title: Fully automated analysis of four tobacco-specific N-nitrosamines in mainstream cigarette smoke using two-dimensional online solid phase extraction combined with liquid chromatography-tandem mass spectrometry.
abstract: A fully automated method for the detection of four tobacco-specific nitrosamines (TSNAs) in mainstream cigarette smoke (MSS) has been developed. The new developed method is based on two-dimensional online solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE/LC-MS/MS). The two dimensional SPE was performed in the method utilizing two cartridges with different extraction mechanisms to cleanup disturbances of different polarity to minimize sample matrix effects on each analyte. Chromatographic separation was achieved using a UPLC C18 reversed phase analytical column. Under the optimum online SPE/LC-MS/MS conditions, N'-nitrosonornicotine (NNN), N'-nitrosoanatabine (NAT), N'-nitrosoanabasine (NAB), and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) were baseline separated with good peak shapes. This method appears to be the most sensitive method yet reported for determination of TSNAs in mainstream cigarette smoke. The limits of quantification for NNN, NNK, NAT and NAB reached the levels of 6.0, 1.0, 3.0 and 0.6 pg/cig, respectively, which were well below the lowest levels of TSNAs in MSS of current commercial cigarettes. The accuracy of the measurement of four TSNAs was from 92.8 to 107.3%. The relative standard deviations of intra-and inter-day analysis were less than 5.4% and 7.5%, respectively. The main advantages of the method developed are fairly high sensitivity, selectivity and accuracy of results, minimum sample pre-treatment, full automation, and high throughput. As a part of the validation procedure, the developed method was applied to evaluate TSNAs yields for 27 top-selling commercial cigarettes in China.
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China.
authors.forename: Jie
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China.
authors.forename: Ruoshi
authors.initials: R
authors.lastname: Bai
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China.
authors.forename: Xiaoli
authors.initials: X
authors.lastname: Yi
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China.
authors.forename: Zhendong
authors.initials: Z
authors.lastname: Yang
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China.
authors.forename: Xingyu
authors.initials: X
authors.lastname: Liu
authors.affiliation: Beijing Third Class Tobacco Supervision Station, Beijing 101121, China. Electronic address: zhoujun100@sohu.com.
authors.forename: Jun
authors.initials: J
authors.lastname: Zhou
authors.affiliation: Esensing Analytical Technology Co., Ltd., Shanghai 200336, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Liang
mesh_terms: D001331:Automation; D002851:Chromatography, High Pressure Liquid; D057230:Limit of Detection; D009602:Nitrosamines / Q000032:analysis* / Q000302:isolation & purification*; D012906:Smoke / Q000032:analysis*; D052616:Solid Phase Extraction / Q000295:instrumentation / Q000379:methods*; D053719:Tandem Mass Spectrometry; D062789:Tobacco Products / Q000032:analysis*
chemical_list: D009602:Nitrosamines; D012906:Smoke
keywords: Liquid chromatography–tandem mass spectrometry; Mainstream cigarette smoke; Online solid phase extraction; Tobacco-specific N-nitrosamines; Two-dimensional