Determination of aromatic primary amines at μg l −1 level in environmental waters by gas chromatography–mass spectrometry involving N-allyl- N′-arylthiourea formation and their on-line pyrolysis to aryl isothiocyanates

Abstract

Derivatization of aromatic primary amines to N-allyl- N′-arylthioureas by reaction with allyl isothiocyanate and GC–MS of the derivatives, when pyrolysis to aryl isothiocyanates occurs in the heated injector, has been used to determine aromatic amines in the range 0.5–50 μg l −1 with a correlation coefficient, r, in the range 0.9902–0.9992. The limit of detection ranged 8 to 30 ng l −1 when 60 ml of sample were preconcentrated, after derivatization, on a styrene–divinylbenzene copolymer sorbent. The pyrolytic cleavage of sym- and unsym-diaryl or alkyl-/arylthioureas has been rationalized. The chromatography of isothiocyanates is much superior to that of aryl amines and the specific mass fragmentation permits positive identification of amines. The method has been applied to spiked drinking water, groundwater and river water samples, when the recovery ranged from 84 to 109% with RSD of 5–9%, and to detect aromatic amines formed by reductive cleavage of azo dyes in effluents when the recovery of amine was in the range 81–95% with RSD 8–15%. The method is not applicable to nitroanilines.