GC/MS analysis of biologically important aromatic amines. Application to human dosimetry

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Abstract
Human exposure to aromatic amines may be monitored by measuring the amount of sulfinamide adduct bound to hemoglobin. In order to develop a sensitive and selective method for measuring aromatic amines present in low concentrations the mass spectra of the pentafluoropropionamide derivatives of a series of aromatic amines were determined under various ionization conditions. With electron ionization the aromatic amine derivatives typically yield intense molecular ions with fragmentation leading to elimination of C2F5 and COC2F5. Higher molecular weight polycyclic aromatic amines, e.g., 6-aminochrysene, give prominent molecular ions as well as intense ions corresponding to M–174 (loss of CNHCOC2F5). With positive chemical ionization using methane as reagent gas the derivatives give protonated molecular ions as the base peaks, as well as the associated ions at M + 29 and M + 41. Negative ion chemical ionization yields, primarily, peaks corresponding to the loss of HF from the molecular anions. Negative ion chemical ionization with selected ion monitoring is generally more suitable than positive chemical ionization or electron ionization for the quantitative analysis of aromatic amines present in biological samples in the mid femtomolar range. Exposure of human subjects to aromatic amines was determined via basic hydrolysis of the isolated sulfinic acid amide hemoglobin adducts. Analysis of the derivatized extracts by gas chromatography/negative ion chemical ionization/mass spectrometry demonstrated the presence of aniline, ortho-, meta-, and para-toluidine, 2-naphthylamine, and 4-aminobiphenyl. The hemoglobin adduct levels of these amines in both cigarette smokers and nonsmokers were determined. The mean values of the adduct levels of ortho- and para-toluidine, 2-naphthylamine, and 4-aminobiphenyl were higher in smokers than in nonsmokers, while the mean adduct values of aniline and meta-toluidine were similar in both groups. Adducts of 2-, 3-, 4-ethylaniline, 2,3-, 2,4-, 2,5-, 2,6-dimethylaniline, and 3-aminobiphenyl have been detected in smokers' blood. 1-Aminoanthracene, 9-aminophenanthrene, and 6-aminochrysene have not been detected. GC/MS procedures were also used to determine the extent of binding of aniline-2,3,4,5,6-d5 to hemoglobin in rats administered aniline-d5.