ANALYTICAL CHEMISTRY OF COSMETICS 417 This concern has recently been highlighted with respect to D & C Green (1,4-bis[(4-methylphenyl)amino]-9,10-anthracenedione), which is listed in the Code of Federal Regulations (CFR) for use in drugs and cosmetics. Because it is a certified dye, each commercially-prepared batch of this color is subject to FDA certification. This material is formed by reacting 1 mole of quinizarin with 2 moles of p-toluidine. D & C Green//16 has been shown to be safe for external use however, literature reports have demonstrated that p-toluidine is a carcinogen in mice (89). Residual amounts of reactants such as p-toluidine are commonly found in this color, and trace levels are unavoidably present even in highly purified reagent grade material. Until recently, there were no validated methods available for detecting trace levels of p-toluidine in D & C Green//16, thus the reluctance of the FDA to "permanently" list this color for use in consumer products. Several methods have since been reported (90,91) which can detect p-toluidine at the 500 ppb level and probably lower. The methods involve separation by HPLC followed by UV or fluorescence detection. This approach by the regulatory agencies of requiring analytical methodology for hazardous trace components in compounds shown to be safe is becoming standard, and the cosmetic analytical chemist will become more involved in developing trace analytical techniques for quality control of these raw materials. REFERENCES (1) L. R. Snyder and J.J. Kirkland, Introduction to Modern Liquid Chromatography, 2nd Edition (John Wiley & Sons, Inc., New York, 1979). (2) R. Namba, H. Nishiya, A. Shibamoto, Y. Morikawa, S. Tahara, and T. Mitsui, "Development of new automated analysis system of cosmetics by means of computer," IFSSC 12th International Congress, Paris, September 13-17, 1982. (3) Anionic Surfactants--Chemical Analysis, Surfactant Science Series, Vol. 8, J. Cross, Ed. (Marcel Dekker, New York, 1977). (4) J. Cross, Cationic Surfactants, E.Jungermann, Ed. (Marcel Dekker, New York, 1970), pp 419-482. (5) J. H. Jones, General colorimetric method for the determination of small quantities of sulfonated or sulfated surface active compounds,J. Assoc. O•c. Ag. Chemists, 28, 389-409 (1945). (6) G. P. Edwards, W. E. Ewers, and W. W. Mansfield, Determination of sodium cetyl sulfate and its solution in water, Analyst, 77, 205-207 (1952). (7) K. Burger, Methods for quantitative micro-determination and trace detection of surface active compounds. I. Detection and determination of very small amounts of anionics and cationics in aqueous solution, Z. Anal. Chem., 196, 15-21 (1963). (8) G. S. Buchanan and J. C. Griffith, Polarographic estimation of anionic detergents, J. Electroanal. Chem., 5, 204-207 (1963). (9) Laboratory Methods in Infrared Spectroscopy, 2nd Edition, R. G.J. Miller and B.C. Stace, Eds. (Heyden and Sons, Ltd., London, 1972). (10) D. Hummel, Identification and Analysis of Surface Active Agents by Infrared and Chemical Methods (Interscience Publishers, New York, 1962). (11) L.J. Bellamy, The Infrared Spectra of Complex Mokcuks, 2nd Edition (Methuen and Co., Ltd., London, 1958). (12) W. Brugel, An Introduction to Infrared Spectroscopy (Methuen and Co., Ltd., London, 1962). (13) N. B. Colthup, L. H. Daly, and S. E. Wiberley, Introduction to Infrared and Raman Spectroscopy (Academic Press, New York, 1964). (14) R. G. Sinclair, A. F. McKay, G. S. Myers, and R. N. Jones, The infrared absorption spectra of unsaturated fatty acids and esters,J. Am. Chem. Soc., 74, 2578-2585 (1952). (15) M. Aoki and Y. Iwayama, Determination of ionic surface active agents with dyes. IV. Applicability of fluorescein dyes and indicator, and stability of anionic detergents in solution, Yakugaku Zasshi (Tokyo), 80, 1749 (1960) (in Japanese). (16) W. E. Link, H. M. Hickman, and R. A. Morrissette, Gas-liquid chromatography of fatty derivatives. II.
