J. $oc. Cosmet. Chem., 30, 1-8 (January/February 1979) The green hair problem: a preliminary investigation G. RAMACHANDRA BHAT, ELVIN R. LUKENBACH, ROBERT R. KENNEDY and ROGERIO M. PARREIRA Johnson &Johnson Baby Products Company, Raritan, NJ 08869. Received July 26, 1978. Synopsis The phenomenon of blond hair acquiring a green tint when exposed to swimming pool water containing copper is examined. The GREEN coloration is attributable to absorption of copper by HAIR which occurs when the former is present in the water in the form of a weak complex such as copper sulfate. Oxidation of the hair enhances copper absorption and pretreatment with a formulated quaternary ammonium compound inhibits the process. The green color cannot be stripped by subsequent shampooing. INTRODUCTION Many people with natural or dyed blond hair encounter the problem of having their hair acquire a green tint after frequent exposure to swimming pool water (1-8). This problem is usually speculatively attributed to the sorption on to the hair of copper, present in swimming pool water either from corrosion of copper plumbing or from copper salts added to the pool as algaecides. It is commonly thought that the green color can be removed by shampooing. The' scientific literature, however, has few references to investigation of hair-copper interactions directed toward the speculations mentioned above. The most informative work in this respect is that of Edman and Marti (9). The authors have shown that hair treated in a solution of copper sulfate acquires a green color and that the copper uptake, which they have calculated from the extent of depletion in solution, provides a method for indicating small oxidation damage to hair fibers. The work reported has three parts: to investigate discoloration of hair by interaction with copper in a simulated swimming pool to determine the effects of mild oxidation of hair on such interaction and to examine the effects of a formulation containing a quarternary ammonium compound as a pretreatment. While this investigation is confined to discoloration of hair due to copper, it is realized that other elements such as chromium, nickel and cobalt may be present in the swimming pool water and may cause similar effects. Copper, however, is certainly a more likely candidate since copper-based algaecides are available in the market as swimming pool additives.

2 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table I Experimental Design and Treatment Bath Compositions Pretreatment Water Conditioner Hair Unoxidized Oxidized Unoxidized Oxidized Treatment Bath//1 --100 mg CuSO4.SH20 dis- solved in 100 ml distilled water Nominal pH = 6.0 --100 ml 1:1000 prediluted Same as//1 Clorox added --volume adjusted to 2000 ml with distilled water --this gave 5.9 pH no pH ad- justment made Treatment Bath//2 Nominal pH = 8.5 Treatment Bath//3 --100 mg CuSO4.5H20 dis- solved in 100 ml distilled water --500 mg citric acid added --100 ml 1:1000 prediluted Clorox added --volume adjusted to 2000 ml with distilled water --pH adjusted to 8.5 pH with NaOH Treatment Bath//4 Same as//3 EXPERIMENTAL PREPARATION OF MATERIAL The material was prepared in accordance with the experimental design shown in Table I. Natural white or blond hair (De Meo Brothers, New York, N.Y.) formed into eight tresses, approximately 0.5 g each, was used in the experiment. Four of the tresses were mildly oxidized by treating with a 3% aqueous solution of hydrogen peroxide adjusted to 10.5 pH using ammonium hydroxide. A drop of Triton X-100 was added to the solution to facilitate wetting of the hair. The oxidation treatment was carried out for a period of 15 min at 22øC. All tresses were then cleaned in warm methanol. Four of the tresses--two unoxidized and two oxidized--were immersed in distilled water and the other four were immersed in a commercial formulation of a quaternary ammonium compound (distearyl-dimethyl ammonium chloride) for 10 min for pretreatment and subsequently blow-dried for 2 hr at 22øC. SIMULATED SWIMMING POOL TREATMENT The experiment was carried out in four different simulated swimming pools or treatment baths--two at a low pH (6.0) and the other two at a high pH (8.5)•as shown in Table I. The compositions of the treatment baths are described in the table. It is to be noted that an attempt to prepare copper sulfate solution at 8.5 pH failed as the copper precipitated out in the form of copper hydroxide. For this reason citric acid was added in order to form the more stable copper citrate complex and thereby keep the copper in solution at the 8.5-pH level.