Continuous solid-phase extraction method for the determination of amines in human urine following on-line microwave-assisted acid hydrolysis

Humans are exposed to endogenous or exogenous formation of aromatic amines (AAs) and N-nitrosamines (NAms), which are considered to be potent carcinogens. The objective of this study was to monitor AAs and NAms in human urine to obtain a way to assess exposure. However, while NAms can be directly detected in urine samples, AAs require hydrolysis to convert their conjugates into free amines. A semiautomatic flow-base method is proposed for the simultaneous determination of aliphatic and aromatic NAms, anilines and chloroanilines in human urine in one analytical run. Conjugated AAs are released from urine by on-line microwave-assisted acid hydrolysis without degradation of NAms; all amines were then preconcentrated using solid-phase extraction. Separation/determinations are carried out by gas chromatography and mass spectrometry operating in selected ion monitoring mode. The method is fast (∼15 min for 25 mL of sample) and provides low limits of detection (from 2 to 26 ng/L) with good precision (relative standard deviation within and between days less than 7%). Finally, the proposed method was successfully applied to check AAs and NAms in the human urine of exposed and unexposed researchers. The kinetics of amine excretion in the urine of the researchers exposed is calculated after termination of the exposure and shows half-life times between 1.3 and 2.1 h, and that the dosage absorbed was eliminated within 6 h after exposure.