418 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Analysis of fatty alcohol mixtures by gas-liquid chromatography, J. Am. Oil. Chem. Soc., 36, 300 (1969). (17) T. H. Liddicoet and L. H. Smithson, Analysis of surfactants using pyrolysis-gas chromatography, J. Am. Oil. Chem. Soc., 42, 1097 (1975). (18) J. Torrnquist, Quantitative analysis of polyethylene glycol monododecyl ethers by gas chromatogra- phy after silylation, Acta Chemica Scandinavica, 23, 1935-1942 (1969). (19) S. I. Hakomori, A rapid permethylation of glycolipid polysaccharide catalyzed methylsulfonyl carbanion in dimethylsulfoxide,J. Biochem., 55, 205-208 (1964). (20) K. Sj8berg, A stable solution of methylsulfinyl carbanion, Tetrahedron Letters, 51, 6383-6384 (1966). (21) G. Schomburg et al., Gas chromatographic analysis with glass capillary columns, J. Chrom., 122, 55-72 (1976). (22) I.E. Rosenberg and E. Fu, Unpublished research. (23) I.E. Rosenberg andJ-S. Wang, Unpublished research. (24) H. J. Vonk et al., Modern analytical methods for ethoxylated surfactants, T. Mezhdunar. Kongr. Poverkhn.- Akt. Veshehestrum, 1,435-449(1977). (25) E. Julia-Dan(•s and A.M. Casanovas, Application of mass spectroscopy to the analysis of nonionic surfactants, Tenside Deterg., 16, 317-323 (1979). (26) C. K. Cross and A. C. Mackay, Analysis of alkyl ethoxylates by NMR, J. Am. Oil Chem. Soc., 50, 249-250 (1973). (27) H. Walz and H. Kirschnek, Nuclear resonance spectroscopy as a valuable complement to infrared and ultraviolet analysis of surface active compounds, Proc. 3rd Intern. Congr. Surface Active Substances, Koln, 3, 92-98 (1960). (28) A. R. Greif, Jr. and ?. W. Flanagan, The characterization of non-ionic surfactants by NMR,J. Am. Oil Chem. Soc., 40, 118-120 (1963). (29) M. M. Crutchfield, R. R. Irani, and J. T. Yoder, Quantitative application of high resolution proton magnetic resonance measurements in the characterization of detergent chemicals, J. Am. Oil Chem. Soc., 41,129-132 (1964). (30) C. C. Hinckley, Paramagnetic shifts in solution of cholesterol and the dipyridine adduct of trisdipivalomethanatoeuropium (III). A shift reagent, J. Am. Chem. Soc., 91, 5160-5162 (1969). (31) J. K. M. Sanders and D. H. Williams, A shift reagent for use in nuclear magnetic resonance spectroscopy. A first order spectrum of n-hexanol, Chem. Commun., 422-423 (1970). (32) J. K. M. Sanders and D. H. Williams, Tris(dipivalomethanato)europium. A paramagnetic shift reagent for use in nuclear magnetic resonance spectroscopy,J. Am. Chem. Soc., 93,641-645 (1971). (33) G. E. Stolzenberg, R. G. Zaylskie, and P. A. Olson, Nuclear magnetic resonance identification of O,P-isomers in an ethoxylated alkylphenol nonionic surfactant as tris(2,2,6,6-tetramethylheptane- 3,5-dione)europium III complex, Anal Chem., 43,908-912 (1971). (34) C. P. Terweij-Groen, S. Heemstra, andJ. C. Kraak, Distribution mechanism of ionizable substances in dynamic anion exchange systems using cationic surfactants in high performance liquid chromatogra- phy,J. Chromatogr., 161, 69-82 (1978). (35) K. Nakamura, Y. Morikawa, and I. Matsumoto, Rapid analysis of ionic and non-ionic surfactant homologs by high performance liquid chromatography,J. Am. Oil Chem. Soc., 58, 72-77 (1981). (36) A. Nozawa and T. Ohnuma, Improved high performance liquid chromatographic analysis of ethylene oxide condensation by their esterification with 3,5-dinitrobenzoyl chloride, J. Chromatogr., 187, 261-263 (1980). (37) K. Nakamura and Y. Morikawa, Separation of surfactant mixtures and their homologs by high pressure liquid chromatography,J. Am. Oil Chem. Soc., 59, 64068 (1982). (38) J. F. K. Huber et al., Rapid separation and determination of nonionic surfactants of the polyethylene glycol-monoalkyl phenyl ether- type by column liquid chromatography, Anal Chem., 44, 105-110 (1972). (39) K. Aitzetmuller, Application of moving-wire detectors for the liquid chromatography of fats and fatty acid derived oleochemicals,J. Chrom. Sci., 13,454-461 (1975). (40) J.J. Kirkland, Analysis of sulfonic acids and salts by gas chromatography of volatile derivatives, Anal Chem., 32, 1388 (1960). (41) T. Nagai, S. Hashimoto, I. Yamane, and A. Mori, Gas chromatographic analysis for alpha-olefin sulfonates,J. Am. Oil Chem. Soc., 47, 505 (1970). (42) L. D. Metcalf, The direct gas chromatographic analysis of long chain quaternary ammonium compounds,J. Am. Oil Chem. Soc., 40, 25 (1963).
