Identification of Aminobiphenyl Derivatives in Commercial Hair Dyes

• Published in: Chemical research in toxicology Vol. 16; no. 9; pp. 1162 - 1173
• Main Authors: Turesky, Robert J, Freeman, James P, Holland, Ricky D, Nestorick, Daniel M, Miller, Dwight W, Ratnasinghe, D. Luke, Kadlubar, Fred F
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.09.2003
• Subjects: aminobiphenyl; Aminobiphenyl Compounds - analysis; Aminobiphenyl Compounds - isolation & purification; Chromatography, High Pressure Liquid - methods; DNA Adducts - analysis; DNA Adducts - biosynthesis; Drug Contamination; hair dyes; Hair Dyes - adverse effects; Hair Dyes - chemistry; Humans; Spectrometry, Mass, Electrospray Ionization - methods; Stereoisomerism
• ISSN: 0893-228X; 1520-5010
• DOI: 10.1021/tx030029r

A recent epidemiological study suggested that aromatic amines present in hair dyes may contribute to an increased risk of bladder cancer (Gago-Dominguez, et al. (2003) Carcinogenesis 24, 483−489). Moreover, a preliminary study linked frequent hair dye usage with elevated levels of DNA adducts of 4-aminobiphenyl (4-ABP) in human epithelial breast cells (Gorlewska, et al. Proc. Am. Assoc. Cancer Res. 43, 1018−1019). Therefore, we sought to determine if 4-ABP, a recognized human urinary bladder carcinogen, is present in commercial hair dyes. 4-ABP was isolated from dyes by solvent extraction with hexane, followed by silica gel chromatography, either with or without chemical treatment of the extract with Zinc/HCl, and a final purification with a mixed cation exchange reversed-phase resin. The identity of 4-ABP was confirmed by both HPLC with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) and gas chromatography with negative ion chemical ionization mass spectrometry (GC-NICI-MS) following chemical derivatization with pentafluoropropionic anhydride (PFPA). The levels of 4-ABP ranged from not detectable (<0.29 parts per billion (ppb)) up to 12.8 ppb. The noncarcinogenic isomer 2-aminobiphenyl (2-ABP) was also found at quantities up to 310 ppb. 4-ABP was detected in eight of the 11 hair dyes and found in black, red, and blonde hair dyes but not in brown hair dyes. 1,4-Phenylenediamine (PPD) is a key constituent for color development of many permanent hair dyes. Some batches of chemical research grade PPD were contaminated with 4-ABP (up to 500 ppb) and 2-ABP (up to 70 parts per million) and may be a source of ABP contamination in hair dyes. These analytical data demonstrate that 4-ABP is present in some hair dyes. Studies on dermal absorption and bioavailability of 4-ABP from hair dyes are required to determine if this aromatic amine contributes to the increased risk of bladder cancer reported in frequent users of hair dyes.