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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 pyrolysis.(a) Py–GC/MS chromatogram (1,000 °C) of pigment B15:3. BDCN, BCN, HCN, and 2-butanone represent the main compounds detected. Some tiny amounts of benzene were also detectable at temperatures >800 °C. (b)–(c) Temperature-dependent formation of HCN and benzene during Py–GC/MS analysis of the pigment phthalocyanine blue (pigment B15:3). The values shown represent extracted ion areas of (b) HCN (m/z = 27), (c) benzene (m/z = 78), and (d) 2-butanone (m/z = 72) that have been normalized to the total chromatogram area. Therefore, absolute numbers do not correlate to peak areas of all ion fragments of the molecules included (cf. Fig. 1a). Similar as with BCN and BDCN (data not shown), HCN and benzene formation increases with pyrolysis temperature while levels of 2-butanone did not.
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f1: Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon pyrolysis.(a) Py–GC/MS chromatogram (1,000 °C) of pigment B15:3. BDCN, BCN, HCN, and 2-butanone represent the main compounds detected. Some tiny amounts of benzene were also detectable at temperatures >800 °C. (b)–(c) Temperature-dependent formation of HCN and benzene during Py–GC/MS analysis of the pigment phthalocyanine blue (pigment B15:3). The values shown represent extracted ion areas of (b) HCN (m/z = 27), (c) benzene (m/z = 78), and (d) 2-butanone (m/z = 72) that have been normalized to the total chromatogram area. Therefore, absolute numbers do not correlate to peak areas of all ion fragments of the molecules included (cf. Fig. 1a). Similar as with BCN and BDCN (data not shown), HCN and benzene formation increases with pyrolysis temperature while levels of 2-butanone did not.

Mentions: Using an online coupling to GC/MS we identified HCN, 1,2-benzene dicarbonitrile (BDCN), benzonitrile (BCN), and 2-butanone as the four main cleavage products of pigment B15:3 upon pyrolysis at ≥800 °C (Fig. 1a). Since the latter is often added as solvent its presence is likely a remainder from pigment synthesis. In addition, some traces of benzene also emerged in the pyrograms at temperatures >800 °C. In contrast to 2-butanone, levels of HCN, BDCN, BCN and benzene were increasing with pyrolysis temperature, thus confirming their occurrence as specific degradation products (Fig. 1b–d). Commercially available standards for HCN (including its isotopes) and BDCN were used for the identification of pyrolysis-dependent descendants of the pigment. Further, retention times and mass spectra were identical to those peaks identified as HCN and BDCN by library comparison. Whereas the decomposition of pigment B15:3 into BDCN has been already shown by a previous study17, additional formation of the lower molecular weight compounds BCN and benzene, and the gaseous HCN has remained undiscovered yet (Fig. 2).


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 pyrolysis.(a) Py–GC/MS chromatogram (1,000 °C) of pigment B15:3. BDCN, BCN, HCN, and 2-butanone represent the main compounds detected. Some tiny amounts of benzene were also detectable at temperatures >800 °C. (b)–(c) Temperature-dependent formation of HCN and benzene during Py–GC/MS analysis of the pigment phthalocyanine blue (pigment B15:3). The values shown represent extracted ion areas of (b) HCN (m/z = 27), (c) benzene (m/z = 78), and (d) 2-butanone (m/z = 72) that have been normalized to the total chromatogram area. Therefore, absolute numbers do not correlate to peak areas of all ion fragments of the molecules included (cf. Fig. 1a). Similar as with BCN and BDCN (data not shown), HCN and benzene formation increases with pyrolysis temperature while levels of 2-butanone did not.
© Copyright Policy - open-access
Related In: Results  -  Collection

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Show All Figures
getmorefigures.php?uid=PMC4525383&req=5

f1: Phthalocyanine blue (pigment B15:3) is cleaved into BDCN, BCN and HCN upon pyrolysis.(a) Py–GC/MS chromatogram (1,000 °C) of pigment B15:3. BDCN, BCN, HCN, and 2-butanone represent the main compounds detected. Some tiny amounts of benzene were also detectable at temperatures >800 °C. (b)–(c) Temperature-dependent formation of HCN and benzene during Py–GC/MS analysis of the pigment phthalocyanine blue (pigment B15:3). The values shown represent extracted ion areas of (b) HCN (m/z = 27), (c) benzene (m/z = 78), and (d) 2-butanone (m/z = 72) that have been normalized to the total chromatogram area. Therefore, absolute numbers do not correlate to peak areas of all ion fragments of the molecules included (cf. Fig. 1a). Similar as with BCN and BDCN (data not shown), HCN and benzene formation increases with pyrolysis temperature while levels of 2-butanone did not.
Mentions: Using an online coupling to GC/MS we identified HCN, 1,2-benzene dicarbonitrile (BDCN), benzonitrile (BCN), and 2-butanone as the four main cleavage products of pigment B15:3 upon pyrolysis at ≥800 °C (Fig. 1a). Since the latter is often added as solvent its presence is likely a remainder from pigment synthesis. In addition, some traces of benzene also emerged in the pyrograms at temperatures >800 °C. In contrast to 2-butanone, levels of HCN, BDCN, BCN and benzene were increasing with pyrolysis temperature, thus confirming their occurrence as specific degradation products (Fig. 1b–d). Commercially available standards for HCN (including its isotopes) and BDCN were used for the identification of pyrolysis-dependent descendants of the pigment. Further, retention times and mass spectra were identical to those peaks identified as HCN and BDCN by library comparison. Whereas the decomposition of pigment B15:3 into BDCN has been already shown by a previous study17, additional formation of the lower molecular weight compounds BCN and benzene, and the gaseous HCN has remained undiscovered yet (Fig. 2).

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