Identification of oestrogen metabolites in human urine by capillary gas chromatography and mass spectrometry.

Oestrogen metabolites from the urine of males and pregnant and non-pregnant females were enriched by a procedure involving column chromatography on adsorber resins, gels and ion exchangers, enzymatic solvolysis and extraction, thereby separating the oestrogens from most of the interfering material. After derivatization of the oestrogens as their trimethylsilyl ethers profiles were measured with a fused silica column and a flame ionization detector by gas chromatography. Using a combination of capillary gas chromatography and mass spectrometry approximately 50 oestrogen metabolites were detected in the human urine of males and females, of which 19 were unknown urine compounds. Not all could be identified definitely owing to the lack of reference material. Mass spectra of trimethylsilylated oestrogens with functional groups at position 11 (11-dehydroestradiol, 11-dehydroestrone and 11 beta-hydroxyestrone) were discussed in their common and discernible fragmentations.