Isocyanic acid (ICA) in vapour phase has been reported to be of unstable nature, making the occupational hygienic relevance of ICA questionable. The stability of pure ICA in clean air at different humidity conditions was investigated by Fourier transform-infrared spectrometric (FT-IR) measurements. Furthermore, the stability of ICA in a complex atmosphere representative thermal degradation hot-work procedures were examined by performing parallel measurements by proton transfer reaction-mass spectrometric (PTR-MS) instrumentation and off-line denuder air sampling using di-n-butylamine (as a derivatization agent prior to liquid chromatography mass spectrometric (LC-MS) determination). The apparent half-life of ICA in pure ICA atmospheres was 16 to 4 hours at absolute humidity (AH) in the range 4.2 to 14.6 g m−3, respectively. In a complex atmosphere at an initial AH of 9.6 g m−3 the apparent half-life of ICA was 8 hours, as measured with the denuder method. Thus, thermally formed ICA is to be considered as a potential occupational hazard with regard to inhalation. The generation pattern of ICA formed during controlled gradient (100–540 °C) thermal decomposition of different polymers in the presence of air was examined by parallel PTR-MS and denuder air sampling. According to measurement by denuder sampling ICA was the dominant aliphatic isocyanate...
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