THE GREEN HAIR PROBLEM 7 were cleaned in boiling methanol for several minutes and treated wi[h a 0.000 5 M aqueous solution of methylene blue dye at 11 pH for several minutes and subsequently washed in distilled water. The "green" hair strands acquired a much deeper blue stain than the "normal" hair strands. Since absorption of methylene blue from an aqueous solution is representative of the chemical hair damage (17), it is inferred that the "green" hair strands had suffered a greater degree of chemical damage. Optical microscopic examination further showed that the "green" hair strands had partially or completely lost the normal cuticle structure. All these results collectively suggest that the green streaks are caused by the enhanced copper absorption from the swimming pool by those parts of the hair fibers which have been subjected to extensive damage, either by a harsh cosmetic treatment or by cumulative exposure to the sun and weathering. CONCLUSIONS The results of the foregoing investigation may be summarized in the form of the following conclusions: a. Blond hair absorbs copper and acquires a green tint when exposed to swimming pool water containing copper in the form of a weak complex such as copper sulfate. Such absorption and consequent coloration does not occur when the copper in the pool water is in the form of a stronger complex such as copper citrate. b. The absorbed copper is primarily located in the peripheral region of the hair fiber. c. Oxidation of the hair by peroxide, even at a very low level, enhances copper absorption. d. Pretreatment of the hair with a formulated quaternary ammonium compound drastically reduces copper absorption and consequently inhibits green coloration. e. The absorbed copper and the resultant green color cannot be washed off by normal shampooing or treatment with a detergent. ACKNOWLEDGEMENT The authors are indebted to Ms. Fidelis Pickup for performing atomic absorption analyses, Mr. Franklin Schiller for providing EDXA-SEM photographs and Dr. Martin K. O. Lindemann for many helpful suggestions. REFERENCES (1) L. B. Holmes and L. A. Goldsmith, The man with green hair, N. Engl. J. Med., 291, 1037 (1974). (2) L. C. Parish, Green hair, N. Engl. J. Med., 292,483 (1975). (3) R. Cooper andJ. Goodman, Green hair, N. Engl. J. Med., 292,483-484 (1975). (4) L. A. Goldsmith and L. B. Hohnes, Green hair, N. Engl. J. Med., 292,484 (1975). (5) R. L. Lampe, A. L. Henderson and G. H. Hansen, Green hair,J. Amer. Med. Assoc., 237, 2092 (1977). (6) Anon., Army physicians weigh causes green hair, C & E News, June 6, 94 (1977). (7) T. E. Nappier, Green hair not due to F, C & E News, Dec. 19, 74 (1977). (8) J. Zercher, More green hair, C & E News, June 16, 64 (1978). (9) W. W. Edman and M. E. Marti, Properties of peroxide-bleached hair, J. Soc. Cosmet. Chem., 12, 133-145 (1961).

8 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS (10) M.j. Taras, A. E. Greenberg, R. D. Hoak and M. C. Rand, "Standard Methods for Examination of Water and Waste Water," 13th ed., American Public Health Association: Washington, D.C., 1971 pp 117-123. (11) Perkin-Elmer, "Analytical Methods for Atomic Absorption Spectrophotometry: Standard Condi- tions," Reference Manual, September 1976. (12) S. Kokot, M. Fenghelman and R. M. Golding, An electron spin resonance study of the Copper (II) interaction with wool-keratin, Part I, Text. Res. J., 42, 704 (1972) Part II, Text. Res. J., 43, 146 (1973) Part III, Text. Res. J., 44, 523 (1974). (13) P. R. Brady, G. N. Freeland, R.J. Hine and R. M. Hoskinson, The absorption of certain metal ions by wool fibers, Text. Res. J, 44, 733-735 (1974). (14) M. S. Masri, "Binding of metallic ions to keratins," Proc. 5th International Wool Textile Res. Conf., Vol. III, 1-10 (1975). (15) R. E. Guthrie and S. H. Laurie, The binding of Copper (III) to mohair keratin, Aust. J. Chem., 21, 2437-2443 (1968). (16) L. J. Wolfram, K. Hall and I. Hui, The mechanism of hair bleaching, J. $oc. Cosmet. Chem., 21, 875-900 (1970). (17) J. Porter and C. Fouweather, An appraisal of human head hair as forensic evidence, J. Soc. Cosmet. Chem., 26, 299-313 (1975).