title: Identification of aminobiphenyl derivatives in commercial hair dyes.
abstract: 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.
authors.affiliation: Division of Chemistry, National Center for Toxicological Research, Jefferson, Arkansas 72079, USA. RTuresky@nctr.fda.gov
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Turesky
authors.forename: James P
authors.initials: JP
authors.lastname: Freeman
authors.forename: Ricky D
authors.initials: RD
authors.lastname: Holland
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Nestorick
authors.forename: Dwight W
authors.initials: DW
authors.lastname: Miller
authors.forename: D Luke
authors.initials: DL
authors.lastname: Ratnasinghe
authors.forename: Fred F
authors.initials: FF
authors.lastname: Kadlubar
mesh_terms: D000611:Aminobiphenyl Compounds / Q000032:analysis* / Q000302:isolation & purification*; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D018736:DNA Adducts / Q000032:analysis / Q000096:biosynthesis; D004340:Drug Contamination; D006202:Hair Dyes / Q000009:adverse effects / Q000737:chemistry*; D006801:Humans; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013237:Stereoisomerism
chemical_list: D000611:Aminobiphenyl Compounds; D018736:DNA Adducts; D006202:Hair Dyes