ANALYSIS OF NITROSAMINES 317 Table XlV Experimental Data From GC-TEA Methods for Consumer Products Product type a Detected range of nitrosamines, ppb No. of Refer- samples NDELA NDOMA NMTDA NDMA NMEA NDEA NMODA NMor ences Hair conditioners 17 11 9 5 25, 28 Hot oil treatments 2 604-873 218-254 25 Dishwashing compounds b -- 1 - 11 2- 5 1- 8 13 Shampoos 56 •660 16-203 8-76 •24 •640 25, 28, 29 Hair rinses 4 •83 •25 25 Shampoos w/SO 4 28-969 26 Hair sprays w/SO 1 56 26 Conditioners w/SO 3 33- 688 26 Conditioners w/SCL 1 67 26 Color enhancer w/SCL 1 42 26 Moisturizer w/SCL 1 261 26 Color toners 7 •46 10 28 Foam baths 12 •90 28, 29 Shower gels 9 •60 10 •380 28 Cream and bath oils 8 •20 •440 28 Children's shampoos 5 •45 •20 •230 28 Children's bath and care products 8 1400 10 •360 28 Body lotion 11 132 28, 29 Facial cleansers, masks, and tonics 29 •200 •3 28 Suntan lotions 5 5 - 2000 29 Abbreviations: NDELA, N-nitrosodiethanolamine NDOMA, N-nitrosododecylmethylamine NMTDA, N-nitrøsømethyltetradecylamine NDMA, N-nitrosodimethylamine NMEA, N-nitrosomethylethylamine NDEA, N-nitrosodiethylamine NMODA, N-nitrosomethyloctadecylamine NMor, N-nitrosomorpholine SO, Stearamine oxide SCL, Stearalkonium chloride. a Product type: Each sample contained none, one, or a combination of several different nitrosamines. Listed are only relative ranges for that particular group. b Dishwashing compounds: Number of samples analyzed not specified. detector of choice for the determination of trace levels of N-nitroso compounds. Alter- nate analytical methods for determining nitrosamines are non-selective for the N-ni- troso functionality, with the exception of mass spectrometry, which has been employed for unequivocal confirmation of the nitrosamine structure. Because of the many matrix
318 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table XV Experimental Data From GC-ECD Application for Consumer Products Product type No. of samples N-nitrosodiethanolamine, ppb References Cleansing gels 3 •6.3 58 Slimming gels 3 1 58 Misc. cosmetic creams 8 •0.38 58 Skin creams 8 •0.25 58 interferences encountered in most cosmetic products, only specific detectors such as the TEA have general utility in this analysis. In certain specific cases, gas chromatography has been used for the quantitation of volatile nitrosamines and volatile derivatives of thermally lablie nitrosamines. Similarly, high-performance liquid chromatography has been used extensively for determining nonvolatile nitrosamines, such as N-nitroso- diethanolamine, in a variety of matrices. Although the high specificity of the TEA makes it the detector of choice for nitrosa- mine analysis, its high initial cost and the complexity of its operation (typically a dedicated operator is required) have encouraged development of simpler, less expensive methods. This would be particularly desirable for routine quality assurance and product stability testing applications. Unfortunately, the routine use of any trace analysis procedure is usually not a simple task to accomplish. In the experience of these authors, the greatest challenge in the successful use of trace analytical techniques occurs in the sample preparation steps, not in the actual analytical determination. Thus, most attempts at developing simple non- TEA methods have resulted in either very limited, matrix-specific methods or quite complex methods involving large numbers of complicated sample preparation steps. For the analyst seeking a quick, inexpensive, simple, specific method for the determination of trace levels of nitrosamines in cosmetics, neither the TEA nor existing non-TEA methods are completely acceptable. Future efforts in this area will undoubtedly focus on addressing this problem in the hope of simplifying the complex task of determining trace amounts of nitrosamines in a variety of environmental matrices. Table XVI Experimental Data From HPLC-TEA Applications for Consumer Products No. of N-nitrosodiethanolamine, Product type samples ppb References Misc. cosmetics 7 1-25000 1 Misc. lotions 13 140 1 Shampoos 16 •4113 1, 57 Liquid soaps 1 20 57 Creams - 1 1 57 Bubble bath 1 26.5 57 Diethanolamine 1 1 57 Triethanolamine lauryl sulfate 1 12.8 57 Triethanolamine alkylamino ethersulfate 1 1 57
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