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416 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS ogy which uses a thermal energy analyzer for the analysis of seven classes of cosmetic raw materials (68): ethanolamines, ethanolamides, monoethanolamine salts, trietha- nolamine salts, amphoteric compounds, quaternary ammonium compounds, and morpholine. NDEIA and other polar nitrosamines are very amenable to separation by reverse phase HPLC using either water or water/alcohol mobile phases (69). The water/alcohol mobile phase provides good solubility for the raw material, eliminating the need to perform multiple isolation steps prior to analysis. Quantitation of the nitrosamine is by UV detection. Methods are in the literature for the analysis of NDEIA in ethanol- amines, alkanoladines, and cosmetic products (70-74). Likewise, polography and conductivity detectors have been used for the analysis of NDoe1A (75,76). Since the initial findings of NDoe1A in cosmetics, other nitrosamines have also been shown to be present in trace quantities, and methodology has been developed for each nitrosamine (77). These have all been polar compounds, and both water soluble and oil soluble nitrosamines have been studied. Some methods are available for total nitrosamine in cosmetic raw materials and finished products however, these are generally not rapid and certainly not specific (78). By far the most absolute method for nitrosamine detection is mass spectrometry and, when possible, should be used to confirm the presence of the nitrosamine of interest. Researchers have reported the determination of NDEIA by first forming its disilyl derivative followed by GC/MS analysis (79). The second half of the nitrosamine problem, that of nitrite analysis, has also been explored. The standard colorimetric test developed by Greiss (80) and its subsequent modifications (70,81) can determine low ppb levels of nitrite, while derivative formation followed by fluorescent spectroscopy can measure in the picogram region (82). The CTFA has published nitrite methodology which is specific for cosmetic raw materials (83). More recently, trace analysis for 1,4-dioxane has become significant for the cosmetic analytical chemist. 1,4-dioxane can be present, at trace levels, in some types of ethylene oxide condensates, and this broad class of compounds is widely used in both the food and cosmetic industry. Presently, the "Birkel procedure" (84), which consists of vacuum distillation of a sample followed by gas chromatographic analysis, is the accepted validated procedure. The total analysis time per sample is 2-3 hours with a 0.5 ppm limit of detection. Several other methods have been generated through the CTFA (85). Samples of widely used cosmetic ingredients (i.e., sodium laureth sulfate, Polysorbate 60, and PEG-8) were chosen for study. A total of seven generally different analytical techniques were employed, including the Birkel and modified Birkel procedures. Other methods generated used GC/MS with perdeuterotoluene as an internal standard (86), purge and trap procedures followed by GC, direct OC injection, headspace GC, and atmospheric azeotropic distillation followed by GC (87,88). The CTFA study showed that these alternate procedures yielded results comparable to the Birkel method, except for the purge and trap technique. It was felt that with some additional methods development work, the purge and trap technique could also be improved to the point where it too would be satisfactory. The last couple of years has seen an increased concern within both industry and government in establishing the safety of the dyes and colors used in cosmetic products.
