Simultaneous quantification of five odorous steroids (16-androstenes) in the axillary hair of men

Five 16-androstenes have been simultaneously quantified in extracts of the axillary hair of men (age range 18-40 years) using combined capillary gas chromatography-mass spectrometry, with specific ion monitoring. Quantities found (pmol/mg.hair, with approximate 24-h totals in parentheses) were: 5 alpha-androst-16-en-3-one, 0-15 (0-433); 4, 16-androstadien-3-one, 0-143 (0-4103); 5,16-androstadien-3 beta-ol, 0-3.5 (0-728); 5 alpha-androst-16-en-3 alpha-ol, 0-17 (0-1752) and 5 alpha-androst-16-en-3 beta-ol, 0-4 (0-416). There were no significant relationships with age of the subjects for any of the steroids measured but significant relationships were found between the amounts of the two ketones and between 5 alpha-androst-16-en-3 alpha- and 3 beta-ols. These findings may indicate the existence of a pathway of metabolism in axillary bacteria in which 4,16-androstadien-3-one is reduced to 5 alpha-androst-16-en-3-one and thence to the 3 alpha- and 3 beta-alcohols. The data are discussed in the context of axillary odour because of the low olfactory thresholds of several of the 16-androstenes measured and because of the relatively large quantities found in some subjects.