GAS-CHROMATOGRAPHIC MASS-SPECTROMETRIC ANALYSIS OF DIOLS AND TETROLS FROM REACTIONS OF POLYCYCLIC AROMATIC HYDROCARBON EPOXIDES WITH HEMOGLOBIN

We have evaluated both electron ionization (EI) and negative-ion chemical ionization (NICI) methods for the analysis of trimethylsilyl derivatives of a series of polycyclic aromatic hydrocarbon (PAH) alcohols including styrene diol, benzo[e]pyrene diol and tetrols, cyclopenta[c,d]pyrene diols, benzo[a]pyrene-4,5-diols, chrysene tetrols, benz[a]anthracene tetrols I and II, and syn- and anti-benzo[a]pyrene tetrols. NICI is the more sensitive method for all compounds except styrene diol. Detection limits are compound-dependent and range from 1 fmol for cyclopental[c,d]pyrene diol to 1 pmol for benzo[e]pyrene diol. The EI detection limit for styrene diol is 60 fmol. PAH alcohols related to the compounds listed above were observed following hydrolysis of hemoglobin which had been reacted with PAH epoxides in vitro. Benzol[a]pyrene tetrols and a chrysene tetrol were observed following hydrolysis of hemoglobin isolated from human smokers' blood. Hydrolysis of styrene oxide treated hemoglobin in O-18-labeled water revealed at least two mechanisms of ester hydrolysis, including the B(AL)1 pathway.