ANALYTICAL CHEMISTRY OF COSMETICS 417 This concern has recently been highlighted with respect to D & C Green (1,4-bis[(4-methylphenyl)amino]-9,10-anthracenedione), which is listed in the Code of Federal Regulations (CFR) for use in drugs and cosmetics. Because it is a certified dye, each commercially-prepared batch of this color is subject to FDA certification. This material is formed by reacting 1 mole of quinizarin with 2 moles of p-toluidine. D & C Green//16 has been shown to be safe for external use however, literature reports have demonstrated that p-toluidine is a carcinogen in mice (89). Residual amounts of reactants such as p-toluidine are commonly found in this color, and trace levels are unavoidably present even in highly purified reagent grade material. Until recently, there were no validated methods available for detecting trace levels of p-toluidine in D & C Green//16, thus the reluctance of the FDA to "permanently" list this color for use in consumer products. Several methods have since been reported (90,91) which can detect p-toluidine at the 500 ppb level and probably lower. The methods involve separation by HPLC followed by UV or fluorescence detection. This approach by the regulatory agencies of requiring analytical methodology for hazardous trace components in compounds shown to be safe is becoming standard, and the cosmetic analytical chemist will become more involved in developing trace analytical techniques for quality control of these raw materials. REFERENCES (1) L. R. Snyder and J.J. Kirkland, Introduction to Modern Liquid Chromatography, 2nd Edition (John Wiley & Sons, Inc., New York, 1979). (2) R. Namba, H. Nishiya, A. Shibamoto, Y. Morikawa, S. Tahara, and T. Mitsui, "Development of new automated analysis system of cosmetics by means of computer," IFSSC 12th International Congress, Paris, September 13-17, 1982. (3) Anionic Surfactants--Chemical Analysis, Surfactant Science Series, Vol. 8, J. Cross, Ed. (Marcel Dekker, New York, 1977). (4) J. Cross, Cationic Surfactants, E.Jungermann, Ed. (Marcel Dekker, New York, 1970), pp 419-482. (5) J. H. Jones, General colorimetric method for the determination of small quantities of sulfonated or sulfated surface active compounds,J. Assoc. O•c. Ag. Chemists, 28, 389-409 (1945). (6) G. P. Edwards, W. E. Ewers, and W. W. Mansfield, Determination of sodium cetyl sulfate and its solution in water, Analyst, 77, 205-207 (1952). (7) K. Burger, Methods for quantitative micro-determination and trace detection of surface active compounds. I. Detection and determination of very small amounts of anionics and cationics in aqueous solution, Z. Anal. Chem., 196, 15-21 (1963). (8) G. S. Buchanan and J. C. Griffith, Polarographic estimation of anionic detergents, J. Electroanal. Chem., 5, 204-207 (1963). (9) Laboratory Methods in Infrared Spectroscopy, 2nd Edition, R. G.J. Miller and B.C. Stace, Eds. (Heyden and Sons, Ltd., London, 1972). (10) D. Hummel, Identification and Analysis of Surface Active Agents by Infrared and Chemical Methods (Interscience Publishers, New York, 1962). (11) L.J. Bellamy, The Infrared Spectra of Complex Mokcuks, 2nd Edition (Methuen and Co., Ltd., London, 1958). (12) W. Brugel, An Introduction to Infrared Spectroscopy (Methuen and Co., Ltd., London, 1962). (13) N. B. Colthup, L. H. Daly, and S. E. Wiberley, Introduction to Infrared and Raman Spectroscopy (Academic Press, New York, 1964). (14) R. G. Sinclair, A. F. McKay, G. S. Myers, and R. N. Jones, The infrared absorption spectra of unsaturated fatty acids and esters,J. Am. Chem. Soc., 74, 2578-2585 (1952). (15) M. Aoki and Y. Iwayama, Determination of ionic surface active agents with dyes. IV. Applicability of fluorescein dyes and indicator, and stability of anionic detergents in solution, Yakugaku Zasshi (Tokyo), 80, 1749 (1960) (in Japanese). (16) W. E. Link, H. M. Hickman, and R. A. Morrissette, Gas-liquid chromatography of fatty derivatives. II.

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