Analysis of Acrylonitrile and alpha-Methacrylonitrile in Vapor Phase of Mainstream Cigarette Smoke Using a Charcoal Trap for Collection

Abstract

A simple procedure for the collection of vapor phase (VP) of mainstream cigarette smoke for analysis has been developed. This procedure consists of collecting the VP on a commercial charcoal trap (ORBO™-32) followed by dissolution in acetone. The acetone extract can be analyzed by a gas chromatography/mass spectrometry (GC/MS) technique. A qualitative analysis of the collected VP has been performed for 3R4F Kentucky reference cigarette, allowing the identification of 138 compounds, some compounds being present in both VP and in particulate phase (PP) of cigarette smoke. A quantitative analysis method for acrylonitrile and α-methacrylonitrile (2-methyl-2-propenenitrile) was also developed, and the level of these compounds in 15 different cigarette brands was measured. Acrylonitrile quantitation was selected since this compound in smoke poses significant health related issues. α-Methacrylonitrile quantitation was selected due to the similar structure of this compound with acrylonitrile. The analyzed cigarettes were several Kentucky reference cigarettes including 1R5F, 2R4F, 3R4F, 2R1F, and 1R3F, several King Size (KS) commercial cigarettes from the US market including Basic Non Filter (NF), Basic Ultra Lights (UL), Newport, Marlboro (Red), Marlboro Menthol, Camel Filter, Camel Lights, Camel Ultra Lights, and two herbal cigarettes, Ecstasy and Dreams. The results for acrylonitrile were in very good agreement with data reported in the literature for 2R4F and 1R5F cigarettes. The levels of α-methacrylonitrile were not previously reported. The correlation between the levels of acrylonitrile and of α-methacrylonitrile with the (wet) total particulate matter (TPM) was evaluated. Although the levels of acrylonitrile and of α-methacrylonitrile in mainstream smoke depend on the TPM values, the correlation is not very strong, indicating that the nature of the cigarette blend and possible other factors in cigarette construction also influence their levels in smoke. The collection method used in this study allows the subsequent dissolution of VP in a much smaller volume of solvent compared to other methods that use impingers, allows the use of standard GC/MS autosamplers for liquid injection and simple addition of internal standards compared to the methods that use gas bags, and allows a simple and immediate collection of VP as it leaves the Cambridge filter pad. These characteristics represent significant advantages versus other methods commonly used for VP analysis.

Comment on amt-2024-94

“…Methyl isocyanate (CH3NCO, MIC) and hydroxyacetonitrile (HOCH2CN, glycolonitrile, HAN) (Wolfsie, 1960) are toxic reduced nitrogen isomers present in an extreme range of environments. MIC has been reported in wildfire and bio-mass burning, e.g., Koss et al (2018), and building fire emissions (Blomqvist et al, 2003), agricultural fumigation plumes (Woodrow et al, 2014), and indoor air (Bekki et al, 2018), particularly where there is cigarette smoke (Moldoveanu, 2010), cooking emissions, and chlorine-disinfectant use. HAN has been observed spectroscopically in interstellar space (see Zhao et al (2021) and references within), while measurements in the Earth's atmosphere have not been reported to date.…”

Calibration of Hydroxyacetonitrile (HOCH2CN) and Methyl isocyanate (CH3NCO) Isomers using I- Chemical Ionization Mass Spectrometry (CIMS)

“…Methyl isocyanate (CH3NCO, MIC) and hydroxyacetonitrile (HOCH2CN, glycolonitrile, HAN) (Wolfsie, 1960) are toxic reduced nitrogen isomers present in an extreme range of environments. MIC has been reported in wildfire and bio-mass burning, e.g., Koss et al (2018), and building fire emissions (Blomqvist et al, 2003), agricultural fumigation plumes (Woodrow et al, 2014), and indoor air (Bekki et al, 2018), particularly where there is cigarette smoke (Moldoveanu, 2010), cooking emissions, and chlorine-disinfectant use. HAN has been observed spectroscopically in interstellar space (see Zhao et al (2021) and references within), while measurements in the Earth's atmosphere have not been reported to date.…”