruby laser irradiation (3 laser pulses at 1 mg/ml pigment; control = no laser beam). (d) left: Fraction (in %) of pigment destroyed depending on the number of ruby laser pulses applied (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (d) right: Fraction (in %) of pigment destroyed depending on the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (e) UV/VIS cuvette after 3 laser pulses (left) compared to an untreated sample (right) containing 0.2 mg/ml of pigment B15:3 each. The laser-treated sample is carbonized at the outer cuvette surface but appears more intensely blue colored (see text for further details). All values are displayed as mean ± SD (n = 3).

Mentions: To investigate whether the decomposition patterns are similar under various laser treatment scenarios applied in cosmetic dermatology, water-based pigment dispersions of pigment B15:3 were either treated with multiple quantities of ruby (5 J/cm2, spot size 5 mm, 694 nm) or Nd:YAG (5 J/cm2, spot size 3 mm, at 1,064 nm or 532 nm) laser pulses. Subsequent to laser irradiations quantitative analysis of both volatiles HCN and benzene was carried out using a DHS–GC/MS method, whereas screening and quantification of the other fragments (i.e. BDCN, BCN) were carried out by extraction with ethyl acetate followed by GCxGC-ToF-MS analysis. So, HCN, BCN and BDCN levels were all found increasing as a function of the number of ruby laser beams applied and the initial pigment concentrations (Fig. 3a–c). On the other hand, quantitative analysis of benzene revealed kind of challenging due to its occurrence only in traces and the necessity for an adaptation of the analytics applied (which were intentionally optimized to target CN-containing compounds). Nevertheless we were able to detect 0.32 μM (25.1 ng/ml) benzene after three ruby laser irradiation pulses applied to 1 mg pigment B15:3 per ml suspension (mean out of n = 3). With this we experimentally confirmed the occurrence of all intermediates in the degradation pathway of phthalocyanine blue according to theoretical and reasonable predictions (Fig. 2). We further demonstrated that the decomposition products in aqueous suspensions of pigment copper phthalocyanine upon ruby laser irradiation correlate well with those found in the corresponding Py-GC/MS analyses (cf. above).


Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue.

Schreiver I, Hutzler C, Laux P, Berlien HP, Luch A - Sci Rep (2015)

Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon laser irradiation.(a)–(c) left: Levels of BDCN, BCN and HCN depending on the number of applied ruby laser pulses (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (a)–(c) middle: BDCN, BCN and HCN levels as function of the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (a)–(c) right: Only slightly increased fragment concentrations were found upon Nd:YAG laser irradiation when compared to ruby laser irradiation (3 laser pulses at 1 mg/ml pigment; control = no laser beam). (d) left: Fraction (in %) of pigment destroyed depending on the number of ruby laser pulses applied (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (d) right: Fraction (in %) of pigment destroyed depending on the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (e) UV/VIS cuvette after 3 laser pulses (left) compared to an untreated sample (right) containing 0.2 mg/ml of pigment B15:3 each. The laser-treated sample is carbonized at the outer cuvette surface but appears more intensely blue colored (see text for further details). All values are displayed as mean ± SD (n = 3).
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Related In: Results  -  Collection

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f3: Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon laser irradiation.(a)–(c) left: Levels of BDCN, BCN and HCN depending on the number of applied ruby laser pulses (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (a)–(c) middle: BDCN, BCN and HCN levels as function of the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (a)–(c) right: Only slightly increased fragment concentrations were found upon Nd:YAG laser irradiation when compared to ruby laser irradiation (3 laser pulses at 1 mg/ml pigment; control = no laser beam). (d) left: Fraction (in %) of pigment destroyed depending on the number of ruby laser pulses applied (1× to 6×; initial pigment concentration used: 0.2 mg/ml; control = no laser beam). (d) right: Fraction (in %) of pigment destroyed depending on the initial pigment concentration (0.2 mg/ml to 2.5 mg/ml; at each concentration 3 laser pulses applied; control = no pigment). (e) UV/VIS cuvette after 3 laser pulses (left) compared to an untreated sample (right) containing 0.2 mg/ml of pigment B15:3 each. The laser-treated sample is carbonized at the outer cuvette surface but appears more intensely blue colored (see text for further details). All values are displayed as mean ± SD (n = 3).
Mentions: To investigate whether the decomposition patterns are similar under various laser treatment scenarios applied in cosmetic dermatology, water-based pigment dispersions of pigment B15:3 were either treated with multiple quantities of ruby (5 J/cm2, spot size 5 mm, 694 nm) or Nd:YAG (5 J/cm2, spot size 3 mm, at 1,064 nm or 532 nm) laser pulses. Subsequent to laser irradiations quantitative analysis of both volatiles HCN and benzene was carried out using a DHS–GC/MS method, whereas screening and quantification of the other fragments (i.e. BDCN, BCN) were carried out by extraction with ethyl acetate followed by GCxGC-ToF-MS analysis. So, HCN, BCN and BDCN levels were all found increasing as a function of the number of ruby laser beams applied and the initial pigment concentrations (Fig. 3a–c). On the other hand, quantitative analysis of benzene revealed kind of challenging due to its occurrence only in traces and the necessity for an adaptation of the analytics applied (which were intentionally optimized to target CN-containing compounds). Nevertheless we were able to detect 0.32 μM (25.1 ng/ml) benzene after three ruby laser irradiation pulses applied to 1 mg pigment B15:3 per ml suspension (mean out of n = 3). With this we experimentally confirmed the occurrence of all intermediates in the degradation pathway of phthalocyanine blue according to theoretical and reasonable predictions (Fig. 2). We further demonstrated that the decomposition products in aqueous suspensions of pigment copper phthalocyanine upon ruby laser irradiation correlate well with those found in the corresponding Py-GC/MS analyses (cf. above).

Bottom Line: Applying dynamic headspace-gas chromatography with mass spectrometric detection (DHS-GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension.Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue.According to the literature such regular tattoos hold up to 9 mg pigment/cm(2) skin.

View Article: PubMed Central - PubMed

Affiliation: German Federal Institute for Risk Assessment (BfR), Department of Chemical and Product Safety, Max-Dohrn-Strasse 8-10, 10589 Berlin, Germany.

ABSTRACT
Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace-gas chromatography with mass spectrometric detection (DHS-GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm(2) skin.

No MeSH data available.


Related in: MedlinePlus